1 International Key Comparison COOMET.QM-K3 Final report L.A. Konopelko 1 , Yu.A. Kustikov 1 , A.V. Kolobova 1 , M.S. Rozhnov 2 N.V. Khairova 3 , A.S. Kluchits 3 , H.-J. Heine 4 1 D.I. Mendeleyev Institute for Metrology (VNIIM), Research Department for the State Standard in the Field of Physical-Chemical Measurements (PCD), 19, Moskovsky pr., St.-Petersburg, 198005, Russia 2 All Ukrainian State Research-Industrial Center of Standardization, Metrology, Certification and Protection of Consumers (Ukrmetrteststandard), Metchimenergotest, 4, Metrologicheskaya str., Kiev, 03143, Ukraine 3 Belorussian State Institute for Metrology (BelGIM), Department of Physical-Chemical and Optical Measurement, Sector of Standards and Gas Mixtures, 93, Starovilenskiy pr., Minsk, Buelorus 4 Federal Institute for Materials Research and Testing (BAM), Labor I.43, Unter den Eichen 87, D-12205, Berlin, Germany Field Amount of substance: gas analysis Subject International comparisons of national measurement standards in the field of analysis of gas mixtures of CO 2 , CO, C 3 H 8 in nitrogen (automobile gases) Participants: Institute City Country VNIIM St. Petersburg Russia Ukrmetrteststandard Kiev Ukraina BelGIM Minsk Belarus BAM Berlin Germany Organising body TC 1.8 «Physical Chemistry» COOMET Rationale This comparison is the first key comparison in the field of gas analysis organized by Technical Committee 1.8 «Physical Chemistry» COOMET. The comparison was registered in international database on key comparison (KCDB), Appendix B of MRA, as COOMET.QM-K3. This comparison is the fourth key comparison on automobile gases. Earlier key comparisons on automobile gases were carried out by Consultative Committee for Amount of Substance CCQM- K3 (the results were published on 21 November 2001) and by regional metrological organizations EUROMET, APMP (EUROMET.QM-K3 – the results were published on 5 July 2002, APMP.QM-K3 - the results were published on 14 November 2003). The relevance of the comparison is founded by tightening of requirements to a control of automobile emissions (putting EURO 4, EURO-5 into operation). Foundation of this comparison:
Transcript
1
International Key Comparison COOMETQM-K3 Final report LA Konopelko1 YuA Kustikov1 AV Kolobova 1 MS Rozhnov2 NV Khairova3 AS Kluchits3 H-J Heine4 1DI Mendeleyev Institute for Metrology (VNIIM) Research Department for the State Standard in the Field of Physical-Chemical Measurements (PCD) 19 Moskovsky pr St-Petersburg 198005 Russia 2All Ukrainian State Research-Industrial Center of Standardization Metrology Certification and Protection of Consumers (Ukrmetrteststandard) Metchimenergotest 4 Metrologicheskaya str Kiev 03143 Ukraine 3Belorussian State Institute for Metrology (BelGIM) Department of Physical-Chemical and Optical Measurement Sector of Standards and Gas Mixtures 93 Starovilenskiy pr Minsk Buelorus 4Federal Institute for Materials Research and Testing (BAM) Labor I43 Unter den Eichen 87 D-12205 Berlin Germany Field Amount of substance gas analysis Subject International comparisons of national measurement standards in the field of analysis of gas mixtures of CO2 CO C3H8 in nitrogen (automobile gases) Participants
Institute City Country VNIIM St Petersburg Russia Ukrmetrteststandard Kiev Ukraina BelGIM Minsk Belarus BAM Berlin Germany Organising body TC 18 laquoPhysical Chemistryraquo COOMET Rationale This comparison is the first key comparison in the field of gas analysis organized by Technical Committee 18 laquoPhysical Chemistryraquo COOMET The comparison was registered in international database on key comparison (KCDB) Appendix B of MRA as COOMETQM-K3 This comparison is the fourth key comparison on automobile gases Earlier key comparisons on automobile gases were carried out by Consultative Committee for Amount of Substance CCQM-K3 (the results were published on 21 November 2001) and by regional metrological organizations EUROMET APMP (EUROMETQM-K3 ndash the results were published on 5 July 2002 APMPQM-K3 - the results were published on 14 November 2003) The relevance of the comparison is founded by tightening of requirements to a control of automobile emissions (putting EURO 4 EURO-5 into operation) Foundation of this comparison
2
bull Formation of circumstances for recognition of national measurement standards of Belarus and Ukraine which earlier did not participate in key comparisons and entering of calibration and measurement capabilities (CMC) of BelGIM and Ukrmetrteststandard in the field of automobile gases to the international database KCDB in accordance with Mutual Recognition Arrangement (CIPM MRA) for national measurement standards and for calibration and measurement certificates issued by NMIs
bull Objective of NMIs which participated in key comparisons on automobile gases earlier (BAM VNIIM) is to support or improve our calibration and measurement capabilities
Measurement standards The design of this comparison was adopted from key comparison CCQM-K3 The gas mixtures for the comparison were prepared by means of gravimetry and were studied thoroughly regarding its composition and stability at the coordinating laboratory (VNIIM PCD) The nominal amount of substance ratios of components in gas mixtures read as follows Carbon dioxide 135 mmolmol Carbon monoxide 30 mmolmol Propane 2 mmolmol Nitrogen balance Schedule The cylinders with gas mixtures were sent out to all participants of the comparison on April 2005 The measurement results were submitted by the participants on August ndash October 2005 All cylinders with gas mixtures were dispatched to the coordinating laboratory on November 2005 In connection with customs delay of the cylinders with gas mixtures the date of re-analysis of these gas mixtures was extended till January 2006 The laboratories were also requested to submit the calculation of expanded uncertainty with the uncertainty budget Measurement protocol The measurement protocol requested each laboratory to perform at least 3 measurements obtained under repeatability conditions including at least three separate calibrations The protocol informed the participants about the nominal concentration ranges Measurement equation The measurement model has been taken from the key comparison CCQM-K3 [3] The gas mixtures for the comparison were prepared by means of gravimetry in accordance with requirements of ISO 6142 [1] and were studied thoroughly regarding its composition and stability at the coordinating laboratory (VNIIM PCD) in accordance with requirements of ISO 6143 [2] A confidence on gravimetric values of gas mixtures used for this key comparison CCQM-K3 is adopted by VNIIM results from CCQM-P23 VNIIM gravimetric capability for 50 mmolmol and 1 mmolmol CO were comparable with other NMIs within 007 It was prepared nine gas mixtures three of which were sent to participants for study Three groups of uncertainty sources have been considered for the gravimetric preparation of gas mixtures 1 gravimetric preparation (weighing process) 2 purity of the parent gases 3 stability of the gas mixtures
There has been no evidence that there would be relevant effect of adsorption and the component of gas mixtures has been known as very stable compounds so that only the first two groups of
3
uncertainty components appear in the model for evaluating the uncertainty from gravimetric preparation
)()()( 222purityweighinggravp xuxuxu ∆+= (1)
A second contributor to the uncertainty of the reference value of gas mixtures ugravR is the uncertainty from verification u(xver) The verification process is used to confirm the gravimetric composition by NDIR analyzer included to the set of National Primary Measurement Standard GET 154-01 as checking internal consistency between prepared cylinders in accordance with requirements of ISO 6143 [2]
gravRgravR kuU = (2) where
)()( 22vergravpgravR xuxuu += (3)
k=2 Measurement methods and calibration procedures The following methods of measurement and calibration methods have been employed (table 1) Table 1 Measurement and calibration methods Laboratory Measurement
method Calibration method Total number of
measurements VNIIM NDIR Three points
linear 3 measurements 5 submeasurements
Ukrmetrteststandard GC-TCD (COCO2) GC-FID (C3H8)
Three points linear Three points linear
2 measurements 3 submeasurements
BelGIM GC-TCD (COCO2) GC-FID (C3H8)
Three points linear Three points linear
3 measurements 6 submeasurements
ВАМ GC-TCD (COCO2) GC-FID (C3H8)
Bracketing Bracketing
5 measurements 9 submeasurements
Results In the current comparison on gas mixtures measurements were performed on individually prepared gas mixtures with (slightly) different concentrations The individual gravimetric values are reference values The difference between the analyzed and gravimetric values has been taken as degree of equivalence Di defined as
igravilabi xxD minus= (4) The combined standard uncertainty of the degree of equivalence can be expressed as
4
2
2
)( igravRilabi uuDu += (5) The expanded uncertainty )( iDU of the degree of equivalence Di
2
2)( igravRilabi uukDU += (6)
where Di ndash Degree of equivalence difference between the laboratory value and the gravimetric value U(Di) ndash Expended uncertainty of the degree of equivalence
gravx - Assigned amount of substance fraction of a component
labx - Result as reported by the participant
gravRu - Standard uncertainty of gravx
labu - Standard uncertainty of labx k - Coverage factor 2=k All results of this key comparison are presented in the tables 2 ndash 4 and shown in figures 1 ndash 3 The tables 2 - 4 contain the following information Lab Laboratory Cylinder Identification code of cylinder
gravx Assigned amount of substance fraction of a component
gravRU Expended Uncertainty of gravx 2=k
labx Result as reported by the participant
labU Expended Uncertainty of labx Di Degree of equivalence
)( iDU Expended Uncertainty of Di
labk Coverage factor as reported by the participant Calculation of expanded uncertainty was carried out with coverage factor k=2 Degrees of equivalence The unilateral degree of equivalence has already been defined (4) For the bilateral degrees of equivalence the model used for CCQM-K1 has been adapted The degree of equivalence between two laboratories is defined as
jgravjlabigravilabij xxxxD minusminusminus= (7) where
igravx - the assigned value for the laboratory i
ilabx -the amount of substance fraction of the laboratory i
jgravx - the assigned value for the laboratory j
5
jlabx - the amount of substance fraction of the laboratory i The expanded uncertainty of the degree of equivalence Dij (k=2)
Discussion and Conclusions All laboratories find the gravimetric value within plusmn07 relative to the gravimetric value This holds for all three components COCO2 and C3H8 in nitrogen This is a satisfying result For all laboratories the observed difference between the gravimetric and reported values does not exceed its combined uncertainty VNIIM and BAM are link laboratories for CCQM-K3 The results of this comparison are linked to the key comparison CCQM-K3 Reference [1] International Organization for Standardization ISO 61422001 Gas analysis - Preparation of calibration gas mixtures - Gravimetric methods 2nd edition [2] International Organization for Standardization ISO 61432001 Gas analysis ndash Comparison methods for determining and checking the composition of calibration gas mixtures [3] Van der Veen AMH De Leer EWB Perrochet J-F Wang Lin Zhen Heine H-JKnopf D Richter W Barbe J Marschal A Vargha G Deaacutek E Takahashi C Kim JS Kim YD Kim BM Kustikov YA Khatskevitch EA Pankratov VV Popova TA Konopelko L Musil S Holland P Milton MJT Miller WR Guenther FR International Comparison CCQM-K3 Final Report Coordinator Leonid Konopelko VNIIM Research Department for the State Standard in the Field of Physical-Chemical Measurements (PCD) 19 Moskovsky pr St-Petersburg 198005 Russia Phone +7 812 3151145 Fax +7 812 3279776 E-mail lkonopmailrcomru Completion Date March 2006
11
Annex 1 Proposal of Degrees of Equivalence Table 5 Degrees of Equivalence for carbon monoxide Lab j VNIIM Ukrmetrteststandard BelGIM BAM Lab i Di Ui Dij Uij Dij Uij Dij Uij Dij Uij mmolmol mmolmol mmolmol mmolmol mmolmol VNIIM 001 006 012 014 007 021 005 016 Ukrmetrteststandard -011 012 -012 014 -005 024 -007 019 BelGIM -006 020 -007 021 005 024 -002 025 BAM -004 015 -005 016 007 019 0016 025 Table 6 Degrees of Equivalence for carbon dioxide Lab j VNIIM Ukrmetrteststandard BelGIM BAM Lab i Di Ui Dij Uij Dij Uij Dij Uij Dij Uij mmolmol mmolmol mmolmol mmolmol mmolmol VNIIM 012 013 026 026 -074 101 0034 043 Ukrmetrteststandard -014 022 -026 026 -10 102 -023 046 BelGIM 086 100 074 101 10 102 077 108 BAM 009 041 -0034 043 023 046 -077 108 Table 7 Degrees of Equivalence for propane Lab j VNIIM Ukrmetrteststandard BelGIM BAM Lab i Di Ui Dij Uij Dij Uij Dij Uij Dij Uij mmolmol mmolmol mmolmol mmolmol mmolmol VNIIM 0001 0004 0002 0006 0005 0020 -0009 0013 Ukrmetrteststandard -0001 0004 -0002 0006 0003 0021 -0011 0013 BelGIM -0004 0020 -0005 0020 -0003 0021 -0014 0023 BAM 0010 0012 0009 0013 0011 0013 0014 0023
12
Annex 2 Results and measurement reports as submitted by participating laboratories Key comparison participants
MEASUREMENT REPORT - DI Mendeleyev Institute for Metrology
Russian Federation (VNIIM)
I Results of Study
Laboratory DI Mendeleyev Institute for Metrology (VNIIM) Research Department for the State Standard in the Field of Physical-Chemical Measurements (PCD)
Instruments Multichannel automatic NDIR analyzer included to the set of the National Primary measurement standard of units of mole fraction and mass concentration of components in gas medium GET 154-01 was used for the analysis Calibration Standards All calibration multicomponent gas mixtures were prepared gravimetrically according to ISO 6142 The calibration multicomponent gas mixtures were prepared from pure gases directly on components CO CO2 and from pre-mixtures which were prepared from pure gases on component С3Н8 The content of the impurities in all pure gases was determined by GC with helium-ionization flame-ionization and thermal-conductivity detectors as well as standard hygrometer apparatus included to the standard complex A1 of analysis of pure gases and substances from GET 154-01 The calibration multicomponent gas mixtures were verified with usage of existing gravimetric gas mixtures in accordance with ISO 6143 Composition of calibration standards
Cylinder 6547 Cylinder 6571 Cylinder 6538 Component x мольmol Standard
Instrument Calibration Three independent measurements were carried out under repeatability conditions Before each measurement an instrument calibration was made One measurement contained 5 submeasurements Sample Handling The time of the cylinder keeping is 24 hrs It was used the automatic unit of commutation for inputting gas mixtures
15
Uncertainty Uncertainty table СО2
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas
mixture
B 0010 1 0010
Analysis A B 0048 1 0048
Coverage factor 2 Expanded uncertainty 01 Uncertainty table СО
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas
mixture
B 002 1 002
Analysis A B 0095 1 0095
Coverage factor 2 Expanded uncertainty 019
16
Uncertainty table С3Н8 Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas
mixture
B 005 1 005
Analysis A B 0045 1 0045
Coverage factor 2 Expanded uncertainty 013
17
MEASUREMENT REPORT ndash Belorussian State Institute for Metrology Belarus (BelGIM)
I Results of experimental study
Laboratory Belarus BelGIM Section for physicochemical and optical measurements sector for standards and gas mixtures 8 Serova st Minsk Cylinder No 0128 9 dm3 aluminium NOMINAL COMPOSITION - Carbon dioxide 13middot10-2 - 14middot10-2 molmol - Carbon oxide 28middot10-2 - 32middot10-2 molmol - Propane 19middot10-4 - 21middot10-4molmol - Nitrogen Residual
Measurement No1 Date
Result (molmol)
x_
Standard deviation
S( x_
) rel
No of observations
n
Carbon dioxide 17062005 13567middot10-2 0096 6
Carbon oxide 17062005 2957middot10-2 014 6
Propane 17062005 1977middot10-4 015 6
Measurement No2 Date
Result (molmol)
x_
Standard deviation
S( x_
) rel
No of observations
n
Carbon dioxide 21062005 13564middot10-2 004 6
Carbon oxide 21062005 2957middot10-2 02 6
Propane 21062005 1979middot10-4 01 6
18
Measurement No3 Date
Result (molmol)
x_
Standard deviation
S( x_
) rel
No of observations
n
Carbon dioxide 23062005 13537middot10-2 007 6
Carbon oxide 23062005 2955middot10-2 01 6
Propane 23062005 1982middot10-4 01 6
Final results
Gas mixture Result
(molmol)
Coverage factor
Expanded uncertainty (molmol)
Carbon dioxide 136middot10-2 2 01 middot10-2
Carbon oxide 296middot10-2 2 002middot10-2
Propane 198middot10-4 2 02middot10-4
II Description of study Apparatus (principle of operation type configuration data collection etc)
Measurements were carried out using gas chromatograph Crystal 2000М (hereinafter
referred to as chromatograph) combined with thermal conductivity detector (hereinafter referred to as TCD) with detection limit of 510-9 gml for propane and flame-ionization detector (hereinafter referred to as FID) with detection limit of 510-12 gs for propane
Computers and software Chromatech Analytic version 121 were used to control chromatograph and collect and process chromatographical data
For the purpose of measurements the following auxiliary devices and materials were used
1 Two-position doser with 10 ports and with doses of 025 cm3 for FID channel and with doses of 025 cm3 for TCD channel (hereinafter referred to as doser)
2 Metallic packed column 3m х 3mm х 2mm - HayeSep N 80100 metallic packed column 1m х 4mm х 2mm-CaA 016025 (TCD channel) capillary column HP PLOTQ 30m х 0536mm (FID channel)
3 Aneroid BАММ-1 with a measurement range of 80-106 kPа and accuracy of plusmn 02 kPа
4 Mercurial thermometer ТL-4 with a measurement range of 0-50ordmС and scale division of 01ordmС
19
5 Fine adjustment valve (hereinafter referred to as FAV) provided to transport a gas sample into chromotograph and set to gas flow-rate of 10-15 mlmin
6 Foamy gas flow meter type YIRG - 2А accuracy of flow measurement plusmn 1 сm3min
7 Helium gas Type A according to TU 51-940-80 8 High purity hydrogen gas according to TU 301-07-27-90 9 Compressed air 10 Multicomponent calibration gas mixtures (hereinafter referred to as CGM)
produced and certified by gravimetric method
Calibration reference materials - calibration gas mixtures used for measurements 1 Quantitative composition of KGS is determined using gravimetric method defined in
ISO 61422001 by calculating weight of each component of a gas mixture The content of CGM components is expressed as a mole fraction Uncertainty of KGS composition is expressed as expanded uncertainty with coverage factor k = 2 Molar masses of components and their uncertainties are taken from ISO 149122003 Performance and metrological characteristics of the equipment used for gravimetric preparation of mixtures are given in Table 1
Table 1
Description of the equipment
Manufacturer Metrological characteristics
Mass-comparator balance type КА10-3Р
Mettler-Toledo
Switzerland
Maximum load 15 kg Scale division 1 mg Standard deviation 19 mg at load of 10 kg Operating temperature range +10divide30degС Maximum temperature change within 1 h plusmn05 degС
Gas mixer type USG 00001 BelGIM
Measurement range 000025 divide 100 МPa Accuracy class for manometers ndash 015 Accuracy class for vacuummeters ndash 025 Vacuummeter with pressure sensor for measuring the residual pressure before filling Residual pressure before filling of each component not more than 20 Pa
2 Purity analysis of primary gas standards
The purity analysis of primary gas standards is based on the information provided by the supplier or on the results of determination of impurity in pure gases using measurement procedure developed inside BelGIM
20
If an analytical method laid down in 43 of ISO 61422001 cannot be used for impurity determination mole fraction of an expected impurity is assumed to be half of the detection limit of the analytical method The content of the undetected impurity produces rectangular distribution
whereby its standard uncertainty is calculated as half of the detection limit divided by 3 The composition of the pure gases used for preparation of calibration mixtures is given
in Table 2 Table 2 - Metrological characteristics of pure gases
N2 999967 00005 Nitrogen Cylinder 40 dm3 Origin Russia O2 00033 00005 Propane Cylinder 2 dm3 Origin Russia
C3H8 9979 0017
3 After preparation of mixture the cylinder was maintained in laboratory room within
24 hours the mixture then was homogenized on the stand by rotating on the rollers within 4-5 hours The chromotograph for CGM was calibrated 2-3 days after its preparation
Calibration of the chromotograph
1 The chromotograph was calibrated using CGMs with composition identical to the analyzed sample The content of each component and its expanded uncertainty (k = 2) are given in Table 1 Table 1 - Calibrationе gas mixtures
2 Number of observations of each calibration sample- 3 Number of calibration samples - 3
3 The analytical function used for determination of the content of the analyzed sample components is as follows
x (y) =b1y+b0 (2) Where x ndash determined content molmol y - chromotograph response for the specific component b1- slope b0 - intercept 4 After completion of calibration the coefficients of analytical function were
calculated according to ISO 61432001 using generalized least-squares method Also the uncertainties of the intercept and slope and covariance between them were calculated After determination of parameters which are part of analytical function and which affect the uncertainty of measurements it was checked whether the analytical function is fit to the experimental data obtained in calibration and subsequently whether the analytical function is applicable
Results of calibration measurements coefficients of analytical function their uncertainties covariance and measure of goodness-of-fit Г (maximum value of the weighted differences of the experimental points and calculated points of the analytical function for each measurement run) are given in Tables 3 and 4 respectively Chromotograph operating conditions in calibration and analysis are given in Table 5
Table 3 - Results of experimental study
Date Component of
calibration mixture
Content x mole fraction
Expanded uncertainty
U(x) mole fraction
Mean of peak area y
mVs
Uncertainty )(yu
mVs
13374 0004 1279500 141 1389 0004 1329150 2899 CO2
12833 0004 1231000 849 2916 0005 404070 240
316 0005 437705 926 CO 2768 0004 383070 467
019 0002 3143200 4101
1706 2005
C3H8 0202 0002 3319150 2051
22
0181 0002 2948750 212 13374 0004 1269833 624
1389 0004 1321000 1272 CO2 12833 0004 1223900 1698
2916 0005 399490 612 316 0005 434010 863 CO
2768 0004 379660 410 019 0002 3157867 6772
0202 0002 3332400 3394
2106 2005
C3H8 0181 0002 2959900 4950
13374 0004 1277100 2152 1389 0004 1329900 2828 CO2
12833 0004 1229100 1980 2916 0005 400330 529
316 0005 434745 969 CO 2768 0004 379695 106
019 0002 3142433 9416 0202 0002 3321600 4101
2306 2005
C3H8 0181 0002 2961000 3111
According to ISO 61432003 calculation of the measure of goodness-of-fit Г is the maximum value of the weighed differences between the coordinates of measured and adjusted calibration points is an effective and simple method to test the compatibility of а prospective analytical function A function is admissible if Г le 2
minus
minus=
)(ˆ
)(ˆ
iii
iii
yuyy
xuxxΓ
(4) Where хi is the reference value of the content of calibration sample component
ix is the CGM component content obtained using the calculated analytical function
уi is the experimental response to the reference content of component iy is the response obtained in calculation of analytical function
u (хi) u (уi) are the uncertainties of reference contents and responses to these contents respectively
i is the number of calibration points i=1 3 This prerequisite is equivalent to the requirement that the curve of calculated response should cross each experimental calibration rectangular [хi plusmn 2u(хi) уi plusmn 2и(уi)] based on an expanded uncertainty U = ku with coverage factor k = 2 Table 4 Calculations of analytical function
Date Component Analytical function parameters
Uncertainty of analytical
function parameters
Covariance of
parameters Г
23
b1 b0 u(b1) u(b0) u(b0b1) 1706 11086E-
03 -81128E-
0119491E-
0524883E-
01 -48497E-06 10544
2106 10729E-03
-26126E-01
22698E-05
28930E-01 -65652E-06 19997
2306
CO2 10593E-
03 -17688E-
0135807E-
0545413E-
01 -16254E-05 10022
1706 71537E-04
26507E-02
14231E-05
57044E-02 -81115E-07 03017
2106 72346E-04
22401E-02
13819E-05
54490E-02 -75209E-07 05935
2306
CO 71321E-
04 60080E-
0212663E-
0549016E-
02 -62026E-07 01341
1706 56521E-06
13712E-02
38279E-07
12015E-02 -45937E-09 12991
2106 56295E-06
13707E-02
39247E-07
12379E-02 -48529E-09 12905
2306
C3H8 58258E-
06 80469E-
0340085E-
0712590E-
02 -50407E-09 08589
Two columns separated by switching device are located one after another in TCD
channel One column is intended for carbon dioxide heavy hydrocarbons and another column is intended for light gases Before the first switch the light gases including carbon oxide flow through the first column without being separated and remain in the second column The switch makes them locked in the second column The analysis of carbon dioxide is carried out up to the second switch Second switch makes the second column unlocked and carbon oxide is analyzed Third switch is required to allow propane escape from a column and prevent it from getting into a second column The analysis of the very propane is carried out using FID Time intervals between switches were selected experimentally when developing the analysis method Such analysis method makes it possible to analyze all three components per one sample inject
Table 5 - Chromotograph operating conditions in calibration and analysis Parameter of the operating conditions Thermostating temperature of TCD and FID degС 170
Temperature of separation columns degС
Program 60 degС within 9 min
than rise to 160 degС at 20degСmin
Rate of flow of carrier gas through TCD channel columns mlmin 15
Rate of flow of carrier gas through TCD comparison channel mlmin 15
Pressure in FID channel column kPa Program
24
80 to 100 Rise from the 1st s of
analysis at 2 kPamin
Flow-rate of hydrogen FID mlmin 20 Flow-rate of air FID mlmin 200 Temperature of switching device degС 65 Response time of switching device s 1 110 2 330 3 540
TCD FID Volume of injected analyzed gas cm3 025 025 Carrier gas Helium Duration of analysis min 17 Calculation of the content of comparison sample components and its uncertainty Results of comparison sample measurements are given in Table 6 Table 6 - Results of comparison sample measurements
1 The content of comparison sample component and its uncertainty were determined
using calculated analytical function according to ISO 61432001 as follows (5) Where G(y)=b1y+b0 is the calculated analytical function и(y) is the standard uncertainty of response y u2(bj) is the variance of analytical function parameter bj
u(bj bI) is the covariance of analytical function parameters bj bI N is the number of function coefficients N=2 j=0 1
sum sumsumminus
= +==
partpart
partpart
+
partpart
+
partpart
=1
0 1
2
2
0
22
)(2)()()(N
jIj
N
jI Ijj
N
j j
bbubG
bGbu
bGyu
yGxu
25
After substitution of analytical function (2) and transformations the expression takes form (5)
)(2)()()()()( 01122
0222
1 bbyubuybuyubxu +++= (6) The contents of comparison sample components under determination and their
uncertainties were calculated using B_LEAST a computer program recommended in ISO 6143 Calculations are summarized in Table 6
Table 6 Calculations of the content of comparison sample components and their
2 The final content of a component was determined as an arithmetiс mean from three measurements Final standard uncertainty was calculated using formula as follows
22
222)( Адаватмтемсериикал uuuuuxu ++++= (7)
Where ucal is the uncertainty of the component content produced by
calibration of chromotograph urun is the uncertainty of the component content produced by
change of chromotograph response in each measurement run ut is the uncertainty of the component content produced by
change of an ambient temperature upressure is the uncertainty of the component content produced by
change of atmospheric pressure u A is the standard uncertainty of three measurement runs
21 Uncertainty of the component content produced by calibration of chromotograph
This uncertainty is calculated using formula (6) but the first term of the sum ie
)()( 221 yub which represents the standard uncertainty of the chromotograph response in a
measurement run is not taken into account Calculations are summarized in Table 7
26
Table 7 Calculation of uncertainty produced by calibration of chromotograph
Date u(b1) u(b0) u(b0b1) x
molmol y Ucal molmol
Ucal rel
1706 19491E-05
24883E-01
-48497E-06
13567middot10-
2129698
3 0005middot1
0-2 003
2106 22698E-05
28930E-01
-65652E-06
13564middot10-
2 128855 0007middot1
0-2 005
2306
CO2
35807E-05
45413E-01
-16254E-05
135374middot10-2
1294633
0016middot10-2 012
1706 14231E-05
57044E-02
-81115E-07 2957middot10-2 409633
0003middot10-2 009
2106 13819E-05
54490E-02
-75209E-07
29577middot10-
2 405663 0003middot1
0-2 01
2306
CO
12663E-05
49016E-02
-62026E-07 2955middot10-2 405882
0003middot10-2 01
1706 38279E-07
12015E-02
-45937E-09 1977middot10-4
3255817
007middot10-
2 038
2106 39247E-07
12379E-02
-48529E-09 1980middot10-4
3273329
008middot10-
2 038
2306
C3H8
40085E-07
12590E-02
-50407E-09 1982middot10-4 32636
008middot10-
2 04 The total estimate of relative uncertainty produced by calibration of chromotograph was
calculated for each component as follows
3
3
1
2sum=
cali
cali
uu (8)
Where ucal i is the relative uncertainty produced by calibration of chromotograph and calculated for each measurement run
The calculations are summarized in Table 8
Table 8 Uncertainty produced by calibration of chromotograph
Component Ucal rel
CO2 008 CO 01
C3H8 04 22 Uncertainty of the component content produced by change of chromotograph response in each measurement run This uncertainty is calculated using the equation (6) whereby the first term of the sum
only ie )()( 221 yub which represents the standard uncertainty of the chromotograph
response in a measurement run is taken into account Calculations are summarized in Table 9
27
Table 9 Calculation of uncertainty produced by change of chromotograph response in each measurement run
The total estimate of relative uncertainty produced by change of chromotograph
response in each measurement run was calculated for each component as follows
3
3
1
2sum=
run
run
uu (9)
Where urun is the relative uncertainty produced by change of chromotograph response in each measurement run Calculations are summarized in Table 10
Table 10 Uncertainty produced by change of chromotograph response in each measurement
run
Component Urun rel
CO2 007 CO 015
C3H8 012 23 Uncertainty of the component content produced by change of temperature in a room
The recorded change of temperature in measurements is plusmn 05 degree The contribution of uncertainty type B (rectangular distribution) is estimated as follows
201003
12931
=sdotsdot=tu rel
28
24 Uncertainty of the component content produced by change of atmospheric pressure The recorded change of atmospheric pressure within three days was
05 kPа The contribution of uncertainty type B (rectangular distribution) is estimated as follows
2801003
13101
50=sdotsdot=pressureu rel
25 Standard deviation of 3 measurement runs Standard deviation is calculated as follows
isu p
A
2
= (10)
Where S2p is the group experimental variation
The group experimental variation is calculated as follows
(11)
Where si
2 is the experimental variation of measurement run i from independent repeated observations ni having freedom degrees
νi = n - 1 n=6 i= 3 Calculations are summarized in Table 11 Table 11 Calculations of standard uncertainty of 3 measurement runs
Date 2iS x
molmol 2iS
rel uA
rel
1706 2953E-05 13567middot10-2 000022
2106 588987E-06 13564middot10-2 0000043
2306
CO2 141137E-
05 135374middot10
-2 000010
0006
1706 225604E-06 2957middot10-2 0000077
2106 681346E-06 29577middot10-2 000023
2306
CO
175166E-06 2955middot10-2 0000060
0006
1706 C3H8 130158E-
08 1977middot10-4 00000066 0001
ss
p
i ii
N
ii
N2
2
1
1
= =
=
sum
sum
ν
ν
29
2106 44616E-09 1980middot10-4 00000023
2306
381032E-09 1982middot10-4 00000019
26 Total standard uncertainty
Uncertainty estimation СО2
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph ucal Normal 008 1 008
Change of temperature ut Rectangular 02 1 02 Change of atmospheric pressure upressure Rectangular 028 1 028
Changes of chromotograph response
urun Normal 007 1 007
Standard deviation of 3 runs uA Normal 0006 1 0006
Relative total standard uncertainty 036 Coverage factor k=2 Expanded uncertainty 01middot10-2 molmol Uncertainty estimation СО
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph ucal Normal 01 1 01 Change of temperature ut Rectangular 02 1 02 Change of atmospheric pressure upressure Rectangular 028 1 028 Changes of chromotograph response
urun Normal 015 1 015
Standard deviation of 3 runs uA Normal 0006 1 0006
Relative total standard uncertainty 039 Coverage factor k=2 Expanded uncertainty 002middot10-2 molmol Uncertainty estimation С3Н8
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph 04 Normal 04 1 008
30
Change of temperature 02 Rectangular 02 1 02 Change of atmospheric pressure 028 Rectangular 028 1 028
Changes of chromotograph response
012 Normal 012 1 007
Standard deviation of 3 runs 0001 Normal 0001 1 0006
Relative total standard uncertainty 054 Coverage factor k=2 Expanded uncertainty 02middot10-4 molmol
Sample handling
Period for exposure of cylinder to measurement conditions and method how to transport sample to the device
1 Stands for storing gas standard cylinders and calibration mixture cylinders and chromotograph are placed in a laboratory room which is not accessible to unauthorized persons The laboratory is equipped with air-conditioner to maintain required temperature and humidity on a continuous basis and some auxiliary measuring instruments as thermometer psychrometric hygrometer and aneroid to control temperature humidity and atmospheric inside the room
2 The comparison sample cylinder was stored in laboratory from the date of its
delivery to Minsk on 25042005 CGM cylinders are stored horizontally on racks and positioned vertically using special support when measurements are carried out
3 The analyzed gas sample is transported through the fine adjustment valve (FAV)
Conjunctions Cylinder - FAV FAV - tube tube - doser are made of metal and use adapters with spherical ends and bushes FAV is made of brass tube is made of copper and doser is made of duralumin
Instrument(s) (principles make type configuration data collection etc) For the analysis a GC were used with specifically applications For the determination of (Nitrogen (N2)) Carbon Dioxide (CO2) Carbon Monoxide (CO) and Propane (C3H8) balance GC Perkin Elmer AutoSystem XL (two channel system) with a stream selection valve for 4 streams and 2 gas sampling valves
Channel A for the determination of N2 CO and CO2 Carrier Gas Helium Columns Column system with two packed columns (6 ft x 18rdquo Porapak R 80100 mesh and 6 ft x 18rdquo Mol-Sieve 13X 80100 mesh) Oven Temperature 960 degC to 180 degC Detector micro-TCD Data Collection Total Chrom Workstation Channel B for the determination of C3H8 Carrier Gas Helium Columns Capillary column 50 m x 032 microm LP-SIL-8-CB Oven Temperature 60 degC to 180 degC Detector FID Data Collection Total Chrom Workstation
34
Calibration Standards
Calibration Standards for the measurements (preparation method purity analyses estimated uncertainty etc)
All standards were prepared individually according to ISO 6142 rdquoGas analysis - Preparation of calibration gases - Gravimetric Methodrdquo
Depending on the concentration of the components standards were prepared individually from pure gases or from pre-mixtures which were individually prepared from pure gases
The content of the impurities in all pure gases were determined before use by GC-DID GC-FID and or GC-TCD
After preparation the standards were verified by analytical comparisons against existing gravimetrically prepared standards Only when no significant difference between the analysed and the calculated gravimetric composition is found the ldquonew prepared candidate rdquo is accepted as a new standards
For the analysis of all components multi component standards with nitrogen as balance gas were used
Composition of calibrants BAM C49250-050722 Component Assigned value( x)
mmol mol Standard uncertainty (u(x)) relativ (k=2)
Calibration procedure (mathematical modelcalibration curve number and concentrations of standards measurement sequence temperaturepressure correction etc)
For the instrument calibration the bracketing technique was used The fraction of the current used standards deviated no more than +10rel and -10rel respectively from those of the sample
Measurement sequence
Sample Handling
How were the cylinders treated after arrival (eg stabilized) and how were samples transferred to the instrument (automatic high pressure mass-flow controller dilution etc) After heating (45 - 50 degC) the cylinder for 8 hours the cylinder were rolled about 16 hours before analysis was started Each cylinder was equipped with a pressure regulator that was purged three times by sequential evacuation and pressurisation with the gas mixture used Continous flow (2 ndash 3mlmin) through the sample loop
Uncertainty The specification of potential uncertainty sources is given in Annex 3
3 injection standard (high)
3 injection sample
3 injection standard (high)
3 injection sample
3 injection standard (low)
3 injection sample
3 injection standard (low)
3 injection standard (low)
36
Uncertainty table CO2
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 002 rel 1 002 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 03 rel
Uncertainty table CO
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 007 rel 1 007 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 05 rel
37
Uncertainty table C3H8
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 010 rel 1 001 rel
Analysis normal 028 rel 1 028 rel
Coverage factor 2
Expanded uncertainty 06 rel
Optional
You may provide additional data like the raw measurement data information on your
measurement procedure chromatograms etc
38
Appendix 3 SPECIFICATION OF POTENTIAL UNCERTAINTY SOURCES
a Uncertainty related to the balance and the weights Resolution of balance Accuracy of balance including linearity Incorrect zero point Drift (thermal and time effects) Instability due to draught Location of cylinder on the balance pan Uncertainties in the weights used Buoyancy effects on the weights used
b Uncertainties related to the gas cylinder Mechanical handling of cylinder
Loss of metal paints or labels from surface of cylinder Loss of metal from threads of valvefitting Dirt on cylinder valves or associated fitting
Absorptiondesorption effects on the external cylinder surface Buoyancy effects on the cylinder itself
Cylinder temperature differs from surrounding air due to eg filling with gas Change of cylinder volume during filling Change of density of surrounding air due to changes in temperature air pressure humidity and carbon dioxide content
Uncertainty in determination of external cylinder volume c Uncertainties related to the component gases Residual gas in cylinder Leakage Leakage of air into the cylinder after evacuation
Leakage of gas from the cylinder valve during filling Escape of gas from cylinder into transport lines
Gas remaining in transfer system when weight loss method is used Absorptionreaction of components on internal cylinder surface Reaction between components Impurities in all the initial gases Insufficient homogenization Uncertainty of molecular mass d Uncertainties related to the analysis
Repeatability and selectivity of the analyzer Appropriateness of the calibration curve
39
MEASUREMENT REPORT - All Ukrainian State Research-Industrial Center of Standardization Metrology Certification and Protection of Consumers Ukraine
gas ndash helium flow rate 15 cm3min detector TCD tdetector = 250 ordmС toven = 70 ordmС It was automatic data collection
Measurement and Calibration Methods Laboratory Measurement method Type of calibration curve
GCFID (С3Н8) 3 points linear Ukrmetrteststandard GCTCD (СО СО2) 3 points linear
GCFID ndash gas-chromatographic with flame-ionization detector GCTCD - gas-chromatographic with thermal-conductivity detector
42
Calibration Standards
Calibration standards ndash primary standard gas mixtures (PSGM) used for measurements by comparison method
PSGM-1 Cylinder 0116
PSGM-2 Cylinder 0107
PSGM-3 Cylinder 0093 Composition
x u(x) x u(x) x u(x) СО 27874 00015 29899 00015 31891 00015 СО2 130187 00015 144456 00016 137016 00016 С3Н8 019003 000008 020017 000008 021013 000008 N2 balance balance balance
Note x ndash mole fraction u(x) ndash absolute standard uncertainty
It was used gravimetric method of preparation of PSGM Electronic balance КА-20-3 of Mettler Toledo max limit of weighing is 20 kg least
limit of weighing is 01 g standard deviation is 0006 g Analysis of purity of parent gases was carried out with usage of chromatographs
НР6890N with helium ndash ionization detector flame ndash ionization detector thermal ndash conductivity detector and mass ndash spectrometric detector as well аs gas analyzers GIAM-15M and Onix condensate-thermometer hygrometer TOROS-3-2B
Calculation of uncertainties was carried out according to ISO 6142-2003 Corrections of temperature pressure and humidity of environment were considered
in calculations according to ISO 6142-2003 (program of ISO-6142 2000-03-17 designer is NMi) Protocols and explanations are in Annex A
Instrument (Comparator) Calibration Calibration of comparator ndash gas chromatograph HP 6890 was carried out with usage
of PSGM Measurement sequence PSGM -1 х 3 PSGM -2 х 3 COOMET gas mixture х 3 PSGM -2 х 3 PSGM -3 х 3 It is necessary to use PSGM-2 repeatedly for estimation of reproducibility of results
Program B_LEAST recommended by ISO 6143-2003 was used for constructing the curve Mathematical model of calibration curve is linear one
Sample Handling The cylinder was kept for 24 hrs at a room where comparators were disposed This room is a thermostatic room with t = (20plusmn2) ordmС
43
A method of sample input to a comparator is a method with flow stabilization Uncertainty The following uncertainties were included to the budget of uncertainty - uncertainty of the balance - uncertainties of impurities in parent gases Contribution from other uncertainty sources was insignificant A cabin of the balance is thermostatically The balance is the one-pan balance
Air transfer is absent in the cabin of the balance Drift of the balance is absent for PSGM preparation
Contribution from other uncertainty sources was considered in software according to ISO 6142-2003
Uncertainties related to the analysis (comparison) were considered in software according to ISO 6143-2003 and enclosed in Annex B
Uncertainty table СО2
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas mixture
B 001 1 001
Analysis A B 008 1 008
Coverage factor 2 Expanded uncertainty 002sdot10-2 molmol Uncertainty table СО
Protocols of analysis (comparison) in accordance with ISO 6143-2003
57
Explanation of protocols of comparison
Chapter I ldquoThe calibration data set isrdquo contains columns 1 mole fraction of a component 2 absolute standard uncertainty of mole fraction of a component 3 a signal of a comparator 4 absolute standard uncertainty of a comparator signal
Chapter II ldquoResults of ISO 6143 methodrdquo contains parameters of a calibration curve including its
uncertainty
Chapter ІІІ ldquoPart II Processing of datardquo contains columns
1 calc x - the results of comparison mole fraction of a component 2 u(x) - absolute standard uncertainty of mole fraction of a component 3 response y - a signal of a comparator 4 u(y) - absolute standard uncertainty of a comparator signal
58
СО2 - measurement 1 Data setCO2_21 The calibration data set is 1302E+01 1510E-03 1022E+04 1820E+00 1370E+01 1560E-03 1077E+04 2730E+00 1445E+01 1620E-03 1135E+04 5900E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 20331E-02 12711E-03 12573E-01 11653E-05 -14638E-06 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 10548E-02 12722E-03 31762E-02 28898E-06 -91698E-08 Remaining SSD is 74346 Weighted distances x-value x-dist y-dist 100E+00 130E+01 490E-01 -755E-01 200E+00 137E+01 -103E+00 228E+00 300E+00 144E+01 539E-01 -250E-01 Goodness-of-fit measure 22837 Parameter set 1 1054788657490729E-2 1272208026684145E-3 3176237146276368E-2 2889798108124711E-6 -
9169821653851327E-8 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_21c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13577E+01 25542E-03 10664E+04 15200E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 547E-06 328E-06 316E-06 784E-06 286E-06 652E-06 Linear model Parameters for the fit were (b0 b1) 10548E-02 12722E-03
59
СО2 - measurement 2
Data setCO2_20 The calibration data set is 1302E+01 1512E-03 1021E+04 4723E+00 1370E+01 1563E-03 1075E+04 1600E+00 1445E+01 1620E-03 1133E+04 7300E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -38760E-02 12784E-03 26817E-02 24890E-06 -66689E-08 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -62452E-02 12805E-03 47930E-02 43243E-06 -20716E-07 Remaining SSD is 03231 Weighted distances x-value x-dist y-dist 100E+00 130E+01 107E-01 -415E-01 200E+00 137E+01 -212E-01 283E-01 300E+00 144E+01 104E-01 -584E-02 Goodness-of-fit measure 04155 Parameter set 1 -6245240430658412E-2 1280492624666799E-3 4792952200361109E-2 4324266278840409E-6 -
2071623966851869E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_20c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13594E+01 10290E-02 10665E+04 78300E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 121E-05 683E-06 651E-06 315E-05 560E-06 106E-04 Linear model Parameters for the fit were (b0 b1) -62452E-02 12805E-03
60
С3Н8 - measurement 1
Data setC3H8 The calibration data set is 1900E-01 7800E-05 9057E+03 1098E+01 2002E-01 7900E-05 9552E+03 8569E+00 2101E-01 7960E-05 1007E+04 4049E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10529E-02 19831E-05 34552E-03 36109E-07 -12465E-09 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11642E-02 19714E-05 23073E-03 23522E-07 -54231E-10 Remaining SSD is 19453 Weighted distances x-value x-dist y-dist 100E+00 190E-01 -239E-01 666E-01 200E+00 200E-01 487E-01 -104E+00 300E+00 210E-01 -247E-01 248E-01 Goodness-of-fit measure 10414 Parameter set 1 1164239985182795E-2 1971441115316992E-5 2307269625077337E-3 2352198415608386E-7 -
5423119774765299E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19837E-01 14840E-04 94718E+03 45610E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
2
bull Formation of circumstances for recognition of national measurement standards of Belarus and Ukraine which earlier did not participate in key comparisons and entering of calibration and measurement capabilities (CMC) of BelGIM and Ukrmetrteststandard in the field of automobile gases to the international database KCDB in accordance with Mutual Recognition Arrangement (CIPM MRA) for national measurement standards and for calibration and measurement certificates issued by NMIs
bull Objective of NMIs which participated in key comparisons on automobile gases earlier (BAM VNIIM) is to support or improve our calibration and measurement capabilities
Measurement standards The design of this comparison was adopted from key comparison CCQM-K3 The gas mixtures for the comparison were prepared by means of gravimetry and were studied thoroughly regarding its composition and stability at the coordinating laboratory (VNIIM PCD) The nominal amount of substance ratios of components in gas mixtures read as follows Carbon dioxide 135 mmolmol Carbon monoxide 30 mmolmol Propane 2 mmolmol Nitrogen balance Schedule The cylinders with gas mixtures were sent out to all participants of the comparison on April 2005 The measurement results were submitted by the participants on August ndash October 2005 All cylinders with gas mixtures were dispatched to the coordinating laboratory on November 2005 In connection with customs delay of the cylinders with gas mixtures the date of re-analysis of these gas mixtures was extended till January 2006 The laboratories were also requested to submit the calculation of expanded uncertainty with the uncertainty budget Measurement protocol The measurement protocol requested each laboratory to perform at least 3 measurements obtained under repeatability conditions including at least three separate calibrations The protocol informed the participants about the nominal concentration ranges Measurement equation The measurement model has been taken from the key comparison CCQM-K3 [3] The gas mixtures for the comparison were prepared by means of gravimetry in accordance with requirements of ISO 6142 [1] and were studied thoroughly regarding its composition and stability at the coordinating laboratory (VNIIM PCD) in accordance with requirements of ISO 6143 [2] A confidence on gravimetric values of gas mixtures used for this key comparison CCQM-K3 is adopted by VNIIM results from CCQM-P23 VNIIM gravimetric capability for 50 mmolmol and 1 mmolmol CO were comparable with other NMIs within 007 It was prepared nine gas mixtures three of which were sent to participants for study Three groups of uncertainty sources have been considered for the gravimetric preparation of gas mixtures 1 gravimetric preparation (weighing process) 2 purity of the parent gases 3 stability of the gas mixtures
There has been no evidence that there would be relevant effect of adsorption and the component of gas mixtures has been known as very stable compounds so that only the first two groups of
3
uncertainty components appear in the model for evaluating the uncertainty from gravimetric preparation
)()()( 222purityweighinggravp xuxuxu ∆+= (1)
A second contributor to the uncertainty of the reference value of gas mixtures ugravR is the uncertainty from verification u(xver) The verification process is used to confirm the gravimetric composition by NDIR analyzer included to the set of National Primary Measurement Standard GET 154-01 as checking internal consistency between prepared cylinders in accordance with requirements of ISO 6143 [2]
gravRgravR kuU = (2) where
)()( 22vergravpgravR xuxuu += (3)
k=2 Measurement methods and calibration procedures The following methods of measurement and calibration methods have been employed (table 1) Table 1 Measurement and calibration methods Laboratory Measurement
method Calibration method Total number of
measurements VNIIM NDIR Three points
linear 3 measurements 5 submeasurements
Ukrmetrteststandard GC-TCD (COCO2) GC-FID (C3H8)
Three points linear Three points linear
2 measurements 3 submeasurements
BelGIM GC-TCD (COCO2) GC-FID (C3H8)
Three points linear Three points linear
3 measurements 6 submeasurements
ВАМ GC-TCD (COCO2) GC-FID (C3H8)
Bracketing Bracketing
5 measurements 9 submeasurements
Results In the current comparison on gas mixtures measurements were performed on individually prepared gas mixtures with (slightly) different concentrations The individual gravimetric values are reference values The difference between the analyzed and gravimetric values has been taken as degree of equivalence Di defined as
igravilabi xxD minus= (4) The combined standard uncertainty of the degree of equivalence can be expressed as
4
2
2
)( igravRilabi uuDu += (5) The expanded uncertainty )( iDU of the degree of equivalence Di
2
2)( igravRilabi uukDU += (6)
where Di ndash Degree of equivalence difference between the laboratory value and the gravimetric value U(Di) ndash Expended uncertainty of the degree of equivalence
gravx - Assigned amount of substance fraction of a component
labx - Result as reported by the participant
gravRu - Standard uncertainty of gravx
labu - Standard uncertainty of labx k - Coverage factor 2=k All results of this key comparison are presented in the tables 2 ndash 4 and shown in figures 1 ndash 3 The tables 2 - 4 contain the following information Lab Laboratory Cylinder Identification code of cylinder
gravx Assigned amount of substance fraction of a component
gravRU Expended Uncertainty of gravx 2=k
labx Result as reported by the participant
labU Expended Uncertainty of labx Di Degree of equivalence
)( iDU Expended Uncertainty of Di
labk Coverage factor as reported by the participant Calculation of expanded uncertainty was carried out with coverage factor k=2 Degrees of equivalence The unilateral degree of equivalence has already been defined (4) For the bilateral degrees of equivalence the model used for CCQM-K1 has been adapted The degree of equivalence between two laboratories is defined as
jgravjlabigravilabij xxxxD minusminusminus= (7) where
igravx - the assigned value for the laboratory i
ilabx -the amount of substance fraction of the laboratory i
jgravx - the assigned value for the laboratory j
5
jlabx - the amount of substance fraction of the laboratory i The expanded uncertainty of the degree of equivalence Dij (k=2)
Discussion and Conclusions All laboratories find the gravimetric value within plusmn07 relative to the gravimetric value This holds for all three components COCO2 and C3H8 in nitrogen This is a satisfying result For all laboratories the observed difference between the gravimetric and reported values does not exceed its combined uncertainty VNIIM and BAM are link laboratories for CCQM-K3 The results of this comparison are linked to the key comparison CCQM-K3 Reference [1] International Organization for Standardization ISO 61422001 Gas analysis - Preparation of calibration gas mixtures - Gravimetric methods 2nd edition [2] International Organization for Standardization ISO 61432001 Gas analysis ndash Comparison methods for determining and checking the composition of calibration gas mixtures [3] Van der Veen AMH De Leer EWB Perrochet J-F Wang Lin Zhen Heine H-JKnopf D Richter W Barbe J Marschal A Vargha G Deaacutek E Takahashi C Kim JS Kim YD Kim BM Kustikov YA Khatskevitch EA Pankratov VV Popova TA Konopelko L Musil S Holland P Milton MJT Miller WR Guenther FR International Comparison CCQM-K3 Final Report Coordinator Leonid Konopelko VNIIM Research Department for the State Standard in the Field of Physical-Chemical Measurements (PCD) 19 Moskovsky pr St-Petersburg 198005 Russia Phone +7 812 3151145 Fax +7 812 3279776 E-mail lkonopmailrcomru Completion Date March 2006
11
Annex 1 Proposal of Degrees of Equivalence Table 5 Degrees of Equivalence for carbon monoxide Lab j VNIIM Ukrmetrteststandard BelGIM BAM Lab i Di Ui Dij Uij Dij Uij Dij Uij Dij Uij mmolmol mmolmol mmolmol mmolmol mmolmol VNIIM 001 006 012 014 007 021 005 016 Ukrmetrteststandard -011 012 -012 014 -005 024 -007 019 BelGIM -006 020 -007 021 005 024 -002 025 BAM -004 015 -005 016 007 019 0016 025 Table 6 Degrees of Equivalence for carbon dioxide Lab j VNIIM Ukrmetrteststandard BelGIM BAM Lab i Di Ui Dij Uij Dij Uij Dij Uij Dij Uij mmolmol mmolmol mmolmol mmolmol mmolmol VNIIM 012 013 026 026 -074 101 0034 043 Ukrmetrteststandard -014 022 -026 026 -10 102 -023 046 BelGIM 086 100 074 101 10 102 077 108 BAM 009 041 -0034 043 023 046 -077 108 Table 7 Degrees of Equivalence for propane Lab j VNIIM Ukrmetrteststandard BelGIM BAM Lab i Di Ui Dij Uij Dij Uij Dij Uij Dij Uij mmolmol mmolmol mmolmol mmolmol mmolmol VNIIM 0001 0004 0002 0006 0005 0020 -0009 0013 Ukrmetrteststandard -0001 0004 -0002 0006 0003 0021 -0011 0013 BelGIM -0004 0020 -0005 0020 -0003 0021 -0014 0023 BAM 0010 0012 0009 0013 0011 0013 0014 0023
12
Annex 2 Results and measurement reports as submitted by participating laboratories Key comparison participants
MEASUREMENT REPORT - DI Mendeleyev Institute for Metrology
Russian Federation (VNIIM)
I Results of Study
Laboratory DI Mendeleyev Institute for Metrology (VNIIM) Research Department for the State Standard in the Field of Physical-Chemical Measurements (PCD)
Instruments Multichannel automatic NDIR analyzer included to the set of the National Primary measurement standard of units of mole fraction and mass concentration of components in gas medium GET 154-01 was used for the analysis Calibration Standards All calibration multicomponent gas mixtures were prepared gravimetrically according to ISO 6142 The calibration multicomponent gas mixtures were prepared from pure gases directly on components CO CO2 and from pre-mixtures which were prepared from pure gases on component С3Н8 The content of the impurities in all pure gases was determined by GC with helium-ionization flame-ionization and thermal-conductivity detectors as well as standard hygrometer apparatus included to the standard complex A1 of analysis of pure gases and substances from GET 154-01 The calibration multicomponent gas mixtures were verified with usage of existing gravimetric gas mixtures in accordance with ISO 6143 Composition of calibration standards
Cylinder 6547 Cylinder 6571 Cylinder 6538 Component x мольmol Standard
Instrument Calibration Three independent measurements were carried out under repeatability conditions Before each measurement an instrument calibration was made One measurement contained 5 submeasurements Sample Handling The time of the cylinder keeping is 24 hrs It was used the automatic unit of commutation for inputting gas mixtures
15
Uncertainty Uncertainty table СО2
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas
mixture
B 0010 1 0010
Analysis A B 0048 1 0048
Coverage factor 2 Expanded uncertainty 01 Uncertainty table СО
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas
mixture
B 002 1 002
Analysis A B 0095 1 0095
Coverage factor 2 Expanded uncertainty 019
16
Uncertainty table С3Н8 Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas
mixture
B 005 1 005
Analysis A B 0045 1 0045
Coverage factor 2 Expanded uncertainty 013
17
MEASUREMENT REPORT ndash Belorussian State Institute for Metrology Belarus (BelGIM)
I Results of experimental study
Laboratory Belarus BelGIM Section for physicochemical and optical measurements sector for standards and gas mixtures 8 Serova st Minsk Cylinder No 0128 9 dm3 aluminium NOMINAL COMPOSITION - Carbon dioxide 13middot10-2 - 14middot10-2 molmol - Carbon oxide 28middot10-2 - 32middot10-2 molmol - Propane 19middot10-4 - 21middot10-4molmol - Nitrogen Residual
Measurement No1 Date
Result (molmol)
x_
Standard deviation
S( x_
) rel
No of observations
n
Carbon dioxide 17062005 13567middot10-2 0096 6
Carbon oxide 17062005 2957middot10-2 014 6
Propane 17062005 1977middot10-4 015 6
Measurement No2 Date
Result (molmol)
x_
Standard deviation
S( x_
) rel
No of observations
n
Carbon dioxide 21062005 13564middot10-2 004 6
Carbon oxide 21062005 2957middot10-2 02 6
Propane 21062005 1979middot10-4 01 6
18
Measurement No3 Date
Result (molmol)
x_
Standard deviation
S( x_
) rel
No of observations
n
Carbon dioxide 23062005 13537middot10-2 007 6
Carbon oxide 23062005 2955middot10-2 01 6
Propane 23062005 1982middot10-4 01 6
Final results
Gas mixture Result
(molmol)
Coverage factor
Expanded uncertainty (molmol)
Carbon dioxide 136middot10-2 2 01 middot10-2
Carbon oxide 296middot10-2 2 002middot10-2
Propane 198middot10-4 2 02middot10-4
II Description of study Apparatus (principle of operation type configuration data collection etc)
Measurements were carried out using gas chromatograph Crystal 2000М (hereinafter
referred to as chromatograph) combined with thermal conductivity detector (hereinafter referred to as TCD) with detection limit of 510-9 gml for propane and flame-ionization detector (hereinafter referred to as FID) with detection limit of 510-12 gs for propane
Computers and software Chromatech Analytic version 121 were used to control chromatograph and collect and process chromatographical data
For the purpose of measurements the following auxiliary devices and materials were used
1 Two-position doser with 10 ports and with doses of 025 cm3 for FID channel and with doses of 025 cm3 for TCD channel (hereinafter referred to as doser)
2 Metallic packed column 3m х 3mm х 2mm - HayeSep N 80100 metallic packed column 1m х 4mm х 2mm-CaA 016025 (TCD channel) capillary column HP PLOTQ 30m х 0536mm (FID channel)
3 Aneroid BАММ-1 with a measurement range of 80-106 kPа and accuracy of plusmn 02 kPа
4 Mercurial thermometer ТL-4 with a measurement range of 0-50ordmС and scale division of 01ordmС
19
5 Fine adjustment valve (hereinafter referred to as FAV) provided to transport a gas sample into chromotograph and set to gas flow-rate of 10-15 mlmin
6 Foamy gas flow meter type YIRG - 2А accuracy of flow measurement plusmn 1 сm3min
7 Helium gas Type A according to TU 51-940-80 8 High purity hydrogen gas according to TU 301-07-27-90 9 Compressed air 10 Multicomponent calibration gas mixtures (hereinafter referred to as CGM)
produced and certified by gravimetric method
Calibration reference materials - calibration gas mixtures used for measurements 1 Quantitative composition of KGS is determined using gravimetric method defined in
ISO 61422001 by calculating weight of each component of a gas mixture The content of CGM components is expressed as a mole fraction Uncertainty of KGS composition is expressed as expanded uncertainty with coverage factor k = 2 Molar masses of components and their uncertainties are taken from ISO 149122003 Performance and metrological characteristics of the equipment used for gravimetric preparation of mixtures are given in Table 1
Table 1
Description of the equipment
Manufacturer Metrological characteristics
Mass-comparator balance type КА10-3Р
Mettler-Toledo
Switzerland
Maximum load 15 kg Scale division 1 mg Standard deviation 19 mg at load of 10 kg Operating temperature range +10divide30degС Maximum temperature change within 1 h plusmn05 degС
Gas mixer type USG 00001 BelGIM
Measurement range 000025 divide 100 МPa Accuracy class for manometers ndash 015 Accuracy class for vacuummeters ndash 025 Vacuummeter with pressure sensor for measuring the residual pressure before filling Residual pressure before filling of each component not more than 20 Pa
2 Purity analysis of primary gas standards
The purity analysis of primary gas standards is based on the information provided by the supplier or on the results of determination of impurity in pure gases using measurement procedure developed inside BelGIM
20
If an analytical method laid down in 43 of ISO 61422001 cannot be used for impurity determination mole fraction of an expected impurity is assumed to be half of the detection limit of the analytical method The content of the undetected impurity produces rectangular distribution
whereby its standard uncertainty is calculated as half of the detection limit divided by 3 The composition of the pure gases used for preparation of calibration mixtures is given
in Table 2 Table 2 - Metrological characteristics of pure gases
N2 999967 00005 Nitrogen Cylinder 40 dm3 Origin Russia O2 00033 00005 Propane Cylinder 2 dm3 Origin Russia
C3H8 9979 0017
3 After preparation of mixture the cylinder was maintained in laboratory room within
24 hours the mixture then was homogenized on the stand by rotating on the rollers within 4-5 hours The chromotograph for CGM was calibrated 2-3 days after its preparation
Calibration of the chromotograph
1 The chromotograph was calibrated using CGMs with composition identical to the analyzed sample The content of each component and its expanded uncertainty (k = 2) are given in Table 1 Table 1 - Calibrationе gas mixtures
2 Number of observations of each calibration sample- 3 Number of calibration samples - 3
3 The analytical function used for determination of the content of the analyzed sample components is as follows
x (y) =b1y+b0 (2) Where x ndash determined content molmol y - chromotograph response for the specific component b1- slope b0 - intercept 4 After completion of calibration the coefficients of analytical function were
calculated according to ISO 61432001 using generalized least-squares method Also the uncertainties of the intercept and slope and covariance between them were calculated After determination of parameters which are part of analytical function and which affect the uncertainty of measurements it was checked whether the analytical function is fit to the experimental data obtained in calibration and subsequently whether the analytical function is applicable
Results of calibration measurements coefficients of analytical function their uncertainties covariance and measure of goodness-of-fit Г (maximum value of the weighted differences of the experimental points and calculated points of the analytical function for each measurement run) are given in Tables 3 and 4 respectively Chromotograph operating conditions in calibration and analysis are given in Table 5
Table 3 - Results of experimental study
Date Component of
calibration mixture
Content x mole fraction
Expanded uncertainty
U(x) mole fraction
Mean of peak area y
mVs
Uncertainty )(yu
mVs
13374 0004 1279500 141 1389 0004 1329150 2899 CO2
12833 0004 1231000 849 2916 0005 404070 240
316 0005 437705 926 CO 2768 0004 383070 467
019 0002 3143200 4101
1706 2005
C3H8 0202 0002 3319150 2051
22
0181 0002 2948750 212 13374 0004 1269833 624
1389 0004 1321000 1272 CO2 12833 0004 1223900 1698
2916 0005 399490 612 316 0005 434010 863 CO
2768 0004 379660 410 019 0002 3157867 6772
0202 0002 3332400 3394
2106 2005
C3H8 0181 0002 2959900 4950
13374 0004 1277100 2152 1389 0004 1329900 2828 CO2
12833 0004 1229100 1980 2916 0005 400330 529
316 0005 434745 969 CO 2768 0004 379695 106
019 0002 3142433 9416 0202 0002 3321600 4101
2306 2005
C3H8 0181 0002 2961000 3111
According to ISO 61432003 calculation of the measure of goodness-of-fit Г is the maximum value of the weighed differences between the coordinates of measured and adjusted calibration points is an effective and simple method to test the compatibility of а prospective analytical function A function is admissible if Г le 2
minus
minus=
)(ˆ
)(ˆ
iii
iii
yuyy
xuxxΓ
(4) Where хi is the reference value of the content of calibration sample component
ix is the CGM component content obtained using the calculated analytical function
уi is the experimental response to the reference content of component iy is the response obtained in calculation of analytical function
u (хi) u (уi) are the uncertainties of reference contents and responses to these contents respectively
i is the number of calibration points i=1 3 This prerequisite is equivalent to the requirement that the curve of calculated response should cross each experimental calibration rectangular [хi plusmn 2u(хi) уi plusmn 2и(уi)] based on an expanded uncertainty U = ku with coverage factor k = 2 Table 4 Calculations of analytical function
Date Component Analytical function parameters
Uncertainty of analytical
function parameters
Covariance of
parameters Г
23
b1 b0 u(b1) u(b0) u(b0b1) 1706 11086E-
03 -81128E-
0119491E-
0524883E-
01 -48497E-06 10544
2106 10729E-03
-26126E-01
22698E-05
28930E-01 -65652E-06 19997
2306
CO2 10593E-
03 -17688E-
0135807E-
0545413E-
01 -16254E-05 10022
1706 71537E-04
26507E-02
14231E-05
57044E-02 -81115E-07 03017
2106 72346E-04
22401E-02
13819E-05
54490E-02 -75209E-07 05935
2306
CO 71321E-
04 60080E-
0212663E-
0549016E-
02 -62026E-07 01341
1706 56521E-06
13712E-02
38279E-07
12015E-02 -45937E-09 12991
2106 56295E-06
13707E-02
39247E-07
12379E-02 -48529E-09 12905
2306
C3H8 58258E-
06 80469E-
0340085E-
0712590E-
02 -50407E-09 08589
Two columns separated by switching device are located one after another in TCD
channel One column is intended for carbon dioxide heavy hydrocarbons and another column is intended for light gases Before the first switch the light gases including carbon oxide flow through the first column without being separated and remain in the second column The switch makes them locked in the second column The analysis of carbon dioxide is carried out up to the second switch Second switch makes the second column unlocked and carbon oxide is analyzed Third switch is required to allow propane escape from a column and prevent it from getting into a second column The analysis of the very propane is carried out using FID Time intervals between switches were selected experimentally when developing the analysis method Such analysis method makes it possible to analyze all three components per one sample inject
Table 5 - Chromotograph operating conditions in calibration and analysis Parameter of the operating conditions Thermostating temperature of TCD and FID degС 170
Temperature of separation columns degС
Program 60 degС within 9 min
than rise to 160 degС at 20degСmin
Rate of flow of carrier gas through TCD channel columns mlmin 15
Rate of flow of carrier gas through TCD comparison channel mlmin 15
Pressure in FID channel column kPa Program
24
80 to 100 Rise from the 1st s of
analysis at 2 kPamin
Flow-rate of hydrogen FID mlmin 20 Flow-rate of air FID mlmin 200 Temperature of switching device degС 65 Response time of switching device s 1 110 2 330 3 540
TCD FID Volume of injected analyzed gas cm3 025 025 Carrier gas Helium Duration of analysis min 17 Calculation of the content of comparison sample components and its uncertainty Results of comparison sample measurements are given in Table 6 Table 6 - Results of comparison sample measurements
1 The content of comparison sample component and its uncertainty were determined
using calculated analytical function according to ISO 61432001 as follows (5) Where G(y)=b1y+b0 is the calculated analytical function и(y) is the standard uncertainty of response y u2(bj) is the variance of analytical function parameter bj
u(bj bI) is the covariance of analytical function parameters bj bI N is the number of function coefficients N=2 j=0 1
sum sumsumminus
= +==
partpart
partpart
+
partpart
+
partpart
=1
0 1
2
2
0
22
)(2)()()(N
jIj
N
jI Ijj
N
j j
bbubG
bGbu
bGyu
yGxu
25
After substitution of analytical function (2) and transformations the expression takes form (5)
)(2)()()()()( 01122
0222
1 bbyubuybuyubxu +++= (6) The contents of comparison sample components under determination and their
uncertainties were calculated using B_LEAST a computer program recommended in ISO 6143 Calculations are summarized in Table 6
Table 6 Calculations of the content of comparison sample components and their
2 The final content of a component was determined as an arithmetiс mean from three measurements Final standard uncertainty was calculated using formula as follows
22
222)( Адаватмтемсериикал uuuuuxu ++++= (7)
Where ucal is the uncertainty of the component content produced by
calibration of chromotograph urun is the uncertainty of the component content produced by
change of chromotograph response in each measurement run ut is the uncertainty of the component content produced by
change of an ambient temperature upressure is the uncertainty of the component content produced by
change of atmospheric pressure u A is the standard uncertainty of three measurement runs
21 Uncertainty of the component content produced by calibration of chromotograph
This uncertainty is calculated using formula (6) but the first term of the sum ie
)()( 221 yub which represents the standard uncertainty of the chromotograph response in a
measurement run is not taken into account Calculations are summarized in Table 7
26
Table 7 Calculation of uncertainty produced by calibration of chromotograph
Date u(b1) u(b0) u(b0b1) x
molmol y Ucal molmol
Ucal rel
1706 19491E-05
24883E-01
-48497E-06
13567middot10-
2129698
3 0005middot1
0-2 003
2106 22698E-05
28930E-01
-65652E-06
13564middot10-
2 128855 0007middot1
0-2 005
2306
CO2
35807E-05
45413E-01
-16254E-05
135374middot10-2
1294633
0016middot10-2 012
1706 14231E-05
57044E-02
-81115E-07 2957middot10-2 409633
0003middot10-2 009
2106 13819E-05
54490E-02
-75209E-07
29577middot10-
2 405663 0003middot1
0-2 01
2306
CO
12663E-05
49016E-02
-62026E-07 2955middot10-2 405882
0003middot10-2 01
1706 38279E-07
12015E-02
-45937E-09 1977middot10-4
3255817
007middot10-
2 038
2106 39247E-07
12379E-02
-48529E-09 1980middot10-4
3273329
008middot10-
2 038
2306
C3H8
40085E-07
12590E-02
-50407E-09 1982middot10-4 32636
008middot10-
2 04 The total estimate of relative uncertainty produced by calibration of chromotograph was
calculated for each component as follows
3
3
1
2sum=
cali
cali
uu (8)
Where ucal i is the relative uncertainty produced by calibration of chromotograph and calculated for each measurement run
The calculations are summarized in Table 8
Table 8 Uncertainty produced by calibration of chromotograph
Component Ucal rel
CO2 008 CO 01
C3H8 04 22 Uncertainty of the component content produced by change of chromotograph response in each measurement run This uncertainty is calculated using the equation (6) whereby the first term of the sum
only ie )()( 221 yub which represents the standard uncertainty of the chromotograph
response in a measurement run is taken into account Calculations are summarized in Table 9
27
Table 9 Calculation of uncertainty produced by change of chromotograph response in each measurement run
The total estimate of relative uncertainty produced by change of chromotograph
response in each measurement run was calculated for each component as follows
3
3
1
2sum=
run
run
uu (9)
Where urun is the relative uncertainty produced by change of chromotograph response in each measurement run Calculations are summarized in Table 10
Table 10 Uncertainty produced by change of chromotograph response in each measurement
run
Component Urun rel
CO2 007 CO 015
C3H8 012 23 Uncertainty of the component content produced by change of temperature in a room
The recorded change of temperature in measurements is plusmn 05 degree The contribution of uncertainty type B (rectangular distribution) is estimated as follows
201003
12931
=sdotsdot=tu rel
28
24 Uncertainty of the component content produced by change of atmospheric pressure The recorded change of atmospheric pressure within three days was
05 kPа The contribution of uncertainty type B (rectangular distribution) is estimated as follows
2801003
13101
50=sdotsdot=pressureu rel
25 Standard deviation of 3 measurement runs Standard deviation is calculated as follows
isu p
A
2
= (10)
Where S2p is the group experimental variation
The group experimental variation is calculated as follows
(11)
Where si
2 is the experimental variation of measurement run i from independent repeated observations ni having freedom degrees
νi = n - 1 n=6 i= 3 Calculations are summarized in Table 11 Table 11 Calculations of standard uncertainty of 3 measurement runs
Date 2iS x
molmol 2iS
rel uA
rel
1706 2953E-05 13567middot10-2 000022
2106 588987E-06 13564middot10-2 0000043
2306
CO2 141137E-
05 135374middot10
-2 000010
0006
1706 225604E-06 2957middot10-2 0000077
2106 681346E-06 29577middot10-2 000023
2306
CO
175166E-06 2955middot10-2 0000060
0006
1706 C3H8 130158E-
08 1977middot10-4 00000066 0001
ss
p
i ii
N
ii
N2
2
1
1
= =
=
sum
sum
ν
ν
29
2106 44616E-09 1980middot10-4 00000023
2306
381032E-09 1982middot10-4 00000019
26 Total standard uncertainty
Uncertainty estimation СО2
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph ucal Normal 008 1 008
Change of temperature ut Rectangular 02 1 02 Change of atmospheric pressure upressure Rectangular 028 1 028
Changes of chromotograph response
urun Normal 007 1 007
Standard deviation of 3 runs uA Normal 0006 1 0006
Relative total standard uncertainty 036 Coverage factor k=2 Expanded uncertainty 01middot10-2 molmol Uncertainty estimation СО
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph ucal Normal 01 1 01 Change of temperature ut Rectangular 02 1 02 Change of atmospheric pressure upressure Rectangular 028 1 028 Changes of chromotograph response
urun Normal 015 1 015
Standard deviation of 3 runs uA Normal 0006 1 0006
Relative total standard uncertainty 039 Coverage factor k=2 Expanded uncertainty 002middot10-2 molmol Uncertainty estimation С3Н8
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph 04 Normal 04 1 008
30
Change of temperature 02 Rectangular 02 1 02 Change of atmospheric pressure 028 Rectangular 028 1 028
Changes of chromotograph response
012 Normal 012 1 007
Standard deviation of 3 runs 0001 Normal 0001 1 0006
Relative total standard uncertainty 054 Coverage factor k=2 Expanded uncertainty 02middot10-4 molmol
Sample handling
Period for exposure of cylinder to measurement conditions and method how to transport sample to the device
1 Stands for storing gas standard cylinders and calibration mixture cylinders and chromotograph are placed in a laboratory room which is not accessible to unauthorized persons The laboratory is equipped with air-conditioner to maintain required temperature and humidity on a continuous basis and some auxiliary measuring instruments as thermometer psychrometric hygrometer and aneroid to control temperature humidity and atmospheric inside the room
2 The comparison sample cylinder was stored in laboratory from the date of its
delivery to Minsk on 25042005 CGM cylinders are stored horizontally on racks and positioned vertically using special support when measurements are carried out
3 The analyzed gas sample is transported through the fine adjustment valve (FAV)
Conjunctions Cylinder - FAV FAV - tube tube - doser are made of metal and use adapters with spherical ends and bushes FAV is made of brass tube is made of copper and doser is made of duralumin
Instrument(s) (principles make type configuration data collection etc) For the analysis a GC were used with specifically applications For the determination of (Nitrogen (N2)) Carbon Dioxide (CO2) Carbon Monoxide (CO) and Propane (C3H8) balance GC Perkin Elmer AutoSystem XL (two channel system) with a stream selection valve for 4 streams and 2 gas sampling valves
Channel A for the determination of N2 CO and CO2 Carrier Gas Helium Columns Column system with two packed columns (6 ft x 18rdquo Porapak R 80100 mesh and 6 ft x 18rdquo Mol-Sieve 13X 80100 mesh) Oven Temperature 960 degC to 180 degC Detector micro-TCD Data Collection Total Chrom Workstation Channel B for the determination of C3H8 Carrier Gas Helium Columns Capillary column 50 m x 032 microm LP-SIL-8-CB Oven Temperature 60 degC to 180 degC Detector FID Data Collection Total Chrom Workstation
34
Calibration Standards
Calibration Standards for the measurements (preparation method purity analyses estimated uncertainty etc)
All standards were prepared individually according to ISO 6142 rdquoGas analysis - Preparation of calibration gases - Gravimetric Methodrdquo
Depending on the concentration of the components standards were prepared individually from pure gases or from pre-mixtures which were individually prepared from pure gases
The content of the impurities in all pure gases were determined before use by GC-DID GC-FID and or GC-TCD
After preparation the standards were verified by analytical comparisons against existing gravimetrically prepared standards Only when no significant difference between the analysed and the calculated gravimetric composition is found the ldquonew prepared candidate rdquo is accepted as a new standards
For the analysis of all components multi component standards with nitrogen as balance gas were used
Composition of calibrants BAM C49250-050722 Component Assigned value( x)
mmol mol Standard uncertainty (u(x)) relativ (k=2)
Calibration procedure (mathematical modelcalibration curve number and concentrations of standards measurement sequence temperaturepressure correction etc)
For the instrument calibration the bracketing technique was used The fraction of the current used standards deviated no more than +10rel and -10rel respectively from those of the sample
Measurement sequence
Sample Handling
How were the cylinders treated after arrival (eg stabilized) and how were samples transferred to the instrument (automatic high pressure mass-flow controller dilution etc) After heating (45 - 50 degC) the cylinder for 8 hours the cylinder were rolled about 16 hours before analysis was started Each cylinder was equipped with a pressure regulator that was purged three times by sequential evacuation and pressurisation with the gas mixture used Continous flow (2 ndash 3mlmin) through the sample loop
Uncertainty The specification of potential uncertainty sources is given in Annex 3
3 injection standard (high)
3 injection sample
3 injection standard (high)
3 injection sample
3 injection standard (low)
3 injection sample
3 injection standard (low)
3 injection standard (low)
36
Uncertainty table CO2
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 002 rel 1 002 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 03 rel
Uncertainty table CO
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 007 rel 1 007 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 05 rel
37
Uncertainty table C3H8
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 010 rel 1 001 rel
Analysis normal 028 rel 1 028 rel
Coverage factor 2
Expanded uncertainty 06 rel
Optional
You may provide additional data like the raw measurement data information on your
measurement procedure chromatograms etc
38
Appendix 3 SPECIFICATION OF POTENTIAL UNCERTAINTY SOURCES
a Uncertainty related to the balance and the weights Resolution of balance Accuracy of balance including linearity Incorrect zero point Drift (thermal and time effects) Instability due to draught Location of cylinder on the balance pan Uncertainties in the weights used Buoyancy effects on the weights used
b Uncertainties related to the gas cylinder Mechanical handling of cylinder
Loss of metal paints or labels from surface of cylinder Loss of metal from threads of valvefitting Dirt on cylinder valves or associated fitting
Absorptiondesorption effects on the external cylinder surface Buoyancy effects on the cylinder itself
Cylinder temperature differs from surrounding air due to eg filling with gas Change of cylinder volume during filling Change of density of surrounding air due to changes in temperature air pressure humidity and carbon dioxide content
Uncertainty in determination of external cylinder volume c Uncertainties related to the component gases Residual gas in cylinder Leakage Leakage of air into the cylinder after evacuation
Leakage of gas from the cylinder valve during filling Escape of gas from cylinder into transport lines
Gas remaining in transfer system when weight loss method is used Absorptionreaction of components on internal cylinder surface Reaction between components Impurities in all the initial gases Insufficient homogenization Uncertainty of molecular mass d Uncertainties related to the analysis
Repeatability and selectivity of the analyzer Appropriateness of the calibration curve
39
MEASUREMENT REPORT - All Ukrainian State Research-Industrial Center of Standardization Metrology Certification and Protection of Consumers Ukraine
gas ndash helium flow rate 15 cm3min detector TCD tdetector = 250 ordmС toven = 70 ordmС It was automatic data collection
Measurement and Calibration Methods Laboratory Measurement method Type of calibration curve
GCFID (С3Н8) 3 points linear Ukrmetrteststandard GCTCD (СО СО2) 3 points linear
GCFID ndash gas-chromatographic with flame-ionization detector GCTCD - gas-chromatographic with thermal-conductivity detector
42
Calibration Standards
Calibration standards ndash primary standard gas mixtures (PSGM) used for measurements by comparison method
PSGM-1 Cylinder 0116
PSGM-2 Cylinder 0107
PSGM-3 Cylinder 0093 Composition
x u(x) x u(x) x u(x) СО 27874 00015 29899 00015 31891 00015 СО2 130187 00015 144456 00016 137016 00016 С3Н8 019003 000008 020017 000008 021013 000008 N2 balance balance balance
Note x ndash mole fraction u(x) ndash absolute standard uncertainty
It was used gravimetric method of preparation of PSGM Electronic balance КА-20-3 of Mettler Toledo max limit of weighing is 20 kg least
limit of weighing is 01 g standard deviation is 0006 g Analysis of purity of parent gases was carried out with usage of chromatographs
НР6890N with helium ndash ionization detector flame ndash ionization detector thermal ndash conductivity detector and mass ndash spectrometric detector as well аs gas analyzers GIAM-15M and Onix condensate-thermometer hygrometer TOROS-3-2B
Calculation of uncertainties was carried out according to ISO 6142-2003 Corrections of temperature pressure and humidity of environment were considered
in calculations according to ISO 6142-2003 (program of ISO-6142 2000-03-17 designer is NMi) Protocols and explanations are in Annex A
Instrument (Comparator) Calibration Calibration of comparator ndash gas chromatograph HP 6890 was carried out with usage
of PSGM Measurement sequence PSGM -1 х 3 PSGM -2 х 3 COOMET gas mixture х 3 PSGM -2 х 3 PSGM -3 х 3 It is necessary to use PSGM-2 repeatedly for estimation of reproducibility of results
Program B_LEAST recommended by ISO 6143-2003 was used for constructing the curve Mathematical model of calibration curve is linear one
Sample Handling The cylinder was kept for 24 hrs at a room where comparators were disposed This room is a thermostatic room with t = (20plusmn2) ordmС
43
A method of sample input to a comparator is a method with flow stabilization Uncertainty The following uncertainties were included to the budget of uncertainty - uncertainty of the balance - uncertainties of impurities in parent gases Contribution from other uncertainty sources was insignificant A cabin of the balance is thermostatically The balance is the one-pan balance
Air transfer is absent in the cabin of the balance Drift of the balance is absent for PSGM preparation
Contribution from other uncertainty sources was considered in software according to ISO 6142-2003
Uncertainties related to the analysis (comparison) were considered in software according to ISO 6143-2003 and enclosed in Annex B
Uncertainty table СО2
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas mixture
B 001 1 001
Analysis A B 008 1 008
Coverage factor 2 Expanded uncertainty 002sdot10-2 molmol Uncertainty table СО
Protocols of analysis (comparison) in accordance with ISO 6143-2003
57
Explanation of protocols of comparison
Chapter I ldquoThe calibration data set isrdquo contains columns 1 mole fraction of a component 2 absolute standard uncertainty of mole fraction of a component 3 a signal of a comparator 4 absolute standard uncertainty of a comparator signal
Chapter II ldquoResults of ISO 6143 methodrdquo contains parameters of a calibration curve including its
uncertainty
Chapter ІІІ ldquoPart II Processing of datardquo contains columns
1 calc x - the results of comparison mole fraction of a component 2 u(x) - absolute standard uncertainty of mole fraction of a component 3 response y - a signal of a comparator 4 u(y) - absolute standard uncertainty of a comparator signal
58
СО2 - measurement 1 Data setCO2_21 The calibration data set is 1302E+01 1510E-03 1022E+04 1820E+00 1370E+01 1560E-03 1077E+04 2730E+00 1445E+01 1620E-03 1135E+04 5900E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 20331E-02 12711E-03 12573E-01 11653E-05 -14638E-06 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 10548E-02 12722E-03 31762E-02 28898E-06 -91698E-08 Remaining SSD is 74346 Weighted distances x-value x-dist y-dist 100E+00 130E+01 490E-01 -755E-01 200E+00 137E+01 -103E+00 228E+00 300E+00 144E+01 539E-01 -250E-01 Goodness-of-fit measure 22837 Parameter set 1 1054788657490729E-2 1272208026684145E-3 3176237146276368E-2 2889798108124711E-6 -
9169821653851327E-8 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_21c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13577E+01 25542E-03 10664E+04 15200E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 547E-06 328E-06 316E-06 784E-06 286E-06 652E-06 Linear model Parameters for the fit were (b0 b1) 10548E-02 12722E-03
59
СО2 - measurement 2
Data setCO2_20 The calibration data set is 1302E+01 1512E-03 1021E+04 4723E+00 1370E+01 1563E-03 1075E+04 1600E+00 1445E+01 1620E-03 1133E+04 7300E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -38760E-02 12784E-03 26817E-02 24890E-06 -66689E-08 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -62452E-02 12805E-03 47930E-02 43243E-06 -20716E-07 Remaining SSD is 03231 Weighted distances x-value x-dist y-dist 100E+00 130E+01 107E-01 -415E-01 200E+00 137E+01 -212E-01 283E-01 300E+00 144E+01 104E-01 -584E-02 Goodness-of-fit measure 04155 Parameter set 1 -6245240430658412E-2 1280492624666799E-3 4792952200361109E-2 4324266278840409E-6 -
2071623966851869E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_20c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13594E+01 10290E-02 10665E+04 78300E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 121E-05 683E-06 651E-06 315E-05 560E-06 106E-04 Linear model Parameters for the fit were (b0 b1) -62452E-02 12805E-03
60
С3Н8 - measurement 1
Data setC3H8 The calibration data set is 1900E-01 7800E-05 9057E+03 1098E+01 2002E-01 7900E-05 9552E+03 8569E+00 2101E-01 7960E-05 1007E+04 4049E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10529E-02 19831E-05 34552E-03 36109E-07 -12465E-09 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11642E-02 19714E-05 23073E-03 23522E-07 -54231E-10 Remaining SSD is 19453 Weighted distances x-value x-dist y-dist 100E+00 190E-01 -239E-01 666E-01 200E+00 200E-01 487E-01 -104E+00 300E+00 210E-01 -247E-01 248E-01 Goodness-of-fit measure 10414 Parameter set 1 1164239985182795E-2 1971441115316992E-5 2307269625077337E-3 2352198415608386E-7 -
5423119774765299E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19837E-01 14840E-04 94718E+03 45610E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
3
uncertainty components appear in the model for evaluating the uncertainty from gravimetric preparation
)()()( 222purityweighinggravp xuxuxu ∆+= (1)
A second contributor to the uncertainty of the reference value of gas mixtures ugravR is the uncertainty from verification u(xver) The verification process is used to confirm the gravimetric composition by NDIR analyzer included to the set of National Primary Measurement Standard GET 154-01 as checking internal consistency between prepared cylinders in accordance with requirements of ISO 6143 [2]
gravRgravR kuU = (2) where
)()( 22vergravpgravR xuxuu += (3)
k=2 Measurement methods and calibration procedures The following methods of measurement and calibration methods have been employed (table 1) Table 1 Measurement and calibration methods Laboratory Measurement
method Calibration method Total number of
measurements VNIIM NDIR Three points
linear 3 measurements 5 submeasurements
Ukrmetrteststandard GC-TCD (COCO2) GC-FID (C3H8)
Three points linear Three points linear
2 measurements 3 submeasurements
BelGIM GC-TCD (COCO2) GC-FID (C3H8)
Three points linear Three points linear
3 measurements 6 submeasurements
ВАМ GC-TCD (COCO2) GC-FID (C3H8)
Bracketing Bracketing
5 measurements 9 submeasurements
Results In the current comparison on gas mixtures measurements were performed on individually prepared gas mixtures with (slightly) different concentrations The individual gravimetric values are reference values The difference between the analyzed and gravimetric values has been taken as degree of equivalence Di defined as
igravilabi xxD minus= (4) The combined standard uncertainty of the degree of equivalence can be expressed as
4
2
2
)( igravRilabi uuDu += (5) The expanded uncertainty )( iDU of the degree of equivalence Di
2
2)( igravRilabi uukDU += (6)
where Di ndash Degree of equivalence difference between the laboratory value and the gravimetric value U(Di) ndash Expended uncertainty of the degree of equivalence
gravx - Assigned amount of substance fraction of a component
labx - Result as reported by the participant
gravRu - Standard uncertainty of gravx
labu - Standard uncertainty of labx k - Coverage factor 2=k All results of this key comparison are presented in the tables 2 ndash 4 and shown in figures 1 ndash 3 The tables 2 - 4 contain the following information Lab Laboratory Cylinder Identification code of cylinder
gravx Assigned amount of substance fraction of a component
gravRU Expended Uncertainty of gravx 2=k
labx Result as reported by the participant
labU Expended Uncertainty of labx Di Degree of equivalence
)( iDU Expended Uncertainty of Di
labk Coverage factor as reported by the participant Calculation of expanded uncertainty was carried out with coverage factor k=2 Degrees of equivalence The unilateral degree of equivalence has already been defined (4) For the bilateral degrees of equivalence the model used for CCQM-K1 has been adapted The degree of equivalence between two laboratories is defined as
jgravjlabigravilabij xxxxD minusminusminus= (7) where
igravx - the assigned value for the laboratory i
ilabx -the amount of substance fraction of the laboratory i
jgravx - the assigned value for the laboratory j
5
jlabx - the amount of substance fraction of the laboratory i The expanded uncertainty of the degree of equivalence Dij (k=2)
Discussion and Conclusions All laboratories find the gravimetric value within plusmn07 relative to the gravimetric value This holds for all three components COCO2 and C3H8 in nitrogen This is a satisfying result For all laboratories the observed difference between the gravimetric and reported values does not exceed its combined uncertainty VNIIM and BAM are link laboratories for CCQM-K3 The results of this comparison are linked to the key comparison CCQM-K3 Reference [1] International Organization for Standardization ISO 61422001 Gas analysis - Preparation of calibration gas mixtures - Gravimetric methods 2nd edition [2] International Organization for Standardization ISO 61432001 Gas analysis ndash Comparison methods for determining and checking the composition of calibration gas mixtures [3] Van der Veen AMH De Leer EWB Perrochet J-F Wang Lin Zhen Heine H-JKnopf D Richter W Barbe J Marschal A Vargha G Deaacutek E Takahashi C Kim JS Kim YD Kim BM Kustikov YA Khatskevitch EA Pankratov VV Popova TA Konopelko L Musil S Holland P Milton MJT Miller WR Guenther FR International Comparison CCQM-K3 Final Report Coordinator Leonid Konopelko VNIIM Research Department for the State Standard in the Field of Physical-Chemical Measurements (PCD) 19 Moskovsky pr St-Petersburg 198005 Russia Phone +7 812 3151145 Fax +7 812 3279776 E-mail lkonopmailrcomru Completion Date March 2006
11
Annex 1 Proposal of Degrees of Equivalence Table 5 Degrees of Equivalence for carbon monoxide Lab j VNIIM Ukrmetrteststandard BelGIM BAM Lab i Di Ui Dij Uij Dij Uij Dij Uij Dij Uij mmolmol mmolmol mmolmol mmolmol mmolmol VNIIM 001 006 012 014 007 021 005 016 Ukrmetrteststandard -011 012 -012 014 -005 024 -007 019 BelGIM -006 020 -007 021 005 024 -002 025 BAM -004 015 -005 016 007 019 0016 025 Table 6 Degrees of Equivalence for carbon dioxide Lab j VNIIM Ukrmetrteststandard BelGIM BAM Lab i Di Ui Dij Uij Dij Uij Dij Uij Dij Uij mmolmol mmolmol mmolmol mmolmol mmolmol VNIIM 012 013 026 026 -074 101 0034 043 Ukrmetrteststandard -014 022 -026 026 -10 102 -023 046 BelGIM 086 100 074 101 10 102 077 108 BAM 009 041 -0034 043 023 046 -077 108 Table 7 Degrees of Equivalence for propane Lab j VNIIM Ukrmetrteststandard BelGIM BAM Lab i Di Ui Dij Uij Dij Uij Dij Uij Dij Uij mmolmol mmolmol mmolmol mmolmol mmolmol VNIIM 0001 0004 0002 0006 0005 0020 -0009 0013 Ukrmetrteststandard -0001 0004 -0002 0006 0003 0021 -0011 0013 BelGIM -0004 0020 -0005 0020 -0003 0021 -0014 0023 BAM 0010 0012 0009 0013 0011 0013 0014 0023
12
Annex 2 Results and measurement reports as submitted by participating laboratories Key comparison participants
MEASUREMENT REPORT - DI Mendeleyev Institute for Metrology
Russian Federation (VNIIM)
I Results of Study
Laboratory DI Mendeleyev Institute for Metrology (VNIIM) Research Department for the State Standard in the Field of Physical-Chemical Measurements (PCD)
Instruments Multichannel automatic NDIR analyzer included to the set of the National Primary measurement standard of units of mole fraction and mass concentration of components in gas medium GET 154-01 was used for the analysis Calibration Standards All calibration multicomponent gas mixtures were prepared gravimetrically according to ISO 6142 The calibration multicomponent gas mixtures were prepared from pure gases directly on components CO CO2 and from pre-mixtures which were prepared from pure gases on component С3Н8 The content of the impurities in all pure gases was determined by GC with helium-ionization flame-ionization and thermal-conductivity detectors as well as standard hygrometer apparatus included to the standard complex A1 of analysis of pure gases and substances from GET 154-01 The calibration multicomponent gas mixtures were verified with usage of existing gravimetric gas mixtures in accordance with ISO 6143 Composition of calibration standards
Cylinder 6547 Cylinder 6571 Cylinder 6538 Component x мольmol Standard
Instrument Calibration Three independent measurements were carried out under repeatability conditions Before each measurement an instrument calibration was made One measurement contained 5 submeasurements Sample Handling The time of the cylinder keeping is 24 hrs It was used the automatic unit of commutation for inputting gas mixtures
15
Uncertainty Uncertainty table СО2
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas
mixture
B 0010 1 0010
Analysis A B 0048 1 0048
Coverage factor 2 Expanded uncertainty 01 Uncertainty table СО
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas
mixture
B 002 1 002
Analysis A B 0095 1 0095
Coverage factor 2 Expanded uncertainty 019
16
Uncertainty table С3Н8 Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas
mixture
B 005 1 005
Analysis A B 0045 1 0045
Coverage factor 2 Expanded uncertainty 013
17
MEASUREMENT REPORT ndash Belorussian State Institute for Metrology Belarus (BelGIM)
I Results of experimental study
Laboratory Belarus BelGIM Section for physicochemical and optical measurements sector for standards and gas mixtures 8 Serova st Minsk Cylinder No 0128 9 dm3 aluminium NOMINAL COMPOSITION - Carbon dioxide 13middot10-2 - 14middot10-2 molmol - Carbon oxide 28middot10-2 - 32middot10-2 molmol - Propane 19middot10-4 - 21middot10-4molmol - Nitrogen Residual
Measurement No1 Date
Result (molmol)
x_
Standard deviation
S( x_
) rel
No of observations
n
Carbon dioxide 17062005 13567middot10-2 0096 6
Carbon oxide 17062005 2957middot10-2 014 6
Propane 17062005 1977middot10-4 015 6
Measurement No2 Date
Result (molmol)
x_
Standard deviation
S( x_
) rel
No of observations
n
Carbon dioxide 21062005 13564middot10-2 004 6
Carbon oxide 21062005 2957middot10-2 02 6
Propane 21062005 1979middot10-4 01 6
18
Measurement No3 Date
Result (molmol)
x_
Standard deviation
S( x_
) rel
No of observations
n
Carbon dioxide 23062005 13537middot10-2 007 6
Carbon oxide 23062005 2955middot10-2 01 6
Propane 23062005 1982middot10-4 01 6
Final results
Gas mixture Result
(molmol)
Coverage factor
Expanded uncertainty (molmol)
Carbon dioxide 136middot10-2 2 01 middot10-2
Carbon oxide 296middot10-2 2 002middot10-2
Propane 198middot10-4 2 02middot10-4
II Description of study Apparatus (principle of operation type configuration data collection etc)
Measurements were carried out using gas chromatograph Crystal 2000М (hereinafter
referred to as chromatograph) combined with thermal conductivity detector (hereinafter referred to as TCD) with detection limit of 510-9 gml for propane and flame-ionization detector (hereinafter referred to as FID) with detection limit of 510-12 gs for propane
Computers and software Chromatech Analytic version 121 were used to control chromatograph and collect and process chromatographical data
For the purpose of measurements the following auxiliary devices and materials were used
1 Two-position doser with 10 ports and with doses of 025 cm3 for FID channel and with doses of 025 cm3 for TCD channel (hereinafter referred to as doser)
2 Metallic packed column 3m х 3mm х 2mm - HayeSep N 80100 metallic packed column 1m х 4mm х 2mm-CaA 016025 (TCD channel) capillary column HP PLOTQ 30m х 0536mm (FID channel)
3 Aneroid BАММ-1 with a measurement range of 80-106 kPа and accuracy of plusmn 02 kPа
4 Mercurial thermometer ТL-4 with a measurement range of 0-50ordmС and scale division of 01ordmС
19
5 Fine adjustment valve (hereinafter referred to as FAV) provided to transport a gas sample into chromotograph and set to gas flow-rate of 10-15 mlmin
6 Foamy gas flow meter type YIRG - 2А accuracy of flow measurement plusmn 1 сm3min
7 Helium gas Type A according to TU 51-940-80 8 High purity hydrogen gas according to TU 301-07-27-90 9 Compressed air 10 Multicomponent calibration gas mixtures (hereinafter referred to as CGM)
produced and certified by gravimetric method
Calibration reference materials - calibration gas mixtures used for measurements 1 Quantitative composition of KGS is determined using gravimetric method defined in
ISO 61422001 by calculating weight of each component of a gas mixture The content of CGM components is expressed as a mole fraction Uncertainty of KGS composition is expressed as expanded uncertainty with coverage factor k = 2 Molar masses of components and their uncertainties are taken from ISO 149122003 Performance and metrological characteristics of the equipment used for gravimetric preparation of mixtures are given in Table 1
Table 1
Description of the equipment
Manufacturer Metrological characteristics
Mass-comparator balance type КА10-3Р
Mettler-Toledo
Switzerland
Maximum load 15 kg Scale division 1 mg Standard deviation 19 mg at load of 10 kg Operating temperature range +10divide30degС Maximum temperature change within 1 h plusmn05 degС
Gas mixer type USG 00001 BelGIM
Measurement range 000025 divide 100 МPa Accuracy class for manometers ndash 015 Accuracy class for vacuummeters ndash 025 Vacuummeter with pressure sensor for measuring the residual pressure before filling Residual pressure before filling of each component not more than 20 Pa
2 Purity analysis of primary gas standards
The purity analysis of primary gas standards is based on the information provided by the supplier or on the results of determination of impurity in pure gases using measurement procedure developed inside BelGIM
20
If an analytical method laid down in 43 of ISO 61422001 cannot be used for impurity determination mole fraction of an expected impurity is assumed to be half of the detection limit of the analytical method The content of the undetected impurity produces rectangular distribution
whereby its standard uncertainty is calculated as half of the detection limit divided by 3 The composition of the pure gases used for preparation of calibration mixtures is given
in Table 2 Table 2 - Metrological characteristics of pure gases
N2 999967 00005 Nitrogen Cylinder 40 dm3 Origin Russia O2 00033 00005 Propane Cylinder 2 dm3 Origin Russia
C3H8 9979 0017
3 After preparation of mixture the cylinder was maintained in laboratory room within
24 hours the mixture then was homogenized on the stand by rotating on the rollers within 4-5 hours The chromotograph for CGM was calibrated 2-3 days after its preparation
Calibration of the chromotograph
1 The chromotograph was calibrated using CGMs with composition identical to the analyzed sample The content of each component and its expanded uncertainty (k = 2) are given in Table 1 Table 1 - Calibrationе gas mixtures
2 Number of observations of each calibration sample- 3 Number of calibration samples - 3
3 The analytical function used for determination of the content of the analyzed sample components is as follows
x (y) =b1y+b0 (2) Where x ndash determined content molmol y - chromotograph response for the specific component b1- slope b0 - intercept 4 After completion of calibration the coefficients of analytical function were
calculated according to ISO 61432001 using generalized least-squares method Also the uncertainties of the intercept and slope and covariance between them were calculated After determination of parameters which are part of analytical function and which affect the uncertainty of measurements it was checked whether the analytical function is fit to the experimental data obtained in calibration and subsequently whether the analytical function is applicable
Results of calibration measurements coefficients of analytical function their uncertainties covariance and measure of goodness-of-fit Г (maximum value of the weighted differences of the experimental points and calculated points of the analytical function for each measurement run) are given in Tables 3 and 4 respectively Chromotograph operating conditions in calibration and analysis are given in Table 5
Table 3 - Results of experimental study
Date Component of
calibration mixture
Content x mole fraction
Expanded uncertainty
U(x) mole fraction
Mean of peak area y
mVs
Uncertainty )(yu
mVs
13374 0004 1279500 141 1389 0004 1329150 2899 CO2
12833 0004 1231000 849 2916 0005 404070 240
316 0005 437705 926 CO 2768 0004 383070 467
019 0002 3143200 4101
1706 2005
C3H8 0202 0002 3319150 2051
22
0181 0002 2948750 212 13374 0004 1269833 624
1389 0004 1321000 1272 CO2 12833 0004 1223900 1698
2916 0005 399490 612 316 0005 434010 863 CO
2768 0004 379660 410 019 0002 3157867 6772
0202 0002 3332400 3394
2106 2005
C3H8 0181 0002 2959900 4950
13374 0004 1277100 2152 1389 0004 1329900 2828 CO2
12833 0004 1229100 1980 2916 0005 400330 529
316 0005 434745 969 CO 2768 0004 379695 106
019 0002 3142433 9416 0202 0002 3321600 4101
2306 2005
C3H8 0181 0002 2961000 3111
According to ISO 61432003 calculation of the measure of goodness-of-fit Г is the maximum value of the weighed differences between the coordinates of measured and adjusted calibration points is an effective and simple method to test the compatibility of а prospective analytical function A function is admissible if Г le 2
minus
minus=
)(ˆ
)(ˆ
iii
iii
yuyy
xuxxΓ
(4) Where хi is the reference value of the content of calibration sample component
ix is the CGM component content obtained using the calculated analytical function
уi is the experimental response to the reference content of component iy is the response obtained in calculation of analytical function
u (хi) u (уi) are the uncertainties of reference contents and responses to these contents respectively
i is the number of calibration points i=1 3 This prerequisite is equivalent to the requirement that the curve of calculated response should cross each experimental calibration rectangular [хi plusmn 2u(хi) уi plusmn 2и(уi)] based on an expanded uncertainty U = ku with coverage factor k = 2 Table 4 Calculations of analytical function
Date Component Analytical function parameters
Uncertainty of analytical
function parameters
Covariance of
parameters Г
23
b1 b0 u(b1) u(b0) u(b0b1) 1706 11086E-
03 -81128E-
0119491E-
0524883E-
01 -48497E-06 10544
2106 10729E-03
-26126E-01
22698E-05
28930E-01 -65652E-06 19997
2306
CO2 10593E-
03 -17688E-
0135807E-
0545413E-
01 -16254E-05 10022
1706 71537E-04
26507E-02
14231E-05
57044E-02 -81115E-07 03017
2106 72346E-04
22401E-02
13819E-05
54490E-02 -75209E-07 05935
2306
CO 71321E-
04 60080E-
0212663E-
0549016E-
02 -62026E-07 01341
1706 56521E-06
13712E-02
38279E-07
12015E-02 -45937E-09 12991
2106 56295E-06
13707E-02
39247E-07
12379E-02 -48529E-09 12905
2306
C3H8 58258E-
06 80469E-
0340085E-
0712590E-
02 -50407E-09 08589
Two columns separated by switching device are located one after another in TCD
channel One column is intended for carbon dioxide heavy hydrocarbons and another column is intended for light gases Before the first switch the light gases including carbon oxide flow through the first column without being separated and remain in the second column The switch makes them locked in the second column The analysis of carbon dioxide is carried out up to the second switch Second switch makes the second column unlocked and carbon oxide is analyzed Third switch is required to allow propane escape from a column and prevent it from getting into a second column The analysis of the very propane is carried out using FID Time intervals between switches were selected experimentally when developing the analysis method Such analysis method makes it possible to analyze all three components per one sample inject
Table 5 - Chromotograph operating conditions in calibration and analysis Parameter of the operating conditions Thermostating temperature of TCD and FID degС 170
Temperature of separation columns degС
Program 60 degС within 9 min
than rise to 160 degС at 20degСmin
Rate of flow of carrier gas through TCD channel columns mlmin 15
Rate of flow of carrier gas through TCD comparison channel mlmin 15
Pressure in FID channel column kPa Program
24
80 to 100 Rise from the 1st s of
analysis at 2 kPamin
Flow-rate of hydrogen FID mlmin 20 Flow-rate of air FID mlmin 200 Temperature of switching device degС 65 Response time of switching device s 1 110 2 330 3 540
TCD FID Volume of injected analyzed gas cm3 025 025 Carrier gas Helium Duration of analysis min 17 Calculation of the content of comparison sample components and its uncertainty Results of comparison sample measurements are given in Table 6 Table 6 - Results of comparison sample measurements
1 The content of comparison sample component and its uncertainty were determined
using calculated analytical function according to ISO 61432001 as follows (5) Where G(y)=b1y+b0 is the calculated analytical function и(y) is the standard uncertainty of response y u2(bj) is the variance of analytical function parameter bj
u(bj bI) is the covariance of analytical function parameters bj bI N is the number of function coefficients N=2 j=0 1
sum sumsumminus
= +==
partpart
partpart
+
partpart
+
partpart
=1
0 1
2
2
0
22
)(2)()()(N
jIj
N
jI Ijj
N
j j
bbubG
bGbu
bGyu
yGxu
25
After substitution of analytical function (2) and transformations the expression takes form (5)
)(2)()()()()( 01122
0222
1 bbyubuybuyubxu +++= (6) The contents of comparison sample components under determination and their
uncertainties were calculated using B_LEAST a computer program recommended in ISO 6143 Calculations are summarized in Table 6
Table 6 Calculations of the content of comparison sample components and their
2 The final content of a component was determined as an arithmetiс mean from three measurements Final standard uncertainty was calculated using formula as follows
22
222)( Адаватмтемсериикал uuuuuxu ++++= (7)
Where ucal is the uncertainty of the component content produced by
calibration of chromotograph urun is the uncertainty of the component content produced by
change of chromotograph response in each measurement run ut is the uncertainty of the component content produced by
change of an ambient temperature upressure is the uncertainty of the component content produced by
change of atmospheric pressure u A is the standard uncertainty of three measurement runs
21 Uncertainty of the component content produced by calibration of chromotograph
This uncertainty is calculated using formula (6) but the first term of the sum ie
)()( 221 yub which represents the standard uncertainty of the chromotograph response in a
measurement run is not taken into account Calculations are summarized in Table 7
26
Table 7 Calculation of uncertainty produced by calibration of chromotograph
Date u(b1) u(b0) u(b0b1) x
molmol y Ucal molmol
Ucal rel
1706 19491E-05
24883E-01
-48497E-06
13567middot10-
2129698
3 0005middot1
0-2 003
2106 22698E-05
28930E-01
-65652E-06
13564middot10-
2 128855 0007middot1
0-2 005
2306
CO2
35807E-05
45413E-01
-16254E-05
135374middot10-2
1294633
0016middot10-2 012
1706 14231E-05
57044E-02
-81115E-07 2957middot10-2 409633
0003middot10-2 009
2106 13819E-05
54490E-02
-75209E-07
29577middot10-
2 405663 0003middot1
0-2 01
2306
CO
12663E-05
49016E-02
-62026E-07 2955middot10-2 405882
0003middot10-2 01
1706 38279E-07
12015E-02
-45937E-09 1977middot10-4
3255817
007middot10-
2 038
2106 39247E-07
12379E-02
-48529E-09 1980middot10-4
3273329
008middot10-
2 038
2306
C3H8
40085E-07
12590E-02
-50407E-09 1982middot10-4 32636
008middot10-
2 04 The total estimate of relative uncertainty produced by calibration of chromotograph was
calculated for each component as follows
3
3
1
2sum=
cali
cali
uu (8)
Where ucal i is the relative uncertainty produced by calibration of chromotograph and calculated for each measurement run
The calculations are summarized in Table 8
Table 8 Uncertainty produced by calibration of chromotograph
Component Ucal rel
CO2 008 CO 01
C3H8 04 22 Uncertainty of the component content produced by change of chromotograph response in each measurement run This uncertainty is calculated using the equation (6) whereby the first term of the sum
only ie )()( 221 yub which represents the standard uncertainty of the chromotograph
response in a measurement run is taken into account Calculations are summarized in Table 9
27
Table 9 Calculation of uncertainty produced by change of chromotograph response in each measurement run
The total estimate of relative uncertainty produced by change of chromotograph
response in each measurement run was calculated for each component as follows
3
3
1
2sum=
run
run
uu (9)
Where urun is the relative uncertainty produced by change of chromotograph response in each measurement run Calculations are summarized in Table 10
Table 10 Uncertainty produced by change of chromotograph response in each measurement
run
Component Urun rel
CO2 007 CO 015
C3H8 012 23 Uncertainty of the component content produced by change of temperature in a room
The recorded change of temperature in measurements is plusmn 05 degree The contribution of uncertainty type B (rectangular distribution) is estimated as follows
201003
12931
=sdotsdot=tu rel
28
24 Uncertainty of the component content produced by change of atmospheric pressure The recorded change of atmospheric pressure within three days was
05 kPа The contribution of uncertainty type B (rectangular distribution) is estimated as follows
2801003
13101
50=sdotsdot=pressureu rel
25 Standard deviation of 3 measurement runs Standard deviation is calculated as follows
isu p
A
2
= (10)
Where S2p is the group experimental variation
The group experimental variation is calculated as follows
(11)
Where si
2 is the experimental variation of measurement run i from independent repeated observations ni having freedom degrees
νi = n - 1 n=6 i= 3 Calculations are summarized in Table 11 Table 11 Calculations of standard uncertainty of 3 measurement runs
Date 2iS x
molmol 2iS
rel uA
rel
1706 2953E-05 13567middot10-2 000022
2106 588987E-06 13564middot10-2 0000043
2306
CO2 141137E-
05 135374middot10
-2 000010
0006
1706 225604E-06 2957middot10-2 0000077
2106 681346E-06 29577middot10-2 000023
2306
CO
175166E-06 2955middot10-2 0000060
0006
1706 C3H8 130158E-
08 1977middot10-4 00000066 0001
ss
p
i ii
N
ii
N2
2
1
1
= =
=
sum
sum
ν
ν
29
2106 44616E-09 1980middot10-4 00000023
2306
381032E-09 1982middot10-4 00000019
26 Total standard uncertainty
Uncertainty estimation СО2
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph ucal Normal 008 1 008
Change of temperature ut Rectangular 02 1 02 Change of atmospheric pressure upressure Rectangular 028 1 028
Changes of chromotograph response
urun Normal 007 1 007
Standard deviation of 3 runs uA Normal 0006 1 0006
Relative total standard uncertainty 036 Coverage factor k=2 Expanded uncertainty 01middot10-2 molmol Uncertainty estimation СО
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph ucal Normal 01 1 01 Change of temperature ut Rectangular 02 1 02 Change of atmospheric pressure upressure Rectangular 028 1 028 Changes of chromotograph response
urun Normal 015 1 015
Standard deviation of 3 runs uA Normal 0006 1 0006
Relative total standard uncertainty 039 Coverage factor k=2 Expanded uncertainty 002middot10-2 molmol Uncertainty estimation С3Н8
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph 04 Normal 04 1 008
30
Change of temperature 02 Rectangular 02 1 02 Change of atmospheric pressure 028 Rectangular 028 1 028
Changes of chromotograph response
012 Normal 012 1 007
Standard deviation of 3 runs 0001 Normal 0001 1 0006
Relative total standard uncertainty 054 Coverage factor k=2 Expanded uncertainty 02middot10-4 molmol
Sample handling
Period for exposure of cylinder to measurement conditions and method how to transport sample to the device
1 Stands for storing gas standard cylinders and calibration mixture cylinders and chromotograph are placed in a laboratory room which is not accessible to unauthorized persons The laboratory is equipped with air-conditioner to maintain required temperature and humidity on a continuous basis and some auxiliary measuring instruments as thermometer psychrometric hygrometer and aneroid to control temperature humidity and atmospheric inside the room
2 The comparison sample cylinder was stored in laboratory from the date of its
delivery to Minsk on 25042005 CGM cylinders are stored horizontally on racks and positioned vertically using special support when measurements are carried out
3 The analyzed gas sample is transported through the fine adjustment valve (FAV)
Conjunctions Cylinder - FAV FAV - tube tube - doser are made of metal and use adapters with spherical ends and bushes FAV is made of brass tube is made of copper and doser is made of duralumin
Instrument(s) (principles make type configuration data collection etc) For the analysis a GC were used with specifically applications For the determination of (Nitrogen (N2)) Carbon Dioxide (CO2) Carbon Monoxide (CO) and Propane (C3H8) balance GC Perkin Elmer AutoSystem XL (two channel system) with a stream selection valve for 4 streams and 2 gas sampling valves
Channel A for the determination of N2 CO and CO2 Carrier Gas Helium Columns Column system with two packed columns (6 ft x 18rdquo Porapak R 80100 mesh and 6 ft x 18rdquo Mol-Sieve 13X 80100 mesh) Oven Temperature 960 degC to 180 degC Detector micro-TCD Data Collection Total Chrom Workstation Channel B for the determination of C3H8 Carrier Gas Helium Columns Capillary column 50 m x 032 microm LP-SIL-8-CB Oven Temperature 60 degC to 180 degC Detector FID Data Collection Total Chrom Workstation
34
Calibration Standards
Calibration Standards for the measurements (preparation method purity analyses estimated uncertainty etc)
All standards were prepared individually according to ISO 6142 rdquoGas analysis - Preparation of calibration gases - Gravimetric Methodrdquo
Depending on the concentration of the components standards were prepared individually from pure gases or from pre-mixtures which were individually prepared from pure gases
The content of the impurities in all pure gases were determined before use by GC-DID GC-FID and or GC-TCD
After preparation the standards were verified by analytical comparisons against existing gravimetrically prepared standards Only when no significant difference between the analysed and the calculated gravimetric composition is found the ldquonew prepared candidate rdquo is accepted as a new standards
For the analysis of all components multi component standards with nitrogen as balance gas were used
Composition of calibrants BAM C49250-050722 Component Assigned value( x)
mmol mol Standard uncertainty (u(x)) relativ (k=2)
Calibration procedure (mathematical modelcalibration curve number and concentrations of standards measurement sequence temperaturepressure correction etc)
For the instrument calibration the bracketing technique was used The fraction of the current used standards deviated no more than +10rel and -10rel respectively from those of the sample
Measurement sequence
Sample Handling
How were the cylinders treated after arrival (eg stabilized) and how were samples transferred to the instrument (automatic high pressure mass-flow controller dilution etc) After heating (45 - 50 degC) the cylinder for 8 hours the cylinder were rolled about 16 hours before analysis was started Each cylinder was equipped with a pressure regulator that was purged three times by sequential evacuation and pressurisation with the gas mixture used Continous flow (2 ndash 3mlmin) through the sample loop
Uncertainty The specification of potential uncertainty sources is given in Annex 3
3 injection standard (high)
3 injection sample
3 injection standard (high)
3 injection sample
3 injection standard (low)
3 injection sample
3 injection standard (low)
3 injection standard (low)
36
Uncertainty table CO2
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 002 rel 1 002 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 03 rel
Uncertainty table CO
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 007 rel 1 007 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 05 rel
37
Uncertainty table C3H8
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 010 rel 1 001 rel
Analysis normal 028 rel 1 028 rel
Coverage factor 2
Expanded uncertainty 06 rel
Optional
You may provide additional data like the raw measurement data information on your
measurement procedure chromatograms etc
38
Appendix 3 SPECIFICATION OF POTENTIAL UNCERTAINTY SOURCES
a Uncertainty related to the balance and the weights Resolution of balance Accuracy of balance including linearity Incorrect zero point Drift (thermal and time effects) Instability due to draught Location of cylinder on the balance pan Uncertainties in the weights used Buoyancy effects on the weights used
b Uncertainties related to the gas cylinder Mechanical handling of cylinder
Loss of metal paints or labels from surface of cylinder Loss of metal from threads of valvefitting Dirt on cylinder valves or associated fitting
Absorptiondesorption effects on the external cylinder surface Buoyancy effects on the cylinder itself
Cylinder temperature differs from surrounding air due to eg filling with gas Change of cylinder volume during filling Change of density of surrounding air due to changes in temperature air pressure humidity and carbon dioxide content
Uncertainty in determination of external cylinder volume c Uncertainties related to the component gases Residual gas in cylinder Leakage Leakage of air into the cylinder after evacuation
Leakage of gas from the cylinder valve during filling Escape of gas from cylinder into transport lines
Gas remaining in transfer system when weight loss method is used Absorptionreaction of components on internal cylinder surface Reaction between components Impurities in all the initial gases Insufficient homogenization Uncertainty of molecular mass d Uncertainties related to the analysis
Repeatability and selectivity of the analyzer Appropriateness of the calibration curve
39
MEASUREMENT REPORT - All Ukrainian State Research-Industrial Center of Standardization Metrology Certification and Protection of Consumers Ukraine
gas ndash helium flow rate 15 cm3min detector TCD tdetector = 250 ordmС toven = 70 ordmС It was automatic data collection
Measurement and Calibration Methods Laboratory Measurement method Type of calibration curve
GCFID (С3Н8) 3 points linear Ukrmetrteststandard GCTCD (СО СО2) 3 points linear
GCFID ndash gas-chromatographic with flame-ionization detector GCTCD - gas-chromatographic with thermal-conductivity detector
42
Calibration Standards
Calibration standards ndash primary standard gas mixtures (PSGM) used for measurements by comparison method
PSGM-1 Cylinder 0116
PSGM-2 Cylinder 0107
PSGM-3 Cylinder 0093 Composition
x u(x) x u(x) x u(x) СО 27874 00015 29899 00015 31891 00015 СО2 130187 00015 144456 00016 137016 00016 С3Н8 019003 000008 020017 000008 021013 000008 N2 balance balance balance
Note x ndash mole fraction u(x) ndash absolute standard uncertainty
It was used gravimetric method of preparation of PSGM Electronic balance КА-20-3 of Mettler Toledo max limit of weighing is 20 kg least
limit of weighing is 01 g standard deviation is 0006 g Analysis of purity of parent gases was carried out with usage of chromatographs
НР6890N with helium ndash ionization detector flame ndash ionization detector thermal ndash conductivity detector and mass ndash spectrometric detector as well аs gas analyzers GIAM-15M and Onix condensate-thermometer hygrometer TOROS-3-2B
Calculation of uncertainties was carried out according to ISO 6142-2003 Corrections of temperature pressure and humidity of environment were considered
in calculations according to ISO 6142-2003 (program of ISO-6142 2000-03-17 designer is NMi) Protocols and explanations are in Annex A
Instrument (Comparator) Calibration Calibration of comparator ndash gas chromatograph HP 6890 was carried out with usage
of PSGM Measurement sequence PSGM -1 х 3 PSGM -2 х 3 COOMET gas mixture х 3 PSGM -2 х 3 PSGM -3 х 3 It is necessary to use PSGM-2 repeatedly for estimation of reproducibility of results
Program B_LEAST recommended by ISO 6143-2003 was used for constructing the curve Mathematical model of calibration curve is linear one
Sample Handling The cylinder was kept for 24 hrs at a room where comparators were disposed This room is a thermostatic room with t = (20plusmn2) ordmС
43
A method of sample input to a comparator is a method with flow stabilization Uncertainty The following uncertainties were included to the budget of uncertainty - uncertainty of the balance - uncertainties of impurities in parent gases Contribution from other uncertainty sources was insignificant A cabin of the balance is thermostatically The balance is the one-pan balance
Air transfer is absent in the cabin of the balance Drift of the balance is absent for PSGM preparation
Contribution from other uncertainty sources was considered in software according to ISO 6142-2003
Uncertainties related to the analysis (comparison) were considered in software according to ISO 6143-2003 and enclosed in Annex B
Uncertainty table СО2
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas mixture
B 001 1 001
Analysis A B 008 1 008
Coverage factor 2 Expanded uncertainty 002sdot10-2 molmol Uncertainty table СО
Protocols of analysis (comparison) in accordance with ISO 6143-2003
57
Explanation of protocols of comparison
Chapter I ldquoThe calibration data set isrdquo contains columns 1 mole fraction of a component 2 absolute standard uncertainty of mole fraction of a component 3 a signal of a comparator 4 absolute standard uncertainty of a comparator signal
Chapter II ldquoResults of ISO 6143 methodrdquo contains parameters of a calibration curve including its
uncertainty
Chapter ІІІ ldquoPart II Processing of datardquo contains columns
1 calc x - the results of comparison mole fraction of a component 2 u(x) - absolute standard uncertainty of mole fraction of a component 3 response y - a signal of a comparator 4 u(y) - absolute standard uncertainty of a comparator signal
58
СО2 - measurement 1 Data setCO2_21 The calibration data set is 1302E+01 1510E-03 1022E+04 1820E+00 1370E+01 1560E-03 1077E+04 2730E+00 1445E+01 1620E-03 1135E+04 5900E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 20331E-02 12711E-03 12573E-01 11653E-05 -14638E-06 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 10548E-02 12722E-03 31762E-02 28898E-06 -91698E-08 Remaining SSD is 74346 Weighted distances x-value x-dist y-dist 100E+00 130E+01 490E-01 -755E-01 200E+00 137E+01 -103E+00 228E+00 300E+00 144E+01 539E-01 -250E-01 Goodness-of-fit measure 22837 Parameter set 1 1054788657490729E-2 1272208026684145E-3 3176237146276368E-2 2889798108124711E-6 -
9169821653851327E-8 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_21c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13577E+01 25542E-03 10664E+04 15200E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 547E-06 328E-06 316E-06 784E-06 286E-06 652E-06 Linear model Parameters for the fit were (b0 b1) 10548E-02 12722E-03
59
СО2 - measurement 2
Data setCO2_20 The calibration data set is 1302E+01 1512E-03 1021E+04 4723E+00 1370E+01 1563E-03 1075E+04 1600E+00 1445E+01 1620E-03 1133E+04 7300E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -38760E-02 12784E-03 26817E-02 24890E-06 -66689E-08 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -62452E-02 12805E-03 47930E-02 43243E-06 -20716E-07 Remaining SSD is 03231 Weighted distances x-value x-dist y-dist 100E+00 130E+01 107E-01 -415E-01 200E+00 137E+01 -212E-01 283E-01 300E+00 144E+01 104E-01 -584E-02 Goodness-of-fit measure 04155 Parameter set 1 -6245240430658412E-2 1280492624666799E-3 4792952200361109E-2 4324266278840409E-6 -
2071623966851869E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_20c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13594E+01 10290E-02 10665E+04 78300E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 121E-05 683E-06 651E-06 315E-05 560E-06 106E-04 Linear model Parameters for the fit were (b0 b1) -62452E-02 12805E-03
60
С3Н8 - measurement 1
Data setC3H8 The calibration data set is 1900E-01 7800E-05 9057E+03 1098E+01 2002E-01 7900E-05 9552E+03 8569E+00 2101E-01 7960E-05 1007E+04 4049E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10529E-02 19831E-05 34552E-03 36109E-07 -12465E-09 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11642E-02 19714E-05 23073E-03 23522E-07 -54231E-10 Remaining SSD is 19453 Weighted distances x-value x-dist y-dist 100E+00 190E-01 -239E-01 666E-01 200E+00 200E-01 487E-01 -104E+00 300E+00 210E-01 -247E-01 248E-01 Goodness-of-fit measure 10414 Parameter set 1 1164239985182795E-2 1971441115316992E-5 2307269625077337E-3 2352198415608386E-7 -
5423119774765299E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19837E-01 14840E-04 94718E+03 45610E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
4
2
2
)( igravRilabi uuDu += (5) The expanded uncertainty )( iDU of the degree of equivalence Di
2
2)( igravRilabi uukDU += (6)
where Di ndash Degree of equivalence difference between the laboratory value and the gravimetric value U(Di) ndash Expended uncertainty of the degree of equivalence
gravx - Assigned amount of substance fraction of a component
labx - Result as reported by the participant
gravRu - Standard uncertainty of gravx
labu - Standard uncertainty of labx k - Coverage factor 2=k All results of this key comparison are presented in the tables 2 ndash 4 and shown in figures 1 ndash 3 The tables 2 - 4 contain the following information Lab Laboratory Cylinder Identification code of cylinder
gravx Assigned amount of substance fraction of a component
gravRU Expended Uncertainty of gravx 2=k
labx Result as reported by the participant
labU Expended Uncertainty of labx Di Degree of equivalence
)( iDU Expended Uncertainty of Di
labk Coverage factor as reported by the participant Calculation of expanded uncertainty was carried out with coverage factor k=2 Degrees of equivalence The unilateral degree of equivalence has already been defined (4) For the bilateral degrees of equivalence the model used for CCQM-K1 has been adapted The degree of equivalence between two laboratories is defined as
jgravjlabigravilabij xxxxD minusminusminus= (7) where
igravx - the assigned value for the laboratory i
ilabx -the amount of substance fraction of the laboratory i
jgravx - the assigned value for the laboratory j
5
jlabx - the amount of substance fraction of the laboratory i The expanded uncertainty of the degree of equivalence Dij (k=2)
Discussion and Conclusions All laboratories find the gravimetric value within plusmn07 relative to the gravimetric value This holds for all three components COCO2 and C3H8 in nitrogen This is a satisfying result For all laboratories the observed difference between the gravimetric and reported values does not exceed its combined uncertainty VNIIM and BAM are link laboratories for CCQM-K3 The results of this comparison are linked to the key comparison CCQM-K3 Reference [1] International Organization for Standardization ISO 61422001 Gas analysis - Preparation of calibration gas mixtures - Gravimetric methods 2nd edition [2] International Organization for Standardization ISO 61432001 Gas analysis ndash Comparison methods for determining and checking the composition of calibration gas mixtures [3] Van der Veen AMH De Leer EWB Perrochet J-F Wang Lin Zhen Heine H-JKnopf D Richter W Barbe J Marschal A Vargha G Deaacutek E Takahashi C Kim JS Kim YD Kim BM Kustikov YA Khatskevitch EA Pankratov VV Popova TA Konopelko L Musil S Holland P Milton MJT Miller WR Guenther FR International Comparison CCQM-K3 Final Report Coordinator Leonid Konopelko VNIIM Research Department for the State Standard in the Field of Physical-Chemical Measurements (PCD) 19 Moskovsky pr St-Petersburg 198005 Russia Phone +7 812 3151145 Fax +7 812 3279776 E-mail lkonopmailrcomru Completion Date March 2006
11
Annex 1 Proposal of Degrees of Equivalence Table 5 Degrees of Equivalence for carbon monoxide Lab j VNIIM Ukrmetrteststandard BelGIM BAM Lab i Di Ui Dij Uij Dij Uij Dij Uij Dij Uij mmolmol mmolmol mmolmol mmolmol mmolmol VNIIM 001 006 012 014 007 021 005 016 Ukrmetrteststandard -011 012 -012 014 -005 024 -007 019 BelGIM -006 020 -007 021 005 024 -002 025 BAM -004 015 -005 016 007 019 0016 025 Table 6 Degrees of Equivalence for carbon dioxide Lab j VNIIM Ukrmetrteststandard BelGIM BAM Lab i Di Ui Dij Uij Dij Uij Dij Uij Dij Uij mmolmol mmolmol mmolmol mmolmol mmolmol VNIIM 012 013 026 026 -074 101 0034 043 Ukrmetrteststandard -014 022 -026 026 -10 102 -023 046 BelGIM 086 100 074 101 10 102 077 108 BAM 009 041 -0034 043 023 046 -077 108 Table 7 Degrees of Equivalence for propane Lab j VNIIM Ukrmetrteststandard BelGIM BAM Lab i Di Ui Dij Uij Dij Uij Dij Uij Dij Uij mmolmol mmolmol mmolmol mmolmol mmolmol VNIIM 0001 0004 0002 0006 0005 0020 -0009 0013 Ukrmetrteststandard -0001 0004 -0002 0006 0003 0021 -0011 0013 BelGIM -0004 0020 -0005 0020 -0003 0021 -0014 0023 BAM 0010 0012 0009 0013 0011 0013 0014 0023
12
Annex 2 Results and measurement reports as submitted by participating laboratories Key comparison participants
MEASUREMENT REPORT - DI Mendeleyev Institute for Metrology
Russian Federation (VNIIM)
I Results of Study
Laboratory DI Mendeleyev Institute for Metrology (VNIIM) Research Department for the State Standard in the Field of Physical-Chemical Measurements (PCD)
Instruments Multichannel automatic NDIR analyzer included to the set of the National Primary measurement standard of units of mole fraction and mass concentration of components in gas medium GET 154-01 was used for the analysis Calibration Standards All calibration multicomponent gas mixtures were prepared gravimetrically according to ISO 6142 The calibration multicomponent gas mixtures were prepared from pure gases directly on components CO CO2 and from pre-mixtures which were prepared from pure gases on component С3Н8 The content of the impurities in all pure gases was determined by GC with helium-ionization flame-ionization and thermal-conductivity detectors as well as standard hygrometer apparatus included to the standard complex A1 of analysis of pure gases and substances from GET 154-01 The calibration multicomponent gas mixtures were verified with usage of existing gravimetric gas mixtures in accordance with ISO 6143 Composition of calibration standards
Cylinder 6547 Cylinder 6571 Cylinder 6538 Component x мольmol Standard
Instrument Calibration Three independent measurements were carried out under repeatability conditions Before each measurement an instrument calibration was made One measurement contained 5 submeasurements Sample Handling The time of the cylinder keeping is 24 hrs It was used the automatic unit of commutation for inputting gas mixtures
15
Uncertainty Uncertainty table СО2
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas
mixture
B 0010 1 0010
Analysis A B 0048 1 0048
Coverage factor 2 Expanded uncertainty 01 Uncertainty table СО
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas
mixture
B 002 1 002
Analysis A B 0095 1 0095
Coverage factor 2 Expanded uncertainty 019
16
Uncertainty table С3Н8 Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas
mixture
B 005 1 005
Analysis A B 0045 1 0045
Coverage factor 2 Expanded uncertainty 013
17
MEASUREMENT REPORT ndash Belorussian State Institute for Metrology Belarus (BelGIM)
I Results of experimental study
Laboratory Belarus BelGIM Section for physicochemical and optical measurements sector for standards and gas mixtures 8 Serova st Minsk Cylinder No 0128 9 dm3 aluminium NOMINAL COMPOSITION - Carbon dioxide 13middot10-2 - 14middot10-2 molmol - Carbon oxide 28middot10-2 - 32middot10-2 molmol - Propane 19middot10-4 - 21middot10-4molmol - Nitrogen Residual
Measurement No1 Date
Result (molmol)
x_
Standard deviation
S( x_
) rel
No of observations
n
Carbon dioxide 17062005 13567middot10-2 0096 6
Carbon oxide 17062005 2957middot10-2 014 6
Propane 17062005 1977middot10-4 015 6
Measurement No2 Date
Result (molmol)
x_
Standard deviation
S( x_
) rel
No of observations
n
Carbon dioxide 21062005 13564middot10-2 004 6
Carbon oxide 21062005 2957middot10-2 02 6
Propane 21062005 1979middot10-4 01 6
18
Measurement No3 Date
Result (molmol)
x_
Standard deviation
S( x_
) rel
No of observations
n
Carbon dioxide 23062005 13537middot10-2 007 6
Carbon oxide 23062005 2955middot10-2 01 6
Propane 23062005 1982middot10-4 01 6
Final results
Gas mixture Result
(molmol)
Coverage factor
Expanded uncertainty (molmol)
Carbon dioxide 136middot10-2 2 01 middot10-2
Carbon oxide 296middot10-2 2 002middot10-2
Propane 198middot10-4 2 02middot10-4
II Description of study Apparatus (principle of operation type configuration data collection etc)
Measurements were carried out using gas chromatograph Crystal 2000М (hereinafter
referred to as chromatograph) combined with thermal conductivity detector (hereinafter referred to as TCD) with detection limit of 510-9 gml for propane and flame-ionization detector (hereinafter referred to as FID) with detection limit of 510-12 gs for propane
Computers and software Chromatech Analytic version 121 were used to control chromatograph and collect and process chromatographical data
For the purpose of measurements the following auxiliary devices and materials were used
1 Two-position doser with 10 ports and with doses of 025 cm3 for FID channel and with doses of 025 cm3 for TCD channel (hereinafter referred to as doser)
2 Metallic packed column 3m х 3mm х 2mm - HayeSep N 80100 metallic packed column 1m х 4mm х 2mm-CaA 016025 (TCD channel) capillary column HP PLOTQ 30m х 0536mm (FID channel)
3 Aneroid BАММ-1 with a measurement range of 80-106 kPа and accuracy of plusmn 02 kPа
4 Mercurial thermometer ТL-4 with a measurement range of 0-50ordmС and scale division of 01ordmС
19
5 Fine adjustment valve (hereinafter referred to as FAV) provided to transport a gas sample into chromotograph and set to gas flow-rate of 10-15 mlmin
6 Foamy gas flow meter type YIRG - 2А accuracy of flow measurement plusmn 1 сm3min
7 Helium gas Type A according to TU 51-940-80 8 High purity hydrogen gas according to TU 301-07-27-90 9 Compressed air 10 Multicomponent calibration gas mixtures (hereinafter referred to as CGM)
produced and certified by gravimetric method
Calibration reference materials - calibration gas mixtures used for measurements 1 Quantitative composition of KGS is determined using gravimetric method defined in
ISO 61422001 by calculating weight of each component of a gas mixture The content of CGM components is expressed as a mole fraction Uncertainty of KGS composition is expressed as expanded uncertainty with coverage factor k = 2 Molar masses of components and their uncertainties are taken from ISO 149122003 Performance and metrological characteristics of the equipment used for gravimetric preparation of mixtures are given in Table 1
Table 1
Description of the equipment
Manufacturer Metrological characteristics
Mass-comparator balance type КА10-3Р
Mettler-Toledo
Switzerland
Maximum load 15 kg Scale division 1 mg Standard deviation 19 mg at load of 10 kg Operating temperature range +10divide30degС Maximum temperature change within 1 h plusmn05 degС
Gas mixer type USG 00001 BelGIM
Measurement range 000025 divide 100 МPa Accuracy class for manometers ndash 015 Accuracy class for vacuummeters ndash 025 Vacuummeter with pressure sensor for measuring the residual pressure before filling Residual pressure before filling of each component not more than 20 Pa
2 Purity analysis of primary gas standards
The purity analysis of primary gas standards is based on the information provided by the supplier or on the results of determination of impurity in pure gases using measurement procedure developed inside BelGIM
20
If an analytical method laid down in 43 of ISO 61422001 cannot be used for impurity determination mole fraction of an expected impurity is assumed to be half of the detection limit of the analytical method The content of the undetected impurity produces rectangular distribution
whereby its standard uncertainty is calculated as half of the detection limit divided by 3 The composition of the pure gases used for preparation of calibration mixtures is given
in Table 2 Table 2 - Metrological characteristics of pure gases
N2 999967 00005 Nitrogen Cylinder 40 dm3 Origin Russia O2 00033 00005 Propane Cylinder 2 dm3 Origin Russia
C3H8 9979 0017
3 After preparation of mixture the cylinder was maintained in laboratory room within
24 hours the mixture then was homogenized on the stand by rotating on the rollers within 4-5 hours The chromotograph for CGM was calibrated 2-3 days after its preparation
Calibration of the chromotograph
1 The chromotograph was calibrated using CGMs with composition identical to the analyzed sample The content of each component and its expanded uncertainty (k = 2) are given in Table 1 Table 1 - Calibrationе gas mixtures
2 Number of observations of each calibration sample- 3 Number of calibration samples - 3
3 The analytical function used for determination of the content of the analyzed sample components is as follows
x (y) =b1y+b0 (2) Where x ndash determined content molmol y - chromotograph response for the specific component b1- slope b0 - intercept 4 After completion of calibration the coefficients of analytical function were
calculated according to ISO 61432001 using generalized least-squares method Also the uncertainties of the intercept and slope and covariance between them were calculated After determination of parameters which are part of analytical function and which affect the uncertainty of measurements it was checked whether the analytical function is fit to the experimental data obtained in calibration and subsequently whether the analytical function is applicable
Results of calibration measurements coefficients of analytical function their uncertainties covariance and measure of goodness-of-fit Г (maximum value of the weighted differences of the experimental points and calculated points of the analytical function for each measurement run) are given in Tables 3 and 4 respectively Chromotograph operating conditions in calibration and analysis are given in Table 5
Table 3 - Results of experimental study
Date Component of
calibration mixture
Content x mole fraction
Expanded uncertainty
U(x) mole fraction
Mean of peak area y
mVs
Uncertainty )(yu
mVs
13374 0004 1279500 141 1389 0004 1329150 2899 CO2
12833 0004 1231000 849 2916 0005 404070 240
316 0005 437705 926 CO 2768 0004 383070 467
019 0002 3143200 4101
1706 2005
C3H8 0202 0002 3319150 2051
22
0181 0002 2948750 212 13374 0004 1269833 624
1389 0004 1321000 1272 CO2 12833 0004 1223900 1698
2916 0005 399490 612 316 0005 434010 863 CO
2768 0004 379660 410 019 0002 3157867 6772
0202 0002 3332400 3394
2106 2005
C3H8 0181 0002 2959900 4950
13374 0004 1277100 2152 1389 0004 1329900 2828 CO2
12833 0004 1229100 1980 2916 0005 400330 529
316 0005 434745 969 CO 2768 0004 379695 106
019 0002 3142433 9416 0202 0002 3321600 4101
2306 2005
C3H8 0181 0002 2961000 3111
According to ISO 61432003 calculation of the measure of goodness-of-fit Г is the maximum value of the weighed differences between the coordinates of measured and adjusted calibration points is an effective and simple method to test the compatibility of а prospective analytical function A function is admissible if Г le 2
minus
minus=
)(ˆ
)(ˆ
iii
iii
yuyy
xuxxΓ
(4) Where хi is the reference value of the content of calibration sample component
ix is the CGM component content obtained using the calculated analytical function
уi is the experimental response to the reference content of component iy is the response obtained in calculation of analytical function
u (хi) u (уi) are the uncertainties of reference contents and responses to these contents respectively
i is the number of calibration points i=1 3 This prerequisite is equivalent to the requirement that the curve of calculated response should cross each experimental calibration rectangular [хi plusmn 2u(хi) уi plusmn 2и(уi)] based on an expanded uncertainty U = ku with coverage factor k = 2 Table 4 Calculations of analytical function
Date Component Analytical function parameters
Uncertainty of analytical
function parameters
Covariance of
parameters Г
23
b1 b0 u(b1) u(b0) u(b0b1) 1706 11086E-
03 -81128E-
0119491E-
0524883E-
01 -48497E-06 10544
2106 10729E-03
-26126E-01
22698E-05
28930E-01 -65652E-06 19997
2306
CO2 10593E-
03 -17688E-
0135807E-
0545413E-
01 -16254E-05 10022
1706 71537E-04
26507E-02
14231E-05
57044E-02 -81115E-07 03017
2106 72346E-04
22401E-02
13819E-05
54490E-02 -75209E-07 05935
2306
CO 71321E-
04 60080E-
0212663E-
0549016E-
02 -62026E-07 01341
1706 56521E-06
13712E-02
38279E-07
12015E-02 -45937E-09 12991
2106 56295E-06
13707E-02
39247E-07
12379E-02 -48529E-09 12905
2306
C3H8 58258E-
06 80469E-
0340085E-
0712590E-
02 -50407E-09 08589
Two columns separated by switching device are located one after another in TCD
channel One column is intended for carbon dioxide heavy hydrocarbons and another column is intended for light gases Before the first switch the light gases including carbon oxide flow through the first column without being separated and remain in the second column The switch makes them locked in the second column The analysis of carbon dioxide is carried out up to the second switch Second switch makes the second column unlocked and carbon oxide is analyzed Third switch is required to allow propane escape from a column and prevent it from getting into a second column The analysis of the very propane is carried out using FID Time intervals between switches were selected experimentally when developing the analysis method Such analysis method makes it possible to analyze all three components per one sample inject
Table 5 - Chromotograph operating conditions in calibration and analysis Parameter of the operating conditions Thermostating temperature of TCD and FID degС 170
Temperature of separation columns degС
Program 60 degС within 9 min
than rise to 160 degС at 20degСmin
Rate of flow of carrier gas through TCD channel columns mlmin 15
Rate of flow of carrier gas through TCD comparison channel mlmin 15
Pressure in FID channel column kPa Program
24
80 to 100 Rise from the 1st s of
analysis at 2 kPamin
Flow-rate of hydrogen FID mlmin 20 Flow-rate of air FID mlmin 200 Temperature of switching device degС 65 Response time of switching device s 1 110 2 330 3 540
TCD FID Volume of injected analyzed gas cm3 025 025 Carrier gas Helium Duration of analysis min 17 Calculation of the content of comparison sample components and its uncertainty Results of comparison sample measurements are given in Table 6 Table 6 - Results of comparison sample measurements
1 The content of comparison sample component and its uncertainty were determined
using calculated analytical function according to ISO 61432001 as follows (5) Where G(y)=b1y+b0 is the calculated analytical function и(y) is the standard uncertainty of response y u2(bj) is the variance of analytical function parameter bj
u(bj bI) is the covariance of analytical function parameters bj bI N is the number of function coefficients N=2 j=0 1
sum sumsumminus
= +==
partpart
partpart
+
partpart
+
partpart
=1
0 1
2
2
0
22
)(2)()()(N
jIj
N
jI Ijj
N
j j
bbubG
bGbu
bGyu
yGxu
25
After substitution of analytical function (2) and transformations the expression takes form (5)
)(2)()()()()( 01122
0222
1 bbyubuybuyubxu +++= (6) The contents of comparison sample components under determination and their
uncertainties were calculated using B_LEAST a computer program recommended in ISO 6143 Calculations are summarized in Table 6
Table 6 Calculations of the content of comparison sample components and their
2 The final content of a component was determined as an arithmetiс mean from three measurements Final standard uncertainty was calculated using formula as follows
22
222)( Адаватмтемсериикал uuuuuxu ++++= (7)
Where ucal is the uncertainty of the component content produced by
calibration of chromotograph urun is the uncertainty of the component content produced by
change of chromotograph response in each measurement run ut is the uncertainty of the component content produced by
change of an ambient temperature upressure is the uncertainty of the component content produced by
change of atmospheric pressure u A is the standard uncertainty of three measurement runs
21 Uncertainty of the component content produced by calibration of chromotograph
This uncertainty is calculated using formula (6) but the first term of the sum ie
)()( 221 yub which represents the standard uncertainty of the chromotograph response in a
measurement run is not taken into account Calculations are summarized in Table 7
26
Table 7 Calculation of uncertainty produced by calibration of chromotograph
Date u(b1) u(b0) u(b0b1) x
molmol y Ucal molmol
Ucal rel
1706 19491E-05
24883E-01
-48497E-06
13567middot10-
2129698
3 0005middot1
0-2 003
2106 22698E-05
28930E-01
-65652E-06
13564middot10-
2 128855 0007middot1
0-2 005
2306
CO2
35807E-05
45413E-01
-16254E-05
135374middot10-2
1294633
0016middot10-2 012
1706 14231E-05
57044E-02
-81115E-07 2957middot10-2 409633
0003middot10-2 009
2106 13819E-05
54490E-02
-75209E-07
29577middot10-
2 405663 0003middot1
0-2 01
2306
CO
12663E-05
49016E-02
-62026E-07 2955middot10-2 405882
0003middot10-2 01
1706 38279E-07
12015E-02
-45937E-09 1977middot10-4
3255817
007middot10-
2 038
2106 39247E-07
12379E-02
-48529E-09 1980middot10-4
3273329
008middot10-
2 038
2306
C3H8
40085E-07
12590E-02
-50407E-09 1982middot10-4 32636
008middot10-
2 04 The total estimate of relative uncertainty produced by calibration of chromotograph was
calculated for each component as follows
3
3
1
2sum=
cali
cali
uu (8)
Where ucal i is the relative uncertainty produced by calibration of chromotograph and calculated for each measurement run
The calculations are summarized in Table 8
Table 8 Uncertainty produced by calibration of chromotograph
Component Ucal rel
CO2 008 CO 01
C3H8 04 22 Uncertainty of the component content produced by change of chromotograph response in each measurement run This uncertainty is calculated using the equation (6) whereby the first term of the sum
only ie )()( 221 yub which represents the standard uncertainty of the chromotograph
response in a measurement run is taken into account Calculations are summarized in Table 9
27
Table 9 Calculation of uncertainty produced by change of chromotograph response in each measurement run
The total estimate of relative uncertainty produced by change of chromotograph
response in each measurement run was calculated for each component as follows
3
3
1
2sum=
run
run
uu (9)
Where urun is the relative uncertainty produced by change of chromotograph response in each measurement run Calculations are summarized in Table 10
Table 10 Uncertainty produced by change of chromotograph response in each measurement
run
Component Urun rel
CO2 007 CO 015
C3H8 012 23 Uncertainty of the component content produced by change of temperature in a room
The recorded change of temperature in measurements is plusmn 05 degree The contribution of uncertainty type B (rectangular distribution) is estimated as follows
201003
12931
=sdotsdot=tu rel
28
24 Uncertainty of the component content produced by change of atmospheric pressure The recorded change of atmospheric pressure within three days was
05 kPа The contribution of uncertainty type B (rectangular distribution) is estimated as follows
2801003
13101
50=sdotsdot=pressureu rel
25 Standard deviation of 3 measurement runs Standard deviation is calculated as follows
isu p
A
2
= (10)
Where S2p is the group experimental variation
The group experimental variation is calculated as follows
(11)
Where si
2 is the experimental variation of measurement run i from independent repeated observations ni having freedom degrees
νi = n - 1 n=6 i= 3 Calculations are summarized in Table 11 Table 11 Calculations of standard uncertainty of 3 measurement runs
Date 2iS x
molmol 2iS
rel uA
rel
1706 2953E-05 13567middot10-2 000022
2106 588987E-06 13564middot10-2 0000043
2306
CO2 141137E-
05 135374middot10
-2 000010
0006
1706 225604E-06 2957middot10-2 0000077
2106 681346E-06 29577middot10-2 000023
2306
CO
175166E-06 2955middot10-2 0000060
0006
1706 C3H8 130158E-
08 1977middot10-4 00000066 0001
ss
p
i ii
N
ii
N2
2
1
1
= =
=
sum
sum
ν
ν
29
2106 44616E-09 1980middot10-4 00000023
2306
381032E-09 1982middot10-4 00000019
26 Total standard uncertainty
Uncertainty estimation СО2
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph ucal Normal 008 1 008
Change of temperature ut Rectangular 02 1 02 Change of atmospheric pressure upressure Rectangular 028 1 028
Changes of chromotograph response
urun Normal 007 1 007
Standard deviation of 3 runs uA Normal 0006 1 0006
Relative total standard uncertainty 036 Coverage factor k=2 Expanded uncertainty 01middot10-2 molmol Uncertainty estimation СО
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph ucal Normal 01 1 01 Change of temperature ut Rectangular 02 1 02 Change of atmospheric pressure upressure Rectangular 028 1 028 Changes of chromotograph response
urun Normal 015 1 015
Standard deviation of 3 runs uA Normal 0006 1 0006
Relative total standard uncertainty 039 Coverage factor k=2 Expanded uncertainty 002middot10-2 molmol Uncertainty estimation С3Н8
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph 04 Normal 04 1 008
30
Change of temperature 02 Rectangular 02 1 02 Change of atmospheric pressure 028 Rectangular 028 1 028
Changes of chromotograph response
012 Normal 012 1 007
Standard deviation of 3 runs 0001 Normal 0001 1 0006
Relative total standard uncertainty 054 Coverage factor k=2 Expanded uncertainty 02middot10-4 molmol
Sample handling
Period for exposure of cylinder to measurement conditions and method how to transport sample to the device
1 Stands for storing gas standard cylinders and calibration mixture cylinders and chromotograph are placed in a laboratory room which is not accessible to unauthorized persons The laboratory is equipped with air-conditioner to maintain required temperature and humidity on a continuous basis and some auxiliary measuring instruments as thermometer psychrometric hygrometer and aneroid to control temperature humidity and atmospheric inside the room
2 The comparison sample cylinder was stored in laboratory from the date of its
delivery to Minsk on 25042005 CGM cylinders are stored horizontally on racks and positioned vertically using special support when measurements are carried out
3 The analyzed gas sample is transported through the fine adjustment valve (FAV)
Conjunctions Cylinder - FAV FAV - tube tube - doser are made of metal and use adapters with spherical ends and bushes FAV is made of brass tube is made of copper and doser is made of duralumin
Instrument(s) (principles make type configuration data collection etc) For the analysis a GC were used with specifically applications For the determination of (Nitrogen (N2)) Carbon Dioxide (CO2) Carbon Monoxide (CO) and Propane (C3H8) balance GC Perkin Elmer AutoSystem XL (two channel system) with a stream selection valve for 4 streams and 2 gas sampling valves
Channel A for the determination of N2 CO and CO2 Carrier Gas Helium Columns Column system with two packed columns (6 ft x 18rdquo Porapak R 80100 mesh and 6 ft x 18rdquo Mol-Sieve 13X 80100 mesh) Oven Temperature 960 degC to 180 degC Detector micro-TCD Data Collection Total Chrom Workstation Channel B for the determination of C3H8 Carrier Gas Helium Columns Capillary column 50 m x 032 microm LP-SIL-8-CB Oven Temperature 60 degC to 180 degC Detector FID Data Collection Total Chrom Workstation
34
Calibration Standards
Calibration Standards for the measurements (preparation method purity analyses estimated uncertainty etc)
All standards were prepared individually according to ISO 6142 rdquoGas analysis - Preparation of calibration gases - Gravimetric Methodrdquo
Depending on the concentration of the components standards were prepared individually from pure gases or from pre-mixtures which were individually prepared from pure gases
The content of the impurities in all pure gases were determined before use by GC-DID GC-FID and or GC-TCD
After preparation the standards were verified by analytical comparisons against existing gravimetrically prepared standards Only when no significant difference between the analysed and the calculated gravimetric composition is found the ldquonew prepared candidate rdquo is accepted as a new standards
For the analysis of all components multi component standards with nitrogen as balance gas were used
Composition of calibrants BAM C49250-050722 Component Assigned value( x)
mmol mol Standard uncertainty (u(x)) relativ (k=2)
Calibration procedure (mathematical modelcalibration curve number and concentrations of standards measurement sequence temperaturepressure correction etc)
For the instrument calibration the bracketing technique was used The fraction of the current used standards deviated no more than +10rel and -10rel respectively from those of the sample
Measurement sequence
Sample Handling
How were the cylinders treated after arrival (eg stabilized) and how were samples transferred to the instrument (automatic high pressure mass-flow controller dilution etc) After heating (45 - 50 degC) the cylinder for 8 hours the cylinder were rolled about 16 hours before analysis was started Each cylinder was equipped with a pressure regulator that was purged three times by sequential evacuation and pressurisation with the gas mixture used Continous flow (2 ndash 3mlmin) through the sample loop
Uncertainty The specification of potential uncertainty sources is given in Annex 3
3 injection standard (high)
3 injection sample
3 injection standard (high)
3 injection sample
3 injection standard (low)
3 injection sample
3 injection standard (low)
3 injection standard (low)
36
Uncertainty table CO2
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 002 rel 1 002 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 03 rel
Uncertainty table CO
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 007 rel 1 007 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 05 rel
37
Uncertainty table C3H8
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 010 rel 1 001 rel
Analysis normal 028 rel 1 028 rel
Coverage factor 2
Expanded uncertainty 06 rel
Optional
You may provide additional data like the raw measurement data information on your
measurement procedure chromatograms etc
38
Appendix 3 SPECIFICATION OF POTENTIAL UNCERTAINTY SOURCES
a Uncertainty related to the balance and the weights Resolution of balance Accuracy of balance including linearity Incorrect zero point Drift (thermal and time effects) Instability due to draught Location of cylinder on the balance pan Uncertainties in the weights used Buoyancy effects on the weights used
b Uncertainties related to the gas cylinder Mechanical handling of cylinder
Loss of metal paints or labels from surface of cylinder Loss of metal from threads of valvefitting Dirt on cylinder valves or associated fitting
Absorptiondesorption effects on the external cylinder surface Buoyancy effects on the cylinder itself
Cylinder temperature differs from surrounding air due to eg filling with gas Change of cylinder volume during filling Change of density of surrounding air due to changes in temperature air pressure humidity and carbon dioxide content
Uncertainty in determination of external cylinder volume c Uncertainties related to the component gases Residual gas in cylinder Leakage Leakage of air into the cylinder after evacuation
Leakage of gas from the cylinder valve during filling Escape of gas from cylinder into transport lines
Gas remaining in transfer system when weight loss method is used Absorptionreaction of components on internal cylinder surface Reaction between components Impurities in all the initial gases Insufficient homogenization Uncertainty of molecular mass d Uncertainties related to the analysis
Repeatability and selectivity of the analyzer Appropriateness of the calibration curve
39
MEASUREMENT REPORT - All Ukrainian State Research-Industrial Center of Standardization Metrology Certification and Protection of Consumers Ukraine
gas ndash helium flow rate 15 cm3min detector TCD tdetector = 250 ordmС toven = 70 ordmС It was automatic data collection
Measurement and Calibration Methods Laboratory Measurement method Type of calibration curve
GCFID (С3Н8) 3 points linear Ukrmetrteststandard GCTCD (СО СО2) 3 points linear
GCFID ndash gas-chromatographic with flame-ionization detector GCTCD - gas-chromatographic with thermal-conductivity detector
42
Calibration Standards
Calibration standards ndash primary standard gas mixtures (PSGM) used for measurements by comparison method
PSGM-1 Cylinder 0116
PSGM-2 Cylinder 0107
PSGM-3 Cylinder 0093 Composition
x u(x) x u(x) x u(x) СО 27874 00015 29899 00015 31891 00015 СО2 130187 00015 144456 00016 137016 00016 С3Н8 019003 000008 020017 000008 021013 000008 N2 balance balance balance
Note x ndash mole fraction u(x) ndash absolute standard uncertainty
It was used gravimetric method of preparation of PSGM Electronic balance КА-20-3 of Mettler Toledo max limit of weighing is 20 kg least
limit of weighing is 01 g standard deviation is 0006 g Analysis of purity of parent gases was carried out with usage of chromatographs
НР6890N with helium ndash ionization detector flame ndash ionization detector thermal ndash conductivity detector and mass ndash spectrometric detector as well аs gas analyzers GIAM-15M and Onix condensate-thermometer hygrometer TOROS-3-2B
Calculation of uncertainties was carried out according to ISO 6142-2003 Corrections of temperature pressure and humidity of environment were considered
in calculations according to ISO 6142-2003 (program of ISO-6142 2000-03-17 designer is NMi) Protocols and explanations are in Annex A
Instrument (Comparator) Calibration Calibration of comparator ndash gas chromatograph HP 6890 was carried out with usage
of PSGM Measurement sequence PSGM -1 х 3 PSGM -2 х 3 COOMET gas mixture х 3 PSGM -2 х 3 PSGM -3 х 3 It is necessary to use PSGM-2 repeatedly for estimation of reproducibility of results
Program B_LEAST recommended by ISO 6143-2003 was used for constructing the curve Mathematical model of calibration curve is linear one
Sample Handling The cylinder was kept for 24 hrs at a room where comparators were disposed This room is a thermostatic room with t = (20plusmn2) ordmС
43
A method of sample input to a comparator is a method with flow stabilization Uncertainty The following uncertainties were included to the budget of uncertainty - uncertainty of the balance - uncertainties of impurities in parent gases Contribution from other uncertainty sources was insignificant A cabin of the balance is thermostatically The balance is the one-pan balance
Air transfer is absent in the cabin of the balance Drift of the balance is absent for PSGM preparation
Contribution from other uncertainty sources was considered in software according to ISO 6142-2003
Uncertainties related to the analysis (comparison) were considered in software according to ISO 6143-2003 and enclosed in Annex B
Uncertainty table СО2
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas mixture
B 001 1 001
Analysis A B 008 1 008
Coverage factor 2 Expanded uncertainty 002sdot10-2 molmol Uncertainty table СО
Protocols of analysis (comparison) in accordance with ISO 6143-2003
57
Explanation of protocols of comparison
Chapter I ldquoThe calibration data set isrdquo contains columns 1 mole fraction of a component 2 absolute standard uncertainty of mole fraction of a component 3 a signal of a comparator 4 absolute standard uncertainty of a comparator signal
Chapter II ldquoResults of ISO 6143 methodrdquo contains parameters of a calibration curve including its
uncertainty
Chapter ІІІ ldquoPart II Processing of datardquo contains columns
1 calc x - the results of comparison mole fraction of a component 2 u(x) - absolute standard uncertainty of mole fraction of a component 3 response y - a signal of a comparator 4 u(y) - absolute standard uncertainty of a comparator signal
58
СО2 - measurement 1 Data setCO2_21 The calibration data set is 1302E+01 1510E-03 1022E+04 1820E+00 1370E+01 1560E-03 1077E+04 2730E+00 1445E+01 1620E-03 1135E+04 5900E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 20331E-02 12711E-03 12573E-01 11653E-05 -14638E-06 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 10548E-02 12722E-03 31762E-02 28898E-06 -91698E-08 Remaining SSD is 74346 Weighted distances x-value x-dist y-dist 100E+00 130E+01 490E-01 -755E-01 200E+00 137E+01 -103E+00 228E+00 300E+00 144E+01 539E-01 -250E-01 Goodness-of-fit measure 22837 Parameter set 1 1054788657490729E-2 1272208026684145E-3 3176237146276368E-2 2889798108124711E-6 -
9169821653851327E-8 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_21c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13577E+01 25542E-03 10664E+04 15200E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 547E-06 328E-06 316E-06 784E-06 286E-06 652E-06 Linear model Parameters for the fit were (b0 b1) 10548E-02 12722E-03
59
СО2 - measurement 2
Data setCO2_20 The calibration data set is 1302E+01 1512E-03 1021E+04 4723E+00 1370E+01 1563E-03 1075E+04 1600E+00 1445E+01 1620E-03 1133E+04 7300E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -38760E-02 12784E-03 26817E-02 24890E-06 -66689E-08 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -62452E-02 12805E-03 47930E-02 43243E-06 -20716E-07 Remaining SSD is 03231 Weighted distances x-value x-dist y-dist 100E+00 130E+01 107E-01 -415E-01 200E+00 137E+01 -212E-01 283E-01 300E+00 144E+01 104E-01 -584E-02 Goodness-of-fit measure 04155 Parameter set 1 -6245240430658412E-2 1280492624666799E-3 4792952200361109E-2 4324266278840409E-6 -
2071623966851869E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_20c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13594E+01 10290E-02 10665E+04 78300E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 121E-05 683E-06 651E-06 315E-05 560E-06 106E-04 Linear model Parameters for the fit were (b0 b1) -62452E-02 12805E-03
60
С3Н8 - measurement 1
Data setC3H8 The calibration data set is 1900E-01 7800E-05 9057E+03 1098E+01 2002E-01 7900E-05 9552E+03 8569E+00 2101E-01 7960E-05 1007E+04 4049E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10529E-02 19831E-05 34552E-03 36109E-07 -12465E-09 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11642E-02 19714E-05 23073E-03 23522E-07 -54231E-10 Remaining SSD is 19453 Weighted distances x-value x-dist y-dist 100E+00 190E-01 -239E-01 666E-01 200E+00 200E-01 487E-01 -104E+00 300E+00 210E-01 -247E-01 248E-01 Goodness-of-fit measure 10414 Parameter set 1 1164239985182795E-2 1971441115316992E-5 2307269625077337E-3 2352198415608386E-7 -
5423119774765299E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19837E-01 14840E-04 94718E+03 45610E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
5
jlabx - the amount of substance fraction of the laboratory i The expanded uncertainty of the degree of equivalence Dij (k=2)
Discussion and Conclusions All laboratories find the gravimetric value within plusmn07 relative to the gravimetric value This holds for all three components COCO2 and C3H8 in nitrogen This is a satisfying result For all laboratories the observed difference between the gravimetric and reported values does not exceed its combined uncertainty VNIIM and BAM are link laboratories for CCQM-K3 The results of this comparison are linked to the key comparison CCQM-K3 Reference [1] International Organization for Standardization ISO 61422001 Gas analysis - Preparation of calibration gas mixtures - Gravimetric methods 2nd edition [2] International Organization for Standardization ISO 61432001 Gas analysis ndash Comparison methods for determining and checking the composition of calibration gas mixtures [3] Van der Veen AMH De Leer EWB Perrochet J-F Wang Lin Zhen Heine H-JKnopf D Richter W Barbe J Marschal A Vargha G Deaacutek E Takahashi C Kim JS Kim YD Kim BM Kustikov YA Khatskevitch EA Pankratov VV Popova TA Konopelko L Musil S Holland P Milton MJT Miller WR Guenther FR International Comparison CCQM-K3 Final Report Coordinator Leonid Konopelko VNIIM Research Department for the State Standard in the Field of Physical-Chemical Measurements (PCD) 19 Moskovsky pr St-Petersburg 198005 Russia Phone +7 812 3151145 Fax +7 812 3279776 E-mail lkonopmailrcomru Completion Date March 2006
11
Annex 1 Proposal of Degrees of Equivalence Table 5 Degrees of Equivalence for carbon monoxide Lab j VNIIM Ukrmetrteststandard BelGIM BAM Lab i Di Ui Dij Uij Dij Uij Dij Uij Dij Uij mmolmol mmolmol mmolmol mmolmol mmolmol VNIIM 001 006 012 014 007 021 005 016 Ukrmetrteststandard -011 012 -012 014 -005 024 -007 019 BelGIM -006 020 -007 021 005 024 -002 025 BAM -004 015 -005 016 007 019 0016 025 Table 6 Degrees of Equivalence for carbon dioxide Lab j VNIIM Ukrmetrteststandard BelGIM BAM Lab i Di Ui Dij Uij Dij Uij Dij Uij Dij Uij mmolmol mmolmol mmolmol mmolmol mmolmol VNIIM 012 013 026 026 -074 101 0034 043 Ukrmetrteststandard -014 022 -026 026 -10 102 -023 046 BelGIM 086 100 074 101 10 102 077 108 BAM 009 041 -0034 043 023 046 -077 108 Table 7 Degrees of Equivalence for propane Lab j VNIIM Ukrmetrteststandard BelGIM BAM Lab i Di Ui Dij Uij Dij Uij Dij Uij Dij Uij mmolmol mmolmol mmolmol mmolmol mmolmol VNIIM 0001 0004 0002 0006 0005 0020 -0009 0013 Ukrmetrteststandard -0001 0004 -0002 0006 0003 0021 -0011 0013 BelGIM -0004 0020 -0005 0020 -0003 0021 -0014 0023 BAM 0010 0012 0009 0013 0011 0013 0014 0023
12
Annex 2 Results and measurement reports as submitted by participating laboratories Key comparison participants
MEASUREMENT REPORT - DI Mendeleyev Institute for Metrology
Russian Federation (VNIIM)
I Results of Study
Laboratory DI Mendeleyev Institute for Metrology (VNIIM) Research Department for the State Standard in the Field of Physical-Chemical Measurements (PCD)
Instruments Multichannel automatic NDIR analyzer included to the set of the National Primary measurement standard of units of mole fraction and mass concentration of components in gas medium GET 154-01 was used for the analysis Calibration Standards All calibration multicomponent gas mixtures were prepared gravimetrically according to ISO 6142 The calibration multicomponent gas mixtures were prepared from pure gases directly on components CO CO2 and from pre-mixtures which were prepared from pure gases on component С3Н8 The content of the impurities in all pure gases was determined by GC with helium-ionization flame-ionization and thermal-conductivity detectors as well as standard hygrometer apparatus included to the standard complex A1 of analysis of pure gases and substances from GET 154-01 The calibration multicomponent gas mixtures were verified with usage of existing gravimetric gas mixtures in accordance with ISO 6143 Composition of calibration standards
Cylinder 6547 Cylinder 6571 Cylinder 6538 Component x мольmol Standard
Instrument Calibration Three independent measurements were carried out under repeatability conditions Before each measurement an instrument calibration was made One measurement contained 5 submeasurements Sample Handling The time of the cylinder keeping is 24 hrs It was used the automatic unit of commutation for inputting gas mixtures
15
Uncertainty Uncertainty table СО2
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas
mixture
B 0010 1 0010
Analysis A B 0048 1 0048
Coverage factor 2 Expanded uncertainty 01 Uncertainty table СО
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas
mixture
B 002 1 002
Analysis A B 0095 1 0095
Coverage factor 2 Expanded uncertainty 019
16
Uncertainty table С3Н8 Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas
mixture
B 005 1 005
Analysis A B 0045 1 0045
Coverage factor 2 Expanded uncertainty 013
17
MEASUREMENT REPORT ndash Belorussian State Institute for Metrology Belarus (BelGIM)
I Results of experimental study
Laboratory Belarus BelGIM Section for physicochemical and optical measurements sector for standards and gas mixtures 8 Serova st Minsk Cylinder No 0128 9 dm3 aluminium NOMINAL COMPOSITION - Carbon dioxide 13middot10-2 - 14middot10-2 molmol - Carbon oxide 28middot10-2 - 32middot10-2 molmol - Propane 19middot10-4 - 21middot10-4molmol - Nitrogen Residual
Measurement No1 Date
Result (molmol)
x_
Standard deviation
S( x_
) rel
No of observations
n
Carbon dioxide 17062005 13567middot10-2 0096 6
Carbon oxide 17062005 2957middot10-2 014 6
Propane 17062005 1977middot10-4 015 6
Measurement No2 Date
Result (molmol)
x_
Standard deviation
S( x_
) rel
No of observations
n
Carbon dioxide 21062005 13564middot10-2 004 6
Carbon oxide 21062005 2957middot10-2 02 6
Propane 21062005 1979middot10-4 01 6
18
Measurement No3 Date
Result (molmol)
x_
Standard deviation
S( x_
) rel
No of observations
n
Carbon dioxide 23062005 13537middot10-2 007 6
Carbon oxide 23062005 2955middot10-2 01 6
Propane 23062005 1982middot10-4 01 6
Final results
Gas mixture Result
(molmol)
Coverage factor
Expanded uncertainty (molmol)
Carbon dioxide 136middot10-2 2 01 middot10-2
Carbon oxide 296middot10-2 2 002middot10-2
Propane 198middot10-4 2 02middot10-4
II Description of study Apparatus (principle of operation type configuration data collection etc)
Measurements were carried out using gas chromatograph Crystal 2000М (hereinafter
referred to as chromatograph) combined with thermal conductivity detector (hereinafter referred to as TCD) with detection limit of 510-9 gml for propane and flame-ionization detector (hereinafter referred to as FID) with detection limit of 510-12 gs for propane
Computers and software Chromatech Analytic version 121 were used to control chromatograph and collect and process chromatographical data
For the purpose of measurements the following auxiliary devices and materials were used
1 Two-position doser with 10 ports and with doses of 025 cm3 for FID channel and with doses of 025 cm3 for TCD channel (hereinafter referred to as doser)
2 Metallic packed column 3m х 3mm х 2mm - HayeSep N 80100 metallic packed column 1m х 4mm х 2mm-CaA 016025 (TCD channel) capillary column HP PLOTQ 30m х 0536mm (FID channel)
3 Aneroid BАММ-1 with a measurement range of 80-106 kPа and accuracy of plusmn 02 kPа
4 Mercurial thermometer ТL-4 with a measurement range of 0-50ordmС and scale division of 01ordmС
19
5 Fine adjustment valve (hereinafter referred to as FAV) provided to transport a gas sample into chromotograph and set to gas flow-rate of 10-15 mlmin
6 Foamy gas flow meter type YIRG - 2А accuracy of flow measurement plusmn 1 сm3min
7 Helium gas Type A according to TU 51-940-80 8 High purity hydrogen gas according to TU 301-07-27-90 9 Compressed air 10 Multicomponent calibration gas mixtures (hereinafter referred to as CGM)
produced and certified by gravimetric method
Calibration reference materials - calibration gas mixtures used for measurements 1 Quantitative composition of KGS is determined using gravimetric method defined in
ISO 61422001 by calculating weight of each component of a gas mixture The content of CGM components is expressed as a mole fraction Uncertainty of KGS composition is expressed as expanded uncertainty with coverage factor k = 2 Molar masses of components and their uncertainties are taken from ISO 149122003 Performance and metrological characteristics of the equipment used for gravimetric preparation of mixtures are given in Table 1
Table 1
Description of the equipment
Manufacturer Metrological characteristics
Mass-comparator balance type КА10-3Р
Mettler-Toledo
Switzerland
Maximum load 15 kg Scale division 1 mg Standard deviation 19 mg at load of 10 kg Operating temperature range +10divide30degС Maximum temperature change within 1 h plusmn05 degС
Gas mixer type USG 00001 BelGIM
Measurement range 000025 divide 100 МPa Accuracy class for manometers ndash 015 Accuracy class for vacuummeters ndash 025 Vacuummeter with pressure sensor for measuring the residual pressure before filling Residual pressure before filling of each component not more than 20 Pa
2 Purity analysis of primary gas standards
The purity analysis of primary gas standards is based on the information provided by the supplier or on the results of determination of impurity in pure gases using measurement procedure developed inside BelGIM
20
If an analytical method laid down in 43 of ISO 61422001 cannot be used for impurity determination mole fraction of an expected impurity is assumed to be half of the detection limit of the analytical method The content of the undetected impurity produces rectangular distribution
whereby its standard uncertainty is calculated as half of the detection limit divided by 3 The composition of the pure gases used for preparation of calibration mixtures is given
in Table 2 Table 2 - Metrological characteristics of pure gases
N2 999967 00005 Nitrogen Cylinder 40 dm3 Origin Russia O2 00033 00005 Propane Cylinder 2 dm3 Origin Russia
C3H8 9979 0017
3 After preparation of mixture the cylinder was maintained in laboratory room within
24 hours the mixture then was homogenized on the stand by rotating on the rollers within 4-5 hours The chromotograph for CGM was calibrated 2-3 days after its preparation
Calibration of the chromotograph
1 The chromotograph was calibrated using CGMs with composition identical to the analyzed sample The content of each component and its expanded uncertainty (k = 2) are given in Table 1 Table 1 - Calibrationе gas mixtures
2 Number of observations of each calibration sample- 3 Number of calibration samples - 3
3 The analytical function used for determination of the content of the analyzed sample components is as follows
x (y) =b1y+b0 (2) Where x ndash determined content molmol y - chromotograph response for the specific component b1- slope b0 - intercept 4 After completion of calibration the coefficients of analytical function were
calculated according to ISO 61432001 using generalized least-squares method Also the uncertainties of the intercept and slope and covariance between them were calculated After determination of parameters which are part of analytical function and which affect the uncertainty of measurements it was checked whether the analytical function is fit to the experimental data obtained in calibration and subsequently whether the analytical function is applicable
Results of calibration measurements coefficients of analytical function their uncertainties covariance and measure of goodness-of-fit Г (maximum value of the weighted differences of the experimental points and calculated points of the analytical function for each measurement run) are given in Tables 3 and 4 respectively Chromotograph operating conditions in calibration and analysis are given in Table 5
Table 3 - Results of experimental study
Date Component of
calibration mixture
Content x mole fraction
Expanded uncertainty
U(x) mole fraction
Mean of peak area y
mVs
Uncertainty )(yu
mVs
13374 0004 1279500 141 1389 0004 1329150 2899 CO2
12833 0004 1231000 849 2916 0005 404070 240
316 0005 437705 926 CO 2768 0004 383070 467
019 0002 3143200 4101
1706 2005
C3H8 0202 0002 3319150 2051
22
0181 0002 2948750 212 13374 0004 1269833 624
1389 0004 1321000 1272 CO2 12833 0004 1223900 1698
2916 0005 399490 612 316 0005 434010 863 CO
2768 0004 379660 410 019 0002 3157867 6772
0202 0002 3332400 3394
2106 2005
C3H8 0181 0002 2959900 4950
13374 0004 1277100 2152 1389 0004 1329900 2828 CO2
12833 0004 1229100 1980 2916 0005 400330 529
316 0005 434745 969 CO 2768 0004 379695 106
019 0002 3142433 9416 0202 0002 3321600 4101
2306 2005
C3H8 0181 0002 2961000 3111
According to ISO 61432003 calculation of the measure of goodness-of-fit Г is the maximum value of the weighed differences between the coordinates of measured and adjusted calibration points is an effective and simple method to test the compatibility of а prospective analytical function A function is admissible if Г le 2
minus
minus=
)(ˆ
)(ˆ
iii
iii
yuyy
xuxxΓ
(4) Where хi is the reference value of the content of calibration sample component
ix is the CGM component content obtained using the calculated analytical function
уi is the experimental response to the reference content of component iy is the response obtained in calculation of analytical function
u (хi) u (уi) are the uncertainties of reference contents and responses to these contents respectively
i is the number of calibration points i=1 3 This prerequisite is equivalent to the requirement that the curve of calculated response should cross each experimental calibration rectangular [хi plusmn 2u(хi) уi plusmn 2и(уi)] based on an expanded uncertainty U = ku with coverage factor k = 2 Table 4 Calculations of analytical function
Date Component Analytical function parameters
Uncertainty of analytical
function parameters
Covariance of
parameters Г
23
b1 b0 u(b1) u(b0) u(b0b1) 1706 11086E-
03 -81128E-
0119491E-
0524883E-
01 -48497E-06 10544
2106 10729E-03
-26126E-01
22698E-05
28930E-01 -65652E-06 19997
2306
CO2 10593E-
03 -17688E-
0135807E-
0545413E-
01 -16254E-05 10022
1706 71537E-04
26507E-02
14231E-05
57044E-02 -81115E-07 03017
2106 72346E-04
22401E-02
13819E-05
54490E-02 -75209E-07 05935
2306
CO 71321E-
04 60080E-
0212663E-
0549016E-
02 -62026E-07 01341
1706 56521E-06
13712E-02
38279E-07
12015E-02 -45937E-09 12991
2106 56295E-06
13707E-02
39247E-07
12379E-02 -48529E-09 12905
2306
C3H8 58258E-
06 80469E-
0340085E-
0712590E-
02 -50407E-09 08589
Two columns separated by switching device are located one after another in TCD
channel One column is intended for carbon dioxide heavy hydrocarbons and another column is intended for light gases Before the first switch the light gases including carbon oxide flow through the first column without being separated and remain in the second column The switch makes them locked in the second column The analysis of carbon dioxide is carried out up to the second switch Second switch makes the second column unlocked and carbon oxide is analyzed Third switch is required to allow propane escape from a column and prevent it from getting into a second column The analysis of the very propane is carried out using FID Time intervals between switches were selected experimentally when developing the analysis method Such analysis method makes it possible to analyze all three components per one sample inject
Table 5 - Chromotograph operating conditions in calibration and analysis Parameter of the operating conditions Thermostating temperature of TCD and FID degС 170
Temperature of separation columns degС
Program 60 degС within 9 min
than rise to 160 degС at 20degСmin
Rate of flow of carrier gas through TCD channel columns mlmin 15
Rate of flow of carrier gas through TCD comparison channel mlmin 15
Pressure in FID channel column kPa Program
24
80 to 100 Rise from the 1st s of
analysis at 2 kPamin
Flow-rate of hydrogen FID mlmin 20 Flow-rate of air FID mlmin 200 Temperature of switching device degС 65 Response time of switching device s 1 110 2 330 3 540
TCD FID Volume of injected analyzed gas cm3 025 025 Carrier gas Helium Duration of analysis min 17 Calculation of the content of comparison sample components and its uncertainty Results of comparison sample measurements are given in Table 6 Table 6 - Results of comparison sample measurements
1 The content of comparison sample component and its uncertainty were determined
using calculated analytical function according to ISO 61432001 as follows (5) Where G(y)=b1y+b0 is the calculated analytical function и(y) is the standard uncertainty of response y u2(bj) is the variance of analytical function parameter bj
u(bj bI) is the covariance of analytical function parameters bj bI N is the number of function coefficients N=2 j=0 1
sum sumsumminus
= +==
partpart
partpart
+
partpart
+
partpart
=1
0 1
2
2
0
22
)(2)()()(N
jIj
N
jI Ijj
N
j j
bbubG
bGbu
bGyu
yGxu
25
After substitution of analytical function (2) and transformations the expression takes form (5)
)(2)()()()()( 01122
0222
1 bbyubuybuyubxu +++= (6) The contents of comparison sample components under determination and their
uncertainties were calculated using B_LEAST a computer program recommended in ISO 6143 Calculations are summarized in Table 6
Table 6 Calculations of the content of comparison sample components and their
2 The final content of a component was determined as an arithmetiс mean from three measurements Final standard uncertainty was calculated using formula as follows
22
222)( Адаватмтемсериикал uuuuuxu ++++= (7)
Where ucal is the uncertainty of the component content produced by
calibration of chromotograph urun is the uncertainty of the component content produced by
change of chromotograph response in each measurement run ut is the uncertainty of the component content produced by
change of an ambient temperature upressure is the uncertainty of the component content produced by
change of atmospheric pressure u A is the standard uncertainty of three measurement runs
21 Uncertainty of the component content produced by calibration of chromotograph
This uncertainty is calculated using formula (6) but the first term of the sum ie
)()( 221 yub which represents the standard uncertainty of the chromotograph response in a
measurement run is not taken into account Calculations are summarized in Table 7
26
Table 7 Calculation of uncertainty produced by calibration of chromotograph
Date u(b1) u(b0) u(b0b1) x
molmol y Ucal molmol
Ucal rel
1706 19491E-05
24883E-01
-48497E-06
13567middot10-
2129698
3 0005middot1
0-2 003
2106 22698E-05
28930E-01
-65652E-06
13564middot10-
2 128855 0007middot1
0-2 005
2306
CO2
35807E-05
45413E-01
-16254E-05
135374middot10-2
1294633
0016middot10-2 012
1706 14231E-05
57044E-02
-81115E-07 2957middot10-2 409633
0003middot10-2 009
2106 13819E-05
54490E-02
-75209E-07
29577middot10-
2 405663 0003middot1
0-2 01
2306
CO
12663E-05
49016E-02
-62026E-07 2955middot10-2 405882
0003middot10-2 01
1706 38279E-07
12015E-02
-45937E-09 1977middot10-4
3255817
007middot10-
2 038
2106 39247E-07
12379E-02
-48529E-09 1980middot10-4
3273329
008middot10-
2 038
2306
C3H8
40085E-07
12590E-02
-50407E-09 1982middot10-4 32636
008middot10-
2 04 The total estimate of relative uncertainty produced by calibration of chromotograph was
calculated for each component as follows
3
3
1
2sum=
cali
cali
uu (8)
Where ucal i is the relative uncertainty produced by calibration of chromotograph and calculated for each measurement run
The calculations are summarized in Table 8
Table 8 Uncertainty produced by calibration of chromotograph
Component Ucal rel
CO2 008 CO 01
C3H8 04 22 Uncertainty of the component content produced by change of chromotograph response in each measurement run This uncertainty is calculated using the equation (6) whereby the first term of the sum
only ie )()( 221 yub which represents the standard uncertainty of the chromotograph
response in a measurement run is taken into account Calculations are summarized in Table 9
27
Table 9 Calculation of uncertainty produced by change of chromotograph response in each measurement run
The total estimate of relative uncertainty produced by change of chromotograph
response in each measurement run was calculated for each component as follows
3
3
1
2sum=
run
run
uu (9)
Where urun is the relative uncertainty produced by change of chromotograph response in each measurement run Calculations are summarized in Table 10
Table 10 Uncertainty produced by change of chromotograph response in each measurement
run
Component Urun rel
CO2 007 CO 015
C3H8 012 23 Uncertainty of the component content produced by change of temperature in a room
The recorded change of temperature in measurements is plusmn 05 degree The contribution of uncertainty type B (rectangular distribution) is estimated as follows
201003
12931
=sdotsdot=tu rel
28
24 Uncertainty of the component content produced by change of atmospheric pressure The recorded change of atmospheric pressure within three days was
05 kPа The contribution of uncertainty type B (rectangular distribution) is estimated as follows
2801003
13101
50=sdotsdot=pressureu rel
25 Standard deviation of 3 measurement runs Standard deviation is calculated as follows
isu p
A
2
= (10)
Where S2p is the group experimental variation
The group experimental variation is calculated as follows
(11)
Where si
2 is the experimental variation of measurement run i from independent repeated observations ni having freedom degrees
νi = n - 1 n=6 i= 3 Calculations are summarized in Table 11 Table 11 Calculations of standard uncertainty of 3 measurement runs
Date 2iS x
molmol 2iS
rel uA
rel
1706 2953E-05 13567middot10-2 000022
2106 588987E-06 13564middot10-2 0000043
2306
CO2 141137E-
05 135374middot10
-2 000010
0006
1706 225604E-06 2957middot10-2 0000077
2106 681346E-06 29577middot10-2 000023
2306
CO
175166E-06 2955middot10-2 0000060
0006
1706 C3H8 130158E-
08 1977middot10-4 00000066 0001
ss
p
i ii
N
ii
N2
2
1
1
= =
=
sum
sum
ν
ν
29
2106 44616E-09 1980middot10-4 00000023
2306
381032E-09 1982middot10-4 00000019
26 Total standard uncertainty
Uncertainty estimation СО2
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph ucal Normal 008 1 008
Change of temperature ut Rectangular 02 1 02 Change of atmospheric pressure upressure Rectangular 028 1 028
Changes of chromotograph response
urun Normal 007 1 007
Standard deviation of 3 runs uA Normal 0006 1 0006
Relative total standard uncertainty 036 Coverage factor k=2 Expanded uncertainty 01middot10-2 molmol Uncertainty estimation СО
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph ucal Normal 01 1 01 Change of temperature ut Rectangular 02 1 02 Change of atmospheric pressure upressure Rectangular 028 1 028 Changes of chromotograph response
urun Normal 015 1 015
Standard deviation of 3 runs uA Normal 0006 1 0006
Relative total standard uncertainty 039 Coverage factor k=2 Expanded uncertainty 002middot10-2 molmol Uncertainty estimation С3Н8
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph 04 Normal 04 1 008
30
Change of temperature 02 Rectangular 02 1 02 Change of atmospheric pressure 028 Rectangular 028 1 028
Changes of chromotograph response
012 Normal 012 1 007
Standard deviation of 3 runs 0001 Normal 0001 1 0006
Relative total standard uncertainty 054 Coverage factor k=2 Expanded uncertainty 02middot10-4 molmol
Sample handling
Period for exposure of cylinder to measurement conditions and method how to transport sample to the device
1 Stands for storing gas standard cylinders and calibration mixture cylinders and chromotograph are placed in a laboratory room which is not accessible to unauthorized persons The laboratory is equipped with air-conditioner to maintain required temperature and humidity on a continuous basis and some auxiliary measuring instruments as thermometer psychrometric hygrometer and aneroid to control temperature humidity and atmospheric inside the room
2 The comparison sample cylinder was stored in laboratory from the date of its
delivery to Minsk on 25042005 CGM cylinders are stored horizontally on racks and positioned vertically using special support when measurements are carried out
3 The analyzed gas sample is transported through the fine adjustment valve (FAV)
Conjunctions Cylinder - FAV FAV - tube tube - doser are made of metal and use adapters with spherical ends and bushes FAV is made of brass tube is made of copper and doser is made of duralumin
Instrument(s) (principles make type configuration data collection etc) For the analysis a GC were used with specifically applications For the determination of (Nitrogen (N2)) Carbon Dioxide (CO2) Carbon Monoxide (CO) and Propane (C3H8) balance GC Perkin Elmer AutoSystem XL (two channel system) with a stream selection valve for 4 streams and 2 gas sampling valves
Channel A for the determination of N2 CO and CO2 Carrier Gas Helium Columns Column system with two packed columns (6 ft x 18rdquo Porapak R 80100 mesh and 6 ft x 18rdquo Mol-Sieve 13X 80100 mesh) Oven Temperature 960 degC to 180 degC Detector micro-TCD Data Collection Total Chrom Workstation Channel B for the determination of C3H8 Carrier Gas Helium Columns Capillary column 50 m x 032 microm LP-SIL-8-CB Oven Temperature 60 degC to 180 degC Detector FID Data Collection Total Chrom Workstation
34
Calibration Standards
Calibration Standards for the measurements (preparation method purity analyses estimated uncertainty etc)
All standards were prepared individually according to ISO 6142 rdquoGas analysis - Preparation of calibration gases - Gravimetric Methodrdquo
Depending on the concentration of the components standards were prepared individually from pure gases or from pre-mixtures which were individually prepared from pure gases
The content of the impurities in all pure gases were determined before use by GC-DID GC-FID and or GC-TCD
After preparation the standards were verified by analytical comparisons against existing gravimetrically prepared standards Only when no significant difference between the analysed and the calculated gravimetric composition is found the ldquonew prepared candidate rdquo is accepted as a new standards
For the analysis of all components multi component standards with nitrogen as balance gas were used
Composition of calibrants BAM C49250-050722 Component Assigned value( x)
mmol mol Standard uncertainty (u(x)) relativ (k=2)
Calibration procedure (mathematical modelcalibration curve number and concentrations of standards measurement sequence temperaturepressure correction etc)
For the instrument calibration the bracketing technique was used The fraction of the current used standards deviated no more than +10rel and -10rel respectively from those of the sample
Measurement sequence
Sample Handling
How were the cylinders treated after arrival (eg stabilized) and how were samples transferred to the instrument (automatic high pressure mass-flow controller dilution etc) After heating (45 - 50 degC) the cylinder for 8 hours the cylinder were rolled about 16 hours before analysis was started Each cylinder was equipped with a pressure regulator that was purged three times by sequential evacuation and pressurisation with the gas mixture used Continous flow (2 ndash 3mlmin) through the sample loop
Uncertainty The specification of potential uncertainty sources is given in Annex 3
3 injection standard (high)
3 injection sample
3 injection standard (high)
3 injection sample
3 injection standard (low)
3 injection sample
3 injection standard (low)
3 injection standard (low)
36
Uncertainty table CO2
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 002 rel 1 002 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 03 rel
Uncertainty table CO
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 007 rel 1 007 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 05 rel
37
Uncertainty table C3H8
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 010 rel 1 001 rel
Analysis normal 028 rel 1 028 rel
Coverage factor 2
Expanded uncertainty 06 rel
Optional
You may provide additional data like the raw measurement data information on your
measurement procedure chromatograms etc
38
Appendix 3 SPECIFICATION OF POTENTIAL UNCERTAINTY SOURCES
a Uncertainty related to the balance and the weights Resolution of balance Accuracy of balance including linearity Incorrect zero point Drift (thermal and time effects) Instability due to draught Location of cylinder on the balance pan Uncertainties in the weights used Buoyancy effects on the weights used
b Uncertainties related to the gas cylinder Mechanical handling of cylinder
Loss of metal paints or labels from surface of cylinder Loss of metal from threads of valvefitting Dirt on cylinder valves or associated fitting
Absorptiondesorption effects on the external cylinder surface Buoyancy effects on the cylinder itself
Cylinder temperature differs from surrounding air due to eg filling with gas Change of cylinder volume during filling Change of density of surrounding air due to changes in temperature air pressure humidity and carbon dioxide content
Uncertainty in determination of external cylinder volume c Uncertainties related to the component gases Residual gas in cylinder Leakage Leakage of air into the cylinder after evacuation
Leakage of gas from the cylinder valve during filling Escape of gas from cylinder into transport lines
Gas remaining in transfer system when weight loss method is used Absorptionreaction of components on internal cylinder surface Reaction between components Impurities in all the initial gases Insufficient homogenization Uncertainty of molecular mass d Uncertainties related to the analysis
Repeatability and selectivity of the analyzer Appropriateness of the calibration curve
39
MEASUREMENT REPORT - All Ukrainian State Research-Industrial Center of Standardization Metrology Certification and Protection of Consumers Ukraine
gas ndash helium flow rate 15 cm3min detector TCD tdetector = 250 ordmС toven = 70 ordmС It was automatic data collection
Measurement and Calibration Methods Laboratory Measurement method Type of calibration curve
GCFID (С3Н8) 3 points linear Ukrmetrteststandard GCTCD (СО СО2) 3 points linear
GCFID ndash gas-chromatographic with flame-ionization detector GCTCD - gas-chromatographic with thermal-conductivity detector
42
Calibration Standards
Calibration standards ndash primary standard gas mixtures (PSGM) used for measurements by comparison method
PSGM-1 Cylinder 0116
PSGM-2 Cylinder 0107
PSGM-3 Cylinder 0093 Composition
x u(x) x u(x) x u(x) СО 27874 00015 29899 00015 31891 00015 СО2 130187 00015 144456 00016 137016 00016 С3Н8 019003 000008 020017 000008 021013 000008 N2 balance balance balance
Note x ndash mole fraction u(x) ndash absolute standard uncertainty
It was used gravimetric method of preparation of PSGM Electronic balance КА-20-3 of Mettler Toledo max limit of weighing is 20 kg least
limit of weighing is 01 g standard deviation is 0006 g Analysis of purity of parent gases was carried out with usage of chromatographs
НР6890N with helium ndash ionization detector flame ndash ionization detector thermal ndash conductivity detector and mass ndash spectrometric detector as well аs gas analyzers GIAM-15M and Onix condensate-thermometer hygrometer TOROS-3-2B
Calculation of uncertainties was carried out according to ISO 6142-2003 Corrections of temperature pressure and humidity of environment were considered
in calculations according to ISO 6142-2003 (program of ISO-6142 2000-03-17 designer is NMi) Protocols and explanations are in Annex A
Instrument (Comparator) Calibration Calibration of comparator ndash gas chromatograph HP 6890 was carried out with usage
of PSGM Measurement sequence PSGM -1 х 3 PSGM -2 х 3 COOMET gas mixture х 3 PSGM -2 х 3 PSGM -3 х 3 It is necessary to use PSGM-2 repeatedly for estimation of reproducibility of results
Program B_LEAST recommended by ISO 6143-2003 was used for constructing the curve Mathematical model of calibration curve is linear one
Sample Handling The cylinder was kept for 24 hrs at a room where comparators were disposed This room is a thermostatic room with t = (20plusmn2) ordmС
43
A method of sample input to a comparator is a method with flow stabilization Uncertainty The following uncertainties were included to the budget of uncertainty - uncertainty of the balance - uncertainties of impurities in parent gases Contribution from other uncertainty sources was insignificant A cabin of the balance is thermostatically The balance is the one-pan balance
Air transfer is absent in the cabin of the balance Drift of the balance is absent for PSGM preparation
Contribution from other uncertainty sources was considered in software according to ISO 6142-2003
Uncertainties related to the analysis (comparison) were considered in software according to ISO 6143-2003 and enclosed in Annex B
Uncertainty table СО2
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas mixture
B 001 1 001
Analysis A B 008 1 008
Coverage factor 2 Expanded uncertainty 002sdot10-2 molmol Uncertainty table СО
Protocols of analysis (comparison) in accordance with ISO 6143-2003
57
Explanation of protocols of comparison
Chapter I ldquoThe calibration data set isrdquo contains columns 1 mole fraction of a component 2 absolute standard uncertainty of mole fraction of a component 3 a signal of a comparator 4 absolute standard uncertainty of a comparator signal
Chapter II ldquoResults of ISO 6143 methodrdquo contains parameters of a calibration curve including its
uncertainty
Chapter ІІІ ldquoPart II Processing of datardquo contains columns
1 calc x - the results of comparison mole fraction of a component 2 u(x) - absolute standard uncertainty of mole fraction of a component 3 response y - a signal of a comparator 4 u(y) - absolute standard uncertainty of a comparator signal
58
СО2 - measurement 1 Data setCO2_21 The calibration data set is 1302E+01 1510E-03 1022E+04 1820E+00 1370E+01 1560E-03 1077E+04 2730E+00 1445E+01 1620E-03 1135E+04 5900E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 20331E-02 12711E-03 12573E-01 11653E-05 -14638E-06 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 10548E-02 12722E-03 31762E-02 28898E-06 -91698E-08 Remaining SSD is 74346 Weighted distances x-value x-dist y-dist 100E+00 130E+01 490E-01 -755E-01 200E+00 137E+01 -103E+00 228E+00 300E+00 144E+01 539E-01 -250E-01 Goodness-of-fit measure 22837 Parameter set 1 1054788657490729E-2 1272208026684145E-3 3176237146276368E-2 2889798108124711E-6 -
9169821653851327E-8 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_21c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13577E+01 25542E-03 10664E+04 15200E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 547E-06 328E-06 316E-06 784E-06 286E-06 652E-06 Linear model Parameters for the fit were (b0 b1) 10548E-02 12722E-03
59
СО2 - measurement 2
Data setCO2_20 The calibration data set is 1302E+01 1512E-03 1021E+04 4723E+00 1370E+01 1563E-03 1075E+04 1600E+00 1445E+01 1620E-03 1133E+04 7300E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -38760E-02 12784E-03 26817E-02 24890E-06 -66689E-08 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -62452E-02 12805E-03 47930E-02 43243E-06 -20716E-07 Remaining SSD is 03231 Weighted distances x-value x-dist y-dist 100E+00 130E+01 107E-01 -415E-01 200E+00 137E+01 -212E-01 283E-01 300E+00 144E+01 104E-01 -584E-02 Goodness-of-fit measure 04155 Parameter set 1 -6245240430658412E-2 1280492624666799E-3 4792952200361109E-2 4324266278840409E-6 -
2071623966851869E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_20c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13594E+01 10290E-02 10665E+04 78300E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 121E-05 683E-06 651E-06 315E-05 560E-06 106E-04 Linear model Parameters for the fit were (b0 b1) -62452E-02 12805E-03
60
С3Н8 - measurement 1
Data setC3H8 The calibration data set is 1900E-01 7800E-05 9057E+03 1098E+01 2002E-01 7900E-05 9552E+03 8569E+00 2101E-01 7960E-05 1007E+04 4049E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10529E-02 19831E-05 34552E-03 36109E-07 -12465E-09 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11642E-02 19714E-05 23073E-03 23522E-07 -54231E-10 Remaining SSD is 19453 Weighted distances x-value x-dist y-dist 100E+00 190E-01 -239E-01 666E-01 200E+00 200E-01 487E-01 -104E+00 300E+00 210E-01 -247E-01 248E-01 Goodness-of-fit measure 10414 Parameter set 1 1164239985182795E-2 1971441115316992E-5 2307269625077337E-3 2352198415608386E-7 -
5423119774765299E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19837E-01 14840E-04 94718E+03 45610E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
Discussion and Conclusions All laboratories find the gravimetric value within plusmn07 relative to the gravimetric value This holds for all three components COCO2 and C3H8 in nitrogen This is a satisfying result For all laboratories the observed difference between the gravimetric and reported values does not exceed its combined uncertainty VNIIM and BAM are link laboratories for CCQM-K3 The results of this comparison are linked to the key comparison CCQM-K3 Reference [1] International Organization for Standardization ISO 61422001 Gas analysis - Preparation of calibration gas mixtures - Gravimetric methods 2nd edition [2] International Organization for Standardization ISO 61432001 Gas analysis ndash Comparison methods for determining and checking the composition of calibration gas mixtures [3] Van der Veen AMH De Leer EWB Perrochet J-F Wang Lin Zhen Heine H-JKnopf D Richter W Barbe J Marschal A Vargha G Deaacutek E Takahashi C Kim JS Kim YD Kim BM Kustikov YA Khatskevitch EA Pankratov VV Popova TA Konopelko L Musil S Holland P Milton MJT Miller WR Guenther FR International Comparison CCQM-K3 Final Report Coordinator Leonid Konopelko VNIIM Research Department for the State Standard in the Field of Physical-Chemical Measurements (PCD) 19 Moskovsky pr St-Petersburg 198005 Russia Phone +7 812 3151145 Fax +7 812 3279776 E-mail lkonopmailrcomru Completion Date March 2006
11
Annex 1 Proposal of Degrees of Equivalence Table 5 Degrees of Equivalence for carbon monoxide Lab j VNIIM Ukrmetrteststandard BelGIM BAM Lab i Di Ui Dij Uij Dij Uij Dij Uij Dij Uij mmolmol mmolmol mmolmol mmolmol mmolmol VNIIM 001 006 012 014 007 021 005 016 Ukrmetrteststandard -011 012 -012 014 -005 024 -007 019 BelGIM -006 020 -007 021 005 024 -002 025 BAM -004 015 -005 016 007 019 0016 025 Table 6 Degrees of Equivalence for carbon dioxide Lab j VNIIM Ukrmetrteststandard BelGIM BAM Lab i Di Ui Dij Uij Dij Uij Dij Uij Dij Uij mmolmol mmolmol mmolmol mmolmol mmolmol VNIIM 012 013 026 026 -074 101 0034 043 Ukrmetrteststandard -014 022 -026 026 -10 102 -023 046 BelGIM 086 100 074 101 10 102 077 108 BAM 009 041 -0034 043 023 046 -077 108 Table 7 Degrees of Equivalence for propane Lab j VNIIM Ukrmetrteststandard BelGIM BAM Lab i Di Ui Dij Uij Dij Uij Dij Uij Dij Uij mmolmol mmolmol mmolmol mmolmol mmolmol VNIIM 0001 0004 0002 0006 0005 0020 -0009 0013 Ukrmetrteststandard -0001 0004 -0002 0006 0003 0021 -0011 0013 BelGIM -0004 0020 -0005 0020 -0003 0021 -0014 0023 BAM 0010 0012 0009 0013 0011 0013 0014 0023
12
Annex 2 Results and measurement reports as submitted by participating laboratories Key comparison participants
MEASUREMENT REPORT - DI Mendeleyev Institute for Metrology
Russian Federation (VNIIM)
I Results of Study
Laboratory DI Mendeleyev Institute for Metrology (VNIIM) Research Department for the State Standard in the Field of Physical-Chemical Measurements (PCD)
Instruments Multichannel automatic NDIR analyzer included to the set of the National Primary measurement standard of units of mole fraction and mass concentration of components in gas medium GET 154-01 was used for the analysis Calibration Standards All calibration multicomponent gas mixtures were prepared gravimetrically according to ISO 6142 The calibration multicomponent gas mixtures were prepared from pure gases directly on components CO CO2 and from pre-mixtures which were prepared from pure gases on component С3Н8 The content of the impurities in all pure gases was determined by GC with helium-ionization flame-ionization and thermal-conductivity detectors as well as standard hygrometer apparatus included to the standard complex A1 of analysis of pure gases and substances from GET 154-01 The calibration multicomponent gas mixtures were verified with usage of existing gravimetric gas mixtures in accordance with ISO 6143 Composition of calibration standards
Cylinder 6547 Cylinder 6571 Cylinder 6538 Component x мольmol Standard
Instrument Calibration Three independent measurements were carried out under repeatability conditions Before each measurement an instrument calibration was made One measurement contained 5 submeasurements Sample Handling The time of the cylinder keeping is 24 hrs It was used the automatic unit of commutation for inputting gas mixtures
15
Uncertainty Uncertainty table СО2
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas
mixture
B 0010 1 0010
Analysis A B 0048 1 0048
Coverage factor 2 Expanded uncertainty 01 Uncertainty table СО
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas
mixture
B 002 1 002
Analysis A B 0095 1 0095
Coverage factor 2 Expanded uncertainty 019
16
Uncertainty table С3Н8 Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas
mixture
B 005 1 005
Analysis A B 0045 1 0045
Coverage factor 2 Expanded uncertainty 013
17
MEASUREMENT REPORT ndash Belorussian State Institute for Metrology Belarus (BelGIM)
I Results of experimental study
Laboratory Belarus BelGIM Section for physicochemical and optical measurements sector for standards and gas mixtures 8 Serova st Minsk Cylinder No 0128 9 dm3 aluminium NOMINAL COMPOSITION - Carbon dioxide 13middot10-2 - 14middot10-2 molmol - Carbon oxide 28middot10-2 - 32middot10-2 molmol - Propane 19middot10-4 - 21middot10-4molmol - Nitrogen Residual
Measurement No1 Date
Result (molmol)
x_
Standard deviation
S( x_
) rel
No of observations
n
Carbon dioxide 17062005 13567middot10-2 0096 6
Carbon oxide 17062005 2957middot10-2 014 6
Propane 17062005 1977middot10-4 015 6
Measurement No2 Date
Result (molmol)
x_
Standard deviation
S( x_
) rel
No of observations
n
Carbon dioxide 21062005 13564middot10-2 004 6
Carbon oxide 21062005 2957middot10-2 02 6
Propane 21062005 1979middot10-4 01 6
18
Measurement No3 Date
Result (molmol)
x_
Standard deviation
S( x_
) rel
No of observations
n
Carbon dioxide 23062005 13537middot10-2 007 6
Carbon oxide 23062005 2955middot10-2 01 6
Propane 23062005 1982middot10-4 01 6
Final results
Gas mixture Result
(molmol)
Coverage factor
Expanded uncertainty (molmol)
Carbon dioxide 136middot10-2 2 01 middot10-2
Carbon oxide 296middot10-2 2 002middot10-2
Propane 198middot10-4 2 02middot10-4
II Description of study Apparatus (principle of operation type configuration data collection etc)
Measurements were carried out using gas chromatograph Crystal 2000М (hereinafter
referred to as chromatograph) combined with thermal conductivity detector (hereinafter referred to as TCD) with detection limit of 510-9 gml for propane and flame-ionization detector (hereinafter referred to as FID) with detection limit of 510-12 gs for propane
Computers and software Chromatech Analytic version 121 were used to control chromatograph and collect and process chromatographical data
For the purpose of measurements the following auxiliary devices and materials were used
1 Two-position doser with 10 ports and with doses of 025 cm3 for FID channel and with doses of 025 cm3 for TCD channel (hereinafter referred to as doser)
2 Metallic packed column 3m х 3mm х 2mm - HayeSep N 80100 metallic packed column 1m х 4mm х 2mm-CaA 016025 (TCD channel) capillary column HP PLOTQ 30m х 0536mm (FID channel)
3 Aneroid BАММ-1 with a measurement range of 80-106 kPа and accuracy of plusmn 02 kPа
4 Mercurial thermometer ТL-4 with a measurement range of 0-50ordmС and scale division of 01ordmС
19
5 Fine adjustment valve (hereinafter referred to as FAV) provided to transport a gas sample into chromotograph and set to gas flow-rate of 10-15 mlmin
6 Foamy gas flow meter type YIRG - 2А accuracy of flow measurement plusmn 1 сm3min
7 Helium gas Type A according to TU 51-940-80 8 High purity hydrogen gas according to TU 301-07-27-90 9 Compressed air 10 Multicomponent calibration gas mixtures (hereinafter referred to as CGM)
produced and certified by gravimetric method
Calibration reference materials - calibration gas mixtures used for measurements 1 Quantitative composition of KGS is determined using gravimetric method defined in
ISO 61422001 by calculating weight of each component of a gas mixture The content of CGM components is expressed as a mole fraction Uncertainty of KGS composition is expressed as expanded uncertainty with coverage factor k = 2 Molar masses of components and their uncertainties are taken from ISO 149122003 Performance and metrological characteristics of the equipment used for gravimetric preparation of mixtures are given in Table 1
Table 1
Description of the equipment
Manufacturer Metrological characteristics
Mass-comparator balance type КА10-3Р
Mettler-Toledo
Switzerland
Maximum load 15 kg Scale division 1 mg Standard deviation 19 mg at load of 10 kg Operating temperature range +10divide30degС Maximum temperature change within 1 h plusmn05 degС
Gas mixer type USG 00001 BelGIM
Measurement range 000025 divide 100 МPa Accuracy class for manometers ndash 015 Accuracy class for vacuummeters ndash 025 Vacuummeter with pressure sensor for measuring the residual pressure before filling Residual pressure before filling of each component not more than 20 Pa
2 Purity analysis of primary gas standards
The purity analysis of primary gas standards is based on the information provided by the supplier or on the results of determination of impurity in pure gases using measurement procedure developed inside BelGIM
20
If an analytical method laid down in 43 of ISO 61422001 cannot be used for impurity determination mole fraction of an expected impurity is assumed to be half of the detection limit of the analytical method The content of the undetected impurity produces rectangular distribution
whereby its standard uncertainty is calculated as half of the detection limit divided by 3 The composition of the pure gases used for preparation of calibration mixtures is given
in Table 2 Table 2 - Metrological characteristics of pure gases
N2 999967 00005 Nitrogen Cylinder 40 dm3 Origin Russia O2 00033 00005 Propane Cylinder 2 dm3 Origin Russia
C3H8 9979 0017
3 After preparation of mixture the cylinder was maintained in laboratory room within
24 hours the mixture then was homogenized on the stand by rotating on the rollers within 4-5 hours The chromotograph for CGM was calibrated 2-3 days after its preparation
Calibration of the chromotograph
1 The chromotograph was calibrated using CGMs with composition identical to the analyzed sample The content of each component and its expanded uncertainty (k = 2) are given in Table 1 Table 1 - Calibrationе gas mixtures
2 Number of observations of each calibration sample- 3 Number of calibration samples - 3
3 The analytical function used for determination of the content of the analyzed sample components is as follows
x (y) =b1y+b0 (2) Where x ndash determined content molmol y - chromotograph response for the specific component b1- slope b0 - intercept 4 After completion of calibration the coefficients of analytical function were
calculated according to ISO 61432001 using generalized least-squares method Also the uncertainties of the intercept and slope and covariance between them were calculated After determination of parameters which are part of analytical function and which affect the uncertainty of measurements it was checked whether the analytical function is fit to the experimental data obtained in calibration and subsequently whether the analytical function is applicable
Results of calibration measurements coefficients of analytical function their uncertainties covariance and measure of goodness-of-fit Г (maximum value of the weighted differences of the experimental points and calculated points of the analytical function for each measurement run) are given in Tables 3 and 4 respectively Chromotograph operating conditions in calibration and analysis are given in Table 5
Table 3 - Results of experimental study
Date Component of
calibration mixture
Content x mole fraction
Expanded uncertainty
U(x) mole fraction
Mean of peak area y
mVs
Uncertainty )(yu
mVs
13374 0004 1279500 141 1389 0004 1329150 2899 CO2
12833 0004 1231000 849 2916 0005 404070 240
316 0005 437705 926 CO 2768 0004 383070 467
019 0002 3143200 4101
1706 2005
C3H8 0202 0002 3319150 2051
22
0181 0002 2948750 212 13374 0004 1269833 624
1389 0004 1321000 1272 CO2 12833 0004 1223900 1698
2916 0005 399490 612 316 0005 434010 863 CO
2768 0004 379660 410 019 0002 3157867 6772
0202 0002 3332400 3394
2106 2005
C3H8 0181 0002 2959900 4950
13374 0004 1277100 2152 1389 0004 1329900 2828 CO2
12833 0004 1229100 1980 2916 0005 400330 529
316 0005 434745 969 CO 2768 0004 379695 106
019 0002 3142433 9416 0202 0002 3321600 4101
2306 2005
C3H8 0181 0002 2961000 3111
According to ISO 61432003 calculation of the measure of goodness-of-fit Г is the maximum value of the weighed differences between the coordinates of measured and adjusted calibration points is an effective and simple method to test the compatibility of а prospective analytical function A function is admissible if Г le 2
minus
minus=
)(ˆ
)(ˆ
iii
iii
yuyy
xuxxΓ
(4) Where хi is the reference value of the content of calibration sample component
ix is the CGM component content obtained using the calculated analytical function
уi is the experimental response to the reference content of component iy is the response obtained in calculation of analytical function
u (хi) u (уi) are the uncertainties of reference contents and responses to these contents respectively
i is the number of calibration points i=1 3 This prerequisite is equivalent to the requirement that the curve of calculated response should cross each experimental calibration rectangular [хi plusmn 2u(хi) уi plusmn 2и(уi)] based on an expanded uncertainty U = ku with coverage factor k = 2 Table 4 Calculations of analytical function
Date Component Analytical function parameters
Uncertainty of analytical
function parameters
Covariance of
parameters Г
23
b1 b0 u(b1) u(b0) u(b0b1) 1706 11086E-
03 -81128E-
0119491E-
0524883E-
01 -48497E-06 10544
2106 10729E-03
-26126E-01
22698E-05
28930E-01 -65652E-06 19997
2306
CO2 10593E-
03 -17688E-
0135807E-
0545413E-
01 -16254E-05 10022
1706 71537E-04
26507E-02
14231E-05
57044E-02 -81115E-07 03017
2106 72346E-04
22401E-02
13819E-05
54490E-02 -75209E-07 05935
2306
CO 71321E-
04 60080E-
0212663E-
0549016E-
02 -62026E-07 01341
1706 56521E-06
13712E-02
38279E-07
12015E-02 -45937E-09 12991
2106 56295E-06
13707E-02
39247E-07
12379E-02 -48529E-09 12905
2306
C3H8 58258E-
06 80469E-
0340085E-
0712590E-
02 -50407E-09 08589
Two columns separated by switching device are located one after another in TCD
channel One column is intended for carbon dioxide heavy hydrocarbons and another column is intended for light gases Before the first switch the light gases including carbon oxide flow through the first column without being separated and remain in the second column The switch makes them locked in the second column The analysis of carbon dioxide is carried out up to the second switch Second switch makes the second column unlocked and carbon oxide is analyzed Third switch is required to allow propane escape from a column and prevent it from getting into a second column The analysis of the very propane is carried out using FID Time intervals between switches were selected experimentally when developing the analysis method Such analysis method makes it possible to analyze all three components per one sample inject
Table 5 - Chromotograph operating conditions in calibration and analysis Parameter of the operating conditions Thermostating temperature of TCD and FID degС 170
Temperature of separation columns degС
Program 60 degС within 9 min
than rise to 160 degС at 20degСmin
Rate of flow of carrier gas through TCD channel columns mlmin 15
Rate of flow of carrier gas through TCD comparison channel mlmin 15
Pressure in FID channel column kPa Program
24
80 to 100 Rise from the 1st s of
analysis at 2 kPamin
Flow-rate of hydrogen FID mlmin 20 Flow-rate of air FID mlmin 200 Temperature of switching device degС 65 Response time of switching device s 1 110 2 330 3 540
TCD FID Volume of injected analyzed gas cm3 025 025 Carrier gas Helium Duration of analysis min 17 Calculation of the content of comparison sample components and its uncertainty Results of comparison sample measurements are given in Table 6 Table 6 - Results of comparison sample measurements
1 The content of comparison sample component and its uncertainty were determined
using calculated analytical function according to ISO 61432001 as follows (5) Where G(y)=b1y+b0 is the calculated analytical function и(y) is the standard uncertainty of response y u2(bj) is the variance of analytical function parameter bj
u(bj bI) is the covariance of analytical function parameters bj bI N is the number of function coefficients N=2 j=0 1
sum sumsumminus
= +==
partpart
partpart
+
partpart
+
partpart
=1
0 1
2
2
0
22
)(2)()()(N
jIj
N
jI Ijj
N
j j
bbubG
bGbu
bGyu
yGxu
25
After substitution of analytical function (2) and transformations the expression takes form (5)
)(2)()()()()( 01122
0222
1 bbyubuybuyubxu +++= (6) The contents of comparison sample components under determination and their
uncertainties were calculated using B_LEAST a computer program recommended in ISO 6143 Calculations are summarized in Table 6
Table 6 Calculations of the content of comparison sample components and their
2 The final content of a component was determined as an arithmetiс mean from three measurements Final standard uncertainty was calculated using formula as follows
22
222)( Адаватмтемсериикал uuuuuxu ++++= (7)
Where ucal is the uncertainty of the component content produced by
calibration of chromotograph urun is the uncertainty of the component content produced by
change of chromotograph response in each measurement run ut is the uncertainty of the component content produced by
change of an ambient temperature upressure is the uncertainty of the component content produced by
change of atmospheric pressure u A is the standard uncertainty of three measurement runs
21 Uncertainty of the component content produced by calibration of chromotograph
This uncertainty is calculated using formula (6) but the first term of the sum ie
)()( 221 yub which represents the standard uncertainty of the chromotograph response in a
measurement run is not taken into account Calculations are summarized in Table 7
26
Table 7 Calculation of uncertainty produced by calibration of chromotograph
Date u(b1) u(b0) u(b0b1) x
molmol y Ucal molmol
Ucal rel
1706 19491E-05
24883E-01
-48497E-06
13567middot10-
2129698
3 0005middot1
0-2 003
2106 22698E-05
28930E-01
-65652E-06
13564middot10-
2 128855 0007middot1
0-2 005
2306
CO2
35807E-05
45413E-01
-16254E-05
135374middot10-2
1294633
0016middot10-2 012
1706 14231E-05
57044E-02
-81115E-07 2957middot10-2 409633
0003middot10-2 009
2106 13819E-05
54490E-02
-75209E-07
29577middot10-
2 405663 0003middot1
0-2 01
2306
CO
12663E-05
49016E-02
-62026E-07 2955middot10-2 405882
0003middot10-2 01
1706 38279E-07
12015E-02
-45937E-09 1977middot10-4
3255817
007middot10-
2 038
2106 39247E-07
12379E-02
-48529E-09 1980middot10-4
3273329
008middot10-
2 038
2306
C3H8
40085E-07
12590E-02
-50407E-09 1982middot10-4 32636
008middot10-
2 04 The total estimate of relative uncertainty produced by calibration of chromotograph was
calculated for each component as follows
3
3
1
2sum=
cali
cali
uu (8)
Where ucal i is the relative uncertainty produced by calibration of chromotograph and calculated for each measurement run
The calculations are summarized in Table 8
Table 8 Uncertainty produced by calibration of chromotograph
Component Ucal rel
CO2 008 CO 01
C3H8 04 22 Uncertainty of the component content produced by change of chromotograph response in each measurement run This uncertainty is calculated using the equation (6) whereby the first term of the sum
only ie )()( 221 yub which represents the standard uncertainty of the chromotograph
response in a measurement run is taken into account Calculations are summarized in Table 9
27
Table 9 Calculation of uncertainty produced by change of chromotograph response in each measurement run
The total estimate of relative uncertainty produced by change of chromotograph
response in each measurement run was calculated for each component as follows
3
3
1
2sum=
run
run
uu (9)
Where urun is the relative uncertainty produced by change of chromotograph response in each measurement run Calculations are summarized in Table 10
Table 10 Uncertainty produced by change of chromotograph response in each measurement
run
Component Urun rel
CO2 007 CO 015
C3H8 012 23 Uncertainty of the component content produced by change of temperature in a room
The recorded change of temperature in measurements is plusmn 05 degree The contribution of uncertainty type B (rectangular distribution) is estimated as follows
201003
12931
=sdotsdot=tu rel
28
24 Uncertainty of the component content produced by change of atmospheric pressure The recorded change of atmospheric pressure within three days was
05 kPа The contribution of uncertainty type B (rectangular distribution) is estimated as follows
2801003
13101
50=sdotsdot=pressureu rel
25 Standard deviation of 3 measurement runs Standard deviation is calculated as follows
isu p
A
2
= (10)
Where S2p is the group experimental variation
The group experimental variation is calculated as follows
(11)
Where si
2 is the experimental variation of measurement run i from independent repeated observations ni having freedom degrees
νi = n - 1 n=6 i= 3 Calculations are summarized in Table 11 Table 11 Calculations of standard uncertainty of 3 measurement runs
Date 2iS x
molmol 2iS
rel uA
rel
1706 2953E-05 13567middot10-2 000022
2106 588987E-06 13564middot10-2 0000043
2306
CO2 141137E-
05 135374middot10
-2 000010
0006
1706 225604E-06 2957middot10-2 0000077
2106 681346E-06 29577middot10-2 000023
2306
CO
175166E-06 2955middot10-2 0000060
0006
1706 C3H8 130158E-
08 1977middot10-4 00000066 0001
ss
p
i ii
N
ii
N2
2
1
1
= =
=
sum
sum
ν
ν
29
2106 44616E-09 1980middot10-4 00000023
2306
381032E-09 1982middot10-4 00000019
26 Total standard uncertainty
Uncertainty estimation СО2
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph ucal Normal 008 1 008
Change of temperature ut Rectangular 02 1 02 Change of atmospheric pressure upressure Rectangular 028 1 028
Changes of chromotograph response
urun Normal 007 1 007
Standard deviation of 3 runs uA Normal 0006 1 0006
Relative total standard uncertainty 036 Coverage factor k=2 Expanded uncertainty 01middot10-2 molmol Uncertainty estimation СО
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph ucal Normal 01 1 01 Change of temperature ut Rectangular 02 1 02 Change of atmospheric pressure upressure Rectangular 028 1 028 Changes of chromotograph response
urun Normal 015 1 015
Standard deviation of 3 runs uA Normal 0006 1 0006
Relative total standard uncertainty 039 Coverage factor k=2 Expanded uncertainty 002middot10-2 molmol Uncertainty estimation С3Н8
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph 04 Normal 04 1 008
30
Change of temperature 02 Rectangular 02 1 02 Change of atmospheric pressure 028 Rectangular 028 1 028
Changes of chromotograph response
012 Normal 012 1 007
Standard deviation of 3 runs 0001 Normal 0001 1 0006
Relative total standard uncertainty 054 Coverage factor k=2 Expanded uncertainty 02middot10-4 molmol
Sample handling
Period for exposure of cylinder to measurement conditions and method how to transport sample to the device
1 Stands for storing gas standard cylinders and calibration mixture cylinders and chromotograph are placed in a laboratory room which is not accessible to unauthorized persons The laboratory is equipped with air-conditioner to maintain required temperature and humidity on a continuous basis and some auxiliary measuring instruments as thermometer psychrometric hygrometer and aneroid to control temperature humidity and atmospheric inside the room
2 The comparison sample cylinder was stored in laboratory from the date of its
delivery to Minsk on 25042005 CGM cylinders are stored horizontally on racks and positioned vertically using special support when measurements are carried out
3 The analyzed gas sample is transported through the fine adjustment valve (FAV)
Conjunctions Cylinder - FAV FAV - tube tube - doser are made of metal and use adapters with spherical ends and bushes FAV is made of brass tube is made of copper and doser is made of duralumin
Instrument(s) (principles make type configuration data collection etc) For the analysis a GC were used with specifically applications For the determination of (Nitrogen (N2)) Carbon Dioxide (CO2) Carbon Monoxide (CO) and Propane (C3H8) balance GC Perkin Elmer AutoSystem XL (two channel system) with a stream selection valve for 4 streams and 2 gas sampling valves
Channel A for the determination of N2 CO and CO2 Carrier Gas Helium Columns Column system with two packed columns (6 ft x 18rdquo Porapak R 80100 mesh and 6 ft x 18rdquo Mol-Sieve 13X 80100 mesh) Oven Temperature 960 degC to 180 degC Detector micro-TCD Data Collection Total Chrom Workstation Channel B for the determination of C3H8 Carrier Gas Helium Columns Capillary column 50 m x 032 microm LP-SIL-8-CB Oven Temperature 60 degC to 180 degC Detector FID Data Collection Total Chrom Workstation
34
Calibration Standards
Calibration Standards for the measurements (preparation method purity analyses estimated uncertainty etc)
All standards were prepared individually according to ISO 6142 rdquoGas analysis - Preparation of calibration gases - Gravimetric Methodrdquo
Depending on the concentration of the components standards were prepared individually from pure gases or from pre-mixtures which were individually prepared from pure gases
The content of the impurities in all pure gases were determined before use by GC-DID GC-FID and or GC-TCD
After preparation the standards were verified by analytical comparisons against existing gravimetrically prepared standards Only when no significant difference between the analysed and the calculated gravimetric composition is found the ldquonew prepared candidate rdquo is accepted as a new standards
For the analysis of all components multi component standards with nitrogen as balance gas were used
Composition of calibrants BAM C49250-050722 Component Assigned value( x)
mmol mol Standard uncertainty (u(x)) relativ (k=2)
Calibration procedure (mathematical modelcalibration curve number and concentrations of standards measurement sequence temperaturepressure correction etc)
For the instrument calibration the bracketing technique was used The fraction of the current used standards deviated no more than +10rel and -10rel respectively from those of the sample
Measurement sequence
Sample Handling
How were the cylinders treated after arrival (eg stabilized) and how were samples transferred to the instrument (automatic high pressure mass-flow controller dilution etc) After heating (45 - 50 degC) the cylinder for 8 hours the cylinder were rolled about 16 hours before analysis was started Each cylinder was equipped with a pressure regulator that was purged three times by sequential evacuation and pressurisation with the gas mixture used Continous flow (2 ndash 3mlmin) through the sample loop
Uncertainty The specification of potential uncertainty sources is given in Annex 3
3 injection standard (high)
3 injection sample
3 injection standard (high)
3 injection sample
3 injection standard (low)
3 injection sample
3 injection standard (low)
3 injection standard (low)
36
Uncertainty table CO2
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 002 rel 1 002 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 03 rel
Uncertainty table CO
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 007 rel 1 007 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 05 rel
37
Uncertainty table C3H8
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 010 rel 1 001 rel
Analysis normal 028 rel 1 028 rel
Coverage factor 2
Expanded uncertainty 06 rel
Optional
You may provide additional data like the raw measurement data information on your
measurement procedure chromatograms etc
38
Appendix 3 SPECIFICATION OF POTENTIAL UNCERTAINTY SOURCES
a Uncertainty related to the balance and the weights Resolution of balance Accuracy of balance including linearity Incorrect zero point Drift (thermal and time effects) Instability due to draught Location of cylinder on the balance pan Uncertainties in the weights used Buoyancy effects on the weights used
b Uncertainties related to the gas cylinder Mechanical handling of cylinder
Loss of metal paints or labels from surface of cylinder Loss of metal from threads of valvefitting Dirt on cylinder valves or associated fitting
Absorptiondesorption effects on the external cylinder surface Buoyancy effects on the cylinder itself
Cylinder temperature differs from surrounding air due to eg filling with gas Change of cylinder volume during filling Change of density of surrounding air due to changes in temperature air pressure humidity and carbon dioxide content
Uncertainty in determination of external cylinder volume c Uncertainties related to the component gases Residual gas in cylinder Leakage Leakage of air into the cylinder after evacuation
Leakage of gas from the cylinder valve during filling Escape of gas from cylinder into transport lines
Gas remaining in transfer system when weight loss method is used Absorptionreaction of components on internal cylinder surface Reaction between components Impurities in all the initial gases Insufficient homogenization Uncertainty of molecular mass d Uncertainties related to the analysis
Repeatability and selectivity of the analyzer Appropriateness of the calibration curve
39
MEASUREMENT REPORT - All Ukrainian State Research-Industrial Center of Standardization Metrology Certification and Protection of Consumers Ukraine
gas ndash helium flow rate 15 cm3min detector TCD tdetector = 250 ordmС toven = 70 ordmС It was automatic data collection
Measurement and Calibration Methods Laboratory Measurement method Type of calibration curve
GCFID (С3Н8) 3 points linear Ukrmetrteststandard GCTCD (СО СО2) 3 points linear
GCFID ndash gas-chromatographic with flame-ionization detector GCTCD - gas-chromatographic with thermal-conductivity detector
42
Calibration Standards
Calibration standards ndash primary standard gas mixtures (PSGM) used for measurements by comparison method
PSGM-1 Cylinder 0116
PSGM-2 Cylinder 0107
PSGM-3 Cylinder 0093 Composition
x u(x) x u(x) x u(x) СО 27874 00015 29899 00015 31891 00015 СО2 130187 00015 144456 00016 137016 00016 С3Н8 019003 000008 020017 000008 021013 000008 N2 balance balance balance
Note x ndash mole fraction u(x) ndash absolute standard uncertainty
It was used gravimetric method of preparation of PSGM Electronic balance КА-20-3 of Mettler Toledo max limit of weighing is 20 kg least
limit of weighing is 01 g standard deviation is 0006 g Analysis of purity of parent gases was carried out with usage of chromatographs
НР6890N with helium ndash ionization detector flame ndash ionization detector thermal ndash conductivity detector and mass ndash spectrometric detector as well аs gas analyzers GIAM-15M and Onix condensate-thermometer hygrometer TOROS-3-2B
Calculation of uncertainties was carried out according to ISO 6142-2003 Corrections of temperature pressure and humidity of environment were considered
in calculations according to ISO 6142-2003 (program of ISO-6142 2000-03-17 designer is NMi) Protocols and explanations are in Annex A
Instrument (Comparator) Calibration Calibration of comparator ndash gas chromatograph HP 6890 was carried out with usage
of PSGM Measurement sequence PSGM -1 х 3 PSGM -2 х 3 COOMET gas mixture х 3 PSGM -2 х 3 PSGM -3 х 3 It is necessary to use PSGM-2 repeatedly for estimation of reproducibility of results
Program B_LEAST recommended by ISO 6143-2003 was used for constructing the curve Mathematical model of calibration curve is linear one
Sample Handling The cylinder was kept for 24 hrs at a room where comparators were disposed This room is a thermostatic room with t = (20plusmn2) ordmС
43
A method of sample input to a comparator is a method with flow stabilization Uncertainty The following uncertainties were included to the budget of uncertainty - uncertainty of the balance - uncertainties of impurities in parent gases Contribution from other uncertainty sources was insignificant A cabin of the balance is thermostatically The balance is the one-pan balance
Air transfer is absent in the cabin of the balance Drift of the balance is absent for PSGM preparation
Contribution from other uncertainty sources was considered in software according to ISO 6142-2003
Uncertainties related to the analysis (comparison) were considered in software according to ISO 6143-2003 and enclosed in Annex B
Uncertainty table СО2
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas mixture
B 001 1 001
Analysis A B 008 1 008
Coverage factor 2 Expanded uncertainty 002sdot10-2 molmol Uncertainty table СО
Protocols of analysis (comparison) in accordance with ISO 6143-2003
57
Explanation of protocols of comparison
Chapter I ldquoThe calibration data set isrdquo contains columns 1 mole fraction of a component 2 absolute standard uncertainty of mole fraction of a component 3 a signal of a comparator 4 absolute standard uncertainty of a comparator signal
Chapter II ldquoResults of ISO 6143 methodrdquo contains parameters of a calibration curve including its
uncertainty
Chapter ІІІ ldquoPart II Processing of datardquo contains columns
1 calc x - the results of comparison mole fraction of a component 2 u(x) - absolute standard uncertainty of mole fraction of a component 3 response y - a signal of a comparator 4 u(y) - absolute standard uncertainty of a comparator signal
58
СО2 - measurement 1 Data setCO2_21 The calibration data set is 1302E+01 1510E-03 1022E+04 1820E+00 1370E+01 1560E-03 1077E+04 2730E+00 1445E+01 1620E-03 1135E+04 5900E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 20331E-02 12711E-03 12573E-01 11653E-05 -14638E-06 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 10548E-02 12722E-03 31762E-02 28898E-06 -91698E-08 Remaining SSD is 74346 Weighted distances x-value x-dist y-dist 100E+00 130E+01 490E-01 -755E-01 200E+00 137E+01 -103E+00 228E+00 300E+00 144E+01 539E-01 -250E-01 Goodness-of-fit measure 22837 Parameter set 1 1054788657490729E-2 1272208026684145E-3 3176237146276368E-2 2889798108124711E-6 -
9169821653851327E-8 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_21c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13577E+01 25542E-03 10664E+04 15200E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 547E-06 328E-06 316E-06 784E-06 286E-06 652E-06 Linear model Parameters for the fit were (b0 b1) 10548E-02 12722E-03
59
СО2 - measurement 2
Data setCO2_20 The calibration data set is 1302E+01 1512E-03 1021E+04 4723E+00 1370E+01 1563E-03 1075E+04 1600E+00 1445E+01 1620E-03 1133E+04 7300E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -38760E-02 12784E-03 26817E-02 24890E-06 -66689E-08 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -62452E-02 12805E-03 47930E-02 43243E-06 -20716E-07 Remaining SSD is 03231 Weighted distances x-value x-dist y-dist 100E+00 130E+01 107E-01 -415E-01 200E+00 137E+01 -212E-01 283E-01 300E+00 144E+01 104E-01 -584E-02 Goodness-of-fit measure 04155 Parameter set 1 -6245240430658412E-2 1280492624666799E-3 4792952200361109E-2 4324266278840409E-6 -
2071623966851869E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_20c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13594E+01 10290E-02 10665E+04 78300E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 121E-05 683E-06 651E-06 315E-05 560E-06 106E-04 Linear model Parameters for the fit were (b0 b1) -62452E-02 12805E-03
60
С3Н8 - measurement 1
Data setC3H8 The calibration data set is 1900E-01 7800E-05 9057E+03 1098E+01 2002E-01 7900E-05 9552E+03 8569E+00 2101E-01 7960E-05 1007E+04 4049E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10529E-02 19831E-05 34552E-03 36109E-07 -12465E-09 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11642E-02 19714E-05 23073E-03 23522E-07 -54231E-10 Remaining SSD is 19453 Weighted distances x-value x-dist y-dist 100E+00 190E-01 -239E-01 666E-01 200E+00 200E-01 487E-01 -104E+00 300E+00 210E-01 -247E-01 248E-01 Goodness-of-fit measure 10414 Parameter set 1 1164239985182795E-2 1971441115316992E-5 2307269625077337E-3 2352198415608386E-7 -
5423119774765299E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19837E-01 14840E-04 94718E+03 45610E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
7
СООМЕТQM-К3 Results for СО
VNIIM
Ukr
met
rtes
tst
anda
rd
Bel
GIM
BA
M
-1
-08
-06
-04
-02
0
02
04
06
0 05 1 15 2 25 3 35 4 45
Participants
Dx
grav
re
lativ
e
Figure 1 Degree of equivalence for СО
8
СООМЕТQM-К3 Results for C3H8
VNIIM
Ukr
met
rtes
tst
anda
rd
Bel
GIM
BA
M
-15
-1
-05
0
05
1
15
0 05 1 15 2 25 3 35 4 45
Participants
Dx
grav
re
lativ
e
Figure 2 Degree of equivalence for С3Н8
9
СООМЕТQM-К3 Results for CO2
VNIIM
Ukr
met
rtes
tst
anda
rd
Bel
GIM
BA
M
-04-02
0020406
081
121416
0 0 5 1 1 5 2 2 5 3 3 5 4 4 5
ParticipantsDx
grav
re
lativ
e
Figure 3 Degree of equivalence for СО2
10
Discussion and Conclusions All laboratories find the gravimetric value within plusmn07 relative to the gravimetric value This holds for all three components COCO2 and C3H8 in nitrogen This is a satisfying result For all laboratories the observed difference between the gravimetric and reported values does not exceed its combined uncertainty VNIIM and BAM are link laboratories for CCQM-K3 The results of this comparison are linked to the key comparison CCQM-K3 Reference [1] International Organization for Standardization ISO 61422001 Gas analysis - Preparation of calibration gas mixtures - Gravimetric methods 2nd edition [2] International Organization for Standardization ISO 61432001 Gas analysis ndash Comparison methods for determining and checking the composition of calibration gas mixtures [3] Van der Veen AMH De Leer EWB Perrochet J-F Wang Lin Zhen Heine H-JKnopf D Richter W Barbe J Marschal A Vargha G Deaacutek E Takahashi C Kim JS Kim YD Kim BM Kustikov YA Khatskevitch EA Pankratov VV Popova TA Konopelko L Musil S Holland P Milton MJT Miller WR Guenther FR International Comparison CCQM-K3 Final Report Coordinator Leonid Konopelko VNIIM Research Department for the State Standard in the Field of Physical-Chemical Measurements (PCD) 19 Moskovsky pr St-Petersburg 198005 Russia Phone +7 812 3151145 Fax +7 812 3279776 E-mail lkonopmailrcomru Completion Date March 2006
11
Annex 1 Proposal of Degrees of Equivalence Table 5 Degrees of Equivalence for carbon monoxide Lab j VNIIM Ukrmetrteststandard BelGIM BAM Lab i Di Ui Dij Uij Dij Uij Dij Uij Dij Uij mmolmol mmolmol mmolmol mmolmol mmolmol VNIIM 001 006 012 014 007 021 005 016 Ukrmetrteststandard -011 012 -012 014 -005 024 -007 019 BelGIM -006 020 -007 021 005 024 -002 025 BAM -004 015 -005 016 007 019 0016 025 Table 6 Degrees of Equivalence for carbon dioxide Lab j VNIIM Ukrmetrteststandard BelGIM BAM Lab i Di Ui Dij Uij Dij Uij Dij Uij Dij Uij mmolmol mmolmol mmolmol mmolmol mmolmol VNIIM 012 013 026 026 -074 101 0034 043 Ukrmetrteststandard -014 022 -026 026 -10 102 -023 046 BelGIM 086 100 074 101 10 102 077 108 BAM 009 041 -0034 043 023 046 -077 108 Table 7 Degrees of Equivalence for propane Lab j VNIIM Ukrmetrteststandard BelGIM BAM Lab i Di Ui Dij Uij Dij Uij Dij Uij Dij Uij mmolmol mmolmol mmolmol mmolmol mmolmol VNIIM 0001 0004 0002 0006 0005 0020 -0009 0013 Ukrmetrteststandard -0001 0004 -0002 0006 0003 0021 -0011 0013 BelGIM -0004 0020 -0005 0020 -0003 0021 -0014 0023 BAM 0010 0012 0009 0013 0011 0013 0014 0023
12
Annex 2 Results and measurement reports as submitted by participating laboratories Key comparison participants
MEASUREMENT REPORT - DI Mendeleyev Institute for Metrology
Russian Federation (VNIIM)
I Results of Study
Laboratory DI Mendeleyev Institute for Metrology (VNIIM) Research Department for the State Standard in the Field of Physical-Chemical Measurements (PCD)
Instruments Multichannel automatic NDIR analyzer included to the set of the National Primary measurement standard of units of mole fraction and mass concentration of components in gas medium GET 154-01 was used for the analysis Calibration Standards All calibration multicomponent gas mixtures were prepared gravimetrically according to ISO 6142 The calibration multicomponent gas mixtures were prepared from pure gases directly on components CO CO2 and from pre-mixtures which were prepared from pure gases on component С3Н8 The content of the impurities in all pure gases was determined by GC with helium-ionization flame-ionization and thermal-conductivity detectors as well as standard hygrometer apparatus included to the standard complex A1 of analysis of pure gases and substances from GET 154-01 The calibration multicomponent gas mixtures were verified with usage of existing gravimetric gas mixtures in accordance with ISO 6143 Composition of calibration standards
Cylinder 6547 Cylinder 6571 Cylinder 6538 Component x мольmol Standard
Instrument Calibration Three independent measurements were carried out under repeatability conditions Before each measurement an instrument calibration was made One measurement contained 5 submeasurements Sample Handling The time of the cylinder keeping is 24 hrs It was used the automatic unit of commutation for inputting gas mixtures
15
Uncertainty Uncertainty table СО2
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas
mixture
B 0010 1 0010
Analysis A B 0048 1 0048
Coverage factor 2 Expanded uncertainty 01 Uncertainty table СО
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas
mixture
B 002 1 002
Analysis A B 0095 1 0095
Coverage factor 2 Expanded uncertainty 019
16
Uncertainty table С3Н8 Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas
mixture
B 005 1 005
Analysis A B 0045 1 0045
Coverage factor 2 Expanded uncertainty 013
17
MEASUREMENT REPORT ndash Belorussian State Institute for Metrology Belarus (BelGIM)
I Results of experimental study
Laboratory Belarus BelGIM Section for physicochemical and optical measurements sector for standards and gas mixtures 8 Serova st Minsk Cylinder No 0128 9 dm3 aluminium NOMINAL COMPOSITION - Carbon dioxide 13middot10-2 - 14middot10-2 molmol - Carbon oxide 28middot10-2 - 32middot10-2 molmol - Propane 19middot10-4 - 21middot10-4molmol - Nitrogen Residual
Measurement No1 Date
Result (molmol)
x_
Standard deviation
S( x_
) rel
No of observations
n
Carbon dioxide 17062005 13567middot10-2 0096 6
Carbon oxide 17062005 2957middot10-2 014 6
Propane 17062005 1977middot10-4 015 6
Measurement No2 Date
Result (molmol)
x_
Standard deviation
S( x_
) rel
No of observations
n
Carbon dioxide 21062005 13564middot10-2 004 6
Carbon oxide 21062005 2957middot10-2 02 6
Propane 21062005 1979middot10-4 01 6
18
Measurement No3 Date
Result (molmol)
x_
Standard deviation
S( x_
) rel
No of observations
n
Carbon dioxide 23062005 13537middot10-2 007 6
Carbon oxide 23062005 2955middot10-2 01 6
Propane 23062005 1982middot10-4 01 6
Final results
Gas mixture Result
(molmol)
Coverage factor
Expanded uncertainty (molmol)
Carbon dioxide 136middot10-2 2 01 middot10-2
Carbon oxide 296middot10-2 2 002middot10-2
Propane 198middot10-4 2 02middot10-4
II Description of study Apparatus (principle of operation type configuration data collection etc)
Measurements were carried out using gas chromatograph Crystal 2000М (hereinafter
referred to as chromatograph) combined with thermal conductivity detector (hereinafter referred to as TCD) with detection limit of 510-9 gml for propane and flame-ionization detector (hereinafter referred to as FID) with detection limit of 510-12 gs for propane
Computers and software Chromatech Analytic version 121 were used to control chromatograph and collect and process chromatographical data
For the purpose of measurements the following auxiliary devices and materials were used
1 Two-position doser with 10 ports and with doses of 025 cm3 for FID channel and with doses of 025 cm3 for TCD channel (hereinafter referred to as doser)
2 Metallic packed column 3m х 3mm х 2mm - HayeSep N 80100 metallic packed column 1m х 4mm х 2mm-CaA 016025 (TCD channel) capillary column HP PLOTQ 30m х 0536mm (FID channel)
3 Aneroid BАММ-1 with a measurement range of 80-106 kPа and accuracy of plusmn 02 kPа
4 Mercurial thermometer ТL-4 with a measurement range of 0-50ordmС and scale division of 01ordmС
19
5 Fine adjustment valve (hereinafter referred to as FAV) provided to transport a gas sample into chromotograph and set to gas flow-rate of 10-15 mlmin
6 Foamy gas flow meter type YIRG - 2А accuracy of flow measurement plusmn 1 сm3min
7 Helium gas Type A according to TU 51-940-80 8 High purity hydrogen gas according to TU 301-07-27-90 9 Compressed air 10 Multicomponent calibration gas mixtures (hereinafter referred to as CGM)
produced and certified by gravimetric method
Calibration reference materials - calibration gas mixtures used for measurements 1 Quantitative composition of KGS is determined using gravimetric method defined in
ISO 61422001 by calculating weight of each component of a gas mixture The content of CGM components is expressed as a mole fraction Uncertainty of KGS composition is expressed as expanded uncertainty with coverage factor k = 2 Molar masses of components and their uncertainties are taken from ISO 149122003 Performance and metrological characteristics of the equipment used for gravimetric preparation of mixtures are given in Table 1
Table 1
Description of the equipment
Manufacturer Metrological characteristics
Mass-comparator balance type КА10-3Р
Mettler-Toledo
Switzerland
Maximum load 15 kg Scale division 1 mg Standard deviation 19 mg at load of 10 kg Operating temperature range +10divide30degС Maximum temperature change within 1 h plusmn05 degС
Gas mixer type USG 00001 BelGIM
Measurement range 000025 divide 100 МPa Accuracy class for manometers ndash 015 Accuracy class for vacuummeters ndash 025 Vacuummeter with pressure sensor for measuring the residual pressure before filling Residual pressure before filling of each component not more than 20 Pa
2 Purity analysis of primary gas standards
The purity analysis of primary gas standards is based on the information provided by the supplier or on the results of determination of impurity in pure gases using measurement procedure developed inside BelGIM
20
If an analytical method laid down in 43 of ISO 61422001 cannot be used for impurity determination mole fraction of an expected impurity is assumed to be half of the detection limit of the analytical method The content of the undetected impurity produces rectangular distribution
whereby its standard uncertainty is calculated as half of the detection limit divided by 3 The composition of the pure gases used for preparation of calibration mixtures is given
in Table 2 Table 2 - Metrological characteristics of pure gases
N2 999967 00005 Nitrogen Cylinder 40 dm3 Origin Russia O2 00033 00005 Propane Cylinder 2 dm3 Origin Russia
C3H8 9979 0017
3 After preparation of mixture the cylinder was maintained in laboratory room within
24 hours the mixture then was homogenized on the stand by rotating on the rollers within 4-5 hours The chromotograph for CGM was calibrated 2-3 days after its preparation
Calibration of the chromotograph
1 The chromotograph was calibrated using CGMs with composition identical to the analyzed sample The content of each component and its expanded uncertainty (k = 2) are given in Table 1 Table 1 - Calibrationе gas mixtures
2 Number of observations of each calibration sample- 3 Number of calibration samples - 3
3 The analytical function used for determination of the content of the analyzed sample components is as follows
x (y) =b1y+b0 (2) Where x ndash determined content molmol y - chromotograph response for the specific component b1- slope b0 - intercept 4 After completion of calibration the coefficients of analytical function were
calculated according to ISO 61432001 using generalized least-squares method Also the uncertainties of the intercept and slope and covariance between them were calculated After determination of parameters which are part of analytical function and which affect the uncertainty of measurements it was checked whether the analytical function is fit to the experimental data obtained in calibration and subsequently whether the analytical function is applicable
Results of calibration measurements coefficients of analytical function their uncertainties covariance and measure of goodness-of-fit Г (maximum value of the weighted differences of the experimental points and calculated points of the analytical function for each measurement run) are given in Tables 3 and 4 respectively Chromotograph operating conditions in calibration and analysis are given in Table 5
Table 3 - Results of experimental study
Date Component of
calibration mixture
Content x mole fraction
Expanded uncertainty
U(x) mole fraction
Mean of peak area y
mVs
Uncertainty )(yu
mVs
13374 0004 1279500 141 1389 0004 1329150 2899 CO2
12833 0004 1231000 849 2916 0005 404070 240
316 0005 437705 926 CO 2768 0004 383070 467
019 0002 3143200 4101
1706 2005
C3H8 0202 0002 3319150 2051
22
0181 0002 2948750 212 13374 0004 1269833 624
1389 0004 1321000 1272 CO2 12833 0004 1223900 1698
2916 0005 399490 612 316 0005 434010 863 CO
2768 0004 379660 410 019 0002 3157867 6772
0202 0002 3332400 3394
2106 2005
C3H8 0181 0002 2959900 4950
13374 0004 1277100 2152 1389 0004 1329900 2828 CO2
12833 0004 1229100 1980 2916 0005 400330 529
316 0005 434745 969 CO 2768 0004 379695 106
019 0002 3142433 9416 0202 0002 3321600 4101
2306 2005
C3H8 0181 0002 2961000 3111
According to ISO 61432003 calculation of the measure of goodness-of-fit Г is the maximum value of the weighed differences between the coordinates of measured and adjusted calibration points is an effective and simple method to test the compatibility of а prospective analytical function A function is admissible if Г le 2
minus
minus=
)(ˆ
)(ˆ
iii
iii
yuyy
xuxxΓ
(4) Where хi is the reference value of the content of calibration sample component
ix is the CGM component content obtained using the calculated analytical function
уi is the experimental response to the reference content of component iy is the response obtained in calculation of analytical function
u (хi) u (уi) are the uncertainties of reference contents and responses to these contents respectively
i is the number of calibration points i=1 3 This prerequisite is equivalent to the requirement that the curve of calculated response should cross each experimental calibration rectangular [хi plusmn 2u(хi) уi plusmn 2и(уi)] based on an expanded uncertainty U = ku with coverage factor k = 2 Table 4 Calculations of analytical function
Date Component Analytical function parameters
Uncertainty of analytical
function parameters
Covariance of
parameters Г
23
b1 b0 u(b1) u(b0) u(b0b1) 1706 11086E-
03 -81128E-
0119491E-
0524883E-
01 -48497E-06 10544
2106 10729E-03
-26126E-01
22698E-05
28930E-01 -65652E-06 19997
2306
CO2 10593E-
03 -17688E-
0135807E-
0545413E-
01 -16254E-05 10022
1706 71537E-04
26507E-02
14231E-05
57044E-02 -81115E-07 03017
2106 72346E-04
22401E-02
13819E-05
54490E-02 -75209E-07 05935
2306
CO 71321E-
04 60080E-
0212663E-
0549016E-
02 -62026E-07 01341
1706 56521E-06
13712E-02
38279E-07
12015E-02 -45937E-09 12991
2106 56295E-06
13707E-02
39247E-07
12379E-02 -48529E-09 12905
2306
C3H8 58258E-
06 80469E-
0340085E-
0712590E-
02 -50407E-09 08589
Two columns separated by switching device are located one after another in TCD
channel One column is intended for carbon dioxide heavy hydrocarbons and another column is intended for light gases Before the first switch the light gases including carbon oxide flow through the first column without being separated and remain in the second column The switch makes them locked in the second column The analysis of carbon dioxide is carried out up to the second switch Second switch makes the second column unlocked and carbon oxide is analyzed Third switch is required to allow propane escape from a column and prevent it from getting into a second column The analysis of the very propane is carried out using FID Time intervals between switches were selected experimentally when developing the analysis method Such analysis method makes it possible to analyze all three components per one sample inject
Table 5 - Chromotograph operating conditions in calibration and analysis Parameter of the operating conditions Thermostating temperature of TCD and FID degС 170
Temperature of separation columns degС
Program 60 degС within 9 min
than rise to 160 degС at 20degСmin
Rate of flow of carrier gas through TCD channel columns mlmin 15
Rate of flow of carrier gas through TCD comparison channel mlmin 15
Pressure in FID channel column kPa Program
24
80 to 100 Rise from the 1st s of
analysis at 2 kPamin
Flow-rate of hydrogen FID mlmin 20 Flow-rate of air FID mlmin 200 Temperature of switching device degС 65 Response time of switching device s 1 110 2 330 3 540
TCD FID Volume of injected analyzed gas cm3 025 025 Carrier gas Helium Duration of analysis min 17 Calculation of the content of comparison sample components and its uncertainty Results of comparison sample measurements are given in Table 6 Table 6 - Results of comparison sample measurements
1 The content of comparison sample component and its uncertainty were determined
using calculated analytical function according to ISO 61432001 as follows (5) Where G(y)=b1y+b0 is the calculated analytical function и(y) is the standard uncertainty of response y u2(bj) is the variance of analytical function parameter bj
u(bj bI) is the covariance of analytical function parameters bj bI N is the number of function coefficients N=2 j=0 1
sum sumsumminus
= +==
partpart
partpart
+
partpart
+
partpart
=1
0 1
2
2
0
22
)(2)()()(N
jIj
N
jI Ijj
N
j j
bbubG
bGbu
bGyu
yGxu
25
After substitution of analytical function (2) and transformations the expression takes form (5)
)(2)()()()()( 01122
0222
1 bbyubuybuyubxu +++= (6) The contents of comparison sample components under determination and their
uncertainties were calculated using B_LEAST a computer program recommended in ISO 6143 Calculations are summarized in Table 6
Table 6 Calculations of the content of comparison sample components and their
2 The final content of a component was determined as an arithmetiс mean from three measurements Final standard uncertainty was calculated using formula as follows
22
222)( Адаватмтемсериикал uuuuuxu ++++= (7)
Where ucal is the uncertainty of the component content produced by
calibration of chromotograph urun is the uncertainty of the component content produced by
change of chromotograph response in each measurement run ut is the uncertainty of the component content produced by
change of an ambient temperature upressure is the uncertainty of the component content produced by
change of atmospheric pressure u A is the standard uncertainty of three measurement runs
21 Uncertainty of the component content produced by calibration of chromotograph
This uncertainty is calculated using formula (6) but the first term of the sum ie
)()( 221 yub which represents the standard uncertainty of the chromotograph response in a
measurement run is not taken into account Calculations are summarized in Table 7
26
Table 7 Calculation of uncertainty produced by calibration of chromotograph
Date u(b1) u(b0) u(b0b1) x
molmol y Ucal molmol
Ucal rel
1706 19491E-05
24883E-01
-48497E-06
13567middot10-
2129698
3 0005middot1
0-2 003
2106 22698E-05
28930E-01
-65652E-06
13564middot10-
2 128855 0007middot1
0-2 005
2306
CO2
35807E-05
45413E-01
-16254E-05
135374middot10-2
1294633
0016middot10-2 012
1706 14231E-05
57044E-02
-81115E-07 2957middot10-2 409633
0003middot10-2 009
2106 13819E-05
54490E-02
-75209E-07
29577middot10-
2 405663 0003middot1
0-2 01
2306
CO
12663E-05
49016E-02
-62026E-07 2955middot10-2 405882
0003middot10-2 01
1706 38279E-07
12015E-02
-45937E-09 1977middot10-4
3255817
007middot10-
2 038
2106 39247E-07
12379E-02
-48529E-09 1980middot10-4
3273329
008middot10-
2 038
2306
C3H8
40085E-07
12590E-02
-50407E-09 1982middot10-4 32636
008middot10-
2 04 The total estimate of relative uncertainty produced by calibration of chromotograph was
calculated for each component as follows
3
3
1
2sum=
cali
cali
uu (8)
Where ucal i is the relative uncertainty produced by calibration of chromotograph and calculated for each measurement run
The calculations are summarized in Table 8
Table 8 Uncertainty produced by calibration of chromotograph
Component Ucal rel
CO2 008 CO 01
C3H8 04 22 Uncertainty of the component content produced by change of chromotograph response in each measurement run This uncertainty is calculated using the equation (6) whereby the first term of the sum
only ie )()( 221 yub which represents the standard uncertainty of the chromotograph
response in a measurement run is taken into account Calculations are summarized in Table 9
27
Table 9 Calculation of uncertainty produced by change of chromotograph response in each measurement run
The total estimate of relative uncertainty produced by change of chromotograph
response in each measurement run was calculated for each component as follows
3
3
1
2sum=
run
run
uu (9)
Where urun is the relative uncertainty produced by change of chromotograph response in each measurement run Calculations are summarized in Table 10
Table 10 Uncertainty produced by change of chromotograph response in each measurement
run
Component Urun rel
CO2 007 CO 015
C3H8 012 23 Uncertainty of the component content produced by change of temperature in a room
The recorded change of temperature in measurements is plusmn 05 degree The contribution of uncertainty type B (rectangular distribution) is estimated as follows
201003
12931
=sdotsdot=tu rel
28
24 Uncertainty of the component content produced by change of atmospheric pressure The recorded change of atmospheric pressure within three days was
05 kPа The contribution of uncertainty type B (rectangular distribution) is estimated as follows
2801003
13101
50=sdotsdot=pressureu rel
25 Standard deviation of 3 measurement runs Standard deviation is calculated as follows
isu p
A
2
= (10)
Where S2p is the group experimental variation
The group experimental variation is calculated as follows
(11)
Where si
2 is the experimental variation of measurement run i from independent repeated observations ni having freedom degrees
νi = n - 1 n=6 i= 3 Calculations are summarized in Table 11 Table 11 Calculations of standard uncertainty of 3 measurement runs
Date 2iS x
molmol 2iS
rel uA
rel
1706 2953E-05 13567middot10-2 000022
2106 588987E-06 13564middot10-2 0000043
2306
CO2 141137E-
05 135374middot10
-2 000010
0006
1706 225604E-06 2957middot10-2 0000077
2106 681346E-06 29577middot10-2 000023
2306
CO
175166E-06 2955middot10-2 0000060
0006
1706 C3H8 130158E-
08 1977middot10-4 00000066 0001
ss
p
i ii
N
ii
N2
2
1
1
= =
=
sum
sum
ν
ν
29
2106 44616E-09 1980middot10-4 00000023
2306
381032E-09 1982middot10-4 00000019
26 Total standard uncertainty
Uncertainty estimation СО2
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph ucal Normal 008 1 008
Change of temperature ut Rectangular 02 1 02 Change of atmospheric pressure upressure Rectangular 028 1 028
Changes of chromotograph response
urun Normal 007 1 007
Standard deviation of 3 runs uA Normal 0006 1 0006
Relative total standard uncertainty 036 Coverage factor k=2 Expanded uncertainty 01middot10-2 molmol Uncertainty estimation СО
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph ucal Normal 01 1 01 Change of temperature ut Rectangular 02 1 02 Change of atmospheric pressure upressure Rectangular 028 1 028 Changes of chromotograph response
urun Normal 015 1 015
Standard deviation of 3 runs uA Normal 0006 1 0006
Relative total standard uncertainty 039 Coverage factor k=2 Expanded uncertainty 002middot10-2 molmol Uncertainty estimation С3Н8
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph 04 Normal 04 1 008
30
Change of temperature 02 Rectangular 02 1 02 Change of atmospheric pressure 028 Rectangular 028 1 028
Changes of chromotograph response
012 Normal 012 1 007
Standard deviation of 3 runs 0001 Normal 0001 1 0006
Relative total standard uncertainty 054 Coverage factor k=2 Expanded uncertainty 02middot10-4 molmol
Sample handling
Period for exposure of cylinder to measurement conditions and method how to transport sample to the device
1 Stands for storing gas standard cylinders and calibration mixture cylinders and chromotograph are placed in a laboratory room which is not accessible to unauthorized persons The laboratory is equipped with air-conditioner to maintain required temperature and humidity on a continuous basis and some auxiliary measuring instruments as thermometer psychrometric hygrometer and aneroid to control temperature humidity and atmospheric inside the room
2 The comparison sample cylinder was stored in laboratory from the date of its
delivery to Minsk on 25042005 CGM cylinders are stored horizontally on racks and positioned vertically using special support when measurements are carried out
3 The analyzed gas sample is transported through the fine adjustment valve (FAV)
Conjunctions Cylinder - FAV FAV - tube tube - doser are made of metal and use adapters with spherical ends and bushes FAV is made of brass tube is made of copper and doser is made of duralumin
Instrument(s) (principles make type configuration data collection etc) For the analysis a GC were used with specifically applications For the determination of (Nitrogen (N2)) Carbon Dioxide (CO2) Carbon Monoxide (CO) and Propane (C3H8) balance GC Perkin Elmer AutoSystem XL (two channel system) with a stream selection valve for 4 streams and 2 gas sampling valves
Channel A for the determination of N2 CO and CO2 Carrier Gas Helium Columns Column system with two packed columns (6 ft x 18rdquo Porapak R 80100 mesh and 6 ft x 18rdquo Mol-Sieve 13X 80100 mesh) Oven Temperature 960 degC to 180 degC Detector micro-TCD Data Collection Total Chrom Workstation Channel B for the determination of C3H8 Carrier Gas Helium Columns Capillary column 50 m x 032 microm LP-SIL-8-CB Oven Temperature 60 degC to 180 degC Detector FID Data Collection Total Chrom Workstation
34
Calibration Standards
Calibration Standards for the measurements (preparation method purity analyses estimated uncertainty etc)
All standards were prepared individually according to ISO 6142 rdquoGas analysis - Preparation of calibration gases - Gravimetric Methodrdquo
Depending on the concentration of the components standards were prepared individually from pure gases or from pre-mixtures which were individually prepared from pure gases
The content of the impurities in all pure gases were determined before use by GC-DID GC-FID and or GC-TCD
After preparation the standards were verified by analytical comparisons against existing gravimetrically prepared standards Only when no significant difference between the analysed and the calculated gravimetric composition is found the ldquonew prepared candidate rdquo is accepted as a new standards
For the analysis of all components multi component standards with nitrogen as balance gas were used
Composition of calibrants BAM C49250-050722 Component Assigned value( x)
mmol mol Standard uncertainty (u(x)) relativ (k=2)
Calibration procedure (mathematical modelcalibration curve number and concentrations of standards measurement sequence temperaturepressure correction etc)
For the instrument calibration the bracketing technique was used The fraction of the current used standards deviated no more than +10rel and -10rel respectively from those of the sample
Measurement sequence
Sample Handling
How were the cylinders treated after arrival (eg stabilized) and how were samples transferred to the instrument (automatic high pressure mass-flow controller dilution etc) After heating (45 - 50 degC) the cylinder for 8 hours the cylinder were rolled about 16 hours before analysis was started Each cylinder was equipped with a pressure regulator that was purged three times by sequential evacuation and pressurisation with the gas mixture used Continous flow (2 ndash 3mlmin) through the sample loop
Uncertainty The specification of potential uncertainty sources is given in Annex 3
3 injection standard (high)
3 injection sample
3 injection standard (high)
3 injection sample
3 injection standard (low)
3 injection sample
3 injection standard (low)
3 injection standard (low)
36
Uncertainty table CO2
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 002 rel 1 002 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 03 rel
Uncertainty table CO
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 007 rel 1 007 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 05 rel
37
Uncertainty table C3H8
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 010 rel 1 001 rel
Analysis normal 028 rel 1 028 rel
Coverage factor 2
Expanded uncertainty 06 rel
Optional
You may provide additional data like the raw measurement data information on your
measurement procedure chromatograms etc
38
Appendix 3 SPECIFICATION OF POTENTIAL UNCERTAINTY SOURCES
a Uncertainty related to the balance and the weights Resolution of balance Accuracy of balance including linearity Incorrect zero point Drift (thermal and time effects) Instability due to draught Location of cylinder on the balance pan Uncertainties in the weights used Buoyancy effects on the weights used
b Uncertainties related to the gas cylinder Mechanical handling of cylinder
Loss of metal paints or labels from surface of cylinder Loss of metal from threads of valvefitting Dirt on cylinder valves or associated fitting
Absorptiondesorption effects on the external cylinder surface Buoyancy effects on the cylinder itself
Cylinder temperature differs from surrounding air due to eg filling with gas Change of cylinder volume during filling Change of density of surrounding air due to changes in temperature air pressure humidity and carbon dioxide content
Uncertainty in determination of external cylinder volume c Uncertainties related to the component gases Residual gas in cylinder Leakage Leakage of air into the cylinder after evacuation
Leakage of gas from the cylinder valve during filling Escape of gas from cylinder into transport lines
Gas remaining in transfer system when weight loss method is used Absorptionreaction of components on internal cylinder surface Reaction between components Impurities in all the initial gases Insufficient homogenization Uncertainty of molecular mass d Uncertainties related to the analysis
Repeatability and selectivity of the analyzer Appropriateness of the calibration curve
39
MEASUREMENT REPORT - All Ukrainian State Research-Industrial Center of Standardization Metrology Certification and Protection of Consumers Ukraine
gas ndash helium flow rate 15 cm3min detector TCD tdetector = 250 ordmС toven = 70 ordmС It was automatic data collection
Measurement and Calibration Methods Laboratory Measurement method Type of calibration curve
GCFID (С3Н8) 3 points linear Ukrmetrteststandard GCTCD (СО СО2) 3 points linear
GCFID ndash gas-chromatographic with flame-ionization detector GCTCD - gas-chromatographic with thermal-conductivity detector
42
Calibration Standards
Calibration standards ndash primary standard gas mixtures (PSGM) used for measurements by comparison method
PSGM-1 Cylinder 0116
PSGM-2 Cylinder 0107
PSGM-3 Cylinder 0093 Composition
x u(x) x u(x) x u(x) СО 27874 00015 29899 00015 31891 00015 СО2 130187 00015 144456 00016 137016 00016 С3Н8 019003 000008 020017 000008 021013 000008 N2 balance balance balance
Note x ndash mole fraction u(x) ndash absolute standard uncertainty
It was used gravimetric method of preparation of PSGM Electronic balance КА-20-3 of Mettler Toledo max limit of weighing is 20 kg least
limit of weighing is 01 g standard deviation is 0006 g Analysis of purity of parent gases was carried out with usage of chromatographs
НР6890N with helium ndash ionization detector flame ndash ionization detector thermal ndash conductivity detector and mass ndash spectrometric detector as well аs gas analyzers GIAM-15M and Onix condensate-thermometer hygrometer TOROS-3-2B
Calculation of uncertainties was carried out according to ISO 6142-2003 Corrections of temperature pressure and humidity of environment were considered
in calculations according to ISO 6142-2003 (program of ISO-6142 2000-03-17 designer is NMi) Protocols and explanations are in Annex A
Instrument (Comparator) Calibration Calibration of comparator ndash gas chromatograph HP 6890 was carried out with usage
of PSGM Measurement sequence PSGM -1 х 3 PSGM -2 х 3 COOMET gas mixture х 3 PSGM -2 х 3 PSGM -3 х 3 It is necessary to use PSGM-2 repeatedly for estimation of reproducibility of results
Program B_LEAST recommended by ISO 6143-2003 was used for constructing the curve Mathematical model of calibration curve is linear one
Sample Handling The cylinder was kept for 24 hrs at a room where comparators were disposed This room is a thermostatic room with t = (20plusmn2) ordmС
43
A method of sample input to a comparator is a method with flow stabilization Uncertainty The following uncertainties were included to the budget of uncertainty - uncertainty of the balance - uncertainties of impurities in parent gases Contribution from other uncertainty sources was insignificant A cabin of the balance is thermostatically The balance is the one-pan balance
Air transfer is absent in the cabin of the balance Drift of the balance is absent for PSGM preparation
Contribution from other uncertainty sources was considered in software according to ISO 6142-2003
Uncertainties related to the analysis (comparison) were considered in software according to ISO 6143-2003 and enclosed in Annex B
Uncertainty table СО2
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas mixture
B 001 1 001
Analysis A B 008 1 008
Coverage factor 2 Expanded uncertainty 002sdot10-2 molmol Uncertainty table СО
Protocols of analysis (comparison) in accordance with ISO 6143-2003
57
Explanation of protocols of comparison
Chapter I ldquoThe calibration data set isrdquo contains columns 1 mole fraction of a component 2 absolute standard uncertainty of mole fraction of a component 3 a signal of a comparator 4 absolute standard uncertainty of a comparator signal
Chapter II ldquoResults of ISO 6143 methodrdquo contains parameters of a calibration curve including its
uncertainty
Chapter ІІІ ldquoPart II Processing of datardquo contains columns
1 calc x - the results of comparison mole fraction of a component 2 u(x) - absolute standard uncertainty of mole fraction of a component 3 response y - a signal of a comparator 4 u(y) - absolute standard uncertainty of a comparator signal
58
СО2 - measurement 1 Data setCO2_21 The calibration data set is 1302E+01 1510E-03 1022E+04 1820E+00 1370E+01 1560E-03 1077E+04 2730E+00 1445E+01 1620E-03 1135E+04 5900E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 20331E-02 12711E-03 12573E-01 11653E-05 -14638E-06 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 10548E-02 12722E-03 31762E-02 28898E-06 -91698E-08 Remaining SSD is 74346 Weighted distances x-value x-dist y-dist 100E+00 130E+01 490E-01 -755E-01 200E+00 137E+01 -103E+00 228E+00 300E+00 144E+01 539E-01 -250E-01 Goodness-of-fit measure 22837 Parameter set 1 1054788657490729E-2 1272208026684145E-3 3176237146276368E-2 2889798108124711E-6 -
9169821653851327E-8 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_21c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13577E+01 25542E-03 10664E+04 15200E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 547E-06 328E-06 316E-06 784E-06 286E-06 652E-06 Linear model Parameters for the fit were (b0 b1) 10548E-02 12722E-03
59
СО2 - measurement 2
Data setCO2_20 The calibration data set is 1302E+01 1512E-03 1021E+04 4723E+00 1370E+01 1563E-03 1075E+04 1600E+00 1445E+01 1620E-03 1133E+04 7300E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -38760E-02 12784E-03 26817E-02 24890E-06 -66689E-08 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -62452E-02 12805E-03 47930E-02 43243E-06 -20716E-07 Remaining SSD is 03231 Weighted distances x-value x-dist y-dist 100E+00 130E+01 107E-01 -415E-01 200E+00 137E+01 -212E-01 283E-01 300E+00 144E+01 104E-01 -584E-02 Goodness-of-fit measure 04155 Parameter set 1 -6245240430658412E-2 1280492624666799E-3 4792952200361109E-2 4324266278840409E-6 -
2071623966851869E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_20c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13594E+01 10290E-02 10665E+04 78300E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 121E-05 683E-06 651E-06 315E-05 560E-06 106E-04 Linear model Parameters for the fit were (b0 b1) -62452E-02 12805E-03
60
С3Н8 - measurement 1
Data setC3H8 The calibration data set is 1900E-01 7800E-05 9057E+03 1098E+01 2002E-01 7900E-05 9552E+03 8569E+00 2101E-01 7960E-05 1007E+04 4049E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10529E-02 19831E-05 34552E-03 36109E-07 -12465E-09 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11642E-02 19714E-05 23073E-03 23522E-07 -54231E-10 Remaining SSD is 19453 Weighted distances x-value x-dist y-dist 100E+00 190E-01 -239E-01 666E-01 200E+00 200E-01 487E-01 -104E+00 300E+00 210E-01 -247E-01 248E-01 Goodness-of-fit measure 10414 Parameter set 1 1164239985182795E-2 1971441115316992E-5 2307269625077337E-3 2352198415608386E-7 -
5423119774765299E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19837E-01 14840E-04 94718E+03 45610E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
8
СООМЕТQM-К3 Results for C3H8
VNIIM
Ukr
met
rtes
tst
anda
rd
Bel
GIM
BA
M
-15
-1
-05
0
05
1
15
0 05 1 15 2 25 3 35 4 45
Participants
Dx
grav
re
lativ
e
Figure 2 Degree of equivalence for С3Н8
9
СООМЕТQM-К3 Results for CO2
VNIIM
Ukr
met
rtes
tst
anda
rd
Bel
GIM
BA
M
-04-02
0020406
081
121416
0 0 5 1 1 5 2 2 5 3 3 5 4 4 5
ParticipantsDx
grav
re
lativ
e
Figure 3 Degree of equivalence for СО2
10
Discussion and Conclusions All laboratories find the gravimetric value within plusmn07 relative to the gravimetric value This holds for all three components COCO2 and C3H8 in nitrogen This is a satisfying result For all laboratories the observed difference between the gravimetric and reported values does not exceed its combined uncertainty VNIIM and BAM are link laboratories for CCQM-K3 The results of this comparison are linked to the key comparison CCQM-K3 Reference [1] International Organization for Standardization ISO 61422001 Gas analysis - Preparation of calibration gas mixtures - Gravimetric methods 2nd edition [2] International Organization for Standardization ISO 61432001 Gas analysis ndash Comparison methods for determining and checking the composition of calibration gas mixtures [3] Van der Veen AMH De Leer EWB Perrochet J-F Wang Lin Zhen Heine H-JKnopf D Richter W Barbe J Marschal A Vargha G Deaacutek E Takahashi C Kim JS Kim YD Kim BM Kustikov YA Khatskevitch EA Pankratov VV Popova TA Konopelko L Musil S Holland P Milton MJT Miller WR Guenther FR International Comparison CCQM-K3 Final Report Coordinator Leonid Konopelko VNIIM Research Department for the State Standard in the Field of Physical-Chemical Measurements (PCD) 19 Moskovsky pr St-Petersburg 198005 Russia Phone +7 812 3151145 Fax +7 812 3279776 E-mail lkonopmailrcomru Completion Date March 2006
11
Annex 1 Proposal of Degrees of Equivalence Table 5 Degrees of Equivalence for carbon monoxide Lab j VNIIM Ukrmetrteststandard BelGIM BAM Lab i Di Ui Dij Uij Dij Uij Dij Uij Dij Uij mmolmol mmolmol mmolmol mmolmol mmolmol VNIIM 001 006 012 014 007 021 005 016 Ukrmetrteststandard -011 012 -012 014 -005 024 -007 019 BelGIM -006 020 -007 021 005 024 -002 025 BAM -004 015 -005 016 007 019 0016 025 Table 6 Degrees of Equivalence for carbon dioxide Lab j VNIIM Ukrmetrteststandard BelGIM BAM Lab i Di Ui Dij Uij Dij Uij Dij Uij Dij Uij mmolmol mmolmol mmolmol mmolmol mmolmol VNIIM 012 013 026 026 -074 101 0034 043 Ukrmetrteststandard -014 022 -026 026 -10 102 -023 046 BelGIM 086 100 074 101 10 102 077 108 BAM 009 041 -0034 043 023 046 -077 108 Table 7 Degrees of Equivalence for propane Lab j VNIIM Ukrmetrteststandard BelGIM BAM Lab i Di Ui Dij Uij Dij Uij Dij Uij Dij Uij mmolmol mmolmol mmolmol mmolmol mmolmol VNIIM 0001 0004 0002 0006 0005 0020 -0009 0013 Ukrmetrteststandard -0001 0004 -0002 0006 0003 0021 -0011 0013 BelGIM -0004 0020 -0005 0020 -0003 0021 -0014 0023 BAM 0010 0012 0009 0013 0011 0013 0014 0023
12
Annex 2 Results and measurement reports as submitted by participating laboratories Key comparison participants
MEASUREMENT REPORT - DI Mendeleyev Institute for Metrology
Russian Federation (VNIIM)
I Results of Study
Laboratory DI Mendeleyev Institute for Metrology (VNIIM) Research Department for the State Standard in the Field of Physical-Chemical Measurements (PCD)
Instruments Multichannel automatic NDIR analyzer included to the set of the National Primary measurement standard of units of mole fraction and mass concentration of components in gas medium GET 154-01 was used for the analysis Calibration Standards All calibration multicomponent gas mixtures were prepared gravimetrically according to ISO 6142 The calibration multicomponent gas mixtures were prepared from pure gases directly on components CO CO2 and from pre-mixtures which were prepared from pure gases on component С3Н8 The content of the impurities in all pure gases was determined by GC with helium-ionization flame-ionization and thermal-conductivity detectors as well as standard hygrometer apparatus included to the standard complex A1 of analysis of pure gases and substances from GET 154-01 The calibration multicomponent gas mixtures were verified with usage of existing gravimetric gas mixtures in accordance with ISO 6143 Composition of calibration standards
Cylinder 6547 Cylinder 6571 Cylinder 6538 Component x мольmol Standard
Instrument Calibration Three independent measurements were carried out under repeatability conditions Before each measurement an instrument calibration was made One measurement contained 5 submeasurements Sample Handling The time of the cylinder keeping is 24 hrs It was used the automatic unit of commutation for inputting gas mixtures
15
Uncertainty Uncertainty table СО2
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas
mixture
B 0010 1 0010
Analysis A B 0048 1 0048
Coverage factor 2 Expanded uncertainty 01 Uncertainty table СО
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas
mixture
B 002 1 002
Analysis A B 0095 1 0095
Coverage factor 2 Expanded uncertainty 019
16
Uncertainty table С3Н8 Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas
mixture
B 005 1 005
Analysis A B 0045 1 0045
Coverage factor 2 Expanded uncertainty 013
17
MEASUREMENT REPORT ndash Belorussian State Institute for Metrology Belarus (BelGIM)
I Results of experimental study
Laboratory Belarus BelGIM Section for physicochemical and optical measurements sector for standards and gas mixtures 8 Serova st Minsk Cylinder No 0128 9 dm3 aluminium NOMINAL COMPOSITION - Carbon dioxide 13middot10-2 - 14middot10-2 molmol - Carbon oxide 28middot10-2 - 32middot10-2 molmol - Propane 19middot10-4 - 21middot10-4molmol - Nitrogen Residual
Measurement No1 Date
Result (molmol)
x_
Standard deviation
S( x_
) rel
No of observations
n
Carbon dioxide 17062005 13567middot10-2 0096 6
Carbon oxide 17062005 2957middot10-2 014 6
Propane 17062005 1977middot10-4 015 6
Measurement No2 Date
Result (molmol)
x_
Standard deviation
S( x_
) rel
No of observations
n
Carbon dioxide 21062005 13564middot10-2 004 6
Carbon oxide 21062005 2957middot10-2 02 6
Propane 21062005 1979middot10-4 01 6
18
Measurement No3 Date
Result (molmol)
x_
Standard deviation
S( x_
) rel
No of observations
n
Carbon dioxide 23062005 13537middot10-2 007 6
Carbon oxide 23062005 2955middot10-2 01 6
Propane 23062005 1982middot10-4 01 6
Final results
Gas mixture Result
(molmol)
Coverage factor
Expanded uncertainty (molmol)
Carbon dioxide 136middot10-2 2 01 middot10-2
Carbon oxide 296middot10-2 2 002middot10-2
Propane 198middot10-4 2 02middot10-4
II Description of study Apparatus (principle of operation type configuration data collection etc)
Measurements were carried out using gas chromatograph Crystal 2000М (hereinafter
referred to as chromatograph) combined with thermal conductivity detector (hereinafter referred to as TCD) with detection limit of 510-9 gml for propane and flame-ionization detector (hereinafter referred to as FID) with detection limit of 510-12 gs for propane
Computers and software Chromatech Analytic version 121 were used to control chromatograph and collect and process chromatographical data
For the purpose of measurements the following auxiliary devices and materials were used
1 Two-position doser with 10 ports and with doses of 025 cm3 for FID channel and with doses of 025 cm3 for TCD channel (hereinafter referred to as doser)
2 Metallic packed column 3m х 3mm х 2mm - HayeSep N 80100 metallic packed column 1m х 4mm х 2mm-CaA 016025 (TCD channel) capillary column HP PLOTQ 30m х 0536mm (FID channel)
3 Aneroid BАММ-1 with a measurement range of 80-106 kPа and accuracy of plusmn 02 kPа
4 Mercurial thermometer ТL-4 with a measurement range of 0-50ordmС and scale division of 01ordmС
19
5 Fine adjustment valve (hereinafter referred to as FAV) provided to transport a gas sample into chromotograph and set to gas flow-rate of 10-15 mlmin
6 Foamy gas flow meter type YIRG - 2А accuracy of flow measurement plusmn 1 сm3min
7 Helium gas Type A according to TU 51-940-80 8 High purity hydrogen gas according to TU 301-07-27-90 9 Compressed air 10 Multicomponent calibration gas mixtures (hereinafter referred to as CGM)
produced and certified by gravimetric method
Calibration reference materials - calibration gas mixtures used for measurements 1 Quantitative composition of KGS is determined using gravimetric method defined in
ISO 61422001 by calculating weight of each component of a gas mixture The content of CGM components is expressed as a mole fraction Uncertainty of KGS composition is expressed as expanded uncertainty with coverage factor k = 2 Molar masses of components and their uncertainties are taken from ISO 149122003 Performance and metrological characteristics of the equipment used for gravimetric preparation of mixtures are given in Table 1
Table 1
Description of the equipment
Manufacturer Metrological characteristics
Mass-comparator balance type КА10-3Р
Mettler-Toledo
Switzerland
Maximum load 15 kg Scale division 1 mg Standard deviation 19 mg at load of 10 kg Operating temperature range +10divide30degС Maximum temperature change within 1 h plusmn05 degС
Gas mixer type USG 00001 BelGIM
Measurement range 000025 divide 100 МPa Accuracy class for manometers ndash 015 Accuracy class for vacuummeters ndash 025 Vacuummeter with pressure sensor for measuring the residual pressure before filling Residual pressure before filling of each component not more than 20 Pa
2 Purity analysis of primary gas standards
The purity analysis of primary gas standards is based on the information provided by the supplier or on the results of determination of impurity in pure gases using measurement procedure developed inside BelGIM
20
If an analytical method laid down in 43 of ISO 61422001 cannot be used for impurity determination mole fraction of an expected impurity is assumed to be half of the detection limit of the analytical method The content of the undetected impurity produces rectangular distribution
whereby its standard uncertainty is calculated as half of the detection limit divided by 3 The composition of the pure gases used for preparation of calibration mixtures is given
in Table 2 Table 2 - Metrological characteristics of pure gases
N2 999967 00005 Nitrogen Cylinder 40 dm3 Origin Russia O2 00033 00005 Propane Cylinder 2 dm3 Origin Russia
C3H8 9979 0017
3 After preparation of mixture the cylinder was maintained in laboratory room within
24 hours the mixture then was homogenized on the stand by rotating on the rollers within 4-5 hours The chromotograph for CGM was calibrated 2-3 days after its preparation
Calibration of the chromotograph
1 The chromotograph was calibrated using CGMs with composition identical to the analyzed sample The content of each component and its expanded uncertainty (k = 2) are given in Table 1 Table 1 - Calibrationе gas mixtures
2 Number of observations of each calibration sample- 3 Number of calibration samples - 3
3 The analytical function used for determination of the content of the analyzed sample components is as follows
x (y) =b1y+b0 (2) Where x ndash determined content molmol y - chromotograph response for the specific component b1- slope b0 - intercept 4 After completion of calibration the coefficients of analytical function were
calculated according to ISO 61432001 using generalized least-squares method Also the uncertainties of the intercept and slope and covariance between them were calculated After determination of parameters which are part of analytical function and which affect the uncertainty of measurements it was checked whether the analytical function is fit to the experimental data obtained in calibration and subsequently whether the analytical function is applicable
Results of calibration measurements coefficients of analytical function their uncertainties covariance and measure of goodness-of-fit Г (maximum value of the weighted differences of the experimental points and calculated points of the analytical function for each measurement run) are given in Tables 3 and 4 respectively Chromotograph operating conditions in calibration and analysis are given in Table 5
Table 3 - Results of experimental study
Date Component of
calibration mixture
Content x mole fraction
Expanded uncertainty
U(x) mole fraction
Mean of peak area y
mVs
Uncertainty )(yu
mVs
13374 0004 1279500 141 1389 0004 1329150 2899 CO2
12833 0004 1231000 849 2916 0005 404070 240
316 0005 437705 926 CO 2768 0004 383070 467
019 0002 3143200 4101
1706 2005
C3H8 0202 0002 3319150 2051
22
0181 0002 2948750 212 13374 0004 1269833 624
1389 0004 1321000 1272 CO2 12833 0004 1223900 1698
2916 0005 399490 612 316 0005 434010 863 CO
2768 0004 379660 410 019 0002 3157867 6772
0202 0002 3332400 3394
2106 2005
C3H8 0181 0002 2959900 4950
13374 0004 1277100 2152 1389 0004 1329900 2828 CO2
12833 0004 1229100 1980 2916 0005 400330 529
316 0005 434745 969 CO 2768 0004 379695 106
019 0002 3142433 9416 0202 0002 3321600 4101
2306 2005
C3H8 0181 0002 2961000 3111
According to ISO 61432003 calculation of the measure of goodness-of-fit Г is the maximum value of the weighed differences between the coordinates of measured and adjusted calibration points is an effective and simple method to test the compatibility of а prospective analytical function A function is admissible if Г le 2
minus
minus=
)(ˆ
)(ˆ
iii
iii
yuyy
xuxxΓ
(4) Where хi is the reference value of the content of calibration sample component
ix is the CGM component content obtained using the calculated analytical function
уi is the experimental response to the reference content of component iy is the response obtained in calculation of analytical function
u (хi) u (уi) are the uncertainties of reference contents and responses to these contents respectively
i is the number of calibration points i=1 3 This prerequisite is equivalent to the requirement that the curve of calculated response should cross each experimental calibration rectangular [хi plusmn 2u(хi) уi plusmn 2и(уi)] based on an expanded uncertainty U = ku with coverage factor k = 2 Table 4 Calculations of analytical function
Date Component Analytical function parameters
Uncertainty of analytical
function parameters
Covariance of
parameters Г
23
b1 b0 u(b1) u(b0) u(b0b1) 1706 11086E-
03 -81128E-
0119491E-
0524883E-
01 -48497E-06 10544
2106 10729E-03
-26126E-01
22698E-05
28930E-01 -65652E-06 19997
2306
CO2 10593E-
03 -17688E-
0135807E-
0545413E-
01 -16254E-05 10022
1706 71537E-04
26507E-02
14231E-05
57044E-02 -81115E-07 03017
2106 72346E-04
22401E-02
13819E-05
54490E-02 -75209E-07 05935
2306
CO 71321E-
04 60080E-
0212663E-
0549016E-
02 -62026E-07 01341
1706 56521E-06
13712E-02
38279E-07
12015E-02 -45937E-09 12991
2106 56295E-06
13707E-02
39247E-07
12379E-02 -48529E-09 12905
2306
C3H8 58258E-
06 80469E-
0340085E-
0712590E-
02 -50407E-09 08589
Two columns separated by switching device are located one after another in TCD
channel One column is intended for carbon dioxide heavy hydrocarbons and another column is intended for light gases Before the first switch the light gases including carbon oxide flow through the first column without being separated and remain in the second column The switch makes them locked in the second column The analysis of carbon dioxide is carried out up to the second switch Second switch makes the second column unlocked and carbon oxide is analyzed Third switch is required to allow propane escape from a column and prevent it from getting into a second column The analysis of the very propane is carried out using FID Time intervals between switches were selected experimentally when developing the analysis method Such analysis method makes it possible to analyze all three components per one sample inject
Table 5 - Chromotograph operating conditions in calibration and analysis Parameter of the operating conditions Thermostating temperature of TCD and FID degС 170
Temperature of separation columns degС
Program 60 degС within 9 min
than rise to 160 degС at 20degСmin
Rate of flow of carrier gas through TCD channel columns mlmin 15
Rate of flow of carrier gas through TCD comparison channel mlmin 15
Pressure in FID channel column kPa Program
24
80 to 100 Rise from the 1st s of
analysis at 2 kPamin
Flow-rate of hydrogen FID mlmin 20 Flow-rate of air FID mlmin 200 Temperature of switching device degС 65 Response time of switching device s 1 110 2 330 3 540
TCD FID Volume of injected analyzed gas cm3 025 025 Carrier gas Helium Duration of analysis min 17 Calculation of the content of comparison sample components and its uncertainty Results of comparison sample measurements are given in Table 6 Table 6 - Results of comparison sample measurements
1 The content of comparison sample component and its uncertainty were determined
using calculated analytical function according to ISO 61432001 as follows (5) Where G(y)=b1y+b0 is the calculated analytical function и(y) is the standard uncertainty of response y u2(bj) is the variance of analytical function parameter bj
u(bj bI) is the covariance of analytical function parameters bj bI N is the number of function coefficients N=2 j=0 1
sum sumsumminus
= +==
partpart
partpart
+
partpart
+
partpart
=1
0 1
2
2
0
22
)(2)()()(N
jIj
N
jI Ijj
N
j j
bbubG
bGbu
bGyu
yGxu
25
After substitution of analytical function (2) and transformations the expression takes form (5)
)(2)()()()()( 01122
0222
1 bbyubuybuyubxu +++= (6) The contents of comparison sample components under determination and their
uncertainties were calculated using B_LEAST a computer program recommended in ISO 6143 Calculations are summarized in Table 6
Table 6 Calculations of the content of comparison sample components and their
2 The final content of a component was determined as an arithmetiс mean from three measurements Final standard uncertainty was calculated using formula as follows
22
222)( Адаватмтемсериикал uuuuuxu ++++= (7)
Where ucal is the uncertainty of the component content produced by
calibration of chromotograph urun is the uncertainty of the component content produced by
change of chromotograph response in each measurement run ut is the uncertainty of the component content produced by
change of an ambient temperature upressure is the uncertainty of the component content produced by
change of atmospheric pressure u A is the standard uncertainty of three measurement runs
21 Uncertainty of the component content produced by calibration of chromotograph
This uncertainty is calculated using formula (6) but the first term of the sum ie
)()( 221 yub which represents the standard uncertainty of the chromotograph response in a
measurement run is not taken into account Calculations are summarized in Table 7
26
Table 7 Calculation of uncertainty produced by calibration of chromotograph
Date u(b1) u(b0) u(b0b1) x
molmol y Ucal molmol
Ucal rel
1706 19491E-05
24883E-01
-48497E-06
13567middot10-
2129698
3 0005middot1
0-2 003
2106 22698E-05
28930E-01
-65652E-06
13564middot10-
2 128855 0007middot1
0-2 005
2306
CO2
35807E-05
45413E-01
-16254E-05
135374middot10-2
1294633
0016middot10-2 012
1706 14231E-05
57044E-02
-81115E-07 2957middot10-2 409633
0003middot10-2 009
2106 13819E-05
54490E-02
-75209E-07
29577middot10-
2 405663 0003middot1
0-2 01
2306
CO
12663E-05
49016E-02
-62026E-07 2955middot10-2 405882
0003middot10-2 01
1706 38279E-07
12015E-02
-45937E-09 1977middot10-4
3255817
007middot10-
2 038
2106 39247E-07
12379E-02
-48529E-09 1980middot10-4
3273329
008middot10-
2 038
2306
C3H8
40085E-07
12590E-02
-50407E-09 1982middot10-4 32636
008middot10-
2 04 The total estimate of relative uncertainty produced by calibration of chromotograph was
calculated for each component as follows
3
3
1
2sum=
cali
cali
uu (8)
Where ucal i is the relative uncertainty produced by calibration of chromotograph and calculated for each measurement run
The calculations are summarized in Table 8
Table 8 Uncertainty produced by calibration of chromotograph
Component Ucal rel
CO2 008 CO 01
C3H8 04 22 Uncertainty of the component content produced by change of chromotograph response in each measurement run This uncertainty is calculated using the equation (6) whereby the first term of the sum
only ie )()( 221 yub which represents the standard uncertainty of the chromotograph
response in a measurement run is taken into account Calculations are summarized in Table 9
27
Table 9 Calculation of uncertainty produced by change of chromotograph response in each measurement run
The total estimate of relative uncertainty produced by change of chromotograph
response in each measurement run was calculated for each component as follows
3
3
1
2sum=
run
run
uu (9)
Where urun is the relative uncertainty produced by change of chromotograph response in each measurement run Calculations are summarized in Table 10
Table 10 Uncertainty produced by change of chromotograph response in each measurement
run
Component Urun rel
CO2 007 CO 015
C3H8 012 23 Uncertainty of the component content produced by change of temperature in a room
The recorded change of temperature in measurements is plusmn 05 degree The contribution of uncertainty type B (rectangular distribution) is estimated as follows
201003
12931
=sdotsdot=tu rel
28
24 Uncertainty of the component content produced by change of atmospheric pressure The recorded change of atmospheric pressure within three days was
05 kPа The contribution of uncertainty type B (rectangular distribution) is estimated as follows
2801003
13101
50=sdotsdot=pressureu rel
25 Standard deviation of 3 measurement runs Standard deviation is calculated as follows
isu p
A
2
= (10)
Where S2p is the group experimental variation
The group experimental variation is calculated as follows
(11)
Where si
2 is the experimental variation of measurement run i from independent repeated observations ni having freedom degrees
νi = n - 1 n=6 i= 3 Calculations are summarized in Table 11 Table 11 Calculations of standard uncertainty of 3 measurement runs
Date 2iS x
molmol 2iS
rel uA
rel
1706 2953E-05 13567middot10-2 000022
2106 588987E-06 13564middot10-2 0000043
2306
CO2 141137E-
05 135374middot10
-2 000010
0006
1706 225604E-06 2957middot10-2 0000077
2106 681346E-06 29577middot10-2 000023
2306
CO
175166E-06 2955middot10-2 0000060
0006
1706 C3H8 130158E-
08 1977middot10-4 00000066 0001
ss
p
i ii
N
ii
N2
2
1
1
= =
=
sum
sum
ν
ν
29
2106 44616E-09 1980middot10-4 00000023
2306
381032E-09 1982middot10-4 00000019
26 Total standard uncertainty
Uncertainty estimation СО2
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph ucal Normal 008 1 008
Change of temperature ut Rectangular 02 1 02 Change of atmospheric pressure upressure Rectangular 028 1 028
Changes of chromotograph response
urun Normal 007 1 007
Standard deviation of 3 runs uA Normal 0006 1 0006
Relative total standard uncertainty 036 Coverage factor k=2 Expanded uncertainty 01middot10-2 molmol Uncertainty estimation СО
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph ucal Normal 01 1 01 Change of temperature ut Rectangular 02 1 02 Change of atmospheric pressure upressure Rectangular 028 1 028 Changes of chromotograph response
urun Normal 015 1 015
Standard deviation of 3 runs uA Normal 0006 1 0006
Relative total standard uncertainty 039 Coverage factor k=2 Expanded uncertainty 002middot10-2 molmol Uncertainty estimation С3Н8
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph 04 Normal 04 1 008
30
Change of temperature 02 Rectangular 02 1 02 Change of atmospheric pressure 028 Rectangular 028 1 028
Changes of chromotograph response
012 Normal 012 1 007
Standard deviation of 3 runs 0001 Normal 0001 1 0006
Relative total standard uncertainty 054 Coverage factor k=2 Expanded uncertainty 02middot10-4 molmol
Sample handling
Period for exposure of cylinder to measurement conditions and method how to transport sample to the device
1 Stands for storing gas standard cylinders and calibration mixture cylinders and chromotograph are placed in a laboratory room which is not accessible to unauthorized persons The laboratory is equipped with air-conditioner to maintain required temperature and humidity on a continuous basis and some auxiliary measuring instruments as thermometer psychrometric hygrometer and aneroid to control temperature humidity and atmospheric inside the room
2 The comparison sample cylinder was stored in laboratory from the date of its
delivery to Minsk on 25042005 CGM cylinders are stored horizontally on racks and positioned vertically using special support when measurements are carried out
3 The analyzed gas sample is transported through the fine adjustment valve (FAV)
Conjunctions Cylinder - FAV FAV - tube tube - doser are made of metal and use adapters with spherical ends and bushes FAV is made of brass tube is made of copper and doser is made of duralumin
Instrument(s) (principles make type configuration data collection etc) For the analysis a GC were used with specifically applications For the determination of (Nitrogen (N2)) Carbon Dioxide (CO2) Carbon Monoxide (CO) and Propane (C3H8) balance GC Perkin Elmer AutoSystem XL (two channel system) with a stream selection valve for 4 streams and 2 gas sampling valves
Channel A for the determination of N2 CO and CO2 Carrier Gas Helium Columns Column system with two packed columns (6 ft x 18rdquo Porapak R 80100 mesh and 6 ft x 18rdquo Mol-Sieve 13X 80100 mesh) Oven Temperature 960 degC to 180 degC Detector micro-TCD Data Collection Total Chrom Workstation Channel B for the determination of C3H8 Carrier Gas Helium Columns Capillary column 50 m x 032 microm LP-SIL-8-CB Oven Temperature 60 degC to 180 degC Detector FID Data Collection Total Chrom Workstation
34
Calibration Standards
Calibration Standards for the measurements (preparation method purity analyses estimated uncertainty etc)
All standards were prepared individually according to ISO 6142 rdquoGas analysis - Preparation of calibration gases - Gravimetric Methodrdquo
Depending on the concentration of the components standards were prepared individually from pure gases or from pre-mixtures which were individually prepared from pure gases
The content of the impurities in all pure gases were determined before use by GC-DID GC-FID and or GC-TCD
After preparation the standards were verified by analytical comparisons against existing gravimetrically prepared standards Only when no significant difference between the analysed and the calculated gravimetric composition is found the ldquonew prepared candidate rdquo is accepted as a new standards
For the analysis of all components multi component standards with nitrogen as balance gas were used
Composition of calibrants BAM C49250-050722 Component Assigned value( x)
mmol mol Standard uncertainty (u(x)) relativ (k=2)
Calibration procedure (mathematical modelcalibration curve number and concentrations of standards measurement sequence temperaturepressure correction etc)
For the instrument calibration the bracketing technique was used The fraction of the current used standards deviated no more than +10rel and -10rel respectively from those of the sample
Measurement sequence
Sample Handling
How were the cylinders treated after arrival (eg stabilized) and how were samples transferred to the instrument (automatic high pressure mass-flow controller dilution etc) After heating (45 - 50 degC) the cylinder for 8 hours the cylinder were rolled about 16 hours before analysis was started Each cylinder was equipped with a pressure regulator that was purged three times by sequential evacuation and pressurisation with the gas mixture used Continous flow (2 ndash 3mlmin) through the sample loop
Uncertainty The specification of potential uncertainty sources is given in Annex 3
3 injection standard (high)
3 injection sample
3 injection standard (high)
3 injection sample
3 injection standard (low)
3 injection sample
3 injection standard (low)
3 injection standard (low)
36
Uncertainty table CO2
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 002 rel 1 002 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 03 rel
Uncertainty table CO
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 007 rel 1 007 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 05 rel
37
Uncertainty table C3H8
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 010 rel 1 001 rel
Analysis normal 028 rel 1 028 rel
Coverage factor 2
Expanded uncertainty 06 rel
Optional
You may provide additional data like the raw measurement data information on your
measurement procedure chromatograms etc
38
Appendix 3 SPECIFICATION OF POTENTIAL UNCERTAINTY SOURCES
a Uncertainty related to the balance and the weights Resolution of balance Accuracy of balance including linearity Incorrect zero point Drift (thermal and time effects) Instability due to draught Location of cylinder on the balance pan Uncertainties in the weights used Buoyancy effects on the weights used
b Uncertainties related to the gas cylinder Mechanical handling of cylinder
Loss of metal paints or labels from surface of cylinder Loss of metal from threads of valvefitting Dirt on cylinder valves or associated fitting
Absorptiondesorption effects on the external cylinder surface Buoyancy effects on the cylinder itself
Cylinder temperature differs from surrounding air due to eg filling with gas Change of cylinder volume during filling Change of density of surrounding air due to changes in temperature air pressure humidity and carbon dioxide content
Uncertainty in determination of external cylinder volume c Uncertainties related to the component gases Residual gas in cylinder Leakage Leakage of air into the cylinder after evacuation
Leakage of gas from the cylinder valve during filling Escape of gas from cylinder into transport lines
Gas remaining in transfer system when weight loss method is used Absorptionreaction of components on internal cylinder surface Reaction between components Impurities in all the initial gases Insufficient homogenization Uncertainty of molecular mass d Uncertainties related to the analysis
Repeatability and selectivity of the analyzer Appropriateness of the calibration curve
39
MEASUREMENT REPORT - All Ukrainian State Research-Industrial Center of Standardization Metrology Certification and Protection of Consumers Ukraine
gas ndash helium flow rate 15 cm3min detector TCD tdetector = 250 ordmС toven = 70 ordmС It was automatic data collection
Measurement and Calibration Methods Laboratory Measurement method Type of calibration curve
GCFID (С3Н8) 3 points linear Ukrmetrteststandard GCTCD (СО СО2) 3 points linear
GCFID ndash gas-chromatographic with flame-ionization detector GCTCD - gas-chromatographic with thermal-conductivity detector
42
Calibration Standards
Calibration standards ndash primary standard gas mixtures (PSGM) used for measurements by comparison method
PSGM-1 Cylinder 0116
PSGM-2 Cylinder 0107
PSGM-3 Cylinder 0093 Composition
x u(x) x u(x) x u(x) СО 27874 00015 29899 00015 31891 00015 СО2 130187 00015 144456 00016 137016 00016 С3Н8 019003 000008 020017 000008 021013 000008 N2 balance balance balance
Note x ndash mole fraction u(x) ndash absolute standard uncertainty
It was used gravimetric method of preparation of PSGM Electronic balance КА-20-3 of Mettler Toledo max limit of weighing is 20 kg least
limit of weighing is 01 g standard deviation is 0006 g Analysis of purity of parent gases was carried out with usage of chromatographs
НР6890N with helium ndash ionization detector flame ndash ionization detector thermal ndash conductivity detector and mass ndash spectrometric detector as well аs gas analyzers GIAM-15M and Onix condensate-thermometer hygrometer TOROS-3-2B
Calculation of uncertainties was carried out according to ISO 6142-2003 Corrections of temperature pressure and humidity of environment were considered
in calculations according to ISO 6142-2003 (program of ISO-6142 2000-03-17 designer is NMi) Protocols and explanations are in Annex A
Instrument (Comparator) Calibration Calibration of comparator ndash gas chromatograph HP 6890 was carried out with usage
of PSGM Measurement sequence PSGM -1 х 3 PSGM -2 х 3 COOMET gas mixture х 3 PSGM -2 х 3 PSGM -3 х 3 It is necessary to use PSGM-2 repeatedly for estimation of reproducibility of results
Program B_LEAST recommended by ISO 6143-2003 was used for constructing the curve Mathematical model of calibration curve is linear one
Sample Handling The cylinder was kept for 24 hrs at a room where comparators were disposed This room is a thermostatic room with t = (20plusmn2) ordmС
43
A method of sample input to a comparator is a method with flow stabilization Uncertainty The following uncertainties were included to the budget of uncertainty - uncertainty of the balance - uncertainties of impurities in parent gases Contribution from other uncertainty sources was insignificant A cabin of the balance is thermostatically The balance is the one-pan balance
Air transfer is absent in the cabin of the balance Drift of the balance is absent for PSGM preparation
Contribution from other uncertainty sources was considered in software according to ISO 6142-2003
Uncertainties related to the analysis (comparison) were considered in software according to ISO 6143-2003 and enclosed in Annex B
Uncertainty table СО2
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas mixture
B 001 1 001
Analysis A B 008 1 008
Coverage factor 2 Expanded uncertainty 002sdot10-2 molmol Uncertainty table СО
Protocols of analysis (comparison) in accordance with ISO 6143-2003
57
Explanation of protocols of comparison
Chapter I ldquoThe calibration data set isrdquo contains columns 1 mole fraction of a component 2 absolute standard uncertainty of mole fraction of a component 3 a signal of a comparator 4 absolute standard uncertainty of a comparator signal
Chapter II ldquoResults of ISO 6143 methodrdquo contains parameters of a calibration curve including its
uncertainty
Chapter ІІІ ldquoPart II Processing of datardquo contains columns
1 calc x - the results of comparison mole fraction of a component 2 u(x) - absolute standard uncertainty of mole fraction of a component 3 response y - a signal of a comparator 4 u(y) - absolute standard uncertainty of a comparator signal
58
СО2 - measurement 1 Data setCO2_21 The calibration data set is 1302E+01 1510E-03 1022E+04 1820E+00 1370E+01 1560E-03 1077E+04 2730E+00 1445E+01 1620E-03 1135E+04 5900E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 20331E-02 12711E-03 12573E-01 11653E-05 -14638E-06 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 10548E-02 12722E-03 31762E-02 28898E-06 -91698E-08 Remaining SSD is 74346 Weighted distances x-value x-dist y-dist 100E+00 130E+01 490E-01 -755E-01 200E+00 137E+01 -103E+00 228E+00 300E+00 144E+01 539E-01 -250E-01 Goodness-of-fit measure 22837 Parameter set 1 1054788657490729E-2 1272208026684145E-3 3176237146276368E-2 2889798108124711E-6 -
9169821653851327E-8 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_21c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13577E+01 25542E-03 10664E+04 15200E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 547E-06 328E-06 316E-06 784E-06 286E-06 652E-06 Linear model Parameters for the fit were (b0 b1) 10548E-02 12722E-03
59
СО2 - measurement 2
Data setCO2_20 The calibration data set is 1302E+01 1512E-03 1021E+04 4723E+00 1370E+01 1563E-03 1075E+04 1600E+00 1445E+01 1620E-03 1133E+04 7300E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -38760E-02 12784E-03 26817E-02 24890E-06 -66689E-08 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -62452E-02 12805E-03 47930E-02 43243E-06 -20716E-07 Remaining SSD is 03231 Weighted distances x-value x-dist y-dist 100E+00 130E+01 107E-01 -415E-01 200E+00 137E+01 -212E-01 283E-01 300E+00 144E+01 104E-01 -584E-02 Goodness-of-fit measure 04155 Parameter set 1 -6245240430658412E-2 1280492624666799E-3 4792952200361109E-2 4324266278840409E-6 -
2071623966851869E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_20c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13594E+01 10290E-02 10665E+04 78300E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 121E-05 683E-06 651E-06 315E-05 560E-06 106E-04 Linear model Parameters for the fit were (b0 b1) -62452E-02 12805E-03
60
С3Н8 - measurement 1
Data setC3H8 The calibration data set is 1900E-01 7800E-05 9057E+03 1098E+01 2002E-01 7900E-05 9552E+03 8569E+00 2101E-01 7960E-05 1007E+04 4049E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10529E-02 19831E-05 34552E-03 36109E-07 -12465E-09 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11642E-02 19714E-05 23073E-03 23522E-07 -54231E-10 Remaining SSD is 19453 Weighted distances x-value x-dist y-dist 100E+00 190E-01 -239E-01 666E-01 200E+00 200E-01 487E-01 -104E+00 300E+00 210E-01 -247E-01 248E-01 Goodness-of-fit measure 10414 Parameter set 1 1164239985182795E-2 1971441115316992E-5 2307269625077337E-3 2352198415608386E-7 -
5423119774765299E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19837E-01 14840E-04 94718E+03 45610E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
9
СООМЕТQM-К3 Results for CO2
VNIIM
Ukr
met
rtes
tst
anda
rd
Bel
GIM
BA
M
-04-02
0020406
081
121416
0 0 5 1 1 5 2 2 5 3 3 5 4 4 5
ParticipantsDx
grav
re
lativ
e
Figure 3 Degree of equivalence for СО2
10
Discussion and Conclusions All laboratories find the gravimetric value within plusmn07 relative to the gravimetric value This holds for all three components COCO2 and C3H8 in nitrogen This is a satisfying result For all laboratories the observed difference between the gravimetric and reported values does not exceed its combined uncertainty VNIIM and BAM are link laboratories for CCQM-K3 The results of this comparison are linked to the key comparison CCQM-K3 Reference [1] International Organization for Standardization ISO 61422001 Gas analysis - Preparation of calibration gas mixtures - Gravimetric methods 2nd edition [2] International Organization for Standardization ISO 61432001 Gas analysis ndash Comparison methods for determining and checking the composition of calibration gas mixtures [3] Van der Veen AMH De Leer EWB Perrochet J-F Wang Lin Zhen Heine H-JKnopf D Richter W Barbe J Marschal A Vargha G Deaacutek E Takahashi C Kim JS Kim YD Kim BM Kustikov YA Khatskevitch EA Pankratov VV Popova TA Konopelko L Musil S Holland P Milton MJT Miller WR Guenther FR International Comparison CCQM-K3 Final Report Coordinator Leonid Konopelko VNIIM Research Department for the State Standard in the Field of Physical-Chemical Measurements (PCD) 19 Moskovsky pr St-Petersburg 198005 Russia Phone +7 812 3151145 Fax +7 812 3279776 E-mail lkonopmailrcomru Completion Date March 2006
11
Annex 1 Proposal of Degrees of Equivalence Table 5 Degrees of Equivalence for carbon monoxide Lab j VNIIM Ukrmetrteststandard BelGIM BAM Lab i Di Ui Dij Uij Dij Uij Dij Uij Dij Uij mmolmol mmolmol mmolmol mmolmol mmolmol VNIIM 001 006 012 014 007 021 005 016 Ukrmetrteststandard -011 012 -012 014 -005 024 -007 019 BelGIM -006 020 -007 021 005 024 -002 025 BAM -004 015 -005 016 007 019 0016 025 Table 6 Degrees of Equivalence for carbon dioxide Lab j VNIIM Ukrmetrteststandard BelGIM BAM Lab i Di Ui Dij Uij Dij Uij Dij Uij Dij Uij mmolmol mmolmol mmolmol mmolmol mmolmol VNIIM 012 013 026 026 -074 101 0034 043 Ukrmetrteststandard -014 022 -026 026 -10 102 -023 046 BelGIM 086 100 074 101 10 102 077 108 BAM 009 041 -0034 043 023 046 -077 108 Table 7 Degrees of Equivalence for propane Lab j VNIIM Ukrmetrteststandard BelGIM BAM Lab i Di Ui Dij Uij Dij Uij Dij Uij Dij Uij mmolmol mmolmol mmolmol mmolmol mmolmol VNIIM 0001 0004 0002 0006 0005 0020 -0009 0013 Ukrmetrteststandard -0001 0004 -0002 0006 0003 0021 -0011 0013 BelGIM -0004 0020 -0005 0020 -0003 0021 -0014 0023 BAM 0010 0012 0009 0013 0011 0013 0014 0023
12
Annex 2 Results and measurement reports as submitted by participating laboratories Key comparison participants
MEASUREMENT REPORT - DI Mendeleyev Institute for Metrology
Russian Federation (VNIIM)
I Results of Study
Laboratory DI Mendeleyev Institute for Metrology (VNIIM) Research Department for the State Standard in the Field of Physical-Chemical Measurements (PCD)
Instruments Multichannel automatic NDIR analyzer included to the set of the National Primary measurement standard of units of mole fraction and mass concentration of components in gas medium GET 154-01 was used for the analysis Calibration Standards All calibration multicomponent gas mixtures were prepared gravimetrically according to ISO 6142 The calibration multicomponent gas mixtures were prepared from pure gases directly on components CO CO2 and from pre-mixtures which were prepared from pure gases on component С3Н8 The content of the impurities in all pure gases was determined by GC with helium-ionization flame-ionization and thermal-conductivity detectors as well as standard hygrometer apparatus included to the standard complex A1 of analysis of pure gases and substances from GET 154-01 The calibration multicomponent gas mixtures were verified with usage of existing gravimetric gas mixtures in accordance with ISO 6143 Composition of calibration standards
Cylinder 6547 Cylinder 6571 Cylinder 6538 Component x мольmol Standard
Instrument Calibration Three independent measurements were carried out under repeatability conditions Before each measurement an instrument calibration was made One measurement contained 5 submeasurements Sample Handling The time of the cylinder keeping is 24 hrs It was used the automatic unit of commutation for inputting gas mixtures
15
Uncertainty Uncertainty table СО2
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas
mixture
B 0010 1 0010
Analysis A B 0048 1 0048
Coverage factor 2 Expanded uncertainty 01 Uncertainty table СО
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas
mixture
B 002 1 002
Analysis A B 0095 1 0095
Coverage factor 2 Expanded uncertainty 019
16
Uncertainty table С3Н8 Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas
mixture
B 005 1 005
Analysis A B 0045 1 0045
Coverage factor 2 Expanded uncertainty 013
17
MEASUREMENT REPORT ndash Belorussian State Institute for Metrology Belarus (BelGIM)
I Results of experimental study
Laboratory Belarus BelGIM Section for physicochemical and optical measurements sector for standards and gas mixtures 8 Serova st Minsk Cylinder No 0128 9 dm3 aluminium NOMINAL COMPOSITION - Carbon dioxide 13middot10-2 - 14middot10-2 molmol - Carbon oxide 28middot10-2 - 32middot10-2 molmol - Propane 19middot10-4 - 21middot10-4molmol - Nitrogen Residual
Measurement No1 Date
Result (molmol)
x_
Standard deviation
S( x_
) rel
No of observations
n
Carbon dioxide 17062005 13567middot10-2 0096 6
Carbon oxide 17062005 2957middot10-2 014 6
Propane 17062005 1977middot10-4 015 6
Measurement No2 Date
Result (molmol)
x_
Standard deviation
S( x_
) rel
No of observations
n
Carbon dioxide 21062005 13564middot10-2 004 6
Carbon oxide 21062005 2957middot10-2 02 6
Propane 21062005 1979middot10-4 01 6
18
Measurement No3 Date
Result (molmol)
x_
Standard deviation
S( x_
) rel
No of observations
n
Carbon dioxide 23062005 13537middot10-2 007 6
Carbon oxide 23062005 2955middot10-2 01 6
Propane 23062005 1982middot10-4 01 6
Final results
Gas mixture Result
(molmol)
Coverage factor
Expanded uncertainty (molmol)
Carbon dioxide 136middot10-2 2 01 middot10-2
Carbon oxide 296middot10-2 2 002middot10-2
Propane 198middot10-4 2 02middot10-4
II Description of study Apparatus (principle of operation type configuration data collection etc)
Measurements were carried out using gas chromatograph Crystal 2000М (hereinafter
referred to as chromatograph) combined with thermal conductivity detector (hereinafter referred to as TCD) with detection limit of 510-9 gml for propane and flame-ionization detector (hereinafter referred to as FID) with detection limit of 510-12 gs for propane
Computers and software Chromatech Analytic version 121 were used to control chromatograph and collect and process chromatographical data
For the purpose of measurements the following auxiliary devices and materials were used
1 Two-position doser with 10 ports and with doses of 025 cm3 for FID channel and with doses of 025 cm3 for TCD channel (hereinafter referred to as doser)
2 Metallic packed column 3m х 3mm х 2mm - HayeSep N 80100 metallic packed column 1m х 4mm х 2mm-CaA 016025 (TCD channel) capillary column HP PLOTQ 30m х 0536mm (FID channel)
3 Aneroid BАММ-1 with a measurement range of 80-106 kPа and accuracy of plusmn 02 kPа
4 Mercurial thermometer ТL-4 with a measurement range of 0-50ordmС and scale division of 01ordmС
19
5 Fine adjustment valve (hereinafter referred to as FAV) provided to transport a gas sample into chromotograph and set to gas flow-rate of 10-15 mlmin
6 Foamy gas flow meter type YIRG - 2А accuracy of flow measurement plusmn 1 сm3min
7 Helium gas Type A according to TU 51-940-80 8 High purity hydrogen gas according to TU 301-07-27-90 9 Compressed air 10 Multicomponent calibration gas mixtures (hereinafter referred to as CGM)
produced and certified by gravimetric method
Calibration reference materials - calibration gas mixtures used for measurements 1 Quantitative composition of KGS is determined using gravimetric method defined in
ISO 61422001 by calculating weight of each component of a gas mixture The content of CGM components is expressed as a mole fraction Uncertainty of KGS composition is expressed as expanded uncertainty with coverage factor k = 2 Molar masses of components and their uncertainties are taken from ISO 149122003 Performance and metrological characteristics of the equipment used for gravimetric preparation of mixtures are given in Table 1
Table 1
Description of the equipment
Manufacturer Metrological characteristics
Mass-comparator balance type КА10-3Р
Mettler-Toledo
Switzerland
Maximum load 15 kg Scale division 1 mg Standard deviation 19 mg at load of 10 kg Operating temperature range +10divide30degС Maximum temperature change within 1 h plusmn05 degС
Gas mixer type USG 00001 BelGIM
Measurement range 000025 divide 100 МPa Accuracy class for manometers ndash 015 Accuracy class for vacuummeters ndash 025 Vacuummeter with pressure sensor for measuring the residual pressure before filling Residual pressure before filling of each component not more than 20 Pa
2 Purity analysis of primary gas standards
The purity analysis of primary gas standards is based on the information provided by the supplier or on the results of determination of impurity in pure gases using measurement procedure developed inside BelGIM
20
If an analytical method laid down in 43 of ISO 61422001 cannot be used for impurity determination mole fraction of an expected impurity is assumed to be half of the detection limit of the analytical method The content of the undetected impurity produces rectangular distribution
whereby its standard uncertainty is calculated as half of the detection limit divided by 3 The composition of the pure gases used for preparation of calibration mixtures is given
in Table 2 Table 2 - Metrological characteristics of pure gases
N2 999967 00005 Nitrogen Cylinder 40 dm3 Origin Russia O2 00033 00005 Propane Cylinder 2 dm3 Origin Russia
C3H8 9979 0017
3 After preparation of mixture the cylinder was maintained in laboratory room within
24 hours the mixture then was homogenized on the stand by rotating on the rollers within 4-5 hours The chromotograph for CGM was calibrated 2-3 days after its preparation
Calibration of the chromotograph
1 The chromotograph was calibrated using CGMs with composition identical to the analyzed sample The content of each component and its expanded uncertainty (k = 2) are given in Table 1 Table 1 - Calibrationе gas mixtures
2 Number of observations of each calibration sample- 3 Number of calibration samples - 3
3 The analytical function used for determination of the content of the analyzed sample components is as follows
x (y) =b1y+b0 (2) Where x ndash determined content molmol y - chromotograph response for the specific component b1- slope b0 - intercept 4 After completion of calibration the coefficients of analytical function were
calculated according to ISO 61432001 using generalized least-squares method Also the uncertainties of the intercept and slope and covariance between them were calculated After determination of parameters which are part of analytical function and which affect the uncertainty of measurements it was checked whether the analytical function is fit to the experimental data obtained in calibration and subsequently whether the analytical function is applicable
Results of calibration measurements coefficients of analytical function their uncertainties covariance and measure of goodness-of-fit Г (maximum value of the weighted differences of the experimental points and calculated points of the analytical function for each measurement run) are given in Tables 3 and 4 respectively Chromotograph operating conditions in calibration and analysis are given in Table 5
Table 3 - Results of experimental study
Date Component of
calibration mixture
Content x mole fraction
Expanded uncertainty
U(x) mole fraction
Mean of peak area y
mVs
Uncertainty )(yu
mVs
13374 0004 1279500 141 1389 0004 1329150 2899 CO2
12833 0004 1231000 849 2916 0005 404070 240
316 0005 437705 926 CO 2768 0004 383070 467
019 0002 3143200 4101
1706 2005
C3H8 0202 0002 3319150 2051
22
0181 0002 2948750 212 13374 0004 1269833 624
1389 0004 1321000 1272 CO2 12833 0004 1223900 1698
2916 0005 399490 612 316 0005 434010 863 CO
2768 0004 379660 410 019 0002 3157867 6772
0202 0002 3332400 3394
2106 2005
C3H8 0181 0002 2959900 4950
13374 0004 1277100 2152 1389 0004 1329900 2828 CO2
12833 0004 1229100 1980 2916 0005 400330 529
316 0005 434745 969 CO 2768 0004 379695 106
019 0002 3142433 9416 0202 0002 3321600 4101
2306 2005
C3H8 0181 0002 2961000 3111
According to ISO 61432003 calculation of the measure of goodness-of-fit Г is the maximum value of the weighed differences between the coordinates of measured and adjusted calibration points is an effective and simple method to test the compatibility of а prospective analytical function A function is admissible if Г le 2
minus
minus=
)(ˆ
)(ˆ
iii
iii
yuyy
xuxxΓ
(4) Where хi is the reference value of the content of calibration sample component
ix is the CGM component content obtained using the calculated analytical function
уi is the experimental response to the reference content of component iy is the response obtained in calculation of analytical function
u (хi) u (уi) are the uncertainties of reference contents and responses to these contents respectively
i is the number of calibration points i=1 3 This prerequisite is equivalent to the requirement that the curve of calculated response should cross each experimental calibration rectangular [хi plusmn 2u(хi) уi plusmn 2и(уi)] based on an expanded uncertainty U = ku with coverage factor k = 2 Table 4 Calculations of analytical function
Date Component Analytical function parameters
Uncertainty of analytical
function parameters
Covariance of
parameters Г
23
b1 b0 u(b1) u(b0) u(b0b1) 1706 11086E-
03 -81128E-
0119491E-
0524883E-
01 -48497E-06 10544
2106 10729E-03
-26126E-01
22698E-05
28930E-01 -65652E-06 19997
2306
CO2 10593E-
03 -17688E-
0135807E-
0545413E-
01 -16254E-05 10022
1706 71537E-04
26507E-02
14231E-05
57044E-02 -81115E-07 03017
2106 72346E-04
22401E-02
13819E-05
54490E-02 -75209E-07 05935
2306
CO 71321E-
04 60080E-
0212663E-
0549016E-
02 -62026E-07 01341
1706 56521E-06
13712E-02
38279E-07
12015E-02 -45937E-09 12991
2106 56295E-06
13707E-02
39247E-07
12379E-02 -48529E-09 12905
2306
C3H8 58258E-
06 80469E-
0340085E-
0712590E-
02 -50407E-09 08589
Two columns separated by switching device are located one after another in TCD
channel One column is intended for carbon dioxide heavy hydrocarbons and another column is intended for light gases Before the first switch the light gases including carbon oxide flow through the first column without being separated and remain in the second column The switch makes them locked in the second column The analysis of carbon dioxide is carried out up to the second switch Second switch makes the second column unlocked and carbon oxide is analyzed Third switch is required to allow propane escape from a column and prevent it from getting into a second column The analysis of the very propane is carried out using FID Time intervals between switches were selected experimentally when developing the analysis method Such analysis method makes it possible to analyze all three components per one sample inject
Table 5 - Chromotograph operating conditions in calibration and analysis Parameter of the operating conditions Thermostating temperature of TCD and FID degС 170
Temperature of separation columns degС
Program 60 degС within 9 min
than rise to 160 degС at 20degСmin
Rate of flow of carrier gas through TCD channel columns mlmin 15
Rate of flow of carrier gas through TCD comparison channel mlmin 15
Pressure in FID channel column kPa Program
24
80 to 100 Rise from the 1st s of
analysis at 2 kPamin
Flow-rate of hydrogen FID mlmin 20 Flow-rate of air FID mlmin 200 Temperature of switching device degС 65 Response time of switching device s 1 110 2 330 3 540
TCD FID Volume of injected analyzed gas cm3 025 025 Carrier gas Helium Duration of analysis min 17 Calculation of the content of comparison sample components and its uncertainty Results of comparison sample measurements are given in Table 6 Table 6 - Results of comparison sample measurements
1 The content of comparison sample component and its uncertainty were determined
using calculated analytical function according to ISO 61432001 as follows (5) Where G(y)=b1y+b0 is the calculated analytical function и(y) is the standard uncertainty of response y u2(bj) is the variance of analytical function parameter bj
u(bj bI) is the covariance of analytical function parameters bj bI N is the number of function coefficients N=2 j=0 1
sum sumsumminus
= +==
partpart
partpart
+
partpart
+
partpart
=1
0 1
2
2
0
22
)(2)()()(N
jIj
N
jI Ijj
N
j j
bbubG
bGbu
bGyu
yGxu
25
After substitution of analytical function (2) and transformations the expression takes form (5)
)(2)()()()()( 01122
0222
1 bbyubuybuyubxu +++= (6) The contents of comparison sample components under determination and their
uncertainties were calculated using B_LEAST a computer program recommended in ISO 6143 Calculations are summarized in Table 6
Table 6 Calculations of the content of comparison sample components and their
2 The final content of a component was determined as an arithmetiс mean from three measurements Final standard uncertainty was calculated using formula as follows
22
222)( Адаватмтемсериикал uuuuuxu ++++= (7)
Where ucal is the uncertainty of the component content produced by
calibration of chromotograph urun is the uncertainty of the component content produced by
change of chromotograph response in each measurement run ut is the uncertainty of the component content produced by
change of an ambient temperature upressure is the uncertainty of the component content produced by
change of atmospheric pressure u A is the standard uncertainty of three measurement runs
21 Uncertainty of the component content produced by calibration of chromotograph
This uncertainty is calculated using formula (6) but the first term of the sum ie
)()( 221 yub which represents the standard uncertainty of the chromotograph response in a
measurement run is not taken into account Calculations are summarized in Table 7
26
Table 7 Calculation of uncertainty produced by calibration of chromotograph
Date u(b1) u(b0) u(b0b1) x
molmol y Ucal molmol
Ucal rel
1706 19491E-05
24883E-01
-48497E-06
13567middot10-
2129698
3 0005middot1
0-2 003
2106 22698E-05
28930E-01
-65652E-06
13564middot10-
2 128855 0007middot1
0-2 005
2306
CO2
35807E-05
45413E-01
-16254E-05
135374middot10-2
1294633
0016middot10-2 012
1706 14231E-05
57044E-02
-81115E-07 2957middot10-2 409633
0003middot10-2 009
2106 13819E-05
54490E-02
-75209E-07
29577middot10-
2 405663 0003middot1
0-2 01
2306
CO
12663E-05
49016E-02
-62026E-07 2955middot10-2 405882
0003middot10-2 01
1706 38279E-07
12015E-02
-45937E-09 1977middot10-4
3255817
007middot10-
2 038
2106 39247E-07
12379E-02
-48529E-09 1980middot10-4
3273329
008middot10-
2 038
2306
C3H8
40085E-07
12590E-02
-50407E-09 1982middot10-4 32636
008middot10-
2 04 The total estimate of relative uncertainty produced by calibration of chromotograph was
calculated for each component as follows
3
3
1
2sum=
cali
cali
uu (8)
Where ucal i is the relative uncertainty produced by calibration of chromotograph and calculated for each measurement run
The calculations are summarized in Table 8
Table 8 Uncertainty produced by calibration of chromotograph
Component Ucal rel
CO2 008 CO 01
C3H8 04 22 Uncertainty of the component content produced by change of chromotograph response in each measurement run This uncertainty is calculated using the equation (6) whereby the first term of the sum
only ie )()( 221 yub which represents the standard uncertainty of the chromotograph
response in a measurement run is taken into account Calculations are summarized in Table 9
27
Table 9 Calculation of uncertainty produced by change of chromotograph response in each measurement run
The total estimate of relative uncertainty produced by change of chromotograph
response in each measurement run was calculated for each component as follows
3
3
1
2sum=
run
run
uu (9)
Where urun is the relative uncertainty produced by change of chromotograph response in each measurement run Calculations are summarized in Table 10
Table 10 Uncertainty produced by change of chromotograph response in each measurement
run
Component Urun rel
CO2 007 CO 015
C3H8 012 23 Uncertainty of the component content produced by change of temperature in a room
The recorded change of temperature in measurements is plusmn 05 degree The contribution of uncertainty type B (rectangular distribution) is estimated as follows
201003
12931
=sdotsdot=tu rel
28
24 Uncertainty of the component content produced by change of atmospheric pressure The recorded change of atmospheric pressure within three days was
05 kPа The contribution of uncertainty type B (rectangular distribution) is estimated as follows
2801003
13101
50=sdotsdot=pressureu rel
25 Standard deviation of 3 measurement runs Standard deviation is calculated as follows
isu p
A
2
= (10)
Where S2p is the group experimental variation
The group experimental variation is calculated as follows
(11)
Where si
2 is the experimental variation of measurement run i from independent repeated observations ni having freedom degrees
νi = n - 1 n=6 i= 3 Calculations are summarized in Table 11 Table 11 Calculations of standard uncertainty of 3 measurement runs
Date 2iS x
molmol 2iS
rel uA
rel
1706 2953E-05 13567middot10-2 000022
2106 588987E-06 13564middot10-2 0000043
2306
CO2 141137E-
05 135374middot10
-2 000010
0006
1706 225604E-06 2957middot10-2 0000077
2106 681346E-06 29577middot10-2 000023
2306
CO
175166E-06 2955middot10-2 0000060
0006
1706 C3H8 130158E-
08 1977middot10-4 00000066 0001
ss
p
i ii
N
ii
N2
2
1
1
= =
=
sum
sum
ν
ν
29
2106 44616E-09 1980middot10-4 00000023
2306
381032E-09 1982middot10-4 00000019
26 Total standard uncertainty
Uncertainty estimation СО2
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph ucal Normal 008 1 008
Change of temperature ut Rectangular 02 1 02 Change of atmospheric pressure upressure Rectangular 028 1 028
Changes of chromotograph response
urun Normal 007 1 007
Standard deviation of 3 runs uA Normal 0006 1 0006
Relative total standard uncertainty 036 Coverage factor k=2 Expanded uncertainty 01middot10-2 molmol Uncertainty estimation СО
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph ucal Normal 01 1 01 Change of temperature ut Rectangular 02 1 02 Change of atmospheric pressure upressure Rectangular 028 1 028 Changes of chromotograph response
urun Normal 015 1 015
Standard deviation of 3 runs uA Normal 0006 1 0006
Relative total standard uncertainty 039 Coverage factor k=2 Expanded uncertainty 002middot10-2 molmol Uncertainty estimation С3Н8
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph 04 Normal 04 1 008
30
Change of temperature 02 Rectangular 02 1 02 Change of atmospheric pressure 028 Rectangular 028 1 028
Changes of chromotograph response
012 Normal 012 1 007
Standard deviation of 3 runs 0001 Normal 0001 1 0006
Relative total standard uncertainty 054 Coverage factor k=2 Expanded uncertainty 02middot10-4 molmol
Sample handling
Period for exposure of cylinder to measurement conditions and method how to transport sample to the device
1 Stands for storing gas standard cylinders and calibration mixture cylinders and chromotograph are placed in a laboratory room which is not accessible to unauthorized persons The laboratory is equipped with air-conditioner to maintain required temperature and humidity on a continuous basis and some auxiliary measuring instruments as thermometer psychrometric hygrometer and aneroid to control temperature humidity and atmospheric inside the room
2 The comparison sample cylinder was stored in laboratory from the date of its
delivery to Minsk on 25042005 CGM cylinders are stored horizontally on racks and positioned vertically using special support when measurements are carried out
3 The analyzed gas sample is transported through the fine adjustment valve (FAV)
Conjunctions Cylinder - FAV FAV - tube tube - doser are made of metal and use adapters with spherical ends and bushes FAV is made of brass tube is made of copper and doser is made of duralumin
Instrument(s) (principles make type configuration data collection etc) For the analysis a GC were used with specifically applications For the determination of (Nitrogen (N2)) Carbon Dioxide (CO2) Carbon Monoxide (CO) and Propane (C3H8) balance GC Perkin Elmer AutoSystem XL (two channel system) with a stream selection valve for 4 streams and 2 gas sampling valves
Channel A for the determination of N2 CO and CO2 Carrier Gas Helium Columns Column system with two packed columns (6 ft x 18rdquo Porapak R 80100 mesh and 6 ft x 18rdquo Mol-Sieve 13X 80100 mesh) Oven Temperature 960 degC to 180 degC Detector micro-TCD Data Collection Total Chrom Workstation Channel B for the determination of C3H8 Carrier Gas Helium Columns Capillary column 50 m x 032 microm LP-SIL-8-CB Oven Temperature 60 degC to 180 degC Detector FID Data Collection Total Chrom Workstation
34
Calibration Standards
Calibration Standards for the measurements (preparation method purity analyses estimated uncertainty etc)
All standards were prepared individually according to ISO 6142 rdquoGas analysis - Preparation of calibration gases - Gravimetric Methodrdquo
Depending on the concentration of the components standards were prepared individually from pure gases or from pre-mixtures which were individually prepared from pure gases
The content of the impurities in all pure gases were determined before use by GC-DID GC-FID and or GC-TCD
After preparation the standards were verified by analytical comparisons against existing gravimetrically prepared standards Only when no significant difference between the analysed and the calculated gravimetric composition is found the ldquonew prepared candidate rdquo is accepted as a new standards
For the analysis of all components multi component standards with nitrogen as balance gas were used
Composition of calibrants BAM C49250-050722 Component Assigned value( x)
mmol mol Standard uncertainty (u(x)) relativ (k=2)
Calibration procedure (mathematical modelcalibration curve number and concentrations of standards measurement sequence temperaturepressure correction etc)
For the instrument calibration the bracketing technique was used The fraction of the current used standards deviated no more than +10rel and -10rel respectively from those of the sample
Measurement sequence
Sample Handling
How were the cylinders treated after arrival (eg stabilized) and how were samples transferred to the instrument (automatic high pressure mass-flow controller dilution etc) After heating (45 - 50 degC) the cylinder for 8 hours the cylinder were rolled about 16 hours before analysis was started Each cylinder was equipped with a pressure regulator that was purged three times by sequential evacuation and pressurisation with the gas mixture used Continous flow (2 ndash 3mlmin) through the sample loop
Uncertainty The specification of potential uncertainty sources is given in Annex 3
3 injection standard (high)
3 injection sample
3 injection standard (high)
3 injection sample
3 injection standard (low)
3 injection sample
3 injection standard (low)
3 injection standard (low)
36
Uncertainty table CO2
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 002 rel 1 002 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 03 rel
Uncertainty table CO
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 007 rel 1 007 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 05 rel
37
Uncertainty table C3H8
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 010 rel 1 001 rel
Analysis normal 028 rel 1 028 rel
Coverage factor 2
Expanded uncertainty 06 rel
Optional
You may provide additional data like the raw measurement data information on your
measurement procedure chromatograms etc
38
Appendix 3 SPECIFICATION OF POTENTIAL UNCERTAINTY SOURCES
a Uncertainty related to the balance and the weights Resolution of balance Accuracy of balance including linearity Incorrect zero point Drift (thermal and time effects) Instability due to draught Location of cylinder on the balance pan Uncertainties in the weights used Buoyancy effects on the weights used
b Uncertainties related to the gas cylinder Mechanical handling of cylinder
Loss of metal paints or labels from surface of cylinder Loss of metal from threads of valvefitting Dirt on cylinder valves or associated fitting
Absorptiondesorption effects on the external cylinder surface Buoyancy effects on the cylinder itself
Cylinder temperature differs from surrounding air due to eg filling with gas Change of cylinder volume during filling Change of density of surrounding air due to changes in temperature air pressure humidity and carbon dioxide content
Uncertainty in determination of external cylinder volume c Uncertainties related to the component gases Residual gas in cylinder Leakage Leakage of air into the cylinder after evacuation
Leakage of gas from the cylinder valve during filling Escape of gas from cylinder into transport lines
Gas remaining in transfer system when weight loss method is used Absorptionreaction of components on internal cylinder surface Reaction between components Impurities in all the initial gases Insufficient homogenization Uncertainty of molecular mass d Uncertainties related to the analysis
Repeatability and selectivity of the analyzer Appropriateness of the calibration curve
39
MEASUREMENT REPORT - All Ukrainian State Research-Industrial Center of Standardization Metrology Certification and Protection of Consumers Ukraine
gas ndash helium flow rate 15 cm3min detector TCD tdetector = 250 ordmС toven = 70 ordmС It was automatic data collection
Measurement and Calibration Methods Laboratory Measurement method Type of calibration curve
GCFID (С3Н8) 3 points linear Ukrmetrteststandard GCTCD (СО СО2) 3 points linear
GCFID ndash gas-chromatographic with flame-ionization detector GCTCD - gas-chromatographic with thermal-conductivity detector
42
Calibration Standards
Calibration standards ndash primary standard gas mixtures (PSGM) used for measurements by comparison method
PSGM-1 Cylinder 0116
PSGM-2 Cylinder 0107
PSGM-3 Cylinder 0093 Composition
x u(x) x u(x) x u(x) СО 27874 00015 29899 00015 31891 00015 СО2 130187 00015 144456 00016 137016 00016 С3Н8 019003 000008 020017 000008 021013 000008 N2 balance balance balance
Note x ndash mole fraction u(x) ndash absolute standard uncertainty
It was used gravimetric method of preparation of PSGM Electronic balance КА-20-3 of Mettler Toledo max limit of weighing is 20 kg least
limit of weighing is 01 g standard deviation is 0006 g Analysis of purity of parent gases was carried out with usage of chromatographs
НР6890N with helium ndash ionization detector flame ndash ionization detector thermal ndash conductivity detector and mass ndash spectrometric detector as well аs gas analyzers GIAM-15M and Onix condensate-thermometer hygrometer TOROS-3-2B
Calculation of uncertainties was carried out according to ISO 6142-2003 Corrections of temperature pressure and humidity of environment were considered
in calculations according to ISO 6142-2003 (program of ISO-6142 2000-03-17 designer is NMi) Protocols and explanations are in Annex A
Instrument (Comparator) Calibration Calibration of comparator ndash gas chromatograph HP 6890 was carried out with usage
of PSGM Measurement sequence PSGM -1 х 3 PSGM -2 х 3 COOMET gas mixture х 3 PSGM -2 х 3 PSGM -3 х 3 It is necessary to use PSGM-2 repeatedly for estimation of reproducibility of results
Program B_LEAST recommended by ISO 6143-2003 was used for constructing the curve Mathematical model of calibration curve is linear one
Sample Handling The cylinder was kept for 24 hrs at a room where comparators were disposed This room is a thermostatic room with t = (20plusmn2) ordmС
43
A method of sample input to a comparator is a method with flow stabilization Uncertainty The following uncertainties were included to the budget of uncertainty - uncertainty of the balance - uncertainties of impurities in parent gases Contribution from other uncertainty sources was insignificant A cabin of the balance is thermostatically The balance is the one-pan balance
Air transfer is absent in the cabin of the balance Drift of the balance is absent for PSGM preparation
Contribution from other uncertainty sources was considered in software according to ISO 6142-2003
Uncertainties related to the analysis (comparison) were considered in software according to ISO 6143-2003 and enclosed in Annex B
Uncertainty table СО2
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas mixture
B 001 1 001
Analysis A B 008 1 008
Coverage factor 2 Expanded uncertainty 002sdot10-2 molmol Uncertainty table СО
Protocols of analysis (comparison) in accordance with ISO 6143-2003
57
Explanation of protocols of comparison
Chapter I ldquoThe calibration data set isrdquo contains columns 1 mole fraction of a component 2 absolute standard uncertainty of mole fraction of a component 3 a signal of a comparator 4 absolute standard uncertainty of a comparator signal
Chapter II ldquoResults of ISO 6143 methodrdquo contains parameters of a calibration curve including its
uncertainty
Chapter ІІІ ldquoPart II Processing of datardquo contains columns
1 calc x - the results of comparison mole fraction of a component 2 u(x) - absolute standard uncertainty of mole fraction of a component 3 response y - a signal of a comparator 4 u(y) - absolute standard uncertainty of a comparator signal
58
СО2 - measurement 1 Data setCO2_21 The calibration data set is 1302E+01 1510E-03 1022E+04 1820E+00 1370E+01 1560E-03 1077E+04 2730E+00 1445E+01 1620E-03 1135E+04 5900E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 20331E-02 12711E-03 12573E-01 11653E-05 -14638E-06 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 10548E-02 12722E-03 31762E-02 28898E-06 -91698E-08 Remaining SSD is 74346 Weighted distances x-value x-dist y-dist 100E+00 130E+01 490E-01 -755E-01 200E+00 137E+01 -103E+00 228E+00 300E+00 144E+01 539E-01 -250E-01 Goodness-of-fit measure 22837 Parameter set 1 1054788657490729E-2 1272208026684145E-3 3176237146276368E-2 2889798108124711E-6 -
9169821653851327E-8 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_21c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13577E+01 25542E-03 10664E+04 15200E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 547E-06 328E-06 316E-06 784E-06 286E-06 652E-06 Linear model Parameters for the fit were (b0 b1) 10548E-02 12722E-03
59
СО2 - measurement 2
Data setCO2_20 The calibration data set is 1302E+01 1512E-03 1021E+04 4723E+00 1370E+01 1563E-03 1075E+04 1600E+00 1445E+01 1620E-03 1133E+04 7300E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -38760E-02 12784E-03 26817E-02 24890E-06 -66689E-08 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -62452E-02 12805E-03 47930E-02 43243E-06 -20716E-07 Remaining SSD is 03231 Weighted distances x-value x-dist y-dist 100E+00 130E+01 107E-01 -415E-01 200E+00 137E+01 -212E-01 283E-01 300E+00 144E+01 104E-01 -584E-02 Goodness-of-fit measure 04155 Parameter set 1 -6245240430658412E-2 1280492624666799E-3 4792952200361109E-2 4324266278840409E-6 -
2071623966851869E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_20c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13594E+01 10290E-02 10665E+04 78300E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 121E-05 683E-06 651E-06 315E-05 560E-06 106E-04 Linear model Parameters for the fit were (b0 b1) -62452E-02 12805E-03
60
С3Н8 - measurement 1
Data setC3H8 The calibration data set is 1900E-01 7800E-05 9057E+03 1098E+01 2002E-01 7900E-05 9552E+03 8569E+00 2101E-01 7960E-05 1007E+04 4049E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10529E-02 19831E-05 34552E-03 36109E-07 -12465E-09 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11642E-02 19714E-05 23073E-03 23522E-07 -54231E-10 Remaining SSD is 19453 Weighted distances x-value x-dist y-dist 100E+00 190E-01 -239E-01 666E-01 200E+00 200E-01 487E-01 -104E+00 300E+00 210E-01 -247E-01 248E-01 Goodness-of-fit measure 10414 Parameter set 1 1164239985182795E-2 1971441115316992E-5 2307269625077337E-3 2352198415608386E-7 -
5423119774765299E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19837E-01 14840E-04 94718E+03 45610E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
10
Discussion and Conclusions All laboratories find the gravimetric value within plusmn07 relative to the gravimetric value This holds for all three components COCO2 and C3H8 in nitrogen This is a satisfying result For all laboratories the observed difference between the gravimetric and reported values does not exceed its combined uncertainty VNIIM and BAM are link laboratories for CCQM-K3 The results of this comparison are linked to the key comparison CCQM-K3 Reference [1] International Organization for Standardization ISO 61422001 Gas analysis - Preparation of calibration gas mixtures - Gravimetric methods 2nd edition [2] International Organization for Standardization ISO 61432001 Gas analysis ndash Comparison methods for determining and checking the composition of calibration gas mixtures [3] Van der Veen AMH De Leer EWB Perrochet J-F Wang Lin Zhen Heine H-JKnopf D Richter W Barbe J Marschal A Vargha G Deaacutek E Takahashi C Kim JS Kim YD Kim BM Kustikov YA Khatskevitch EA Pankratov VV Popova TA Konopelko L Musil S Holland P Milton MJT Miller WR Guenther FR International Comparison CCQM-K3 Final Report Coordinator Leonid Konopelko VNIIM Research Department for the State Standard in the Field of Physical-Chemical Measurements (PCD) 19 Moskovsky pr St-Petersburg 198005 Russia Phone +7 812 3151145 Fax +7 812 3279776 E-mail lkonopmailrcomru Completion Date March 2006
11
Annex 1 Proposal of Degrees of Equivalence Table 5 Degrees of Equivalence for carbon monoxide Lab j VNIIM Ukrmetrteststandard BelGIM BAM Lab i Di Ui Dij Uij Dij Uij Dij Uij Dij Uij mmolmol mmolmol mmolmol mmolmol mmolmol VNIIM 001 006 012 014 007 021 005 016 Ukrmetrteststandard -011 012 -012 014 -005 024 -007 019 BelGIM -006 020 -007 021 005 024 -002 025 BAM -004 015 -005 016 007 019 0016 025 Table 6 Degrees of Equivalence for carbon dioxide Lab j VNIIM Ukrmetrteststandard BelGIM BAM Lab i Di Ui Dij Uij Dij Uij Dij Uij Dij Uij mmolmol mmolmol mmolmol mmolmol mmolmol VNIIM 012 013 026 026 -074 101 0034 043 Ukrmetrteststandard -014 022 -026 026 -10 102 -023 046 BelGIM 086 100 074 101 10 102 077 108 BAM 009 041 -0034 043 023 046 -077 108 Table 7 Degrees of Equivalence for propane Lab j VNIIM Ukrmetrteststandard BelGIM BAM Lab i Di Ui Dij Uij Dij Uij Dij Uij Dij Uij mmolmol mmolmol mmolmol mmolmol mmolmol VNIIM 0001 0004 0002 0006 0005 0020 -0009 0013 Ukrmetrteststandard -0001 0004 -0002 0006 0003 0021 -0011 0013 BelGIM -0004 0020 -0005 0020 -0003 0021 -0014 0023 BAM 0010 0012 0009 0013 0011 0013 0014 0023
12
Annex 2 Results and measurement reports as submitted by participating laboratories Key comparison participants
MEASUREMENT REPORT - DI Mendeleyev Institute for Metrology
Russian Federation (VNIIM)
I Results of Study
Laboratory DI Mendeleyev Institute for Metrology (VNIIM) Research Department for the State Standard in the Field of Physical-Chemical Measurements (PCD)
Instruments Multichannel automatic NDIR analyzer included to the set of the National Primary measurement standard of units of mole fraction and mass concentration of components in gas medium GET 154-01 was used for the analysis Calibration Standards All calibration multicomponent gas mixtures were prepared gravimetrically according to ISO 6142 The calibration multicomponent gas mixtures were prepared from pure gases directly on components CO CO2 and from pre-mixtures which were prepared from pure gases on component С3Н8 The content of the impurities in all pure gases was determined by GC with helium-ionization flame-ionization and thermal-conductivity detectors as well as standard hygrometer apparatus included to the standard complex A1 of analysis of pure gases and substances from GET 154-01 The calibration multicomponent gas mixtures were verified with usage of existing gravimetric gas mixtures in accordance with ISO 6143 Composition of calibration standards
Cylinder 6547 Cylinder 6571 Cylinder 6538 Component x мольmol Standard
Instrument Calibration Three independent measurements were carried out under repeatability conditions Before each measurement an instrument calibration was made One measurement contained 5 submeasurements Sample Handling The time of the cylinder keeping is 24 hrs It was used the automatic unit of commutation for inputting gas mixtures
15
Uncertainty Uncertainty table СО2
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas
mixture
B 0010 1 0010
Analysis A B 0048 1 0048
Coverage factor 2 Expanded uncertainty 01 Uncertainty table СО
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas
mixture
B 002 1 002
Analysis A B 0095 1 0095
Coverage factor 2 Expanded uncertainty 019
16
Uncertainty table С3Н8 Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas
mixture
B 005 1 005
Analysis A B 0045 1 0045
Coverage factor 2 Expanded uncertainty 013
17
MEASUREMENT REPORT ndash Belorussian State Institute for Metrology Belarus (BelGIM)
I Results of experimental study
Laboratory Belarus BelGIM Section for physicochemical and optical measurements sector for standards and gas mixtures 8 Serova st Minsk Cylinder No 0128 9 dm3 aluminium NOMINAL COMPOSITION - Carbon dioxide 13middot10-2 - 14middot10-2 molmol - Carbon oxide 28middot10-2 - 32middot10-2 molmol - Propane 19middot10-4 - 21middot10-4molmol - Nitrogen Residual
Measurement No1 Date
Result (molmol)
x_
Standard deviation
S( x_
) rel
No of observations
n
Carbon dioxide 17062005 13567middot10-2 0096 6
Carbon oxide 17062005 2957middot10-2 014 6
Propane 17062005 1977middot10-4 015 6
Measurement No2 Date
Result (molmol)
x_
Standard deviation
S( x_
) rel
No of observations
n
Carbon dioxide 21062005 13564middot10-2 004 6
Carbon oxide 21062005 2957middot10-2 02 6
Propane 21062005 1979middot10-4 01 6
18
Measurement No3 Date
Result (molmol)
x_
Standard deviation
S( x_
) rel
No of observations
n
Carbon dioxide 23062005 13537middot10-2 007 6
Carbon oxide 23062005 2955middot10-2 01 6
Propane 23062005 1982middot10-4 01 6
Final results
Gas mixture Result
(molmol)
Coverage factor
Expanded uncertainty (molmol)
Carbon dioxide 136middot10-2 2 01 middot10-2
Carbon oxide 296middot10-2 2 002middot10-2
Propane 198middot10-4 2 02middot10-4
II Description of study Apparatus (principle of operation type configuration data collection etc)
Measurements were carried out using gas chromatograph Crystal 2000М (hereinafter
referred to as chromatograph) combined with thermal conductivity detector (hereinafter referred to as TCD) with detection limit of 510-9 gml for propane and flame-ionization detector (hereinafter referred to as FID) with detection limit of 510-12 gs for propane
Computers and software Chromatech Analytic version 121 were used to control chromatograph and collect and process chromatographical data
For the purpose of measurements the following auxiliary devices and materials were used
1 Two-position doser with 10 ports and with doses of 025 cm3 for FID channel and with doses of 025 cm3 for TCD channel (hereinafter referred to as doser)
2 Metallic packed column 3m х 3mm х 2mm - HayeSep N 80100 metallic packed column 1m х 4mm х 2mm-CaA 016025 (TCD channel) capillary column HP PLOTQ 30m х 0536mm (FID channel)
3 Aneroid BАММ-1 with a measurement range of 80-106 kPа and accuracy of plusmn 02 kPа
4 Mercurial thermometer ТL-4 with a measurement range of 0-50ordmС and scale division of 01ordmС
19
5 Fine adjustment valve (hereinafter referred to as FAV) provided to transport a gas sample into chromotograph and set to gas flow-rate of 10-15 mlmin
6 Foamy gas flow meter type YIRG - 2А accuracy of flow measurement plusmn 1 сm3min
7 Helium gas Type A according to TU 51-940-80 8 High purity hydrogen gas according to TU 301-07-27-90 9 Compressed air 10 Multicomponent calibration gas mixtures (hereinafter referred to as CGM)
produced and certified by gravimetric method
Calibration reference materials - calibration gas mixtures used for measurements 1 Quantitative composition of KGS is determined using gravimetric method defined in
ISO 61422001 by calculating weight of each component of a gas mixture The content of CGM components is expressed as a mole fraction Uncertainty of KGS composition is expressed as expanded uncertainty with coverage factor k = 2 Molar masses of components and their uncertainties are taken from ISO 149122003 Performance and metrological characteristics of the equipment used for gravimetric preparation of mixtures are given in Table 1
Table 1
Description of the equipment
Manufacturer Metrological characteristics
Mass-comparator balance type КА10-3Р
Mettler-Toledo
Switzerland
Maximum load 15 kg Scale division 1 mg Standard deviation 19 mg at load of 10 kg Operating temperature range +10divide30degС Maximum temperature change within 1 h plusmn05 degС
Gas mixer type USG 00001 BelGIM
Measurement range 000025 divide 100 МPa Accuracy class for manometers ndash 015 Accuracy class for vacuummeters ndash 025 Vacuummeter with pressure sensor for measuring the residual pressure before filling Residual pressure before filling of each component not more than 20 Pa
2 Purity analysis of primary gas standards
The purity analysis of primary gas standards is based on the information provided by the supplier or on the results of determination of impurity in pure gases using measurement procedure developed inside BelGIM
20
If an analytical method laid down in 43 of ISO 61422001 cannot be used for impurity determination mole fraction of an expected impurity is assumed to be half of the detection limit of the analytical method The content of the undetected impurity produces rectangular distribution
whereby its standard uncertainty is calculated as half of the detection limit divided by 3 The composition of the pure gases used for preparation of calibration mixtures is given
in Table 2 Table 2 - Metrological characteristics of pure gases
N2 999967 00005 Nitrogen Cylinder 40 dm3 Origin Russia O2 00033 00005 Propane Cylinder 2 dm3 Origin Russia
C3H8 9979 0017
3 After preparation of mixture the cylinder was maintained in laboratory room within
24 hours the mixture then was homogenized on the stand by rotating on the rollers within 4-5 hours The chromotograph for CGM was calibrated 2-3 days after its preparation
Calibration of the chromotograph
1 The chromotograph was calibrated using CGMs with composition identical to the analyzed sample The content of each component and its expanded uncertainty (k = 2) are given in Table 1 Table 1 - Calibrationе gas mixtures
2 Number of observations of each calibration sample- 3 Number of calibration samples - 3
3 The analytical function used for determination of the content of the analyzed sample components is as follows
x (y) =b1y+b0 (2) Where x ndash determined content molmol y - chromotograph response for the specific component b1- slope b0 - intercept 4 After completion of calibration the coefficients of analytical function were
calculated according to ISO 61432001 using generalized least-squares method Also the uncertainties of the intercept and slope and covariance between them were calculated After determination of parameters which are part of analytical function and which affect the uncertainty of measurements it was checked whether the analytical function is fit to the experimental data obtained in calibration and subsequently whether the analytical function is applicable
Results of calibration measurements coefficients of analytical function their uncertainties covariance and measure of goodness-of-fit Г (maximum value of the weighted differences of the experimental points and calculated points of the analytical function for each measurement run) are given in Tables 3 and 4 respectively Chromotograph operating conditions in calibration and analysis are given in Table 5
Table 3 - Results of experimental study
Date Component of
calibration mixture
Content x mole fraction
Expanded uncertainty
U(x) mole fraction
Mean of peak area y
mVs
Uncertainty )(yu
mVs
13374 0004 1279500 141 1389 0004 1329150 2899 CO2
12833 0004 1231000 849 2916 0005 404070 240
316 0005 437705 926 CO 2768 0004 383070 467
019 0002 3143200 4101
1706 2005
C3H8 0202 0002 3319150 2051
22
0181 0002 2948750 212 13374 0004 1269833 624
1389 0004 1321000 1272 CO2 12833 0004 1223900 1698
2916 0005 399490 612 316 0005 434010 863 CO
2768 0004 379660 410 019 0002 3157867 6772
0202 0002 3332400 3394
2106 2005
C3H8 0181 0002 2959900 4950
13374 0004 1277100 2152 1389 0004 1329900 2828 CO2
12833 0004 1229100 1980 2916 0005 400330 529
316 0005 434745 969 CO 2768 0004 379695 106
019 0002 3142433 9416 0202 0002 3321600 4101
2306 2005
C3H8 0181 0002 2961000 3111
According to ISO 61432003 calculation of the measure of goodness-of-fit Г is the maximum value of the weighed differences between the coordinates of measured and adjusted calibration points is an effective and simple method to test the compatibility of а prospective analytical function A function is admissible if Г le 2
minus
minus=
)(ˆ
)(ˆ
iii
iii
yuyy
xuxxΓ
(4) Where хi is the reference value of the content of calibration sample component
ix is the CGM component content obtained using the calculated analytical function
уi is the experimental response to the reference content of component iy is the response obtained in calculation of analytical function
u (хi) u (уi) are the uncertainties of reference contents and responses to these contents respectively
i is the number of calibration points i=1 3 This prerequisite is equivalent to the requirement that the curve of calculated response should cross each experimental calibration rectangular [хi plusmn 2u(хi) уi plusmn 2и(уi)] based on an expanded uncertainty U = ku with coverage factor k = 2 Table 4 Calculations of analytical function
Date Component Analytical function parameters
Uncertainty of analytical
function parameters
Covariance of
parameters Г
23
b1 b0 u(b1) u(b0) u(b0b1) 1706 11086E-
03 -81128E-
0119491E-
0524883E-
01 -48497E-06 10544
2106 10729E-03
-26126E-01
22698E-05
28930E-01 -65652E-06 19997
2306
CO2 10593E-
03 -17688E-
0135807E-
0545413E-
01 -16254E-05 10022
1706 71537E-04
26507E-02
14231E-05
57044E-02 -81115E-07 03017
2106 72346E-04
22401E-02
13819E-05
54490E-02 -75209E-07 05935
2306
CO 71321E-
04 60080E-
0212663E-
0549016E-
02 -62026E-07 01341
1706 56521E-06
13712E-02
38279E-07
12015E-02 -45937E-09 12991
2106 56295E-06
13707E-02
39247E-07
12379E-02 -48529E-09 12905
2306
C3H8 58258E-
06 80469E-
0340085E-
0712590E-
02 -50407E-09 08589
Two columns separated by switching device are located one after another in TCD
channel One column is intended for carbon dioxide heavy hydrocarbons and another column is intended for light gases Before the first switch the light gases including carbon oxide flow through the first column without being separated and remain in the second column The switch makes them locked in the second column The analysis of carbon dioxide is carried out up to the second switch Second switch makes the second column unlocked and carbon oxide is analyzed Third switch is required to allow propane escape from a column and prevent it from getting into a second column The analysis of the very propane is carried out using FID Time intervals between switches were selected experimentally when developing the analysis method Such analysis method makes it possible to analyze all three components per one sample inject
Table 5 - Chromotograph operating conditions in calibration and analysis Parameter of the operating conditions Thermostating temperature of TCD and FID degС 170
Temperature of separation columns degС
Program 60 degС within 9 min
than rise to 160 degС at 20degСmin
Rate of flow of carrier gas through TCD channel columns mlmin 15
Rate of flow of carrier gas through TCD comparison channel mlmin 15
Pressure in FID channel column kPa Program
24
80 to 100 Rise from the 1st s of
analysis at 2 kPamin
Flow-rate of hydrogen FID mlmin 20 Flow-rate of air FID mlmin 200 Temperature of switching device degС 65 Response time of switching device s 1 110 2 330 3 540
TCD FID Volume of injected analyzed gas cm3 025 025 Carrier gas Helium Duration of analysis min 17 Calculation of the content of comparison sample components and its uncertainty Results of comparison sample measurements are given in Table 6 Table 6 - Results of comparison sample measurements
1 The content of comparison sample component and its uncertainty were determined
using calculated analytical function according to ISO 61432001 as follows (5) Where G(y)=b1y+b0 is the calculated analytical function и(y) is the standard uncertainty of response y u2(bj) is the variance of analytical function parameter bj
u(bj bI) is the covariance of analytical function parameters bj bI N is the number of function coefficients N=2 j=0 1
sum sumsumminus
= +==
partpart
partpart
+
partpart
+
partpart
=1
0 1
2
2
0
22
)(2)()()(N
jIj
N
jI Ijj
N
j j
bbubG
bGbu
bGyu
yGxu
25
After substitution of analytical function (2) and transformations the expression takes form (5)
)(2)()()()()( 01122
0222
1 bbyubuybuyubxu +++= (6) The contents of comparison sample components under determination and their
uncertainties were calculated using B_LEAST a computer program recommended in ISO 6143 Calculations are summarized in Table 6
Table 6 Calculations of the content of comparison sample components and their
2 The final content of a component was determined as an arithmetiс mean from three measurements Final standard uncertainty was calculated using formula as follows
22
222)( Адаватмтемсериикал uuuuuxu ++++= (7)
Where ucal is the uncertainty of the component content produced by
calibration of chromotograph urun is the uncertainty of the component content produced by
change of chromotograph response in each measurement run ut is the uncertainty of the component content produced by
change of an ambient temperature upressure is the uncertainty of the component content produced by
change of atmospheric pressure u A is the standard uncertainty of three measurement runs
21 Uncertainty of the component content produced by calibration of chromotograph
This uncertainty is calculated using formula (6) but the first term of the sum ie
)()( 221 yub which represents the standard uncertainty of the chromotograph response in a
measurement run is not taken into account Calculations are summarized in Table 7
26
Table 7 Calculation of uncertainty produced by calibration of chromotograph
Date u(b1) u(b0) u(b0b1) x
molmol y Ucal molmol
Ucal rel
1706 19491E-05
24883E-01
-48497E-06
13567middot10-
2129698
3 0005middot1
0-2 003
2106 22698E-05
28930E-01
-65652E-06
13564middot10-
2 128855 0007middot1
0-2 005
2306
CO2
35807E-05
45413E-01
-16254E-05
135374middot10-2
1294633
0016middot10-2 012
1706 14231E-05
57044E-02
-81115E-07 2957middot10-2 409633
0003middot10-2 009
2106 13819E-05
54490E-02
-75209E-07
29577middot10-
2 405663 0003middot1
0-2 01
2306
CO
12663E-05
49016E-02
-62026E-07 2955middot10-2 405882
0003middot10-2 01
1706 38279E-07
12015E-02
-45937E-09 1977middot10-4
3255817
007middot10-
2 038
2106 39247E-07
12379E-02
-48529E-09 1980middot10-4
3273329
008middot10-
2 038
2306
C3H8
40085E-07
12590E-02
-50407E-09 1982middot10-4 32636
008middot10-
2 04 The total estimate of relative uncertainty produced by calibration of chromotograph was
calculated for each component as follows
3
3
1
2sum=
cali
cali
uu (8)
Where ucal i is the relative uncertainty produced by calibration of chromotograph and calculated for each measurement run
The calculations are summarized in Table 8
Table 8 Uncertainty produced by calibration of chromotograph
Component Ucal rel
CO2 008 CO 01
C3H8 04 22 Uncertainty of the component content produced by change of chromotograph response in each measurement run This uncertainty is calculated using the equation (6) whereby the first term of the sum
only ie )()( 221 yub which represents the standard uncertainty of the chromotograph
response in a measurement run is taken into account Calculations are summarized in Table 9
27
Table 9 Calculation of uncertainty produced by change of chromotograph response in each measurement run
The total estimate of relative uncertainty produced by change of chromotograph
response in each measurement run was calculated for each component as follows
3
3
1
2sum=
run
run
uu (9)
Where urun is the relative uncertainty produced by change of chromotograph response in each measurement run Calculations are summarized in Table 10
Table 10 Uncertainty produced by change of chromotograph response in each measurement
run
Component Urun rel
CO2 007 CO 015
C3H8 012 23 Uncertainty of the component content produced by change of temperature in a room
The recorded change of temperature in measurements is plusmn 05 degree The contribution of uncertainty type B (rectangular distribution) is estimated as follows
201003
12931
=sdotsdot=tu rel
28
24 Uncertainty of the component content produced by change of atmospheric pressure The recorded change of atmospheric pressure within three days was
05 kPа The contribution of uncertainty type B (rectangular distribution) is estimated as follows
2801003
13101
50=sdotsdot=pressureu rel
25 Standard deviation of 3 measurement runs Standard deviation is calculated as follows
isu p
A
2
= (10)
Where S2p is the group experimental variation
The group experimental variation is calculated as follows
(11)
Where si
2 is the experimental variation of measurement run i from independent repeated observations ni having freedom degrees
νi = n - 1 n=6 i= 3 Calculations are summarized in Table 11 Table 11 Calculations of standard uncertainty of 3 measurement runs
Date 2iS x
molmol 2iS
rel uA
rel
1706 2953E-05 13567middot10-2 000022
2106 588987E-06 13564middot10-2 0000043
2306
CO2 141137E-
05 135374middot10
-2 000010
0006
1706 225604E-06 2957middot10-2 0000077
2106 681346E-06 29577middot10-2 000023
2306
CO
175166E-06 2955middot10-2 0000060
0006
1706 C3H8 130158E-
08 1977middot10-4 00000066 0001
ss
p
i ii
N
ii
N2
2
1
1
= =
=
sum
sum
ν
ν
29
2106 44616E-09 1980middot10-4 00000023
2306
381032E-09 1982middot10-4 00000019
26 Total standard uncertainty
Uncertainty estimation СО2
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph ucal Normal 008 1 008
Change of temperature ut Rectangular 02 1 02 Change of atmospheric pressure upressure Rectangular 028 1 028
Changes of chromotograph response
urun Normal 007 1 007
Standard deviation of 3 runs uA Normal 0006 1 0006
Relative total standard uncertainty 036 Coverage factor k=2 Expanded uncertainty 01middot10-2 molmol Uncertainty estimation СО
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph ucal Normal 01 1 01 Change of temperature ut Rectangular 02 1 02 Change of atmospheric pressure upressure Rectangular 028 1 028 Changes of chromotograph response
urun Normal 015 1 015
Standard deviation of 3 runs uA Normal 0006 1 0006
Relative total standard uncertainty 039 Coverage factor k=2 Expanded uncertainty 002middot10-2 molmol Uncertainty estimation С3Н8
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph 04 Normal 04 1 008
30
Change of temperature 02 Rectangular 02 1 02 Change of atmospheric pressure 028 Rectangular 028 1 028
Changes of chromotograph response
012 Normal 012 1 007
Standard deviation of 3 runs 0001 Normal 0001 1 0006
Relative total standard uncertainty 054 Coverage factor k=2 Expanded uncertainty 02middot10-4 molmol
Sample handling
Period for exposure of cylinder to measurement conditions and method how to transport sample to the device
1 Stands for storing gas standard cylinders and calibration mixture cylinders and chromotograph are placed in a laboratory room which is not accessible to unauthorized persons The laboratory is equipped with air-conditioner to maintain required temperature and humidity on a continuous basis and some auxiliary measuring instruments as thermometer psychrometric hygrometer and aneroid to control temperature humidity and atmospheric inside the room
2 The comparison sample cylinder was stored in laboratory from the date of its
delivery to Minsk on 25042005 CGM cylinders are stored horizontally on racks and positioned vertically using special support when measurements are carried out
3 The analyzed gas sample is transported through the fine adjustment valve (FAV)
Conjunctions Cylinder - FAV FAV - tube tube - doser are made of metal and use adapters with spherical ends and bushes FAV is made of brass tube is made of copper and doser is made of duralumin
Instrument(s) (principles make type configuration data collection etc) For the analysis a GC were used with specifically applications For the determination of (Nitrogen (N2)) Carbon Dioxide (CO2) Carbon Monoxide (CO) and Propane (C3H8) balance GC Perkin Elmer AutoSystem XL (two channel system) with a stream selection valve for 4 streams and 2 gas sampling valves
Channel A for the determination of N2 CO and CO2 Carrier Gas Helium Columns Column system with two packed columns (6 ft x 18rdquo Porapak R 80100 mesh and 6 ft x 18rdquo Mol-Sieve 13X 80100 mesh) Oven Temperature 960 degC to 180 degC Detector micro-TCD Data Collection Total Chrom Workstation Channel B for the determination of C3H8 Carrier Gas Helium Columns Capillary column 50 m x 032 microm LP-SIL-8-CB Oven Temperature 60 degC to 180 degC Detector FID Data Collection Total Chrom Workstation
34
Calibration Standards
Calibration Standards for the measurements (preparation method purity analyses estimated uncertainty etc)
All standards were prepared individually according to ISO 6142 rdquoGas analysis - Preparation of calibration gases - Gravimetric Methodrdquo
Depending on the concentration of the components standards were prepared individually from pure gases or from pre-mixtures which were individually prepared from pure gases
The content of the impurities in all pure gases were determined before use by GC-DID GC-FID and or GC-TCD
After preparation the standards were verified by analytical comparisons against existing gravimetrically prepared standards Only when no significant difference between the analysed and the calculated gravimetric composition is found the ldquonew prepared candidate rdquo is accepted as a new standards
For the analysis of all components multi component standards with nitrogen as balance gas were used
Composition of calibrants BAM C49250-050722 Component Assigned value( x)
mmol mol Standard uncertainty (u(x)) relativ (k=2)
Calibration procedure (mathematical modelcalibration curve number and concentrations of standards measurement sequence temperaturepressure correction etc)
For the instrument calibration the bracketing technique was used The fraction of the current used standards deviated no more than +10rel and -10rel respectively from those of the sample
Measurement sequence
Sample Handling
How were the cylinders treated after arrival (eg stabilized) and how were samples transferred to the instrument (automatic high pressure mass-flow controller dilution etc) After heating (45 - 50 degC) the cylinder for 8 hours the cylinder were rolled about 16 hours before analysis was started Each cylinder was equipped with a pressure regulator that was purged three times by sequential evacuation and pressurisation with the gas mixture used Continous flow (2 ndash 3mlmin) through the sample loop
Uncertainty The specification of potential uncertainty sources is given in Annex 3
3 injection standard (high)
3 injection sample
3 injection standard (high)
3 injection sample
3 injection standard (low)
3 injection sample
3 injection standard (low)
3 injection standard (low)
36
Uncertainty table CO2
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 002 rel 1 002 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 03 rel
Uncertainty table CO
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 007 rel 1 007 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 05 rel
37
Uncertainty table C3H8
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 010 rel 1 001 rel
Analysis normal 028 rel 1 028 rel
Coverage factor 2
Expanded uncertainty 06 rel
Optional
You may provide additional data like the raw measurement data information on your
measurement procedure chromatograms etc
38
Appendix 3 SPECIFICATION OF POTENTIAL UNCERTAINTY SOURCES
a Uncertainty related to the balance and the weights Resolution of balance Accuracy of balance including linearity Incorrect zero point Drift (thermal and time effects) Instability due to draught Location of cylinder on the balance pan Uncertainties in the weights used Buoyancy effects on the weights used
b Uncertainties related to the gas cylinder Mechanical handling of cylinder
Loss of metal paints or labels from surface of cylinder Loss of metal from threads of valvefitting Dirt on cylinder valves or associated fitting
Absorptiondesorption effects on the external cylinder surface Buoyancy effects on the cylinder itself
Cylinder temperature differs from surrounding air due to eg filling with gas Change of cylinder volume during filling Change of density of surrounding air due to changes in temperature air pressure humidity and carbon dioxide content
Uncertainty in determination of external cylinder volume c Uncertainties related to the component gases Residual gas in cylinder Leakage Leakage of air into the cylinder after evacuation
Leakage of gas from the cylinder valve during filling Escape of gas from cylinder into transport lines
Gas remaining in transfer system when weight loss method is used Absorptionreaction of components on internal cylinder surface Reaction between components Impurities in all the initial gases Insufficient homogenization Uncertainty of molecular mass d Uncertainties related to the analysis
Repeatability and selectivity of the analyzer Appropriateness of the calibration curve
39
MEASUREMENT REPORT - All Ukrainian State Research-Industrial Center of Standardization Metrology Certification and Protection of Consumers Ukraine
gas ndash helium flow rate 15 cm3min detector TCD tdetector = 250 ordmС toven = 70 ordmС It was automatic data collection
Measurement and Calibration Methods Laboratory Measurement method Type of calibration curve
GCFID (С3Н8) 3 points linear Ukrmetrteststandard GCTCD (СО СО2) 3 points linear
GCFID ndash gas-chromatographic with flame-ionization detector GCTCD - gas-chromatographic with thermal-conductivity detector
42
Calibration Standards
Calibration standards ndash primary standard gas mixtures (PSGM) used for measurements by comparison method
PSGM-1 Cylinder 0116
PSGM-2 Cylinder 0107
PSGM-3 Cylinder 0093 Composition
x u(x) x u(x) x u(x) СО 27874 00015 29899 00015 31891 00015 СО2 130187 00015 144456 00016 137016 00016 С3Н8 019003 000008 020017 000008 021013 000008 N2 balance balance balance
Note x ndash mole fraction u(x) ndash absolute standard uncertainty
It was used gravimetric method of preparation of PSGM Electronic balance КА-20-3 of Mettler Toledo max limit of weighing is 20 kg least
limit of weighing is 01 g standard deviation is 0006 g Analysis of purity of parent gases was carried out with usage of chromatographs
НР6890N with helium ndash ionization detector flame ndash ionization detector thermal ndash conductivity detector and mass ndash spectrometric detector as well аs gas analyzers GIAM-15M and Onix condensate-thermometer hygrometer TOROS-3-2B
Calculation of uncertainties was carried out according to ISO 6142-2003 Corrections of temperature pressure and humidity of environment were considered
in calculations according to ISO 6142-2003 (program of ISO-6142 2000-03-17 designer is NMi) Protocols and explanations are in Annex A
Instrument (Comparator) Calibration Calibration of comparator ndash gas chromatograph HP 6890 was carried out with usage
of PSGM Measurement sequence PSGM -1 х 3 PSGM -2 х 3 COOMET gas mixture х 3 PSGM -2 х 3 PSGM -3 х 3 It is necessary to use PSGM-2 repeatedly for estimation of reproducibility of results
Program B_LEAST recommended by ISO 6143-2003 was used for constructing the curve Mathematical model of calibration curve is linear one
Sample Handling The cylinder was kept for 24 hrs at a room where comparators were disposed This room is a thermostatic room with t = (20plusmn2) ordmС
43
A method of sample input to a comparator is a method with flow stabilization Uncertainty The following uncertainties were included to the budget of uncertainty - uncertainty of the balance - uncertainties of impurities in parent gases Contribution from other uncertainty sources was insignificant A cabin of the balance is thermostatically The balance is the one-pan balance
Air transfer is absent in the cabin of the balance Drift of the balance is absent for PSGM preparation
Contribution from other uncertainty sources was considered in software according to ISO 6142-2003
Uncertainties related to the analysis (comparison) were considered in software according to ISO 6143-2003 and enclosed in Annex B
Uncertainty table СО2
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas mixture
B 001 1 001
Analysis A B 008 1 008
Coverage factor 2 Expanded uncertainty 002sdot10-2 molmol Uncertainty table СО
Protocols of analysis (comparison) in accordance with ISO 6143-2003
57
Explanation of protocols of comparison
Chapter I ldquoThe calibration data set isrdquo contains columns 1 mole fraction of a component 2 absolute standard uncertainty of mole fraction of a component 3 a signal of a comparator 4 absolute standard uncertainty of a comparator signal
Chapter II ldquoResults of ISO 6143 methodrdquo contains parameters of a calibration curve including its
uncertainty
Chapter ІІІ ldquoPart II Processing of datardquo contains columns
1 calc x - the results of comparison mole fraction of a component 2 u(x) - absolute standard uncertainty of mole fraction of a component 3 response y - a signal of a comparator 4 u(y) - absolute standard uncertainty of a comparator signal
58
СО2 - measurement 1 Data setCO2_21 The calibration data set is 1302E+01 1510E-03 1022E+04 1820E+00 1370E+01 1560E-03 1077E+04 2730E+00 1445E+01 1620E-03 1135E+04 5900E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 20331E-02 12711E-03 12573E-01 11653E-05 -14638E-06 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 10548E-02 12722E-03 31762E-02 28898E-06 -91698E-08 Remaining SSD is 74346 Weighted distances x-value x-dist y-dist 100E+00 130E+01 490E-01 -755E-01 200E+00 137E+01 -103E+00 228E+00 300E+00 144E+01 539E-01 -250E-01 Goodness-of-fit measure 22837 Parameter set 1 1054788657490729E-2 1272208026684145E-3 3176237146276368E-2 2889798108124711E-6 -
9169821653851327E-8 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_21c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13577E+01 25542E-03 10664E+04 15200E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 547E-06 328E-06 316E-06 784E-06 286E-06 652E-06 Linear model Parameters for the fit were (b0 b1) 10548E-02 12722E-03
59
СО2 - measurement 2
Data setCO2_20 The calibration data set is 1302E+01 1512E-03 1021E+04 4723E+00 1370E+01 1563E-03 1075E+04 1600E+00 1445E+01 1620E-03 1133E+04 7300E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -38760E-02 12784E-03 26817E-02 24890E-06 -66689E-08 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -62452E-02 12805E-03 47930E-02 43243E-06 -20716E-07 Remaining SSD is 03231 Weighted distances x-value x-dist y-dist 100E+00 130E+01 107E-01 -415E-01 200E+00 137E+01 -212E-01 283E-01 300E+00 144E+01 104E-01 -584E-02 Goodness-of-fit measure 04155 Parameter set 1 -6245240430658412E-2 1280492624666799E-3 4792952200361109E-2 4324266278840409E-6 -
2071623966851869E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_20c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13594E+01 10290E-02 10665E+04 78300E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 121E-05 683E-06 651E-06 315E-05 560E-06 106E-04 Linear model Parameters for the fit were (b0 b1) -62452E-02 12805E-03
60
С3Н8 - measurement 1
Data setC3H8 The calibration data set is 1900E-01 7800E-05 9057E+03 1098E+01 2002E-01 7900E-05 9552E+03 8569E+00 2101E-01 7960E-05 1007E+04 4049E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10529E-02 19831E-05 34552E-03 36109E-07 -12465E-09 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11642E-02 19714E-05 23073E-03 23522E-07 -54231E-10 Remaining SSD is 19453 Weighted distances x-value x-dist y-dist 100E+00 190E-01 -239E-01 666E-01 200E+00 200E-01 487E-01 -104E+00 300E+00 210E-01 -247E-01 248E-01 Goodness-of-fit measure 10414 Parameter set 1 1164239985182795E-2 1971441115316992E-5 2307269625077337E-3 2352198415608386E-7 -
5423119774765299E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19837E-01 14840E-04 94718E+03 45610E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
11
Annex 1 Proposal of Degrees of Equivalence Table 5 Degrees of Equivalence for carbon monoxide Lab j VNIIM Ukrmetrteststandard BelGIM BAM Lab i Di Ui Dij Uij Dij Uij Dij Uij Dij Uij mmolmol mmolmol mmolmol mmolmol mmolmol VNIIM 001 006 012 014 007 021 005 016 Ukrmetrteststandard -011 012 -012 014 -005 024 -007 019 BelGIM -006 020 -007 021 005 024 -002 025 BAM -004 015 -005 016 007 019 0016 025 Table 6 Degrees of Equivalence for carbon dioxide Lab j VNIIM Ukrmetrteststandard BelGIM BAM Lab i Di Ui Dij Uij Dij Uij Dij Uij Dij Uij mmolmol mmolmol mmolmol mmolmol mmolmol VNIIM 012 013 026 026 -074 101 0034 043 Ukrmetrteststandard -014 022 -026 026 -10 102 -023 046 BelGIM 086 100 074 101 10 102 077 108 BAM 009 041 -0034 043 023 046 -077 108 Table 7 Degrees of Equivalence for propane Lab j VNIIM Ukrmetrteststandard BelGIM BAM Lab i Di Ui Dij Uij Dij Uij Dij Uij Dij Uij mmolmol mmolmol mmolmol mmolmol mmolmol VNIIM 0001 0004 0002 0006 0005 0020 -0009 0013 Ukrmetrteststandard -0001 0004 -0002 0006 0003 0021 -0011 0013 BelGIM -0004 0020 -0005 0020 -0003 0021 -0014 0023 BAM 0010 0012 0009 0013 0011 0013 0014 0023
12
Annex 2 Results and measurement reports as submitted by participating laboratories Key comparison participants
MEASUREMENT REPORT - DI Mendeleyev Institute for Metrology
Russian Federation (VNIIM)
I Results of Study
Laboratory DI Mendeleyev Institute for Metrology (VNIIM) Research Department for the State Standard in the Field of Physical-Chemical Measurements (PCD)
Instruments Multichannel automatic NDIR analyzer included to the set of the National Primary measurement standard of units of mole fraction and mass concentration of components in gas medium GET 154-01 was used for the analysis Calibration Standards All calibration multicomponent gas mixtures were prepared gravimetrically according to ISO 6142 The calibration multicomponent gas mixtures were prepared from pure gases directly on components CO CO2 and from pre-mixtures which were prepared from pure gases on component С3Н8 The content of the impurities in all pure gases was determined by GC with helium-ionization flame-ionization and thermal-conductivity detectors as well as standard hygrometer apparatus included to the standard complex A1 of analysis of pure gases and substances from GET 154-01 The calibration multicomponent gas mixtures were verified with usage of existing gravimetric gas mixtures in accordance with ISO 6143 Composition of calibration standards
Cylinder 6547 Cylinder 6571 Cylinder 6538 Component x мольmol Standard
Instrument Calibration Three independent measurements were carried out under repeatability conditions Before each measurement an instrument calibration was made One measurement contained 5 submeasurements Sample Handling The time of the cylinder keeping is 24 hrs It was used the automatic unit of commutation for inputting gas mixtures
15
Uncertainty Uncertainty table СО2
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas
mixture
B 0010 1 0010
Analysis A B 0048 1 0048
Coverage factor 2 Expanded uncertainty 01 Uncertainty table СО
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas
mixture
B 002 1 002
Analysis A B 0095 1 0095
Coverage factor 2 Expanded uncertainty 019
16
Uncertainty table С3Н8 Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas
mixture
B 005 1 005
Analysis A B 0045 1 0045
Coverage factor 2 Expanded uncertainty 013
17
MEASUREMENT REPORT ndash Belorussian State Institute for Metrology Belarus (BelGIM)
I Results of experimental study
Laboratory Belarus BelGIM Section for physicochemical and optical measurements sector for standards and gas mixtures 8 Serova st Minsk Cylinder No 0128 9 dm3 aluminium NOMINAL COMPOSITION - Carbon dioxide 13middot10-2 - 14middot10-2 molmol - Carbon oxide 28middot10-2 - 32middot10-2 molmol - Propane 19middot10-4 - 21middot10-4molmol - Nitrogen Residual
Measurement No1 Date
Result (molmol)
x_
Standard deviation
S( x_
) rel
No of observations
n
Carbon dioxide 17062005 13567middot10-2 0096 6
Carbon oxide 17062005 2957middot10-2 014 6
Propane 17062005 1977middot10-4 015 6
Measurement No2 Date
Result (molmol)
x_
Standard deviation
S( x_
) rel
No of observations
n
Carbon dioxide 21062005 13564middot10-2 004 6
Carbon oxide 21062005 2957middot10-2 02 6
Propane 21062005 1979middot10-4 01 6
18
Measurement No3 Date
Result (molmol)
x_
Standard deviation
S( x_
) rel
No of observations
n
Carbon dioxide 23062005 13537middot10-2 007 6
Carbon oxide 23062005 2955middot10-2 01 6
Propane 23062005 1982middot10-4 01 6
Final results
Gas mixture Result
(molmol)
Coverage factor
Expanded uncertainty (molmol)
Carbon dioxide 136middot10-2 2 01 middot10-2
Carbon oxide 296middot10-2 2 002middot10-2
Propane 198middot10-4 2 02middot10-4
II Description of study Apparatus (principle of operation type configuration data collection etc)
Measurements were carried out using gas chromatograph Crystal 2000М (hereinafter
referred to as chromatograph) combined with thermal conductivity detector (hereinafter referred to as TCD) with detection limit of 510-9 gml for propane and flame-ionization detector (hereinafter referred to as FID) with detection limit of 510-12 gs for propane
Computers and software Chromatech Analytic version 121 were used to control chromatograph and collect and process chromatographical data
For the purpose of measurements the following auxiliary devices and materials were used
1 Two-position doser with 10 ports and with doses of 025 cm3 for FID channel and with doses of 025 cm3 for TCD channel (hereinafter referred to as doser)
2 Metallic packed column 3m х 3mm х 2mm - HayeSep N 80100 metallic packed column 1m х 4mm х 2mm-CaA 016025 (TCD channel) capillary column HP PLOTQ 30m х 0536mm (FID channel)
3 Aneroid BАММ-1 with a measurement range of 80-106 kPа and accuracy of plusmn 02 kPа
4 Mercurial thermometer ТL-4 with a measurement range of 0-50ordmС and scale division of 01ordmС
19
5 Fine adjustment valve (hereinafter referred to as FAV) provided to transport a gas sample into chromotograph and set to gas flow-rate of 10-15 mlmin
6 Foamy gas flow meter type YIRG - 2А accuracy of flow measurement plusmn 1 сm3min
7 Helium gas Type A according to TU 51-940-80 8 High purity hydrogen gas according to TU 301-07-27-90 9 Compressed air 10 Multicomponent calibration gas mixtures (hereinafter referred to as CGM)
produced and certified by gravimetric method
Calibration reference materials - calibration gas mixtures used for measurements 1 Quantitative composition of KGS is determined using gravimetric method defined in
ISO 61422001 by calculating weight of each component of a gas mixture The content of CGM components is expressed as a mole fraction Uncertainty of KGS composition is expressed as expanded uncertainty with coverage factor k = 2 Molar masses of components and their uncertainties are taken from ISO 149122003 Performance and metrological characteristics of the equipment used for gravimetric preparation of mixtures are given in Table 1
Table 1
Description of the equipment
Manufacturer Metrological characteristics
Mass-comparator balance type КА10-3Р
Mettler-Toledo
Switzerland
Maximum load 15 kg Scale division 1 mg Standard deviation 19 mg at load of 10 kg Operating temperature range +10divide30degС Maximum temperature change within 1 h plusmn05 degС
Gas mixer type USG 00001 BelGIM
Measurement range 000025 divide 100 МPa Accuracy class for manometers ndash 015 Accuracy class for vacuummeters ndash 025 Vacuummeter with pressure sensor for measuring the residual pressure before filling Residual pressure before filling of each component not more than 20 Pa
2 Purity analysis of primary gas standards
The purity analysis of primary gas standards is based on the information provided by the supplier or on the results of determination of impurity in pure gases using measurement procedure developed inside BelGIM
20
If an analytical method laid down in 43 of ISO 61422001 cannot be used for impurity determination mole fraction of an expected impurity is assumed to be half of the detection limit of the analytical method The content of the undetected impurity produces rectangular distribution
whereby its standard uncertainty is calculated as half of the detection limit divided by 3 The composition of the pure gases used for preparation of calibration mixtures is given
in Table 2 Table 2 - Metrological characteristics of pure gases
N2 999967 00005 Nitrogen Cylinder 40 dm3 Origin Russia O2 00033 00005 Propane Cylinder 2 dm3 Origin Russia
C3H8 9979 0017
3 After preparation of mixture the cylinder was maintained in laboratory room within
24 hours the mixture then was homogenized on the stand by rotating on the rollers within 4-5 hours The chromotograph for CGM was calibrated 2-3 days after its preparation
Calibration of the chromotograph
1 The chromotograph was calibrated using CGMs with composition identical to the analyzed sample The content of each component and its expanded uncertainty (k = 2) are given in Table 1 Table 1 - Calibrationе gas mixtures
2 Number of observations of each calibration sample- 3 Number of calibration samples - 3
3 The analytical function used for determination of the content of the analyzed sample components is as follows
x (y) =b1y+b0 (2) Where x ndash determined content molmol y - chromotograph response for the specific component b1- slope b0 - intercept 4 After completion of calibration the coefficients of analytical function were
calculated according to ISO 61432001 using generalized least-squares method Also the uncertainties of the intercept and slope and covariance between them were calculated After determination of parameters which are part of analytical function and which affect the uncertainty of measurements it was checked whether the analytical function is fit to the experimental data obtained in calibration and subsequently whether the analytical function is applicable
Results of calibration measurements coefficients of analytical function their uncertainties covariance and measure of goodness-of-fit Г (maximum value of the weighted differences of the experimental points and calculated points of the analytical function for each measurement run) are given in Tables 3 and 4 respectively Chromotograph operating conditions in calibration and analysis are given in Table 5
Table 3 - Results of experimental study
Date Component of
calibration mixture
Content x mole fraction
Expanded uncertainty
U(x) mole fraction
Mean of peak area y
mVs
Uncertainty )(yu
mVs
13374 0004 1279500 141 1389 0004 1329150 2899 CO2
12833 0004 1231000 849 2916 0005 404070 240
316 0005 437705 926 CO 2768 0004 383070 467
019 0002 3143200 4101
1706 2005
C3H8 0202 0002 3319150 2051
22
0181 0002 2948750 212 13374 0004 1269833 624
1389 0004 1321000 1272 CO2 12833 0004 1223900 1698
2916 0005 399490 612 316 0005 434010 863 CO
2768 0004 379660 410 019 0002 3157867 6772
0202 0002 3332400 3394
2106 2005
C3H8 0181 0002 2959900 4950
13374 0004 1277100 2152 1389 0004 1329900 2828 CO2
12833 0004 1229100 1980 2916 0005 400330 529
316 0005 434745 969 CO 2768 0004 379695 106
019 0002 3142433 9416 0202 0002 3321600 4101
2306 2005
C3H8 0181 0002 2961000 3111
According to ISO 61432003 calculation of the measure of goodness-of-fit Г is the maximum value of the weighed differences between the coordinates of measured and adjusted calibration points is an effective and simple method to test the compatibility of а prospective analytical function A function is admissible if Г le 2
minus
minus=
)(ˆ
)(ˆ
iii
iii
yuyy
xuxxΓ
(4) Where хi is the reference value of the content of calibration sample component
ix is the CGM component content obtained using the calculated analytical function
уi is the experimental response to the reference content of component iy is the response obtained in calculation of analytical function
u (хi) u (уi) are the uncertainties of reference contents and responses to these contents respectively
i is the number of calibration points i=1 3 This prerequisite is equivalent to the requirement that the curve of calculated response should cross each experimental calibration rectangular [хi plusmn 2u(хi) уi plusmn 2и(уi)] based on an expanded uncertainty U = ku with coverage factor k = 2 Table 4 Calculations of analytical function
Date Component Analytical function parameters
Uncertainty of analytical
function parameters
Covariance of
parameters Г
23
b1 b0 u(b1) u(b0) u(b0b1) 1706 11086E-
03 -81128E-
0119491E-
0524883E-
01 -48497E-06 10544
2106 10729E-03
-26126E-01
22698E-05
28930E-01 -65652E-06 19997
2306
CO2 10593E-
03 -17688E-
0135807E-
0545413E-
01 -16254E-05 10022
1706 71537E-04
26507E-02
14231E-05
57044E-02 -81115E-07 03017
2106 72346E-04
22401E-02
13819E-05
54490E-02 -75209E-07 05935
2306
CO 71321E-
04 60080E-
0212663E-
0549016E-
02 -62026E-07 01341
1706 56521E-06
13712E-02
38279E-07
12015E-02 -45937E-09 12991
2106 56295E-06
13707E-02
39247E-07
12379E-02 -48529E-09 12905
2306
C3H8 58258E-
06 80469E-
0340085E-
0712590E-
02 -50407E-09 08589
Two columns separated by switching device are located one after another in TCD
channel One column is intended for carbon dioxide heavy hydrocarbons and another column is intended for light gases Before the first switch the light gases including carbon oxide flow through the first column without being separated and remain in the second column The switch makes them locked in the second column The analysis of carbon dioxide is carried out up to the second switch Second switch makes the second column unlocked and carbon oxide is analyzed Third switch is required to allow propane escape from a column and prevent it from getting into a second column The analysis of the very propane is carried out using FID Time intervals between switches were selected experimentally when developing the analysis method Such analysis method makes it possible to analyze all three components per one sample inject
Table 5 - Chromotograph operating conditions in calibration and analysis Parameter of the operating conditions Thermostating temperature of TCD and FID degС 170
Temperature of separation columns degС
Program 60 degС within 9 min
than rise to 160 degС at 20degСmin
Rate of flow of carrier gas through TCD channel columns mlmin 15
Rate of flow of carrier gas through TCD comparison channel mlmin 15
Pressure in FID channel column kPa Program
24
80 to 100 Rise from the 1st s of
analysis at 2 kPamin
Flow-rate of hydrogen FID mlmin 20 Flow-rate of air FID mlmin 200 Temperature of switching device degС 65 Response time of switching device s 1 110 2 330 3 540
TCD FID Volume of injected analyzed gas cm3 025 025 Carrier gas Helium Duration of analysis min 17 Calculation of the content of comparison sample components and its uncertainty Results of comparison sample measurements are given in Table 6 Table 6 - Results of comparison sample measurements
1 The content of comparison sample component and its uncertainty were determined
using calculated analytical function according to ISO 61432001 as follows (5) Where G(y)=b1y+b0 is the calculated analytical function и(y) is the standard uncertainty of response y u2(bj) is the variance of analytical function parameter bj
u(bj bI) is the covariance of analytical function parameters bj bI N is the number of function coefficients N=2 j=0 1
sum sumsumminus
= +==
partpart
partpart
+
partpart
+
partpart
=1
0 1
2
2
0
22
)(2)()()(N
jIj
N
jI Ijj
N
j j
bbubG
bGbu
bGyu
yGxu
25
After substitution of analytical function (2) and transformations the expression takes form (5)
)(2)()()()()( 01122
0222
1 bbyubuybuyubxu +++= (6) The contents of comparison sample components under determination and their
uncertainties were calculated using B_LEAST a computer program recommended in ISO 6143 Calculations are summarized in Table 6
Table 6 Calculations of the content of comparison sample components and their
2 The final content of a component was determined as an arithmetiс mean from three measurements Final standard uncertainty was calculated using formula as follows
22
222)( Адаватмтемсериикал uuuuuxu ++++= (7)
Where ucal is the uncertainty of the component content produced by
calibration of chromotograph urun is the uncertainty of the component content produced by
change of chromotograph response in each measurement run ut is the uncertainty of the component content produced by
change of an ambient temperature upressure is the uncertainty of the component content produced by
change of atmospheric pressure u A is the standard uncertainty of three measurement runs
21 Uncertainty of the component content produced by calibration of chromotograph
This uncertainty is calculated using formula (6) but the first term of the sum ie
)()( 221 yub which represents the standard uncertainty of the chromotograph response in a
measurement run is not taken into account Calculations are summarized in Table 7
26
Table 7 Calculation of uncertainty produced by calibration of chromotograph
Date u(b1) u(b0) u(b0b1) x
molmol y Ucal molmol
Ucal rel
1706 19491E-05
24883E-01
-48497E-06
13567middot10-
2129698
3 0005middot1
0-2 003
2106 22698E-05
28930E-01
-65652E-06
13564middot10-
2 128855 0007middot1
0-2 005
2306
CO2
35807E-05
45413E-01
-16254E-05
135374middot10-2
1294633
0016middot10-2 012
1706 14231E-05
57044E-02
-81115E-07 2957middot10-2 409633
0003middot10-2 009
2106 13819E-05
54490E-02
-75209E-07
29577middot10-
2 405663 0003middot1
0-2 01
2306
CO
12663E-05
49016E-02
-62026E-07 2955middot10-2 405882
0003middot10-2 01
1706 38279E-07
12015E-02
-45937E-09 1977middot10-4
3255817
007middot10-
2 038
2106 39247E-07
12379E-02
-48529E-09 1980middot10-4
3273329
008middot10-
2 038
2306
C3H8
40085E-07
12590E-02
-50407E-09 1982middot10-4 32636
008middot10-
2 04 The total estimate of relative uncertainty produced by calibration of chromotograph was
calculated for each component as follows
3
3
1
2sum=
cali
cali
uu (8)
Where ucal i is the relative uncertainty produced by calibration of chromotograph and calculated for each measurement run
The calculations are summarized in Table 8
Table 8 Uncertainty produced by calibration of chromotograph
Component Ucal rel
CO2 008 CO 01
C3H8 04 22 Uncertainty of the component content produced by change of chromotograph response in each measurement run This uncertainty is calculated using the equation (6) whereby the first term of the sum
only ie )()( 221 yub which represents the standard uncertainty of the chromotograph
response in a measurement run is taken into account Calculations are summarized in Table 9
27
Table 9 Calculation of uncertainty produced by change of chromotograph response in each measurement run
The total estimate of relative uncertainty produced by change of chromotograph
response in each measurement run was calculated for each component as follows
3
3
1
2sum=
run
run
uu (9)
Where urun is the relative uncertainty produced by change of chromotograph response in each measurement run Calculations are summarized in Table 10
Table 10 Uncertainty produced by change of chromotograph response in each measurement
run
Component Urun rel
CO2 007 CO 015
C3H8 012 23 Uncertainty of the component content produced by change of temperature in a room
The recorded change of temperature in measurements is plusmn 05 degree The contribution of uncertainty type B (rectangular distribution) is estimated as follows
201003
12931
=sdotsdot=tu rel
28
24 Uncertainty of the component content produced by change of atmospheric pressure The recorded change of atmospheric pressure within three days was
05 kPа The contribution of uncertainty type B (rectangular distribution) is estimated as follows
2801003
13101
50=sdotsdot=pressureu rel
25 Standard deviation of 3 measurement runs Standard deviation is calculated as follows
isu p
A
2
= (10)
Where S2p is the group experimental variation
The group experimental variation is calculated as follows
(11)
Where si
2 is the experimental variation of measurement run i from independent repeated observations ni having freedom degrees
νi = n - 1 n=6 i= 3 Calculations are summarized in Table 11 Table 11 Calculations of standard uncertainty of 3 measurement runs
Date 2iS x
molmol 2iS
rel uA
rel
1706 2953E-05 13567middot10-2 000022
2106 588987E-06 13564middot10-2 0000043
2306
CO2 141137E-
05 135374middot10
-2 000010
0006
1706 225604E-06 2957middot10-2 0000077
2106 681346E-06 29577middot10-2 000023
2306
CO
175166E-06 2955middot10-2 0000060
0006
1706 C3H8 130158E-
08 1977middot10-4 00000066 0001
ss
p
i ii
N
ii
N2
2
1
1
= =
=
sum
sum
ν
ν
29
2106 44616E-09 1980middot10-4 00000023
2306
381032E-09 1982middot10-4 00000019
26 Total standard uncertainty
Uncertainty estimation СО2
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph ucal Normal 008 1 008
Change of temperature ut Rectangular 02 1 02 Change of atmospheric pressure upressure Rectangular 028 1 028
Changes of chromotograph response
urun Normal 007 1 007
Standard deviation of 3 runs uA Normal 0006 1 0006
Relative total standard uncertainty 036 Coverage factor k=2 Expanded uncertainty 01middot10-2 molmol Uncertainty estimation СО
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph ucal Normal 01 1 01 Change of temperature ut Rectangular 02 1 02 Change of atmospheric pressure upressure Rectangular 028 1 028 Changes of chromotograph response
urun Normal 015 1 015
Standard deviation of 3 runs uA Normal 0006 1 0006
Relative total standard uncertainty 039 Coverage factor k=2 Expanded uncertainty 002middot10-2 molmol Uncertainty estimation С3Н8
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph 04 Normal 04 1 008
30
Change of temperature 02 Rectangular 02 1 02 Change of atmospheric pressure 028 Rectangular 028 1 028
Changes of chromotograph response
012 Normal 012 1 007
Standard deviation of 3 runs 0001 Normal 0001 1 0006
Relative total standard uncertainty 054 Coverage factor k=2 Expanded uncertainty 02middot10-4 molmol
Sample handling
Period for exposure of cylinder to measurement conditions and method how to transport sample to the device
1 Stands for storing gas standard cylinders and calibration mixture cylinders and chromotograph are placed in a laboratory room which is not accessible to unauthorized persons The laboratory is equipped with air-conditioner to maintain required temperature and humidity on a continuous basis and some auxiliary measuring instruments as thermometer psychrometric hygrometer and aneroid to control temperature humidity and atmospheric inside the room
2 The comparison sample cylinder was stored in laboratory from the date of its
delivery to Minsk on 25042005 CGM cylinders are stored horizontally on racks and positioned vertically using special support when measurements are carried out
3 The analyzed gas sample is transported through the fine adjustment valve (FAV)
Conjunctions Cylinder - FAV FAV - tube tube - doser are made of metal and use adapters with spherical ends and bushes FAV is made of brass tube is made of copper and doser is made of duralumin
Instrument(s) (principles make type configuration data collection etc) For the analysis a GC were used with specifically applications For the determination of (Nitrogen (N2)) Carbon Dioxide (CO2) Carbon Monoxide (CO) and Propane (C3H8) balance GC Perkin Elmer AutoSystem XL (two channel system) with a stream selection valve for 4 streams and 2 gas sampling valves
Channel A for the determination of N2 CO and CO2 Carrier Gas Helium Columns Column system with two packed columns (6 ft x 18rdquo Porapak R 80100 mesh and 6 ft x 18rdquo Mol-Sieve 13X 80100 mesh) Oven Temperature 960 degC to 180 degC Detector micro-TCD Data Collection Total Chrom Workstation Channel B for the determination of C3H8 Carrier Gas Helium Columns Capillary column 50 m x 032 microm LP-SIL-8-CB Oven Temperature 60 degC to 180 degC Detector FID Data Collection Total Chrom Workstation
34
Calibration Standards
Calibration Standards for the measurements (preparation method purity analyses estimated uncertainty etc)
All standards were prepared individually according to ISO 6142 rdquoGas analysis - Preparation of calibration gases - Gravimetric Methodrdquo
Depending on the concentration of the components standards were prepared individually from pure gases or from pre-mixtures which were individually prepared from pure gases
The content of the impurities in all pure gases were determined before use by GC-DID GC-FID and or GC-TCD
After preparation the standards were verified by analytical comparisons against existing gravimetrically prepared standards Only when no significant difference between the analysed and the calculated gravimetric composition is found the ldquonew prepared candidate rdquo is accepted as a new standards
For the analysis of all components multi component standards with nitrogen as balance gas were used
Composition of calibrants BAM C49250-050722 Component Assigned value( x)
mmol mol Standard uncertainty (u(x)) relativ (k=2)
Calibration procedure (mathematical modelcalibration curve number and concentrations of standards measurement sequence temperaturepressure correction etc)
For the instrument calibration the bracketing technique was used The fraction of the current used standards deviated no more than +10rel and -10rel respectively from those of the sample
Measurement sequence
Sample Handling
How were the cylinders treated after arrival (eg stabilized) and how were samples transferred to the instrument (automatic high pressure mass-flow controller dilution etc) After heating (45 - 50 degC) the cylinder for 8 hours the cylinder were rolled about 16 hours before analysis was started Each cylinder was equipped with a pressure regulator that was purged three times by sequential evacuation and pressurisation with the gas mixture used Continous flow (2 ndash 3mlmin) through the sample loop
Uncertainty The specification of potential uncertainty sources is given in Annex 3
3 injection standard (high)
3 injection sample
3 injection standard (high)
3 injection sample
3 injection standard (low)
3 injection sample
3 injection standard (low)
3 injection standard (low)
36
Uncertainty table CO2
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 002 rel 1 002 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 03 rel
Uncertainty table CO
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 007 rel 1 007 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 05 rel
37
Uncertainty table C3H8
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 010 rel 1 001 rel
Analysis normal 028 rel 1 028 rel
Coverage factor 2
Expanded uncertainty 06 rel
Optional
You may provide additional data like the raw measurement data information on your
measurement procedure chromatograms etc
38
Appendix 3 SPECIFICATION OF POTENTIAL UNCERTAINTY SOURCES
a Uncertainty related to the balance and the weights Resolution of balance Accuracy of balance including linearity Incorrect zero point Drift (thermal and time effects) Instability due to draught Location of cylinder on the balance pan Uncertainties in the weights used Buoyancy effects on the weights used
b Uncertainties related to the gas cylinder Mechanical handling of cylinder
Loss of metal paints or labels from surface of cylinder Loss of metal from threads of valvefitting Dirt on cylinder valves or associated fitting
Absorptiondesorption effects on the external cylinder surface Buoyancy effects on the cylinder itself
Cylinder temperature differs from surrounding air due to eg filling with gas Change of cylinder volume during filling Change of density of surrounding air due to changes in temperature air pressure humidity and carbon dioxide content
Uncertainty in determination of external cylinder volume c Uncertainties related to the component gases Residual gas in cylinder Leakage Leakage of air into the cylinder after evacuation
Leakage of gas from the cylinder valve during filling Escape of gas from cylinder into transport lines
Gas remaining in transfer system when weight loss method is used Absorptionreaction of components on internal cylinder surface Reaction between components Impurities in all the initial gases Insufficient homogenization Uncertainty of molecular mass d Uncertainties related to the analysis
Repeatability and selectivity of the analyzer Appropriateness of the calibration curve
39
MEASUREMENT REPORT - All Ukrainian State Research-Industrial Center of Standardization Metrology Certification and Protection of Consumers Ukraine
gas ndash helium flow rate 15 cm3min detector TCD tdetector = 250 ordmС toven = 70 ordmС It was automatic data collection
Measurement and Calibration Methods Laboratory Measurement method Type of calibration curve
GCFID (С3Н8) 3 points linear Ukrmetrteststandard GCTCD (СО СО2) 3 points linear
GCFID ndash gas-chromatographic with flame-ionization detector GCTCD - gas-chromatographic with thermal-conductivity detector
42
Calibration Standards
Calibration standards ndash primary standard gas mixtures (PSGM) used for measurements by comparison method
PSGM-1 Cylinder 0116
PSGM-2 Cylinder 0107
PSGM-3 Cylinder 0093 Composition
x u(x) x u(x) x u(x) СО 27874 00015 29899 00015 31891 00015 СО2 130187 00015 144456 00016 137016 00016 С3Н8 019003 000008 020017 000008 021013 000008 N2 balance balance balance
Note x ndash mole fraction u(x) ndash absolute standard uncertainty
It was used gravimetric method of preparation of PSGM Electronic balance КА-20-3 of Mettler Toledo max limit of weighing is 20 kg least
limit of weighing is 01 g standard deviation is 0006 g Analysis of purity of parent gases was carried out with usage of chromatographs
НР6890N with helium ndash ionization detector flame ndash ionization detector thermal ndash conductivity detector and mass ndash spectrometric detector as well аs gas analyzers GIAM-15M and Onix condensate-thermometer hygrometer TOROS-3-2B
Calculation of uncertainties was carried out according to ISO 6142-2003 Corrections of temperature pressure and humidity of environment were considered
in calculations according to ISO 6142-2003 (program of ISO-6142 2000-03-17 designer is NMi) Protocols and explanations are in Annex A
Instrument (Comparator) Calibration Calibration of comparator ndash gas chromatograph HP 6890 was carried out with usage
of PSGM Measurement sequence PSGM -1 х 3 PSGM -2 х 3 COOMET gas mixture х 3 PSGM -2 х 3 PSGM -3 х 3 It is necessary to use PSGM-2 repeatedly for estimation of reproducibility of results
Program B_LEAST recommended by ISO 6143-2003 was used for constructing the curve Mathematical model of calibration curve is linear one
Sample Handling The cylinder was kept for 24 hrs at a room where comparators were disposed This room is a thermostatic room with t = (20plusmn2) ordmС
43
A method of sample input to a comparator is a method with flow stabilization Uncertainty The following uncertainties were included to the budget of uncertainty - uncertainty of the balance - uncertainties of impurities in parent gases Contribution from other uncertainty sources was insignificant A cabin of the balance is thermostatically The balance is the one-pan balance
Air transfer is absent in the cabin of the balance Drift of the balance is absent for PSGM preparation
Contribution from other uncertainty sources was considered in software according to ISO 6142-2003
Uncertainties related to the analysis (comparison) were considered in software according to ISO 6143-2003 and enclosed in Annex B
Uncertainty table СО2
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas mixture
B 001 1 001
Analysis A B 008 1 008
Coverage factor 2 Expanded uncertainty 002sdot10-2 molmol Uncertainty table СО
Protocols of analysis (comparison) in accordance with ISO 6143-2003
57
Explanation of protocols of comparison
Chapter I ldquoThe calibration data set isrdquo contains columns 1 mole fraction of a component 2 absolute standard uncertainty of mole fraction of a component 3 a signal of a comparator 4 absolute standard uncertainty of a comparator signal
Chapter II ldquoResults of ISO 6143 methodrdquo contains parameters of a calibration curve including its
uncertainty
Chapter ІІІ ldquoPart II Processing of datardquo contains columns
1 calc x - the results of comparison mole fraction of a component 2 u(x) - absolute standard uncertainty of mole fraction of a component 3 response y - a signal of a comparator 4 u(y) - absolute standard uncertainty of a comparator signal
58
СО2 - measurement 1 Data setCO2_21 The calibration data set is 1302E+01 1510E-03 1022E+04 1820E+00 1370E+01 1560E-03 1077E+04 2730E+00 1445E+01 1620E-03 1135E+04 5900E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 20331E-02 12711E-03 12573E-01 11653E-05 -14638E-06 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 10548E-02 12722E-03 31762E-02 28898E-06 -91698E-08 Remaining SSD is 74346 Weighted distances x-value x-dist y-dist 100E+00 130E+01 490E-01 -755E-01 200E+00 137E+01 -103E+00 228E+00 300E+00 144E+01 539E-01 -250E-01 Goodness-of-fit measure 22837 Parameter set 1 1054788657490729E-2 1272208026684145E-3 3176237146276368E-2 2889798108124711E-6 -
9169821653851327E-8 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_21c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13577E+01 25542E-03 10664E+04 15200E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 547E-06 328E-06 316E-06 784E-06 286E-06 652E-06 Linear model Parameters for the fit were (b0 b1) 10548E-02 12722E-03
59
СО2 - measurement 2
Data setCO2_20 The calibration data set is 1302E+01 1512E-03 1021E+04 4723E+00 1370E+01 1563E-03 1075E+04 1600E+00 1445E+01 1620E-03 1133E+04 7300E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -38760E-02 12784E-03 26817E-02 24890E-06 -66689E-08 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -62452E-02 12805E-03 47930E-02 43243E-06 -20716E-07 Remaining SSD is 03231 Weighted distances x-value x-dist y-dist 100E+00 130E+01 107E-01 -415E-01 200E+00 137E+01 -212E-01 283E-01 300E+00 144E+01 104E-01 -584E-02 Goodness-of-fit measure 04155 Parameter set 1 -6245240430658412E-2 1280492624666799E-3 4792952200361109E-2 4324266278840409E-6 -
2071623966851869E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_20c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13594E+01 10290E-02 10665E+04 78300E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 121E-05 683E-06 651E-06 315E-05 560E-06 106E-04 Linear model Parameters for the fit were (b0 b1) -62452E-02 12805E-03
60
С3Н8 - measurement 1
Data setC3H8 The calibration data set is 1900E-01 7800E-05 9057E+03 1098E+01 2002E-01 7900E-05 9552E+03 8569E+00 2101E-01 7960E-05 1007E+04 4049E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10529E-02 19831E-05 34552E-03 36109E-07 -12465E-09 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11642E-02 19714E-05 23073E-03 23522E-07 -54231E-10 Remaining SSD is 19453 Weighted distances x-value x-dist y-dist 100E+00 190E-01 -239E-01 666E-01 200E+00 200E-01 487E-01 -104E+00 300E+00 210E-01 -247E-01 248E-01 Goodness-of-fit measure 10414 Parameter set 1 1164239985182795E-2 1971441115316992E-5 2307269625077337E-3 2352198415608386E-7 -
5423119774765299E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19837E-01 14840E-04 94718E+03 45610E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
12
Annex 2 Results and measurement reports as submitted by participating laboratories Key comparison participants
MEASUREMENT REPORT - DI Mendeleyev Institute for Metrology
Russian Federation (VNIIM)
I Results of Study
Laboratory DI Mendeleyev Institute for Metrology (VNIIM) Research Department for the State Standard in the Field of Physical-Chemical Measurements (PCD)
Instruments Multichannel automatic NDIR analyzer included to the set of the National Primary measurement standard of units of mole fraction and mass concentration of components in gas medium GET 154-01 was used for the analysis Calibration Standards All calibration multicomponent gas mixtures were prepared gravimetrically according to ISO 6142 The calibration multicomponent gas mixtures were prepared from pure gases directly on components CO CO2 and from pre-mixtures which were prepared from pure gases on component С3Н8 The content of the impurities in all pure gases was determined by GC with helium-ionization flame-ionization and thermal-conductivity detectors as well as standard hygrometer apparatus included to the standard complex A1 of analysis of pure gases and substances from GET 154-01 The calibration multicomponent gas mixtures were verified with usage of existing gravimetric gas mixtures in accordance with ISO 6143 Composition of calibration standards
Cylinder 6547 Cylinder 6571 Cylinder 6538 Component x мольmol Standard
Instrument Calibration Three independent measurements were carried out under repeatability conditions Before each measurement an instrument calibration was made One measurement contained 5 submeasurements Sample Handling The time of the cylinder keeping is 24 hrs It was used the automatic unit of commutation for inputting gas mixtures
15
Uncertainty Uncertainty table СО2
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas
mixture
B 0010 1 0010
Analysis A B 0048 1 0048
Coverage factor 2 Expanded uncertainty 01 Uncertainty table СО
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas
mixture
B 002 1 002
Analysis A B 0095 1 0095
Coverage factor 2 Expanded uncertainty 019
16
Uncertainty table С3Н8 Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas
mixture
B 005 1 005
Analysis A B 0045 1 0045
Coverage factor 2 Expanded uncertainty 013
17
MEASUREMENT REPORT ndash Belorussian State Institute for Metrology Belarus (BelGIM)
I Results of experimental study
Laboratory Belarus BelGIM Section for physicochemical and optical measurements sector for standards and gas mixtures 8 Serova st Minsk Cylinder No 0128 9 dm3 aluminium NOMINAL COMPOSITION - Carbon dioxide 13middot10-2 - 14middot10-2 molmol - Carbon oxide 28middot10-2 - 32middot10-2 molmol - Propane 19middot10-4 - 21middot10-4molmol - Nitrogen Residual
Measurement No1 Date
Result (molmol)
x_
Standard deviation
S( x_
) rel
No of observations
n
Carbon dioxide 17062005 13567middot10-2 0096 6
Carbon oxide 17062005 2957middot10-2 014 6
Propane 17062005 1977middot10-4 015 6
Measurement No2 Date
Result (molmol)
x_
Standard deviation
S( x_
) rel
No of observations
n
Carbon dioxide 21062005 13564middot10-2 004 6
Carbon oxide 21062005 2957middot10-2 02 6
Propane 21062005 1979middot10-4 01 6
18
Measurement No3 Date
Result (molmol)
x_
Standard deviation
S( x_
) rel
No of observations
n
Carbon dioxide 23062005 13537middot10-2 007 6
Carbon oxide 23062005 2955middot10-2 01 6
Propane 23062005 1982middot10-4 01 6
Final results
Gas mixture Result
(molmol)
Coverage factor
Expanded uncertainty (molmol)
Carbon dioxide 136middot10-2 2 01 middot10-2
Carbon oxide 296middot10-2 2 002middot10-2
Propane 198middot10-4 2 02middot10-4
II Description of study Apparatus (principle of operation type configuration data collection etc)
Measurements were carried out using gas chromatograph Crystal 2000М (hereinafter
referred to as chromatograph) combined with thermal conductivity detector (hereinafter referred to as TCD) with detection limit of 510-9 gml for propane and flame-ionization detector (hereinafter referred to as FID) with detection limit of 510-12 gs for propane
Computers and software Chromatech Analytic version 121 were used to control chromatograph and collect and process chromatographical data
For the purpose of measurements the following auxiliary devices and materials were used
1 Two-position doser with 10 ports and with doses of 025 cm3 for FID channel and with doses of 025 cm3 for TCD channel (hereinafter referred to as doser)
2 Metallic packed column 3m х 3mm х 2mm - HayeSep N 80100 metallic packed column 1m х 4mm х 2mm-CaA 016025 (TCD channel) capillary column HP PLOTQ 30m х 0536mm (FID channel)
3 Aneroid BАММ-1 with a measurement range of 80-106 kPа and accuracy of plusmn 02 kPа
4 Mercurial thermometer ТL-4 with a measurement range of 0-50ordmС and scale division of 01ordmС
19
5 Fine adjustment valve (hereinafter referred to as FAV) provided to transport a gas sample into chromotograph and set to gas flow-rate of 10-15 mlmin
6 Foamy gas flow meter type YIRG - 2А accuracy of flow measurement plusmn 1 сm3min
7 Helium gas Type A according to TU 51-940-80 8 High purity hydrogen gas according to TU 301-07-27-90 9 Compressed air 10 Multicomponent calibration gas mixtures (hereinafter referred to as CGM)
produced and certified by gravimetric method
Calibration reference materials - calibration gas mixtures used for measurements 1 Quantitative composition of KGS is determined using gravimetric method defined in
ISO 61422001 by calculating weight of each component of a gas mixture The content of CGM components is expressed as a mole fraction Uncertainty of KGS composition is expressed as expanded uncertainty with coverage factor k = 2 Molar masses of components and their uncertainties are taken from ISO 149122003 Performance and metrological characteristics of the equipment used for gravimetric preparation of mixtures are given in Table 1
Table 1
Description of the equipment
Manufacturer Metrological characteristics
Mass-comparator balance type КА10-3Р
Mettler-Toledo
Switzerland
Maximum load 15 kg Scale division 1 mg Standard deviation 19 mg at load of 10 kg Operating temperature range +10divide30degС Maximum temperature change within 1 h plusmn05 degС
Gas mixer type USG 00001 BelGIM
Measurement range 000025 divide 100 МPa Accuracy class for manometers ndash 015 Accuracy class for vacuummeters ndash 025 Vacuummeter with pressure sensor for measuring the residual pressure before filling Residual pressure before filling of each component not more than 20 Pa
2 Purity analysis of primary gas standards
The purity analysis of primary gas standards is based on the information provided by the supplier or on the results of determination of impurity in pure gases using measurement procedure developed inside BelGIM
20
If an analytical method laid down in 43 of ISO 61422001 cannot be used for impurity determination mole fraction of an expected impurity is assumed to be half of the detection limit of the analytical method The content of the undetected impurity produces rectangular distribution
whereby its standard uncertainty is calculated as half of the detection limit divided by 3 The composition of the pure gases used for preparation of calibration mixtures is given
in Table 2 Table 2 - Metrological characteristics of pure gases
N2 999967 00005 Nitrogen Cylinder 40 dm3 Origin Russia O2 00033 00005 Propane Cylinder 2 dm3 Origin Russia
C3H8 9979 0017
3 After preparation of mixture the cylinder was maintained in laboratory room within
24 hours the mixture then was homogenized on the stand by rotating on the rollers within 4-5 hours The chromotograph for CGM was calibrated 2-3 days after its preparation
Calibration of the chromotograph
1 The chromotograph was calibrated using CGMs with composition identical to the analyzed sample The content of each component and its expanded uncertainty (k = 2) are given in Table 1 Table 1 - Calibrationе gas mixtures
2 Number of observations of each calibration sample- 3 Number of calibration samples - 3
3 The analytical function used for determination of the content of the analyzed sample components is as follows
x (y) =b1y+b0 (2) Where x ndash determined content molmol y - chromotograph response for the specific component b1- slope b0 - intercept 4 After completion of calibration the coefficients of analytical function were
calculated according to ISO 61432001 using generalized least-squares method Also the uncertainties of the intercept and slope and covariance between them were calculated After determination of parameters which are part of analytical function and which affect the uncertainty of measurements it was checked whether the analytical function is fit to the experimental data obtained in calibration and subsequently whether the analytical function is applicable
Results of calibration measurements coefficients of analytical function their uncertainties covariance and measure of goodness-of-fit Г (maximum value of the weighted differences of the experimental points and calculated points of the analytical function for each measurement run) are given in Tables 3 and 4 respectively Chromotograph operating conditions in calibration and analysis are given in Table 5
Table 3 - Results of experimental study
Date Component of
calibration mixture
Content x mole fraction
Expanded uncertainty
U(x) mole fraction
Mean of peak area y
mVs
Uncertainty )(yu
mVs
13374 0004 1279500 141 1389 0004 1329150 2899 CO2
12833 0004 1231000 849 2916 0005 404070 240
316 0005 437705 926 CO 2768 0004 383070 467
019 0002 3143200 4101
1706 2005
C3H8 0202 0002 3319150 2051
22
0181 0002 2948750 212 13374 0004 1269833 624
1389 0004 1321000 1272 CO2 12833 0004 1223900 1698
2916 0005 399490 612 316 0005 434010 863 CO
2768 0004 379660 410 019 0002 3157867 6772
0202 0002 3332400 3394
2106 2005
C3H8 0181 0002 2959900 4950
13374 0004 1277100 2152 1389 0004 1329900 2828 CO2
12833 0004 1229100 1980 2916 0005 400330 529
316 0005 434745 969 CO 2768 0004 379695 106
019 0002 3142433 9416 0202 0002 3321600 4101
2306 2005
C3H8 0181 0002 2961000 3111
According to ISO 61432003 calculation of the measure of goodness-of-fit Г is the maximum value of the weighed differences between the coordinates of measured and adjusted calibration points is an effective and simple method to test the compatibility of а prospective analytical function A function is admissible if Г le 2
minus
minus=
)(ˆ
)(ˆ
iii
iii
yuyy
xuxxΓ
(4) Where хi is the reference value of the content of calibration sample component
ix is the CGM component content obtained using the calculated analytical function
уi is the experimental response to the reference content of component iy is the response obtained in calculation of analytical function
u (хi) u (уi) are the uncertainties of reference contents and responses to these contents respectively
i is the number of calibration points i=1 3 This prerequisite is equivalent to the requirement that the curve of calculated response should cross each experimental calibration rectangular [хi plusmn 2u(хi) уi plusmn 2и(уi)] based on an expanded uncertainty U = ku with coverage factor k = 2 Table 4 Calculations of analytical function
Date Component Analytical function parameters
Uncertainty of analytical
function parameters
Covariance of
parameters Г
23
b1 b0 u(b1) u(b0) u(b0b1) 1706 11086E-
03 -81128E-
0119491E-
0524883E-
01 -48497E-06 10544
2106 10729E-03
-26126E-01
22698E-05
28930E-01 -65652E-06 19997
2306
CO2 10593E-
03 -17688E-
0135807E-
0545413E-
01 -16254E-05 10022
1706 71537E-04
26507E-02
14231E-05
57044E-02 -81115E-07 03017
2106 72346E-04
22401E-02
13819E-05
54490E-02 -75209E-07 05935
2306
CO 71321E-
04 60080E-
0212663E-
0549016E-
02 -62026E-07 01341
1706 56521E-06
13712E-02
38279E-07
12015E-02 -45937E-09 12991
2106 56295E-06
13707E-02
39247E-07
12379E-02 -48529E-09 12905
2306
C3H8 58258E-
06 80469E-
0340085E-
0712590E-
02 -50407E-09 08589
Two columns separated by switching device are located one after another in TCD
channel One column is intended for carbon dioxide heavy hydrocarbons and another column is intended for light gases Before the first switch the light gases including carbon oxide flow through the first column without being separated and remain in the second column The switch makes them locked in the second column The analysis of carbon dioxide is carried out up to the second switch Second switch makes the second column unlocked and carbon oxide is analyzed Third switch is required to allow propane escape from a column and prevent it from getting into a second column The analysis of the very propane is carried out using FID Time intervals between switches were selected experimentally when developing the analysis method Such analysis method makes it possible to analyze all three components per one sample inject
Table 5 - Chromotograph operating conditions in calibration and analysis Parameter of the operating conditions Thermostating temperature of TCD and FID degС 170
Temperature of separation columns degС
Program 60 degС within 9 min
than rise to 160 degС at 20degСmin
Rate of flow of carrier gas through TCD channel columns mlmin 15
Rate of flow of carrier gas through TCD comparison channel mlmin 15
Pressure in FID channel column kPa Program
24
80 to 100 Rise from the 1st s of
analysis at 2 kPamin
Flow-rate of hydrogen FID mlmin 20 Flow-rate of air FID mlmin 200 Temperature of switching device degС 65 Response time of switching device s 1 110 2 330 3 540
TCD FID Volume of injected analyzed gas cm3 025 025 Carrier gas Helium Duration of analysis min 17 Calculation of the content of comparison sample components and its uncertainty Results of comparison sample measurements are given in Table 6 Table 6 - Results of comparison sample measurements
1 The content of comparison sample component and its uncertainty were determined
using calculated analytical function according to ISO 61432001 as follows (5) Where G(y)=b1y+b0 is the calculated analytical function и(y) is the standard uncertainty of response y u2(bj) is the variance of analytical function parameter bj
u(bj bI) is the covariance of analytical function parameters bj bI N is the number of function coefficients N=2 j=0 1
sum sumsumminus
= +==
partpart
partpart
+
partpart
+
partpart
=1
0 1
2
2
0
22
)(2)()()(N
jIj
N
jI Ijj
N
j j
bbubG
bGbu
bGyu
yGxu
25
After substitution of analytical function (2) and transformations the expression takes form (5)
)(2)()()()()( 01122
0222
1 bbyubuybuyubxu +++= (6) The contents of comparison sample components under determination and their
uncertainties were calculated using B_LEAST a computer program recommended in ISO 6143 Calculations are summarized in Table 6
Table 6 Calculations of the content of comparison sample components and their
2 The final content of a component was determined as an arithmetiс mean from three measurements Final standard uncertainty was calculated using formula as follows
22
222)( Адаватмтемсериикал uuuuuxu ++++= (7)
Where ucal is the uncertainty of the component content produced by
calibration of chromotograph urun is the uncertainty of the component content produced by
change of chromotograph response in each measurement run ut is the uncertainty of the component content produced by
change of an ambient temperature upressure is the uncertainty of the component content produced by
change of atmospheric pressure u A is the standard uncertainty of three measurement runs
21 Uncertainty of the component content produced by calibration of chromotograph
This uncertainty is calculated using formula (6) but the first term of the sum ie
)()( 221 yub which represents the standard uncertainty of the chromotograph response in a
measurement run is not taken into account Calculations are summarized in Table 7
26
Table 7 Calculation of uncertainty produced by calibration of chromotograph
Date u(b1) u(b0) u(b0b1) x
molmol y Ucal molmol
Ucal rel
1706 19491E-05
24883E-01
-48497E-06
13567middot10-
2129698
3 0005middot1
0-2 003
2106 22698E-05
28930E-01
-65652E-06
13564middot10-
2 128855 0007middot1
0-2 005
2306
CO2
35807E-05
45413E-01
-16254E-05
135374middot10-2
1294633
0016middot10-2 012
1706 14231E-05
57044E-02
-81115E-07 2957middot10-2 409633
0003middot10-2 009
2106 13819E-05
54490E-02
-75209E-07
29577middot10-
2 405663 0003middot1
0-2 01
2306
CO
12663E-05
49016E-02
-62026E-07 2955middot10-2 405882
0003middot10-2 01
1706 38279E-07
12015E-02
-45937E-09 1977middot10-4
3255817
007middot10-
2 038
2106 39247E-07
12379E-02
-48529E-09 1980middot10-4
3273329
008middot10-
2 038
2306
C3H8
40085E-07
12590E-02
-50407E-09 1982middot10-4 32636
008middot10-
2 04 The total estimate of relative uncertainty produced by calibration of chromotograph was
calculated for each component as follows
3
3
1
2sum=
cali
cali
uu (8)
Where ucal i is the relative uncertainty produced by calibration of chromotograph and calculated for each measurement run
The calculations are summarized in Table 8
Table 8 Uncertainty produced by calibration of chromotograph
Component Ucal rel
CO2 008 CO 01
C3H8 04 22 Uncertainty of the component content produced by change of chromotograph response in each measurement run This uncertainty is calculated using the equation (6) whereby the first term of the sum
only ie )()( 221 yub which represents the standard uncertainty of the chromotograph
response in a measurement run is taken into account Calculations are summarized in Table 9
27
Table 9 Calculation of uncertainty produced by change of chromotograph response in each measurement run
The total estimate of relative uncertainty produced by change of chromotograph
response in each measurement run was calculated for each component as follows
3
3
1
2sum=
run
run
uu (9)
Where urun is the relative uncertainty produced by change of chromotograph response in each measurement run Calculations are summarized in Table 10
Table 10 Uncertainty produced by change of chromotograph response in each measurement
run
Component Urun rel
CO2 007 CO 015
C3H8 012 23 Uncertainty of the component content produced by change of temperature in a room
The recorded change of temperature in measurements is plusmn 05 degree The contribution of uncertainty type B (rectangular distribution) is estimated as follows
201003
12931
=sdotsdot=tu rel
28
24 Uncertainty of the component content produced by change of atmospheric pressure The recorded change of atmospheric pressure within three days was
05 kPа The contribution of uncertainty type B (rectangular distribution) is estimated as follows
2801003
13101
50=sdotsdot=pressureu rel
25 Standard deviation of 3 measurement runs Standard deviation is calculated as follows
isu p
A
2
= (10)
Where S2p is the group experimental variation
The group experimental variation is calculated as follows
(11)
Where si
2 is the experimental variation of measurement run i from independent repeated observations ni having freedom degrees
νi = n - 1 n=6 i= 3 Calculations are summarized in Table 11 Table 11 Calculations of standard uncertainty of 3 measurement runs
Date 2iS x
molmol 2iS
rel uA
rel
1706 2953E-05 13567middot10-2 000022
2106 588987E-06 13564middot10-2 0000043
2306
CO2 141137E-
05 135374middot10
-2 000010
0006
1706 225604E-06 2957middot10-2 0000077
2106 681346E-06 29577middot10-2 000023
2306
CO
175166E-06 2955middot10-2 0000060
0006
1706 C3H8 130158E-
08 1977middot10-4 00000066 0001
ss
p
i ii
N
ii
N2
2
1
1
= =
=
sum
sum
ν
ν
29
2106 44616E-09 1980middot10-4 00000023
2306
381032E-09 1982middot10-4 00000019
26 Total standard uncertainty
Uncertainty estimation СО2
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph ucal Normal 008 1 008
Change of temperature ut Rectangular 02 1 02 Change of atmospheric pressure upressure Rectangular 028 1 028
Changes of chromotograph response
urun Normal 007 1 007
Standard deviation of 3 runs uA Normal 0006 1 0006
Relative total standard uncertainty 036 Coverage factor k=2 Expanded uncertainty 01middot10-2 molmol Uncertainty estimation СО
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph ucal Normal 01 1 01 Change of temperature ut Rectangular 02 1 02 Change of atmospheric pressure upressure Rectangular 028 1 028 Changes of chromotograph response
urun Normal 015 1 015
Standard deviation of 3 runs uA Normal 0006 1 0006
Relative total standard uncertainty 039 Coverage factor k=2 Expanded uncertainty 002middot10-2 molmol Uncertainty estimation С3Н8
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph 04 Normal 04 1 008
30
Change of temperature 02 Rectangular 02 1 02 Change of atmospheric pressure 028 Rectangular 028 1 028
Changes of chromotograph response
012 Normal 012 1 007
Standard deviation of 3 runs 0001 Normal 0001 1 0006
Relative total standard uncertainty 054 Coverage factor k=2 Expanded uncertainty 02middot10-4 molmol
Sample handling
Period for exposure of cylinder to measurement conditions and method how to transport sample to the device
1 Stands for storing gas standard cylinders and calibration mixture cylinders and chromotograph are placed in a laboratory room which is not accessible to unauthorized persons The laboratory is equipped with air-conditioner to maintain required temperature and humidity on a continuous basis and some auxiliary measuring instruments as thermometer psychrometric hygrometer and aneroid to control temperature humidity and atmospheric inside the room
2 The comparison sample cylinder was stored in laboratory from the date of its
delivery to Minsk on 25042005 CGM cylinders are stored horizontally on racks and positioned vertically using special support when measurements are carried out
3 The analyzed gas sample is transported through the fine adjustment valve (FAV)
Conjunctions Cylinder - FAV FAV - tube tube - doser are made of metal and use adapters with spherical ends and bushes FAV is made of brass tube is made of copper and doser is made of duralumin
Instrument(s) (principles make type configuration data collection etc) For the analysis a GC were used with specifically applications For the determination of (Nitrogen (N2)) Carbon Dioxide (CO2) Carbon Monoxide (CO) and Propane (C3H8) balance GC Perkin Elmer AutoSystem XL (two channel system) with a stream selection valve for 4 streams and 2 gas sampling valves
Channel A for the determination of N2 CO and CO2 Carrier Gas Helium Columns Column system with two packed columns (6 ft x 18rdquo Porapak R 80100 mesh and 6 ft x 18rdquo Mol-Sieve 13X 80100 mesh) Oven Temperature 960 degC to 180 degC Detector micro-TCD Data Collection Total Chrom Workstation Channel B for the determination of C3H8 Carrier Gas Helium Columns Capillary column 50 m x 032 microm LP-SIL-8-CB Oven Temperature 60 degC to 180 degC Detector FID Data Collection Total Chrom Workstation
34
Calibration Standards
Calibration Standards for the measurements (preparation method purity analyses estimated uncertainty etc)
All standards were prepared individually according to ISO 6142 rdquoGas analysis - Preparation of calibration gases - Gravimetric Methodrdquo
Depending on the concentration of the components standards were prepared individually from pure gases or from pre-mixtures which were individually prepared from pure gases
The content of the impurities in all pure gases were determined before use by GC-DID GC-FID and or GC-TCD
After preparation the standards were verified by analytical comparisons against existing gravimetrically prepared standards Only when no significant difference between the analysed and the calculated gravimetric composition is found the ldquonew prepared candidate rdquo is accepted as a new standards
For the analysis of all components multi component standards with nitrogen as balance gas were used
Composition of calibrants BAM C49250-050722 Component Assigned value( x)
mmol mol Standard uncertainty (u(x)) relativ (k=2)
Calibration procedure (mathematical modelcalibration curve number and concentrations of standards measurement sequence temperaturepressure correction etc)
For the instrument calibration the bracketing technique was used The fraction of the current used standards deviated no more than +10rel and -10rel respectively from those of the sample
Measurement sequence
Sample Handling
How were the cylinders treated after arrival (eg stabilized) and how were samples transferred to the instrument (automatic high pressure mass-flow controller dilution etc) After heating (45 - 50 degC) the cylinder for 8 hours the cylinder were rolled about 16 hours before analysis was started Each cylinder was equipped with a pressure regulator that was purged three times by sequential evacuation and pressurisation with the gas mixture used Continous flow (2 ndash 3mlmin) through the sample loop
Uncertainty The specification of potential uncertainty sources is given in Annex 3
3 injection standard (high)
3 injection sample
3 injection standard (high)
3 injection sample
3 injection standard (low)
3 injection sample
3 injection standard (low)
3 injection standard (low)
36
Uncertainty table CO2
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 002 rel 1 002 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 03 rel
Uncertainty table CO
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 007 rel 1 007 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 05 rel
37
Uncertainty table C3H8
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 010 rel 1 001 rel
Analysis normal 028 rel 1 028 rel
Coverage factor 2
Expanded uncertainty 06 rel
Optional
You may provide additional data like the raw measurement data information on your
measurement procedure chromatograms etc
38
Appendix 3 SPECIFICATION OF POTENTIAL UNCERTAINTY SOURCES
a Uncertainty related to the balance and the weights Resolution of balance Accuracy of balance including linearity Incorrect zero point Drift (thermal and time effects) Instability due to draught Location of cylinder on the balance pan Uncertainties in the weights used Buoyancy effects on the weights used
b Uncertainties related to the gas cylinder Mechanical handling of cylinder
Loss of metal paints or labels from surface of cylinder Loss of metal from threads of valvefitting Dirt on cylinder valves or associated fitting
Absorptiondesorption effects on the external cylinder surface Buoyancy effects on the cylinder itself
Cylinder temperature differs from surrounding air due to eg filling with gas Change of cylinder volume during filling Change of density of surrounding air due to changes in temperature air pressure humidity and carbon dioxide content
Uncertainty in determination of external cylinder volume c Uncertainties related to the component gases Residual gas in cylinder Leakage Leakage of air into the cylinder after evacuation
Leakage of gas from the cylinder valve during filling Escape of gas from cylinder into transport lines
Gas remaining in transfer system when weight loss method is used Absorptionreaction of components on internal cylinder surface Reaction between components Impurities in all the initial gases Insufficient homogenization Uncertainty of molecular mass d Uncertainties related to the analysis
Repeatability and selectivity of the analyzer Appropriateness of the calibration curve
39
MEASUREMENT REPORT - All Ukrainian State Research-Industrial Center of Standardization Metrology Certification and Protection of Consumers Ukraine
gas ndash helium flow rate 15 cm3min detector TCD tdetector = 250 ordmС toven = 70 ordmС It was automatic data collection
Measurement and Calibration Methods Laboratory Measurement method Type of calibration curve
GCFID (С3Н8) 3 points linear Ukrmetrteststandard GCTCD (СО СО2) 3 points linear
GCFID ndash gas-chromatographic with flame-ionization detector GCTCD - gas-chromatographic with thermal-conductivity detector
42
Calibration Standards
Calibration standards ndash primary standard gas mixtures (PSGM) used for measurements by comparison method
PSGM-1 Cylinder 0116
PSGM-2 Cylinder 0107
PSGM-3 Cylinder 0093 Composition
x u(x) x u(x) x u(x) СО 27874 00015 29899 00015 31891 00015 СО2 130187 00015 144456 00016 137016 00016 С3Н8 019003 000008 020017 000008 021013 000008 N2 balance balance balance
Note x ndash mole fraction u(x) ndash absolute standard uncertainty
It was used gravimetric method of preparation of PSGM Electronic balance КА-20-3 of Mettler Toledo max limit of weighing is 20 kg least
limit of weighing is 01 g standard deviation is 0006 g Analysis of purity of parent gases was carried out with usage of chromatographs
НР6890N with helium ndash ionization detector flame ndash ionization detector thermal ndash conductivity detector and mass ndash spectrometric detector as well аs gas analyzers GIAM-15M and Onix condensate-thermometer hygrometer TOROS-3-2B
Calculation of uncertainties was carried out according to ISO 6142-2003 Corrections of temperature pressure and humidity of environment were considered
in calculations according to ISO 6142-2003 (program of ISO-6142 2000-03-17 designer is NMi) Protocols and explanations are in Annex A
Instrument (Comparator) Calibration Calibration of comparator ndash gas chromatograph HP 6890 was carried out with usage
of PSGM Measurement sequence PSGM -1 х 3 PSGM -2 х 3 COOMET gas mixture х 3 PSGM -2 х 3 PSGM -3 х 3 It is necessary to use PSGM-2 repeatedly for estimation of reproducibility of results
Program B_LEAST recommended by ISO 6143-2003 was used for constructing the curve Mathematical model of calibration curve is linear one
Sample Handling The cylinder was kept for 24 hrs at a room where comparators were disposed This room is a thermostatic room with t = (20plusmn2) ordmС
43
A method of sample input to a comparator is a method with flow stabilization Uncertainty The following uncertainties were included to the budget of uncertainty - uncertainty of the balance - uncertainties of impurities in parent gases Contribution from other uncertainty sources was insignificant A cabin of the balance is thermostatically The balance is the one-pan balance
Air transfer is absent in the cabin of the balance Drift of the balance is absent for PSGM preparation
Contribution from other uncertainty sources was considered in software according to ISO 6142-2003
Uncertainties related to the analysis (comparison) were considered in software according to ISO 6143-2003 and enclosed in Annex B
Uncertainty table СО2
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas mixture
B 001 1 001
Analysis A B 008 1 008
Coverage factor 2 Expanded uncertainty 002sdot10-2 molmol Uncertainty table СО
Protocols of analysis (comparison) in accordance with ISO 6143-2003
57
Explanation of protocols of comparison
Chapter I ldquoThe calibration data set isrdquo contains columns 1 mole fraction of a component 2 absolute standard uncertainty of mole fraction of a component 3 a signal of a comparator 4 absolute standard uncertainty of a comparator signal
Chapter II ldquoResults of ISO 6143 methodrdquo contains parameters of a calibration curve including its
uncertainty
Chapter ІІІ ldquoPart II Processing of datardquo contains columns
1 calc x - the results of comparison mole fraction of a component 2 u(x) - absolute standard uncertainty of mole fraction of a component 3 response y - a signal of a comparator 4 u(y) - absolute standard uncertainty of a comparator signal
58
СО2 - measurement 1 Data setCO2_21 The calibration data set is 1302E+01 1510E-03 1022E+04 1820E+00 1370E+01 1560E-03 1077E+04 2730E+00 1445E+01 1620E-03 1135E+04 5900E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 20331E-02 12711E-03 12573E-01 11653E-05 -14638E-06 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 10548E-02 12722E-03 31762E-02 28898E-06 -91698E-08 Remaining SSD is 74346 Weighted distances x-value x-dist y-dist 100E+00 130E+01 490E-01 -755E-01 200E+00 137E+01 -103E+00 228E+00 300E+00 144E+01 539E-01 -250E-01 Goodness-of-fit measure 22837 Parameter set 1 1054788657490729E-2 1272208026684145E-3 3176237146276368E-2 2889798108124711E-6 -
9169821653851327E-8 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_21c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13577E+01 25542E-03 10664E+04 15200E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 547E-06 328E-06 316E-06 784E-06 286E-06 652E-06 Linear model Parameters for the fit were (b0 b1) 10548E-02 12722E-03
59
СО2 - measurement 2
Data setCO2_20 The calibration data set is 1302E+01 1512E-03 1021E+04 4723E+00 1370E+01 1563E-03 1075E+04 1600E+00 1445E+01 1620E-03 1133E+04 7300E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -38760E-02 12784E-03 26817E-02 24890E-06 -66689E-08 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -62452E-02 12805E-03 47930E-02 43243E-06 -20716E-07 Remaining SSD is 03231 Weighted distances x-value x-dist y-dist 100E+00 130E+01 107E-01 -415E-01 200E+00 137E+01 -212E-01 283E-01 300E+00 144E+01 104E-01 -584E-02 Goodness-of-fit measure 04155 Parameter set 1 -6245240430658412E-2 1280492624666799E-3 4792952200361109E-2 4324266278840409E-6 -
2071623966851869E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_20c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13594E+01 10290E-02 10665E+04 78300E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 121E-05 683E-06 651E-06 315E-05 560E-06 106E-04 Linear model Parameters for the fit were (b0 b1) -62452E-02 12805E-03
60
С3Н8 - measurement 1
Data setC3H8 The calibration data set is 1900E-01 7800E-05 9057E+03 1098E+01 2002E-01 7900E-05 9552E+03 8569E+00 2101E-01 7960E-05 1007E+04 4049E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10529E-02 19831E-05 34552E-03 36109E-07 -12465E-09 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11642E-02 19714E-05 23073E-03 23522E-07 -54231E-10 Remaining SSD is 19453 Weighted distances x-value x-dist y-dist 100E+00 190E-01 -239E-01 666E-01 200E+00 200E-01 487E-01 -104E+00 300E+00 210E-01 -247E-01 248E-01 Goodness-of-fit measure 10414 Parameter set 1 1164239985182795E-2 1971441115316992E-5 2307269625077337E-3 2352198415608386E-7 -
5423119774765299E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19837E-01 14840E-04 94718E+03 45610E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
13
Measurement 2
Date Result (molmol)
stand deviation ( relative)
number of sub measurements
Carbon dioxide 20050614 0135554 0048 5
Carbon monoxide 20050614 0029815 0075 5
Propane 20050614 0002001 0045 5
Measurement 3
Date Result (molmol)
stand deviation ( relative)
number of sub measurements
Carbon dioxide 20050718 0135500 0049 5
Carbon monoxide 20050718 0029820 0105 5
Propane 20050718 0002003 0050 5
Results
Gas mixture Result (assigned value)
Coverage factor
Assigned expanded
uncertainty
Carbon dioxide 013557 2 000013
Carbon monoxide 002980 2 000006
Propane 0002002 2 0000003
14
II Description of Study
Instruments Multichannel automatic NDIR analyzer included to the set of the National Primary measurement standard of units of mole fraction and mass concentration of components in gas medium GET 154-01 was used for the analysis Calibration Standards All calibration multicomponent gas mixtures were prepared gravimetrically according to ISO 6142 The calibration multicomponent gas mixtures were prepared from pure gases directly on components CO CO2 and from pre-mixtures which were prepared from pure gases on component С3Н8 The content of the impurities in all pure gases was determined by GC with helium-ionization flame-ionization and thermal-conductivity detectors as well as standard hygrometer apparatus included to the standard complex A1 of analysis of pure gases and substances from GET 154-01 The calibration multicomponent gas mixtures were verified with usage of existing gravimetric gas mixtures in accordance with ISO 6143 Composition of calibration standards
Cylinder 6547 Cylinder 6571 Cylinder 6538 Component x мольmol Standard
Instrument Calibration Three independent measurements were carried out under repeatability conditions Before each measurement an instrument calibration was made One measurement contained 5 submeasurements Sample Handling The time of the cylinder keeping is 24 hrs It was used the automatic unit of commutation for inputting gas mixtures
15
Uncertainty Uncertainty table СО2
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas
mixture
B 0010 1 0010
Analysis A B 0048 1 0048
Coverage factor 2 Expanded uncertainty 01 Uncertainty table СО
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas
mixture
B 002 1 002
Analysis A B 0095 1 0095
Coverage factor 2 Expanded uncertainty 019
16
Uncertainty table С3Н8 Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas
mixture
B 005 1 005
Analysis A B 0045 1 0045
Coverage factor 2 Expanded uncertainty 013
17
MEASUREMENT REPORT ndash Belorussian State Institute for Metrology Belarus (BelGIM)
I Results of experimental study
Laboratory Belarus BelGIM Section for physicochemical and optical measurements sector for standards and gas mixtures 8 Serova st Minsk Cylinder No 0128 9 dm3 aluminium NOMINAL COMPOSITION - Carbon dioxide 13middot10-2 - 14middot10-2 molmol - Carbon oxide 28middot10-2 - 32middot10-2 molmol - Propane 19middot10-4 - 21middot10-4molmol - Nitrogen Residual
Measurement No1 Date
Result (molmol)
x_
Standard deviation
S( x_
) rel
No of observations
n
Carbon dioxide 17062005 13567middot10-2 0096 6
Carbon oxide 17062005 2957middot10-2 014 6
Propane 17062005 1977middot10-4 015 6
Measurement No2 Date
Result (molmol)
x_
Standard deviation
S( x_
) rel
No of observations
n
Carbon dioxide 21062005 13564middot10-2 004 6
Carbon oxide 21062005 2957middot10-2 02 6
Propane 21062005 1979middot10-4 01 6
18
Measurement No3 Date
Result (molmol)
x_
Standard deviation
S( x_
) rel
No of observations
n
Carbon dioxide 23062005 13537middot10-2 007 6
Carbon oxide 23062005 2955middot10-2 01 6
Propane 23062005 1982middot10-4 01 6
Final results
Gas mixture Result
(molmol)
Coverage factor
Expanded uncertainty (molmol)
Carbon dioxide 136middot10-2 2 01 middot10-2
Carbon oxide 296middot10-2 2 002middot10-2
Propane 198middot10-4 2 02middot10-4
II Description of study Apparatus (principle of operation type configuration data collection etc)
Measurements were carried out using gas chromatograph Crystal 2000М (hereinafter
referred to as chromatograph) combined with thermal conductivity detector (hereinafter referred to as TCD) with detection limit of 510-9 gml for propane and flame-ionization detector (hereinafter referred to as FID) with detection limit of 510-12 gs for propane
Computers and software Chromatech Analytic version 121 were used to control chromatograph and collect and process chromatographical data
For the purpose of measurements the following auxiliary devices and materials were used
1 Two-position doser with 10 ports and with doses of 025 cm3 for FID channel and with doses of 025 cm3 for TCD channel (hereinafter referred to as doser)
2 Metallic packed column 3m х 3mm х 2mm - HayeSep N 80100 metallic packed column 1m х 4mm х 2mm-CaA 016025 (TCD channel) capillary column HP PLOTQ 30m х 0536mm (FID channel)
3 Aneroid BАММ-1 with a measurement range of 80-106 kPа and accuracy of plusmn 02 kPа
4 Mercurial thermometer ТL-4 with a measurement range of 0-50ordmС and scale division of 01ordmС
19
5 Fine adjustment valve (hereinafter referred to as FAV) provided to transport a gas sample into chromotograph and set to gas flow-rate of 10-15 mlmin
6 Foamy gas flow meter type YIRG - 2А accuracy of flow measurement plusmn 1 сm3min
7 Helium gas Type A according to TU 51-940-80 8 High purity hydrogen gas according to TU 301-07-27-90 9 Compressed air 10 Multicomponent calibration gas mixtures (hereinafter referred to as CGM)
produced and certified by gravimetric method
Calibration reference materials - calibration gas mixtures used for measurements 1 Quantitative composition of KGS is determined using gravimetric method defined in
ISO 61422001 by calculating weight of each component of a gas mixture The content of CGM components is expressed as a mole fraction Uncertainty of KGS composition is expressed as expanded uncertainty with coverage factor k = 2 Molar masses of components and their uncertainties are taken from ISO 149122003 Performance and metrological characteristics of the equipment used for gravimetric preparation of mixtures are given in Table 1
Table 1
Description of the equipment
Manufacturer Metrological characteristics
Mass-comparator balance type КА10-3Р
Mettler-Toledo
Switzerland
Maximum load 15 kg Scale division 1 mg Standard deviation 19 mg at load of 10 kg Operating temperature range +10divide30degС Maximum temperature change within 1 h plusmn05 degС
Gas mixer type USG 00001 BelGIM
Measurement range 000025 divide 100 МPa Accuracy class for manometers ndash 015 Accuracy class for vacuummeters ndash 025 Vacuummeter with pressure sensor for measuring the residual pressure before filling Residual pressure before filling of each component not more than 20 Pa
2 Purity analysis of primary gas standards
The purity analysis of primary gas standards is based on the information provided by the supplier or on the results of determination of impurity in pure gases using measurement procedure developed inside BelGIM
20
If an analytical method laid down in 43 of ISO 61422001 cannot be used for impurity determination mole fraction of an expected impurity is assumed to be half of the detection limit of the analytical method The content of the undetected impurity produces rectangular distribution
whereby its standard uncertainty is calculated as half of the detection limit divided by 3 The composition of the pure gases used for preparation of calibration mixtures is given
in Table 2 Table 2 - Metrological characteristics of pure gases
N2 999967 00005 Nitrogen Cylinder 40 dm3 Origin Russia O2 00033 00005 Propane Cylinder 2 dm3 Origin Russia
C3H8 9979 0017
3 After preparation of mixture the cylinder was maintained in laboratory room within
24 hours the mixture then was homogenized on the stand by rotating on the rollers within 4-5 hours The chromotograph for CGM was calibrated 2-3 days after its preparation
Calibration of the chromotograph
1 The chromotograph was calibrated using CGMs with composition identical to the analyzed sample The content of each component and its expanded uncertainty (k = 2) are given in Table 1 Table 1 - Calibrationе gas mixtures
2 Number of observations of each calibration sample- 3 Number of calibration samples - 3
3 The analytical function used for determination of the content of the analyzed sample components is as follows
x (y) =b1y+b0 (2) Where x ndash determined content molmol y - chromotograph response for the specific component b1- slope b0 - intercept 4 After completion of calibration the coefficients of analytical function were
calculated according to ISO 61432001 using generalized least-squares method Also the uncertainties of the intercept and slope and covariance between them were calculated After determination of parameters which are part of analytical function and which affect the uncertainty of measurements it was checked whether the analytical function is fit to the experimental data obtained in calibration and subsequently whether the analytical function is applicable
Results of calibration measurements coefficients of analytical function their uncertainties covariance and measure of goodness-of-fit Г (maximum value of the weighted differences of the experimental points and calculated points of the analytical function for each measurement run) are given in Tables 3 and 4 respectively Chromotograph operating conditions in calibration and analysis are given in Table 5
Table 3 - Results of experimental study
Date Component of
calibration mixture
Content x mole fraction
Expanded uncertainty
U(x) mole fraction
Mean of peak area y
mVs
Uncertainty )(yu
mVs
13374 0004 1279500 141 1389 0004 1329150 2899 CO2
12833 0004 1231000 849 2916 0005 404070 240
316 0005 437705 926 CO 2768 0004 383070 467
019 0002 3143200 4101
1706 2005
C3H8 0202 0002 3319150 2051
22
0181 0002 2948750 212 13374 0004 1269833 624
1389 0004 1321000 1272 CO2 12833 0004 1223900 1698
2916 0005 399490 612 316 0005 434010 863 CO
2768 0004 379660 410 019 0002 3157867 6772
0202 0002 3332400 3394
2106 2005
C3H8 0181 0002 2959900 4950
13374 0004 1277100 2152 1389 0004 1329900 2828 CO2
12833 0004 1229100 1980 2916 0005 400330 529
316 0005 434745 969 CO 2768 0004 379695 106
019 0002 3142433 9416 0202 0002 3321600 4101
2306 2005
C3H8 0181 0002 2961000 3111
According to ISO 61432003 calculation of the measure of goodness-of-fit Г is the maximum value of the weighed differences between the coordinates of measured and adjusted calibration points is an effective and simple method to test the compatibility of а prospective analytical function A function is admissible if Г le 2
minus
minus=
)(ˆ
)(ˆ
iii
iii
yuyy
xuxxΓ
(4) Where хi is the reference value of the content of calibration sample component
ix is the CGM component content obtained using the calculated analytical function
уi is the experimental response to the reference content of component iy is the response obtained in calculation of analytical function
u (хi) u (уi) are the uncertainties of reference contents and responses to these contents respectively
i is the number of calibration points i=1 3 This prerequisite is equivalent to the requirement that the curve of calculated response should cross each experimental calibration rectangular [хi plusmn 2u(хi) уi plusmn 2и(уi)] based on an expanded uncertainty U = ku with coverage factor k = 2 Table 4 Calculations of analytical function
Date Component Analytical function parameters
Uncertainty of analytical
function parameters
Covariance of
parameters Г
23
b1 b0 u(b1) u(b0) u(b0b1) 1706 11086E-
03 -81128E-
0119491E-
0524883E-
01 -48497E-06 10544
2106 10729E-03
-26126E-01
22698E-05
28930E-01 -65652E-06 19997
2306
CO2 10593E-
03 -17688E-
0135807E-
0545413E-
01 -16254E-05 10022
1706 71537E-04
26507E-02
14231E-05
57044E-02 -81115E-07 03017
2106 72346E-04
22401E-02
13819E-05
54490E-02 -75209E-07 05935
2306
CO 71321E-
04 60080E-
0212663E-
0549016E-
02 -62026E-07 01341
1706 56521E-06
13712E-02
38279E-07
12015E-02 -45937E-09 12991
2106 56295E-06
13707E-02
39247E-07
12379E-02 -48529E-09 12905
2306
C3H8 58258E-
06 80469E-
0340085E-
0712590E-
02 -50407E-09 08589
Two columns separated by switching device are located one after another in TCD
channel One column is intended for carbon dioxide heavy hydrocarbons and another column is intended for light gases Before the first switch the light gases including carbon oxide flow through the first column without being separated and remain in the second column The switch makes them locked in the second column The analysis of carbon dioxide is carried out up to the second switch Second switch makes the second column unlocked and carbon oxide is analyzed Third switch is required to allow propane escape from a column and prevent it from getting into a second column The analysis of the very propane is carried out using FID Time intervals between switches were selected experimentally when developing the analysis method Such analysis method makes it possible to analyze all three components per one sample inject
Table 5 - Chromotograph operating conditions in calibration and analysis Parameter of the operating conditions Thermostating temperature of TCD and FID degС 170
Temperature of separation columns degС
Program 60 degС within 9 min
than rise to 160 degС at 20degСmin
Rate of flow of carrier gas through TCD channel columns mlmin 15
Rate of flow of carrier gas through TCD comparison channel mlmin 15
Pressure in FID channel column kPa Program
24
80 to 100 Rise from the 1st s of
analysis at 2 kPamin
Flow-rate of hydrogen FID mlmin 20 Flow-rate of air FID mlmin 200 Temperature of switching device degС 65 Response time of switching device s 1 110 2 330 3 540
TCD FID Volume of injected analyzed gas cm3 025 025 Carrier gas Helium Duration of analysis min 17 Calculation of the content of comparison sample components and its uncertainty Results of comparison sample measurements are given in Table 6 Table 6 - Results of comparison sample measurements
1 The content of comparison sample component and its uncertainty were determined
using calculated analytical function according to ISO 61432001 as follows (5) Where G(y)=b1y+b0 is the calculated analytical function и(y) is the standard uncertainty of response y u2(bj) is the variance of analytical function parameter bj
u(bj bI) is the covariance of analytical function parameters bj bI N is the number of function coefficients N=2 j=0 1
sum sumsumminus
= +==
partpart
partpart
+
partpart
+
partpart
=1
0 1
2
2
0
22
)(2)()()(N
jIj
N
jI Ijj
N
j j
bbubG
bGbu
bGyu
yGxu
25
After substitution of analytical function (2) and transformations the expression takes form (5)
)(2)()()()()( 01122
0222
1 bbyubuybuyubxu +++= (6) The contents of comparison sample components under determination and their
uncertainties were calculated using B_LEAST a computer program recommended in ISO 6143 Calculations are summarized in Table 6
Table 6 Calculations of the content of comparison sample components and their
2 The final content of a component was determined as an arithmetiс mean from three measurements Final standard uncertainty was calculated using formula as follows
22
222)( Адаватмтемсериикал uuuuuxu ++++= (7)
Where ucal is the uncertainty of the component content produced by
calibration of chromotograph urun is the uncertainty of the component content produced by
change of chromotograph response in each measurement run ut is the uncertainty of the component content produced by
change of an ambient temperature upressure is the uncertainty of the component content produced by
change of atmospheric pressure u A is the standard uncertainty of three measurement runs
21 Uncertainty of the component content produced by calibration of chromotograph
This uncertainty is calculated using formula (6) but the first term of the sum ie
)()( 221 yub which represents the standard uncertainty of the chromotograph response in a
measurement run is not taken into account Calculations are summarized in Table 7
26
Table 7 Calculation of uncertainty produced by calibration of chromotograph
Date u(b1) u(b0) u(b0b1) x
molmol y Ucal molmol
Ucal rel
1706 19491E-05
24883E-01
-48497E-06
13567middot10-
2129698
3 0005middot1
0-2 003
2106 22698E-05
28930E-01
-65652E-06
13564middot10-
2 128855 0007middot1
0-2 005
2306
CO2
35807E-05
45413E-01
-16254E-05
135374middot10-2
1294633
0016middot10-2 012
1706 14231E-05
57044E-02
-81115E-07 2957middot10-2 409633
0003middot10-2 009
2106 13819E-05
54490E-02
-75209E-07
29577middot10-
2 405663 0003middot1
0-2 01
2306
CO
12663E-05
49016E-02
-62026E-07 2955middot10-2 405882
0003middot10-2 01
1706 38279E-07
12015E-02
-45937E-09 1977middot10-4
3255817
007middot10-
2 038
2106 39247E-07
12379E-02
-48529E-09 1980middot10-4
3273329
008middot10-
2 038
2306
C3H8
40085E-07
12590E-02
-50407E-09 1982middot10-4 32636
008middot10-
2 04 The total estimate of relative uncertainty produced by calibration of chromotograph was
calculated for each component as follows
3
3
1
2sum=
cali
cali
uu (8)
Where ucal i is the relative uncertainty produced by calibration of chromotograph and calculated for each measurement run
The calculations are summarized in Table 8
Table 8 Uncertainty produced by calibration of chromotograph
Component Ucal rel
CO2 008 CO 01
C3H8 04 22 Uncertainty of the component content produced by change of chromotograph response in each measurement run This uncertainty is calculated using the equation (6) whereby the first term of the sum
only ie )()( 221 yub which represents the standard uncertainty of the chromotograph
response in a measurement run is taken into account Calculations are summarized in Table 9
27
Table 9 Calculation of uncertainty produced by change of chromotograph response in each measurement run
The total estimate of relative uncertainty produced by change of chromotograph
response in each measurement run was calculated for each component as follows
3
3
1
2sum=
run
run
uu (9)
Where urun is the relative uncertainty produced by change of chromotograph response in each measurement run Calculations are summarized in Table 10
Table 10 Uncertainty produced by change of chromotograph response in each measurement
run
Component Urun rel
CO2 007 CO 015
C3H8 012 23 Uncertainty of the component content produced by change of temperature in a room
The recorded change of temperature in measurements is plusmn 05 degree The contribution of uncertainty type B (rectangular distribution) is estimated as follows
201003
12931
=sdotsdot=tu rel
28
24 Uncertainty of the component content produced by change of atmospheric pressure The recorded change of atmospheric pressure within three days was
05 kPа The contribution of uncertainty type B (rectangular distribution) is estimated as follows
2801003
13101
50=sdotsdot=pressureu rel
25 Standard deviation of 3 measurement runs Standard deviation is calculated as follows
isu p
A
2
= (10)
Where S2p is the group experimental variation
The group experimental variation is calculated as follows
(11)
Where si
2 is the experimental variation of measurement run i from independent repeated observations ni having freedom degrees
νi = n - 1 n=6 i= 3 Calculations are summarized in Table 11 Table 11 Calculations of standard uncertainty of 3 measurement runs
Date 2iS x
molmol 2iS
rel uA
rel
1706 2953E-05 13567middot10-2 000022
2106 588987E-06 13564middot10-2 0000043
2306
CO2 141137E-
05 135374middot10
-2 000010
0006
1706 225604E-06 2957middot10-2 0000077
2106 681346E-06 29577middot10-2 000023
2306
CO
175166E-06 2955middot10-2 0000060
0006
1706 C3H8 130158E-
08 1977middot10-4 00000066 0001
ss
p
i ii
N
ii
N2
2
1
1
= =
=
sum
sum
ν
ν
29
2106 44616E-09 1980middot10-4 00000023
2306
381032E-09 1982middot10-4 00000019
26 Total standard uncertainty
Uncertainty estimation СО2
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph ucal Normal 008 1 008
Change of temperature ut Rectangular 02 1 02 Change of atmospheric pressure upressure Rectangular 028 1 028
Changes of chromotograph response
urun Normal 007 1 007
Standard deviation of 3 runs uA Normal 0006 1 0006
Relative total standard uncertainty 036 Coverage factor k=2 Expanded uncertainty 01middot10-2 molmol Uncertainty estimation СО
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph ucal Normal 01 1 01 Change of temperature ut Rectangular 02 1 02 Change of atmospheric pressure upressure Rectangular 028 1 028 Changes of chromotograph response
urun Normal 015 1 015
Standard deviation of 3 runs uA Normal 0006 1 0006
Relative total standard uncertainty 039 Coverage factor k=2 Expanded uncertainty 002middot10-2 molmol Uncertainty estimation С3Н8
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph 04 Normal 04 1 008
30
Change of temperature 02 Rectangular 02 1 02 Change of atmospheric pressure 028 Rectangular 028 1 028
Changes of chromotograph response
012 Normal 012 1 007
Standard deviation of 3 runs 0001 Normal 0001 1 0006
Relative total standard uncertainty 054 Coverage factor k=2 Expanded uncertainty 02middot10-4 molmol
Sample handling
Period for exposure of cylinder to measurement conditions and method how to transport sample to the device
1 Stands for storing gas standard cylinders and calibration mixture cylinders and chromotograph are placed in a laboratory room which is not accessible to unauthorized persons The laboratory is equipped with air-conditioner to maintain required temperature and humidity on a continuous basis and some auxiliary measuring instruments as thermometer psychrometric hygrometer and aneroid to control temperature humidity and atmospheric inside the room
2 The comparison sample cylinder was stored in laboratory from the date of its
delivery to Minsk on 25042005 CGM cylinders are stored horizontally on racks and positioned vertically using special support when measurements are carried out
3 The analyzed gas sample is transported through the fine adjustment valve (FAV)
Conjunctions Cylinder - FAV FAV - tube tube - doser are made of metal and use adapters with spherical ends and bushes FAV is made of brass tube is made of copper and doser is made of duralumin
Instrument(s) (principles make type configuration data collection etc) For the analysis a GC were used with specifically applications For the determination of (Nitrogen (N2)) Carbon Dioxide (CO2) Carbon Monoxide (CO) and Propane (C3H8) balance GC Perkin Elmer AutoSystem XL (two channel system) with a stream selection valve for 4 streams and 2 gas sampling valves
Channel A for the determination of N2 CO and CO2 Carrier Gas Helium Columns Column system with two packed columns (6 ft x 18rdquo Porapak R 80100 mesh and 6 ft x 18rdquo Mol-Sieve 13X 80100 mesh) Oven Temperature 960 degC to 180 degC Detector micro-TCD Data Collection Total Chrom Workstation Channel B for the determination of C3H8 Carrier Gas Helium Columns Capillary column 50 m x 032 microm LP-SIL-8-CB Oven Temperature 60 degC to 180 degC Detector FID Data Collection Total Chrom Workstation
34
Calibration Standards
Calibration Standards for the measurements (preparation method purity analyses estimated uncertainty etc)
All standards were prepared individually according to ISO 6142 rdquoGas analysis - Preparation of calibration gases - Gravimetric Methodrdquo
Depending on the concentration of the components standards were prepared individually from pure gases or from pre-mixtures which were individually prepared from pure gases
The content of the impurities in all pure gases were determined before use by GC-DID GC-FID and or GC-TCD
After preparation the standards were verified by analytical comparisons against existing gravimetrically prepared standards Only when no significant difference between the analysed and the calculated gravimetric composition is found the ldquonew prepared candidate rdquo is accepted as a new standards
For the analysis of all components multi component standards with nitrogen as balance gas were used
Composition of calibrants BAM C49250-050722 Component Assigned value( x)
mmol mol Standard uncertainty (u(x)) relativ (k=2)
Calibration procedure (mathematical modelcalibration curve number and concentrations of standards measurement sequence temperaturepressure correction etc)
For the instrument calibration the bracketing technique was used The fraction of the current used standards deviated no more than +10rel and -10rel respectively from those of the sample
Measurement sequence
Sample Handling
How were the cylinders treated after arrival (eg stabilized) and how were samples transferred to the instrument (automatic high pressure mass-flow controller dilution etc) After heating (45 - 50 degC) the cylinder for 8 hours the cylinder were rolled about 16 hours before analysis was started Each cylinder was equipped with a pressure regulator that was purged three times by sequential evacuation and pressurisation with the gas mixture used Continous flow (2 ndash 3mlmin) through the sample loop
Uncertainty The specification of potential uncertainty sources is given in Annex 3
3 injection standard (high)
3 injection sample
3 injection standard (high)
3 injection sample
3 injection standard (low)
3 injection sample
3 injection standard (low)
3 injection standard (low)
36
Uncertainty table CO2
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 002 rel 1 002 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 03 rel
Uncertainty table CO
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 007 rel 1 007 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 05 rel
37
Uncertainty table C3H8
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 010 rel 1 001 rel
Analysis normal 028 rel 1 028 rel
Coverage factor 2
Expanded uncertainty 06 rel
Optional
You may provide additional data like the raw measurement data information on your
measurement procedure chromatograms etc
38
Appendix 3 SPECIFICATION OF POTENTIAL UNCERTAINTY SOURCES
a Uncertainty related to the balance and the weights Resolution of balance Accuracy of balance including linearity Incorrect zero point Drift (thermal and time effects) Instability due to draught Location of cylinder on the balance pan Uncertainties in the weights used Buoyancy effects on the weights used
b Uncertainties related to the gas cylinder Mechanical handling of cylinder
Loss of metal paints or labels from surface of cylinder Loss of metal from threads of valvefitting Dirt on cylinder valves or associated fitting
Absorptiondesorption effects on the external cylinder surface Buoyancy effects on the cylinder itself
Cylinder temperature differs from surrounding air due to eg filling with gas Change of cylinder volume during filling Change of density of surrounding air due to changes in temperature air pressure humidity and carbon dioxide content
Uncertainty in determination of external cylinder volume c Uncertainties related to the component gases Residual gas in cylinder Leakage Leakage of air into the cylinder after evacuation
Leakage of gas from the cylinder valve during filling Escape of gas from cylinder into transport lines
Gas remaining in transfer system when weight loss method is used Absorptionreaction of components on internal cylinder surface Reaction between components Impurities in all the initial gases Insufficient homogenization Uncertainty of molecular mass d Uncertainties related to the analysis
Repeatability and selectivity of the analyzer Appropriateness of the calibration curve
39
MEASUREMENT REPORT - All Ukrainian State Research-Industrial Center of Standardization Metrology Certification and Protection of Consumers Ukraine
gas ndash helium flow rate 15 cm3min detector TCD tdetector = 250 ordmС toven = 70 ordmС It was automatic data collection
Measurement and Calibration Methods Laboratory Measurement method Type of calibration curve
GCFID (С3Н8) 3 points linear Ukrmetrteststandard GCTCD (СО СО2) 3 points linear
GCFID ndash gas-chromatographic with flame-ionization detector GCTCD - gas-chromatographic with thermal-conductivity detector
42
Calibration Standards
Calibration standards ndash primary standard gas mixtures (PSGM) used for measurements by comparison method
PSGM-1 Cylinder 0116
PSGM-2 Cylinder 0107
PSGM-3 Cylinder 0093 Composition
x u(x) x u(x) x u(x) СО 27874 00015 29899 00015 31891 00015 СО2 130187 00015 144456 00016 137016 00016 С3Н8 019003 000008 020017 000008 021013 000008 N2 balance balance balance
Note x ndash mole fraction u(x) ndash absolute standard uncertainty
It was used gravimetric method of preparation of PSGM Electronic balance КА-20-3 of Mettler Toledo max limit of weighing is 20 kg least
limit of weighing is 01 g standard deviation is 0006 g Analysis of purity of parent gases was carried out with usage of chromatographs
НР6890N with helium ndash ionization detector flame ndash ionization detector thermal ndash conductivity detector and mass ndash spectrometric detector as well аs gas analyzers GIAM-15M and Onix condensate-thermometer hygrometer TOROS-3-2B
Calculation of uncertainties was carried out according to ISO 6142-2003 Corrections of temperature pressure and humidity of environment were considered
in calculations according to ISO 6142-2003 (program of ISO-6142 2000-03-17 designer is NMi) Protocols and explanations are in Annex A
Instrument (Comparator) Calibration Calibration of comparator ndash gas chromatograph HP 6890 was carried out with usage
of PSGM Measurement sequence PSGM -1 х 3 PSGM -2 х 3 COOMET gas mixture х 3 PSGM -2 х 3 PSGM -3 х 3 It is necessary to use PSGM-2 repeatedly for estimation of reproducibility of results
Program B_LEAST recommended by ISO 6143-2003 was used for constructing the curve Mathematical model of calibration curve is linear one
Sample Handling The cylinder was kept for 24 hrs at a room where comparators were disposed This room is a thermostatic room with t = (20plusmn2) ordmС
43
A method of sample input to a comparator is a method with flow stabilization Uncertainty The following uncertainties were included to the budget of uncertainty - uncertainty of the balance - uncertainties of impurities in parent gases Contribution from other uncertainty sources was insignificant A cabin of the balance is thermostatically The balance is the one-pan balance
Air transfer is absent in the cabin of the balance Drift of the balance is absent for PSGM preparation
Contribution from other uncertainty sources was considered in software according to ISO 6142-2003
Uncertainties related to the analysis (comparison) were considered in software according to ISO 6143-2003 and enclosed in Annex B
Uncertainty table СО2
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas mixture
B 001 1 001
Analysis A B 008 1 008
Coverage factor 2 Expanded uncertainty 002sdot10-2 molmol Uncertainty table СО
Protocols of analysis (comparison) in accordance with ISO 6143-2003
57
Explanation of protocols of comparison
Chapter I ldquoThe calibration data set isrdquo contains columns 1 mole fraction of a component 2 absolute standard uncertainty of mole fraction of a component 3 a signal of a comparator 4 absolute standard uncertainty of a comparator signal
Chapter II ldquoResults of ISO 6143 methodrdquo contains parameters of a calibration curve including its
uncertainty
Chapter ІІІ ldquoPart II Processing of datardquo contains columns
1 calc x - the results of comparison mole fraction of a component 2 u(x) - absolute standard uncertainty of mole fraction of a component 3 response y - a signal of a comparator 4 u(y) - absolute standard uncertainty of a comparator signal
58
СО2 - measurement 1 Data setCO2_21 The calibration data set is 1302E+01 1510E-03 1022E+04 1820E+00 1370E+01 1560E-03 1077E+04 2730E+00 1445E+01 1620E-03 1135E+04 5900E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 20331E-02 12711E-03 12573E-01 11653E-05 -14638E-06 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 10548E-02 12722E-03 31762E-02 28898E-06 -91698E-08 Remaining SSD is 74346 Weighted distances x-value x-dist y-dist 100E+00 130E+01 490E-01 -755E-01 200E+00 137E+01 -103E+00 228E+00 300E+00 144E+01 539E-01 -250E-01 Goodness-of-fit measure 22837 Parameter set 1 1054788657490729E-2 1272208026684145E-3 3176237146276368E-2 2889798108124711E-6 -
9169821653851327E-8 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_21c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13577E+01 25542E-03 10664E+04 15200E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 547E-06 328E-06 316E-06 784E-06 286E-06 652E-06 Linear model Parameters for the fit were (b0 b1) 10548E-02 12722E-03
59
СО2 - measurement 2
Data setCO2_20 The calibration data set is 1302E+01 1512E-03 1021E+04 4723E+00 1370E+01 1563E-03 1075E+04 1600E+00 1445E+01 1620E-03 1133E+04 7300E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -38760E-02 12784E-03 26817E-02 24890E-06 -66689E-08 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -62452E-02 12805E-03 47930E-02 43243E-06 -20716E-07 Remaining SSD is 03231 Weighted distances x-value x-dist y-dist 100E+00 130E+01 107E-01 -415E-01 200E+00 137E+01 -212E-01 283E-01 300E+00 144E+01 104E-01 -584E-02 Goodness-of-fit measure 04155 Parameter set 1 -6245240430658412E-2 1280492624666799E-3 4792952200361109E-2 4324266278840409E-6 -
2071623966851869E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_20c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13594E+01 10290E-02 10665E+04 78300E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 121E-05 683E-06 651E-06 315E-05 560E-06 106E-04 Linear model Parameters for the fit were (b0 b1) -62452E-02 12805E-03
60
С3Н8 - measurement 1
Data setC3H8 The calibration data set is 1900E-01 7800E-05 9057E+03 1098E+01 2002E-01 7900E-05 9552E+03 8569E+00 2101E-01 7960E-05 1007E+04 4049E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10529E-02 19831E-05 34552E-03 36109E-07 -12465E-09 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11642E-02 19714E-05 23073E-03 23522E-07 -54231E-10 Remaining SSD is 19453 Weighted distances x-value x-dist y-dist 100E+00 190E-01 -239E-01 666E-01 200E+00 200E-01 487E-01 -104E+00 300E+00 210E-01 -247E-01 248E-01 Goodness-of-fit measure 10414 Parameter set 1 1164239985182795E-2 1971441115316992E-5 2307269625077337E-3 2352198415608386E-7 -
5423119774765299E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19837E-01 14840E-04 94718E+03 45610E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
14
II Description of Study
Instruments Multichannel automatic NDIR analyzer included to the set of the National Primary measurement standard of units of mole fraction and mass concentration of components in gas medium GET 154-01 was used for the analysis Calibration Standards All calibration multicomponent gas mixtures were prepared gravimetrically according to ISO 6142 The calibration multicomponent gas mixtures were prepared from pure gases directly on components CO CO2 and from pre-mixtures which were prepared from pure gases on component С3Н8 The content of the impurities in all pure gases was determined by GC with helium-ionization flame-ionization and thermal-conductivity detectors as well as standard hygrometer apparatus included to the standard complex A1 of analysis of pure gases and substances from GET 154-01 The calibration multicomponent gas mixtures were verified with usage of existing gravimetric gas mixtures in accordance with ISO 6143 Composition of calibration standards
Cylinder 6547 Cylinder 6571 Cylinder 6538 Component x мольmol Standard
Instrument Calibration Three independent measurements were carried out under repeatability conditions Before each measurement an instrument calibration was made One measurement contained 5 submeasurements Sample Handling The time of the cylinder keeping is 24 hrs It was used the automatic unit of commutation for inputting gas mixtures
15
Uncertainty Uncertainty table СО2
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas
mixture
B 0010 1 0010
Analysis A B 0048 1 0048
Coverage factor 2 Expanded uncertainty 01 Uncertainty table СО
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas
mixture
B 002 1 002
Analysis A B 0095 1 0095
Coverage factor 2 Expanded uncertainty 019
16
Uncertainty table С3Н8 Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas
mixture
B 005 1 005
Analysis A B 0045 1 0045
Coverage factor 2 Expanded uncertainty 013
17
MEASUREMENT REPORT ndash Belorussian State Institute for Metrology Belarus (BelGIM)
I Results of experimental study
Laboratory Belarus BelGIM Section for physicochemical and optical measurements sector for standards and gas mixtures 8 Serova st Minsk Cylinder No 0128 9 dm3 aluminium NOMINAL COMPOSITION - Carbon dioxide 13middot10-2 - 14middot10-2 molmol - Carbon oxide 28middot10-2 - 32middot10-2 molmol - Propane 19middot10-4 - 21middot10-4molmol - Nitrogen Residual
Measurement No1 Date
Result (molmol)
x_
Standard deviation
S( x_
) rel
No of observations
n
Carbon dioxide 17062005 13567middot10-2 0096 6
Carbon oxide 17062005 2957middot10-2 014 6
Propane 17062005 1977middot10-4 015 6
Measurement No2 Date
Result (molmol)
x_
Standard deviation
S( x_
) rel
No of observations
n
Carbon dioxide 21062005 13564middot10-2 004 6
Carbon oxide 21062005 2957middot10-2 02 6
Propane 21062005 1979middot10-4 01 6
18
Measurement No3 Date
Result (molmol)
x_
Standard deviation
S( x_
) rel
No of observations
n
Carbon dioxide 23062005 13537middot10-2 007 6
Carbon oxide 23062005 2955middot10-2 01 6
Propane 23062005 1982middot10-4 01 6
Final results
Gas mixture Result
(molmol)
Coverage factor
Expanded uncertainty (molmol)
Carbon dioxide 136middot10-2 2 01 middot10-2
Carbon oxide 296middot10-2 2 002middot10-2
Propane 198middot10-4 2 02middot10-4
II Description of study Apparatus (principle of operation type configuration data collection etc)
Measurements were carried out using gas chromatograph Crystal 2000М (hereinafter
referred to as chromatograph) combined with thermal conductivity detector (hereinafter referred to as TCD) with detection limit of 510-9 gml for propane and flame-ionization detector (hereinafter referred to as FID) with detection limit of 510-12 gs for propane
Computers and software Chromatech Analytic version 121 were used to control chromatograph and collect and process chromatographical data
For the purpose of measurements the following auxiliary devices and materials were used
1 Two-position doser with 10 ports and with doses of 025 cm3 for FID channel and with doses of 025 cm3 for TCD channel (hereinafter referred to as doser)
2 Metallic packed column 3m х 3mm х 2mm - HayeSep N 80100 metallic packed column 1m х 4mm х 2mm-CaA 016025 (TCD channel) capillary column HP PLOTQ 30m х 0536mm (FID channel)
3 Aneroid BАММ-1 with a measurement range of 80-106 kPа and accuracy of plusmn 02 kPа
4 Mercurial thermometer ТL-4 with a measurement range of 0-50ordmС and scale division of 01ordmС
19
5 Fine adjustment valve (hereinafter referred to as FAV) provided to transport a gas sample into chromotograph and set to gas flow-rate of 10-15 mlmin
6 Foamy gas flow meter type YIRG - 2А accuracy of flow measurement plusmn 1 сm3min
7 Helium gas Type A according to TU 51-940-80 8 High purity hydrogen gas according to TU 301-07-27-90 9 Compressed air 10 Multicomponent calibration gas mixtures (hereinafter referred to as CGM)
produced and certified by gravimetric method
Calibration reference materials - calibration gas mixtures used for measurements 1 Quantitative composition of KGS is determined using gravimetric method defined in
ISO 61422001 by calculating weight of each component of a gas mixture The content of CGM components is expressed as a mole fraction Uncertainty of KGS composition is expressed as expanded uncertainty with coverage factor k = 2 Molar masses of components and their uncertainties are taken from ISO 149122003 Performance and metrological characteristics of the equipment used for gravimetric preparation of mixtures are given in Table 1
Table 1
Description of the equipment
Manufacturer Metrological characteristics
Mass-comparator balance type КА10-3Р
Mettler-Toledo
Switzerland
Maximum load 15 kg Scale division 1 mg Standard deviation 19 mg at load of 10 kg Operating temperature range +10divide30degС Maximum temperature change within 1 h plusmn05 degС
Gas mixer type USG 00001 BelGIM
Measurement range 000025 divide 100 МPa Accuracy class for manometers ndash 015 Accuracy class for vacuummeters ndash 025 Vacuummeter with pressure sensor for measuring the residual pressure before filling Residual pressure before filling of each component not more than 20 Pa
2 Purity analysis of primary gas standards
The purity analysis of primary gas standards is based on the information provided by the supplier or on the results of determination of impurity in pure gases using measurement procedure developed inside BelGIM
20
If an analytical method laid down in 43 of ISO 61422001 cannot be used for impurity determination mole fraction of an expected impurity is assumed to be half of the detection limit of the analytical method The content of the undetected impurity produces rectangular distribution
whereby its standard uncertainty is calculated as half of the detection limit divided by 3 The composition of the pure gases used for preparation of calibration mixtures is given
in Table 2 Table 2 - Metrological characteristics of pure gases
N2 999967 00005 Nitrogen Cylinder 40 dm3 Origin Russia O2 00033 00005 Propane Cylinder 2 dm3 Origin Russia
C3H8 9979 0017
3 After preparation of mixture the cylinder was maintained in laboratory room within
24 hours the mixture then was homogenized on the stand by rotating on the rollers within 4-5 hours The chromotograph for CGM was calibrated 2-3 days after its preparation
Calibration of the chromotograph
1 The chromotograph was calibrated using CGMs with composition identical to the analyzed sample The content of each component and its expanded uncertainty (k = 2) are given in Table 1 Table 1 - Calibrationе gas mixtures
2 Number of observations of each calibration sample- 3 Number of calibration samples - 3
3 The analytical function used for determination of the content of the analyzed sample components is as follows
x (y) =b1y+b0 (2) Where x ndash determined content molmol y - chromotograph response for the specific component b1- slope b0 - intercept 4 After completion of calibration the coefficients of analytical function were
calculated according to ISO 61432001 using generalized least-squares method Also the uncertainties of the intercept and slope and covariance between them were calculated After determination of parameters which are part of analytical function and which affect the uncertainty of measurements it was checked whether the analytical function is fit to the experimental data obtained in calibration and subsequently whether the analytical function is applicable
Results of calibration measurements coefficients of analytical function their uncertainties covariance and measure of goodness-of-fit Г (maximum value of the weighted differences of the experimental points and calculated points of the analytical function for each measurement run) are given in Tables 3 and 4 respectively Chromotograph operating conditions in calibration and analysis are given in Table 5
Table 3 - Results of experimental study
Date Component of
calibration mixture
Content x mole fraction
Expanded uncertainty
U(x) mole fraction
Mean of peak area y
mVs
Uncertainty )(yu
mVs
13374 0004 1279500 141 1389 0004 1329150 2899 CO2
12833 0004 1231000 849 2916 0005 404070 240
316 0005 437705 926 CO 2768 0004 383070 467
019 0002 3143200 4101
1706 2005
C3H8 0202 0002 3319150 2051
22
0181 0002 2948750 212 13374 0004 1269833 624
1389 0004 1321000 1272 CO2 12833 0004 1223900 1698
2916 0005 399490 612 316 0005 434010 863 CO
2768 0004 379660 410 019 0002 3157867 6772
0202 0002 3332400 3394
2106 2005
C3H8 0181 0002 2959900 4950
13374 0004 1277100 2152 1389 0004 1329900 2828 CO2
12833 0004 1229100 1980 2916 0005 400330 529
316 0005 434745 969 CO 2768 0004 379695 106
019 0002 3142433 9416 0202 0002 3321600 4101
2306 2005
C3H8 0181 0002 2961000 3111
According to ISO 61432003 calculation of the measure of goodness-of-fit Г is the maximum value of the weighed differences between the coordinates of measured and adjusted calibration points is an effective and simple method to test the compatibility of а prospective analytical function A function is admissible if Г le 2
minus
minus=
)(ˆ
)(ˆ
iii
iii
yuyy
xuxxΓ
(4) Where хi is the reference value of the content of calibration sample component
ix is the CGM component content obtained using the calculated analytical function
уi is the experimental response to the reference content of component iy is the response obtained in calculation of analytical function
u (хi) u (уi) are the uncertainties of reference contents and responses to these contents respectively
i is the number of calibration points i=1 3 This prerequisite is equivalent to the requirement that the curve of calculated response should cross each experimental calibration rectangular [хi plusmn 2u(хi) уi plusmn 2и(уi)] based on an expanded uncertainty U = ku with coverage factor k = 2 Table 4 Calculations of analytical function
Date Component Analytical function parameters
Uncertainty of analytical
function parameters
Covariance of
parameters Г
23
b1 b0 u(b1) u(b0) u(b0b1) 1706 11086E-
03 -81128E-
0119491E-
0524883E-
01 -48497E-06 10544
2106 10729E-03
-26126E-01
22698E-05
28930E-01 -65652E-06 19997
2306
CO2 10593E-
03 -17688E-
0135807E-
0545413E-
01 -16254E-05 10022
1706 71537E-04
26507E-02
14231E-05
57044E-02 -81115E-07 03017
2106 72346E-04
22401E-02
13819E-05
54490E-02 -75209E-07 05935
2306
CO 71321E-
04 60080E-
0212663E-
0549016E-
02 -62026E-07 01341
1706 56521E-06
13712E-02
38279E-07
12015E-02 -45937E-09 12991
2106 56295E-06
13707E-02
39247E-07
12379E-02 -48529E-09 12905
2306
C3H8 58258E-
06 80469E-
0340085E-
0712590E-
02 -50407E-09 08589
Two columns separated by switching device are located one after another in TCD
channel One column is intended for carbon dioxide heavy hydrocarbons and another column is intended for light gases Before the first switch the light gases including carbon oxide flow through the first column without being separated and remain in the second column The switch makes them locked in the second column The analysis of carbon dioxide is carried out up to the second switch Second switch makes the second column unlocked and carbon oxide is analyzed Third switch is required to allow propane escape from a column and prevent it from getting into a second column The analysis of the very propane is carried out using FID Time intervals between switches were selected experimentally when developing the analysis method Such analysis method makes it possible to analyze all three components per one sample inject
Table 5 - Chromotograph operating conditions in calibration and analysis Parameter of the operating conditions Thermostating temperature of TCD and FID degС 170
Temperature of separation columns degС
Program 60 degС within 9 min
than rise to 160 degС at 20degСmin
Rate of flow of carrier gas through TCD channel columns mlmin 15
Rate of flow of carrier gas through TCD comparison channel mlmin 15
Pressure in FID channel column kPa Program
24
80 to 100 Rise from the 1st s of
analysis at 2 kPamin
Flow-rate of hydrogen FID mlmin 20 Flow-rate of air FID mlmin 200 Temperature of switching device degС 65 Response time of switching device s 1 110 2 330 3 540
TCD FID Volume of injected analyzed gas cm3 025 025 Carrier gas Helium Duration of analysis min 17 Calculation of the content of comparison sample components and its uncertainty Results of comparison sample measurements are given in Table 6 Table 6 - Results of comparison sample measurements
1 The content of comparison sample component and its uncertainty were determined
using calculated analytical function according to ISO 61432001 as follows (5) Where G(y)=b1y+b0 is the calculated analytical function и(y) is the standard uncertainty of response y u2(bj) is the variance of analytical function parameter bj
u(bj bI) is the covariance of analytical function parameters bj bI N is the number of function coefficients N=2 j=0 1
sum sumsumminus
= +==
partpart
partpart
+
partpart
+
partpart
=1
0 1
2
2
0
22
)(2)()()(N
jIj
N
jI Ijj
N
j j
bbubG
bGbu
bGyu
yGxu
25
After substitution of analytical function (2) and transformations the expression takes form (5)
)(2)()()()()( 01122
0222
1 bbyubuybuyubxu +++= (6) The contents of comparison sample components under determination and their
uncertainties were calculated using B_LEAST a computer program recommended in ISO 6143 Calculations are summarized in Table 6
Table 6 Calculations of the content of comparison sample components and their
2 The final content of a component was determined as an arithmetiс mean from three measurements Final standard uncertainty was calculated using formula as follows
22
222)( Адаватмтемсериикал uuuuuxu ++++= (7)
Where ucal is the uncertainty of the component content produced by
calibration of chromotograph urun is the uncertainty of the component content produced by
change of chromotograph response in each measurement run ut is the uncertainty of the component content produced by
change of an ambient temperature upressure is the uncertainty of the component content produced by
change of atmospheric pressure u A is the standard uncertainty of three measurement runs
21 Uncertainty of the component content produced by calibration of chromotograph
This uncertainty is calculated using formula (6) but the first term of the sum ie
)()( 221 yub which represents the standard uncertainty of the chromotograph response in a
measurement run is not taken into account Calculations are summarized in Table 7
26
Table 7 Calculation of uncertainty produced by calibration of chromotograph
Date u(b1) u(b0) u(b0b1) x
molmol y Ucal molmol
Ucal rel
1706 19491E-05
24883E-01
-48497E-06
13567middot10-
2129698
3 0005middot1
0-2 003
2106 22698E-05
28930E-01
-65652E-06
13564middot10-
2 128855 0007middot1
0-2 005
2306
CO2
35807E-05
45413E-01
-16254E-05
135374middot10-2
1294633
0016middot10-2 012
1706 14231E-05
57044E-02
-81115E-07 2957middot10-2 409633
0003middot10-2 009
2106 13819E-05
54490E-02
-75209E-07
29577middot10-
2 405663 0003middot1
0-2 01
2306
CO
12663E-05
49016E-02
-62026E-07 2955middot10-2 405882
0003middot10-2 01
1706 38279E-07
12015E-02
-45937E-09 1977middot10-4
3255817
007middot10-
2 038
2106 39247E-07
12379E-02
-48529E-09 1980middot10-4
3273329
008middot10-
2 038
2306
C3H8
40085E-07
12590E-02
-50407E-09 1982middot10-4 32636
008middot10-
2 04 The total estimate of relative uncertainty produced by calibration of chromotograph was
calculated for each component as follows
3
3
1
2sum=
cali
cali
uu (8)
Where ucal i is the relative uncertainty produced by calibration of chromotograph and calculated for each measurement run
The calculations are summarized in Table 8
Table 8 Uncertainty produced by calibration of chromotograph
Component Ucal rel
CO2 008 CO 01
C3H8 04 22 Uncertainty of the component content produced by change of chromotograph response in each measurement run This uncertainty is calculated using the equation (6) whereby the first term of the sum
only ie )()( 221 yub which represents the standard uncertainty of the chromotograph
response in a measurement run is taken into account Calculations are summarized in Table 9
27
Table 9 Calculation of uncertainty produced by change of chromotograph response in each measurement run
The total estimate of relative uncertainty produced by change of chromotograph
response in each measurement run was calculated for each component as follows
3
3
1
2sum=
run
run
uu (9)
Where urun is the relative uncertainty produced by change of chromotograph response in each measurement run Calculations are summarized in Table 10
Table 10 Uncertainty produced by change of chromotograph response in each measurement
run
Component Urun rel
CO2 007 CO 015
C3H8 012 23 Uncertainty of the component content produced by change of temperature in a room
The recorded change of temperature in measurements is plusmn 05 degree The contribution of uncertainty type B (rectangular distribution) is estimated as follows
201003
12931
=sdotsdot=tu rel
28
24 Uncertainty of the component content produced by change of atmospheric pressure The recorded change of atmospheric pressure within three days was
05 kPа The contribution of uncertainty type B (rectangular distribution) is estimated as follows
2801003
13101
50=sdotsdot=pressureu rel
25 Standard deviation of 3 measurement runs Standard deviation is calculated as follows
isu p
A
2
= (10)
Where S2p is the group experimental variation
The group experimental variation is calculated as follows
(11)
Where si
2 is the experimental variation of measurement run i from independent repeated observations ni having freedom degrees
νi = n - 1 n=6 i= 3 Calculations are summarized in Table 11 Table 11 Calculations of standard uncertainty of 3 measurement runs
Date 2iS x
molmol 2iS
rel uA
rel
1706 2953E-05 13567middot10-2 000022
2106 588987E-06 13564middot10-2 0000043
2306
CO2 141137E-
05 135374middot10
-2 000010
0006
1706 225604E-06 2957middot10-2 0000077
2106 681346E-06 29577middot10-2 000023
2306
CO
175166E-06 2955middot10-2 0000060
0006
1706 C3H8 130158E-
08 1977middot10-4 00000066 0001
ss
p
i ii
N
ii
N2
2
1
1
= =
=
sum
sum
ν
ν
29
2106 44616E-09 1980middot10-4 00000023
2306
381032E-09 1982middot10-4 00000019
26 Total standard uncertainty
Uncertainty estimation СО2
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph ucal Normal 008 1 008
Change of temperature ut Rectangular 02 1 02 Change of atmospheric pressure upressure Rectangular 028 1 028
Changes of chromotograph response
urun Normal 007 1 007
Standard deviation of 3 runs uA Normal 0006 1 0006
Relative total standard uncertainty 036 Coverage factor k=2 Expanded uncertainty 01middot10-2 molmol Uncertainty estimation СО
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph ucal Normal 01 1 01 Change of temperature ut Rectangular 02 1 02 Change of atmospheric pressure upressure Rectangular 028 1 028 Changes of chromotograph response
urun Normal 015 1 015
Standard deviation of 3 runs uA Normal 0006 1 0006
Relative total standard uncertainty 039 Coverage factor k=2 Expanded uncertainty 002middot10-2 molmol Uncertainty estimation С3Н8
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph 04 Normal 04 1 008
30
Change of temperature 02 Rectangular 02 1 02 Change of atmospheric pressure 028 Rectangular 028 1 028
Changes of chromotograph response
012 Normal 012 1 007
Standard deviation of 3 runs 0001 Normal 0001 1 0006
Relative total standard uncertainty 054 Coverage factor k=2 Expanded uncertainty 02middot10-4 molmol
Sample handling
Period for exposure of cylinder to measurement conditions and method how to transport sample to the device
1 Stands for storing gas standard cylinders and calibration mixture cylinders and chromotograph are placed in a laboratory room which is not accessible to unauthorized persons The laboratory is equipped with air-conditioner to maintain required temperature and humidity on a continuous basis and some auxiliary measuring instruments as thermometer psychrometric hygrometer and aneroid to control temperature humidity and atmospheric inside the room
2 The comparison sample cylinder was stored in laboratory from the date of its
delivery to Minsk on 25042005 CGM cylinders are stored horizontally on racks and positioned vertically using special support when measurements are carried out
3 The analyzed gas sample is transported through the fine adjustment valve (FAV)
Conjunctions Cylinder - FAV FAV - tube tube - doser are made of metal and use adapters with spherical ends and bushes FAV is made of brass tube is made of copper and doser is made of duralumin
Instrument(s) (principles make type configuration data collection etc) For the analysis a GC were used with specifically applications For the determination of (Nitrogen (N2)) Carbon Dioxide (CO2) Carbon Monoxide (CO) and Propane (C3H8) balance GC Perkin Elmer AutoSystem XL (two channel system) with a stream selection valve for 4 streams and 2 gas sampling valves
Channel A for the determination of N2 CO and CO2 Carrier Gas Helium Columns Column system with two packed columns (6 ft x 18rdquo Porapak R 80100 mesh and 6 ft x 18rdquo Mol-Sieve 13X 80100 mesh) Oven Temperature 960 degC to 180 degC Detector micro-TCD Data Collection Total Chrom Workstation Channel B for the determination of C3H8 Carrier Gas Helium Columns Capillary column 50 m x 032 microm LP-SIL-8-CB Oven Temperature 60 degC to 180 degC Detector FID Data Collection Total Chrom Workstation
34
Calibration Standards
Calibration Standards for the measurements (preparation method purity analyses estimated uncertainty etc)
All standards were prepared individually according to ISO 6142 rdquoGas analysis - Preparation of calibration gases - Gravimetric Methodrdquo
Depending on the concentration of the components standards were prepared individually from pure gases or from pre-mixtures which were individually prepared from pure gases
The content of the impurities in all pure gases were determined before use by GC-DID GC-FID and or GC-TCD
After preparation the standards were verified by analytical comparisons against existing gravimetrically prepared standards Only when no significant difference between the analysed and the calculated gravimetric composition is found the ldquonew prepared candidate rdquo is accepted as a new standards
For the analysis of all components multi component standards with nitrogen as balance gas were used
Composition of calibrants BAM C49250-050722 Component Assigned value( x)
mmol mol Standard uncertainty (u(x)) relativ (k=2)
Calibration procedure (mathematical modelcalibration curve number and concentrations of standards measurement sequence temperaturepressure correction etc)
For the instrument calibration the bracketing technique was used The fraction of the current used standards deviated no more than +10rel and -10rel respectively from those of the sample
Measurement sequence
Sample Handling
How were the cylinders treated after arrival (eg stabilized) and how were samples transferred to the instrument (automatic high pressure mass-flow controller dilution etc) After heating (45 - 50 degC) the cylinder for 8 hours the cylinder were rolled about 16 hours before analysis was started Each cylinder was equipped with a pressure regulator that was purged three times by sequential evacuation and pressurisation with the gas mixture used Continous flow (2 ndash 3mlmin) through the sample loop
Uncertainty The specification of potential uncertainty sources is given in Annex 3
3 injection standard (high)
3 injection sample
3 injection standard (high)
3 injection sample
3 injection standard (low)
3 injection sample
3 injection standard (low)
3 injection standard (low)
36
Uncertainty table CO2
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 002 rel 1 002 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 03 rel
Uncertainty table CO
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 007 rel 1 007 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 05 rel
37
Uncertainty table C3H8
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 010 rel 1 001 rel
Analysis normal 028 rel 1 028 rel
Coverage factor 2
Expanded uncertainty 06 rel
Optional
You may provide additional data like the raw measurement data information on your
measurement procedure chromatograms etc
38
Appendix 3 SPECIFICATION OF POTENTIAL UNCERTAINTY SOURCES
a Uncertainty related to the balance and the weights Resolution of balance Accuracy of balance including linearity Incorrect zero point Drift (thermal and time effects) Instability due to draught Location of cylinder on the balance pan Uncertainties in the weights used Buoyancy effects on the weights used
b Uncertainties related to the gas cylinder Mechanical handling of cylinder
Loss of metal paints or labels from surface of cylinder Loss of metal from threads of valvefitting Dirt on cylinder valves or associated fitting
Absorptiondesorption effects on the external cylinder surface Buoyancy effects on the cylinder itself
Cylinder temperature differs from surrounding air due to eg filling with gas Change of cylinder volume during filling Change of density of surrounding air due to changes in temperature air pressure humidity and carbon dioxide content
Uncertainty in determination of external cylinder volume c Uncertainties related to the component gases Residual gas in cylinder Leakage Leakage of air into the cylinder after evacuation
Leakage of gas from the cylinder valve during filling Escape of gas from cylinder into transport lines
Gas remaining in transfer system when weight loss method is used Absorptionreaction of components on internal cylinder surface Reaction between components Impurities in all the initial gases Insufficient homogenization Uncertainty of molecular mass d Uncertainties related to the analysis
Repeatability and selectivity of the analyzer Appropriateness of the calibration curve
39
MEASUREMENT REPORT - All Ukrainian State Research-Industrial Center of Standardization Metrology Certification and Protection of Consumers Ukraine
gas ndash helium flow rate 15 cm3min detector TCD tdetector = 250 ordmС toven = 70 ordmС It was automatic data collection
Measurement and Calibration Methods Laboratory Measurement method Type of calibration curve
GCFID (С3Н8) 3 points linear Ukrmetrteststandard GCTCD (СО СО2) 3 points linear
GCFID ndash gas-chromatographic with flame-ionization detector GCTCD - gas-chromatographic with thermal-conductivity detector
42
Calibration Standards
Calibration standards ndash primary standard gas mixtures (PSGM) used for measurements by comparison method
PSGM-1 Cylinder 0116
PSGM-2 Cylinder 0107
PSGM-3 Cylinder 0093 Composition
x u(x) x u(x) x u(x) СО 27874 00015 29899 00015 31891 00015 СО2 130187 00015 144456 00016 137016 00016 С3Н8 019003 000008 020017 000008 021013 000008 N2 balance balance balance
Note x ndash mole fraction u(x) ndash absolute standard uncertainty
It was used gravimetric method of preparation of PSGM Electronic balance КА-20-3 of Mettler Toledo max limit of weighing is 20 kg least
limit of weighing is 01 g standard deviation is 0006 g Analysis of purity of parent gases was carried out with usage of chromatographs
НР6890N with helium ndash ionization detector flame ndash ionization detector thermal ndash conductivity detector and mass ndash spectrometric detector as well аs gas analyzers GIAM-15M and Onix condensate-thermometer hygrometer TOROS-3-2B
Calculation of uncertainties was carried out according to ISO 6142-2003 Corrections of temperature pressure and humidity of environment were considered
in calculations according to ISO 6142-2003 (program of ISO-6142 2000-03-17 designer is NMi) Protocols and explanations are in Annex A
Instrument (Comparator) Calibration Calibration of comparator ndash gas chromatograph HP 6890 was carried out with usage
of PSGM Measurement sequence PSGM -1 х 3 PSGM -2 х 3 COOMET gas mixture х 3 PSGM -2 х 3 PSGM -3 х 3 It is necessary to use PSGM-2 repeatedly for estimation of reproducibility of results
Program B_LEAST recommended by ISO 6143-2003 was used for constructing the curve Mathematical model of calibration curve is linear one
Sample Handling The cylinder was kept for 24 hrs at a room where comparators were disposed This room is a thermostatic room with t = (20plusmn2) ordmС
43
A method of sample input to a comparator is a method with flow stabilization Uncertainty The following uncertainties were included to the budget of uncertainty - uncertainty of the balance - uncertainties of impurities in parent gases Contribution from other uncertainty sources was insignificant A cabin of the balance is thermostatically The balance is the one-pan balance
Air transfer is absent in the cabin of the balance Drift of the balance is absent for PSGM preparation
Contribution from other uncertainty sources was considered in software according to ISO 6142-2003
Uncertainties related to the analysis (comparison) were considered in software according to ISO 6143-2003 and enclosed in Annex B
Uncertainty table СО2
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas mixture
B 001 1 001
Analysis A B 008 1 008
Coverage factor 2 Expanded uncertainty 002sdot10-2 molmol Uncertainty table СО
Protocols of analysis (comparison) in accordance with ISO 6143-2003
57
Explanation of protocols of comparison
Chapter I ldquoThe calibration data set isrdquo contains columns 1 mole fraction of a component 2 absolute standard uncertainty of mole fraction of a component 3 a signal of a comparator 4 absolute standard uncertainty of a comparator signal
Chapter II ldquoResults of ISO 6143 methodrdquo contains parameters of a calibration curve including its
uncertainty
Chapter ІІІ ldquoPart II Processing of datardquo contains columns
1 calc x - the results of comparison mole fraction of a component 2 u(x) - absolute standard uncertainty of mole fraction of a component 3 response y - a signal of a comparator 4 u(y) - absolute standard uncertainty of a comparator signal
58
СО2 - measurement 1 Data setCO2_21 The calibration data set is 1302E+01 1510E-03 1022E+04 1820E+00 1370E+01 1560E-03 1077E+04 2730E+00 1445E+01 1620E-03 1135E+04 5900E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 20331E-02 12711E-03 12573E-01 11653E-05 -14638E-06 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 10548E-02 12722E-03 31762E-02 28898E-06 -91698E-08 Remaining SSD is 74346 Weighted distances x-value x-dist y-dist 100E+00 130E+01 490E-01 -755E-01 200E+00 137E+01 -103E+00 228E+00 300E+00 144E+01 539E-01 -250E-01 Goodness-of-fit measure 22837 Parameter set 1 1054788657490729E-2 1272208026684145E-3 3176237146276368E-2 2889798108124711E-6 -
9169821653851327E-8 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_21c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13577E+01 25542E-03 10664E+04 15200E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 547E-06 328E-06 316E-06 784E-06 286E-06 652E-06 Linear model Parameters for the fit were (b0 b1) 10548E-02 12722E-03
59
СО2 - measurement 2
Data setCO2_20 The calibration data set is 1302E+01 1512E-03 1021E+04 4723E+00 1370E+01 1563E-03 1075E+04 1600E+00 1445E+01 1620E-03 1133E+04 7300E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -38760E-02 12784E-03 26817E-02 24890E-06 -66689E-08 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -62452E-02 12805E-03 47930E-02 43243E-06 -20716E-07 Remaining SSD is 03231 Weighted distances x-value x-dist y-dist 100E+00 130E+01 107E-01 -415E-01 200E+00 137E+01 -212E-01 283E-01 300E+00 144E+01 104E-01 -584E-02 Goodness-of-fit measure 04155 Parameter set 1 -6245240430658412E-2 1280492624666799E-3 4792952200361109E-2 4324266278840409E-6 -
2071623966851869E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_20c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13594E+01 10290E-02 10665E+04 78300E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 121E-05 683E-06 651E-06 315E-05 560E-06 106E-04 Linear model Parameters for the fit were (b0 b1) -62452E-02 12805E-03
60
С3Н8 - measurement 1
Data setC3H8 The calibration data set is 1900E-01 7800E-05 9057E+03 1098E+01 2002E-01 7900E-05 9552E+03 8569E+00 2101E-01 7960E-05 1007E+04 4049E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10529E-02 19831E-05 34552E-03 36109E-07 -12465E-09 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11642E-02 19714E-05 23073E-03 23522E-07 -54231E-10 Remaining SSD is 19453 Weighted distances x-value x-dist y-dist 100E+00 190E-01 -239E-01 666E-01 200E+00 200E-01 487E-01 -104E+00 300E+00 210E-01 -247E-01 248E-01 Goodness-of-fit measure 10414 Parameter set 1 1164239985182795E-2 1971441115316992E-5 2307269625077337E-3 2352198415608386E-7 -
5423119774765299E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19837E-01 14840E-04 94718E+03 45610E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
15
Uncertainty Uncertainty table СО2
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas
mixture
B 0010 1 0010
Analysis A B 0048 1 0048
Coverage factor 2 Expanded uncertainty 01 Uncertainty table СО
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas
mixture
B 002 1 002
Analysis A B 0095 1 0095
Coverage factor 2 Expanded uncertainty 019
16
Uncertainty table С3Н8 Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas
mixture
B 005 1 005
Analysis A B 0045 1 0045
Coverage factor 2 Expanded uncertainty 013
17
MEASUREMENT REPORT ndash Belorussian State Institute for Metrology Belarus (BelGIM)
I Results of experimental study
Laboratory Belarus BelGIM Section for physicochemical and optical measurements sector for standards and gas mixtures 8 Serova st Minsk Cylinder No 0128 9 dm3 aluminium NOMINAL COMPOSITION - Carbon dioxide 13middot10-2 - 14middot10-2 molmol - Carbon oxide 28middot10-2 - 32middot10-2 molmol - Propane 19middot10-4 - 21middot10-4molmol - Nitrogen Residual
Measurement No1 Date
Result (molmol)
x_
Standard deviation
S( x_
) rel
No of observations
n
Carbon dioxide 17062005 13567middot10-2 0096 6
Carbon oxide 17062005 2957middot10-2 014 6
Propane 17062005 1977middot10-4 015 6
Measurement No2 Date
Result (molmol)
x_
Standard deviation
S( x_
) rel
No of observations
n
Carbon dioxide 21062005 13564middot10-2 004 6
Carbon oxide 21062005 2957middot10-2 02 6
Propane 21062005 1979middot10-4 01 6
18
Measurement No3 Date
Result (molmol)
x_
Standard deviation
S( x_
) rel
No of observations
n
Carbon dioxide 23062005 13537middot10-2 007 6
Carbon oxide 23062005 2955middot10-2 01 6
Propane 23062005 1982middot10-4 01 6
Final results
Gas mixture Result
(molmol)
Coverage factor
Expanded uncertainty (molmol)
Carbon dioxide 136middot10-2 2 01 middot10-2
Carbon oxide 296middot10-2 2 002middot10-2
Propane 198middot10-4 2 02middot10-4
II Description of study Apparatus (principle of operation type configuration data collection etc)
Measurements were carried out using gas chromatograph Crystal 2000М (hereinafter
referred to as chromatograph) combined with thermal conductivity detector (hereinafter referred to as TCD) with detection limit of 510-9 gml for propane and flame-ionization detector (hereinafter referred to as FID) with detection limit of 510-12 gs for propane
Computers and software Chromatech Analytic version 121 were used to control chromatograph and collect and process chromatographical data
For the purpose of measurements the following auxiliary devices and materials were used
1 Two-position doser with 10 ports and with doses of 025 cm3 for FID channel and with doses of 025 cm3 for TCD channel (hereinafter referred to as doser)
2 Metallic packed column 3m х 3mm х 2mm - HayeSep N 80100 metallic packed column 1m х 4mm х 2mm-CaA 016025 (TCD channel) capillary column HP PLOTQ 30m х 0536mm (FID channel)
3 Aneroid BАММ-1 with a measurement range of 80-106 kPа and accuracy of plusmn 02 kPа
4 Mercurial thermometer ТL-4 with a measurement range of 0-50ordmС and scale division of 01ordmС
19
5 Fine adjustment valve (hereinafter referred to as FAV) provided to transport a gas sample into chromotograph and set to gas flow-rate of 10-15 mlmin
6 Foamy gas flow meter type YIRG - 2А accuracy of flow measurement plusmn 1 сm3min
7 Helium gas Type A according to TU 51-940-80 8 High purity hydrogen gas according to TU 301-07-27-90 9 Compressed air 10 Multicomponent calibration gas mixtures (hereinafter referred to as CGM)
produced and certified by gravimetric method
Calibration reference materials - calibration gas mixtures used for measurements 1 Quantitative composition of KGS is determined using gravimetric method defined in
ISO 61422001 by calculating weight of each component of a gas mixture The content of CGM components is expressed as a mole fraction Uncertainty of KGS composition is expressed as expanded uncertainty with coverage factor k = 2 Molar masses of components and their uncertainties are taken from ISO 149122003 Performance and metrological characteristics of the equipment used for gravimetric preparation of mixtures are given in Table 1
Table 1
Description of the equipment
Manufacturer Metrological characteristics
Mass-comparator balance type КА10-3Р
Mettler-Toledo
Switzerland
Maximum load 15 kg Scale division 1 mg Standard deviation 19 mg at load of 10 kg Operating temperature range +10divide30degС Maximum temperature change within 1 h plusmn05 degС
Gas mixer type USG 00001 BelGIM
Measurement range 000025 divide 100 МPa Accuracy class for manometers ndash 015 Accuracy class for vacuummeters ndash 025 Vacuummeter with pressure sensor for measuring the residual pressure before filling Residual pressure before filling of each component not more than 20 Pa
2 Purity analysis of primary gas standards
The purity analysis of primary gas standards is based on the information provided by the supplier or on the results of determination of impurity in pure gases using measurement procedure developed inside BelGIM
20
If an analytical method laid down in 43 of ISO 61422001 cannot be used for impurity determination mole fraction of an expected impurity is assumed to be half of the detection limit of the analytical method The content of the undetected impurity produces rectangular distribution
whereby its standard uncertainty is calculated as half of the detection limit divided by 3 The composition of the pure gases used for preparation of calibration mixtures is given
in Table 2 Table 2 - Metrological characteristics of pure gases
N2 999967 00005 Nitrogen Cylinder 40 dm3 Origin Russia O2 00033 00005 Propane Cylinder 2 dm3 Origin Russia
C3H8 9979 0017
3 After preparation of mixture the cylinder was maintained in laboratory room within
24 hours the mixture then was homogenized on the stand by rotating on the rollers within 4-5 hours The chromotograph for CGM was calibrated 2-3 days after its preparation
Calibration of the chromotograph
1 The chromotograph was calibrated using CGMs with composition identical to the analyzed sample The content of each component and its expanded uncertainty (k = 2) are given in Table 1 Table 1 - Calibrationе gas mixtures
2 Number of observations of each calibration sample- 3 Number of calibration samples - 3
3 The analytical function used for determination of the content of the analyzed sample components is as follows
x (y) =b1y+b0 (2) Where x ndash determined content molmol y - chromotograph response for the specific component b1- slope b0 - intercept 4 After completion of calibration the coefficients of analytical function were
calculated according to ISO 61432001 using generalized least-squares method Also the uncertainties of the intercept and slope and covariance between them were calculated After determination of parameters which are part of analytical function and which affect the uncertainty of measurements it was checked whether the analytical function is fit to the experimental data obtained in calibration and subsequently whether the analytical function is applicable
Results of calibration measurements coefficients of analytical function their uncertainties covariance and measure of goodness-of-fit Г (maximum value of the weighted differences of the experimental points and calculated points of the analytical function for each measurement run) are given in Tables 3 and 4 respectively Chromotograph operating conditions in calibration and analysis are given in Table 5
Table 3 - Results of experimental study
Date Component of
calibration mixture
Content x mole fraction
Expanded uncertainty
U(x) mole fraction
Mean of peak area y
mVs
Uncertainty )(yu
mVs
13374 0004 1279500 141 1389 0004 1329150 2899 CO2
12833 0004 1231000 849 2916 0005 404070 240
316 0005 437705 926 CO 2768 0004 383070 467
019 0002 3143200 4101
1706 2005
C3H8 0202 0002 3319150 2051
22
0181 0002 2948750 212 13374 0004 1269833 624
1389 0004 1321000 1272 CO2 12833 0004 1223900 1698
2916 0005 399490 612 316 0005 434010 863 CO
2768 0004 379660 410 019 0002 3157867 6772
0202 0002 3332400 3394
2106 2005
C3H8 0181 0002 2959900 4950
13374 0004 1277100 2152 1389 0004 1329900 2828 CO2
12833 0004 1229100 1980 2916 0005 400330 529
316 0005 434745 969 CO 2768 0004 379695 106
019 0002 3142433 9416 0202 0002 3321600 4101
2306 2005
C3H8 0181 0002 2961000 3111
According to ISO 61432003 calculation of the measure of goodness-of-fit Г is the maximum value of the weighed differences between the coordinates of measured and adjusted calibration points is an effective and simple method to test the compatibility of а prospective analytical function A function is admissible if Г le 2
minus
minus=
)(ˆ
)(ˆ
iii
iii
yuyy
xuxxΓ
(4) Where хi is the reference value of the content of calibration sample component
ix is the CGM component content obtained using the calculated analytical function
уi is the experimental response to the reference content of component iy is the response obtained in calculation of analytical function
u (хi) u (уi) are the uncertainties of reference contents and responses to these contents respectively
i is the number of calibration points i=1 3 This prerequisite is equivalent to the requirement that the curve of calculated response should cross each experimental calibration rectangular [хi plusmn 2u(хi) уi plusmn 2и(уi)] based on an expanded uncertainty U = ku with coverage factor k = 2 Table 4 Calculations of analytical function
Date Component Analytical function parameters
Uncertainty of analytical
function parameters
Covariance of
parameters Г
23
b1 b0 u(b1) u(b0) u(b0b1) 1706 11086E-
03 -81128E-
0119491E-
0524883E-
01 -48497E-06 10544
2106 10729E-03
-26126E-01
22698E-05
28930E-01 -65652E-06 19997
2306
CO2 10593E-
03 -17688E-
0135807E-
0545413E-
01 -16254E-05 10022
1706 71537E-04
26507E-02
14231E-05
57044E-02 -81115E-07 03017
2106 72346E-04
22401E-02
13819E-05
54490E-02 -75209E-07 05935
2306
CO 71321E-
04 60080E-
0212663E-
0549016E-
02 -62026E-07 01341
1706 56521E-06
13712E-02
38279E-07
12015E-02 -45937E-09 12991
2106 56295E-06
13707E-02
39247E-07
12379E-02 -48529E-09 12905
2306
C3H8 58258E-
06 80469E-
0340085E-
0712590E-
02 -50407E-09 08589
Two columns separated by switching device are located one after another in TCD
channel One column is intended for carbon dioxide heavy hydrocarbons and another column is intended for light gases Before the first switch the light gases including carbon oxide flow through the first column without being separated and remain in the second column The switch makes them locked in the second column The analysis of carbon dioxide is carried out up to the second switch Second switch makes the second column unlocked and carbon oxide is analyzed Third switch is required to allow propane escape from a column and prevent it from getting into a second column The analysis of the very propane is carried out using FID Time intervals between switches were selected experimentally when developing the analysis method Such analysis method makes it possible to analyze all three components per one sample inject
Table 5 - Chromotograph operating conditions in calibration and analysis Parameter of the operating conditions Thermostating temperature of TCD and FID degС 170
Temperature of separation columns degС
Program 60 degС within 9 min
than rise to 160 degС at 20degСmin
Rate of flow of carrier gas through TCD channel columns mlmin 15
Rate of flow of carrier gas through TCD comparison channel mlmin 15
Pressure in FID channel column kPa Program
24
80 to 100 Rise from the 1st s of
analysis at 2 kPamin
Flow-rate of hydrogen FID mlmin 20 Flow-rate of air FID mlmin 200 Temperature of switching device degС 65 Response time of switching device s 1 110 2 330 3 540
TCD FID Volume of injected analyzed gas cm3 025 025 Carrier gas Helium Duration of analysis min 17 Calculation of the content of comparison sample components and its uncertainty Results of comparison sample measurements are given in Table 6 Table 6 - Results of comparison sample measurements
1 The content of comparison sample component and its uncertainty were determined
using calculated analytical function according to ISO 61432001 as follows (5) Where G(y)=b1y+b0 is the calculated analytical function и(y) is the standard uncertainty of response y u2(bj) is the variance of analytical function parameter bj
u(bj bI) is the covariance of analytical function parameters bj bI N is the number of function coefficients N=2 j=0 1
sum sumsumminus
= +==
partpart
partpart
+
partpart
+
partpart
=1
0 1
2
2
0
22
)(2)()()(N
jIj
N
jI Ijj
N
j j
bbubG
bGbu
bGyu
yGxu
25
After substitution of analytical function (2) and transformations the expression takes form (5)
)(2)()()()()( 01122
0222
1 bbyubuybuyubxu +++= (6) The contents of comparison sample components under determination and their
uncertainties were calculated using B_LEAST a computer program recommended in ISO 6143 Calculations are summarized in Table 6
Table 6 Calculations of the content of comparison sample components and their
2 The final content of a component was determined as an arithmetiс mean from three measurements Final standard uncertainty was calculated using formula as follows
22
222)( Адаватмтемсериикал uuuuuxu ++++= (7)
Where ucal is the uncertainty of the component content produced by
calibration of chromotograph urun is the uncertainty of the component content produced by
change of chromotograph response in each measurement run ut is the uncertainty of the component content produced by
change of an ambient temperature upressure is the uncertainty of the component content produced by
change of atmospheric pressure u A is the standard uncertainty of three measurement runs
21 Uncertainty of the component content produced by calibration of chromotograph
This uncertainty is calculated using formula (6) but the first term of the sum ie
)()( 221 yub which represents the standard uncertainty of the chromotograph response in a
measurement run is not taken into account Calculations are summarized in Table 7
26
Table 7 Calculation of uncertainty produced by calibration of chromotograph
Date u(b1) u(b0) u(b0b1) x
molmol y Ucal molmol
Ucal rel
1706 19491E-05
24883E-01
-48497E-06
13567middot10-
2129698
3 0005middot1
0-2 003
2106 22698E-05
28930E-01
-65652E-06
13564middot10-
2 128855 0007middot1
0-2 005
2306
CO2
35807E-05
45413E-01
-16254E-05
135374middot10-2
1294633
0016middot10-2 012
1706 14231E-05
57044E-02
-81115E-07 2957middot10-2 409633
0003middot10-2 009
2106 13819E-05
54490E-02
-75209E-07
29577middot10-
2 405663 0003middot1
0-2 01
2306
CO
12663E-05
49016E-02
-62026E-07 2955middot10-2 405882
0003middot10-2 01
1706 38279E-07
12015E-02
-45937E-09 1977middot10-4
3255817
007middot10-
2 038
2106 39247E-07
12379E-02
-48529E-09 1980middot10-4
3273329
008middot10-
2 038
2306
C3H8
40085E-07
12590E-02
-50407E-09 1982middot10-4 32636
008middot10-
2 04 The total estimate of relative uncertainty produced by calibration of chromotograph was
calculated for each component as follows
3
3
1
2sum=
cali
cali
uu (8)
Where ucal i is the relative uncertainty produced by calibration of chromotograph and calculated for each measurement run
The calculations are summarized in Table 8
Table 8 Uncertainty produced by calibration of chromotograph
Component Ucal rel
CO2 008 CO 01
C3H8 04 22 Uncertainty of the component content produced by change of chromotograph response in each measurement run This uncertainty is calculated using the equation (6) whereby the first term of the sum
only ie )()( 221 yub which represents the standard uncertainty of the chromotograph
response in a measurement run is taken into account Calculations are summarized in Table 9
27
Table 9 Calculation of uncertainty produced by change of chromotograph response in each measurement run
The total estimate of relative uncertainty produced by change of chromotograph
response in each measurement run was calculated for each component as follows
3
3
1
2sum=
run
run
uu (9)
Where urun is the relative uncertainty produced by change of chromotograph response in each measurement run Calculations are summarized in Table 10
Table 10 Uncertainty produced by change of chromotograph response in each measurement
run
Component Urun rel
CO2 007 CO 015
C3H8 012 23 Uncertainty of the component content produced by change of temperature in a room
The recorded change of temperature in measurements is plusmn 05 degree The contribution of uncertainty type B (rectangular distribution) is estimated as follows
201003
12931
=sdotsdot=tu rel
28
24 Uncertainty of the component content produced by change of atmospheric pressure The recorded change of atmospheric pressure within three days was
05 kPа The contribution of uncertainty type B (rectangular distribution) is estimated as follows
2801003
13101
50=sdotsdot=pressureu rel
25 Standard deviation of 3 measurement runs Standard deviation is calculated as follows
isu p
A
2
= (10)
Where S2p is the group experimental variation
The group experimental variation is calculated as follows
(11)
Where si
2 is the experimental variation of measurement run i from independent repeated observations ni having freedom degrees
νi = n - 1 n=6 i= 3 Calculations are summarized in Table 11 Table 11 Calculations of standard uncertainty of 3 measurement runs
Date 2iS x
molmol 2iS
rel uA
rel
1706 2953E-05 13567middot10-2 000022
2106 588987E-06 13564middot10-2 0000043
2306
CO2 141137E-
05 135374middot10
-2 000010
0006
1706 225604E-06 2957middot10-2 0000077
2106 681346E-06 29577middot10-2 000023
2306
CO
175166E-06 2955middot10-2 0000060
0006
1706 C3H8 130158E-
08 1977middot10-4 00000066 0001
ss
p
i ii
N
ii
N2
2
1
1
= =
=
sum
sum
ν
ν
29
2106 44616E-09 1980middot10-4 00000023
2306
381032E-09 1982middot10-4 00000019
26 Total standard uncertainty
Uncertainty estimation СО2
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph ucal Normal 008 1 008
Change of temperature ut Rectangular 02 1 02 Change of atmospheric pressure upressure Rectangular 028 1 028
Changes of chromotograph response
urun Normal 007 1 007
Standard deviation of 3 runs uA Normal 0006 1 0006
Relative total standard uncertainty 036 Coverage factor k=2 Expanded uncertainty 01middot10-2 molmol Uncertainty estimation СО
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph ucal Normal 01 1 01 Change of temperature ut Rectangular 02 1 02 Change of atmospheric pressure upressure Rectangular 028 1 028 Changes of chromotograph response
urun Normal 015 1 015
Standard deviation of 3 runs uA Normal 0006 1 0006
Relative total standard uncertainty 039 Coverage factor k=2 Expanded uncertainty 002middot10-2 molmol Uncertainty estimation С3Н8
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph 04 Normal 04 1 008
30
Change of temperature 02 Rectangular 02 1 02 Change of atmospheric pressure 028 Rectangular 028 1 028
Changes of chromotograph response
012 Normal 012 1 007
Standard deviation of 3 runs 0001 Normal 0001 1 0006
Relative total standard uncertainty 054 Coverage factor k=2 Expanded uncertainty 02middot10-4 molmol
Sample handling
Period for exposure of cylinder to measurement conditions and method how to transport sample to the device
1 Stands for storing gas standard cylinders and calibration mixture cylinders and chromotograph are placed in a laboratory room which is not accessible to unauthorized persons The laboratory is equipped with air-conditioner to maintain required temperature and humidity on a continuous basis and some auxiliary measuring instruments as thermometer psychrometric hygrometer and aneroid to control temperature humidity and atmospheric inside the room
2 The comparison sample cylinder was stored in laboratory from the date of its
delivery to Minsk on 25042005 CGM cylinders are stored horizontally on racks and positioned vertically using special support when measurements are carried out
3 The analyzed gas sample is transported through the fine adjustment valve (FAV)
Conjunctions Cylinder - FAV FAV - tube tube - doser are made of metal and use adapters with spherical ends and bushes FAV is made of brass tube is made of copper and doser is made of duralumin
Instrument(s) (principles make type configuration data collection etc) For the analysis a GC were used with specifically applications For the determination of (Nitrogen (N2)) Carbon Dioxide (CO2) Carbon Monoxide (CO) and Propane (C3H8) balance GC Perkin Elmer AutoSystem XL (two channel system) with a stream selection valve for 4 streams and 2 gas sampling valves
Channel A for the determination of N2 CO and CO2 Carrier Gas Helium Columns Column system with two packed columns (6 ft x 18rdquo Porapak R 80100 mesh and 6 ft x 18rdquo Mol-Sieve 13X 80100 mesh) Oven Temperature 960 degC to 180 degC Detector micro-TCD Data Collection Total Chrom Workstation Channel B for the determination of C3H8 Carrier Gas Helium Columns Capillary column 50 m x 032 microm LP-SIL-8-CB Oven Temperature 60 degC to 180 degC Detector FID Data Collection Total Chrom Workstation
34
Calibration Standards
Calibration Standards for the measurements (preparation method purity analyses estimated uncertainty etc)
All standards were prepared individually according to ISO 6142 rdquoGas analysis - Preparation of calibration gases - Gravimetric Methodrdquo
Depending on the concentration of the components standards were prepared individually from pure gases or from pre-mixtures which were individually prepared from pure gases
The content of the impurities in all pure gases were determined before use by GC-DID GC-FID and or GC-TCD
After preparation the standards were verified by analytical comparisons against existing gravimetrically prepared standards Only when no significant difference between the analysed and the calculated gravimetric composition is found the ldquonew prepared candidate rdquo is accepted as a new standards
For the analysis of all components multi component standards with nitrogen as balance gas were used
Composition of calibrants BAM C49250-050722 Component Assigned value( x)
mmol mol Standard uncertainty (u(x)) relativ (k=2)
Calibration procedure (mathematical modelcalibration curve number and concentrations of standards measurement sequence temperaturepressure correction etc)
For the instrument calibration the bracketing technique was used The fraction of the current used standards deviated no more than +10rel and -10rel respectively from those of the sample
Measurement sequence
Sample Handling
How were the cylinders treated after arrival (eg stabilized) and how were samples transferred to the instrument (automatic high pressure mass-flow controller dilution etc) After heating (45 - 50 degC) the cylinder for 8 hours the cylinder were rolled about 16 hours before analysis was started Each cylinder was equipped with a pressure regulator that was purged three times by sequential evacuation and pressurisation with the gas mixture used Continous flow (2 ndash 3mlmin) through the sample loop
Uncertainty The specification of potential uncertainty sources is given in Annex 3
3 injection standard (high)
3 injection sample
3 injection standard (high)
3 injection sample
3 injection standard (low)
3 injection sample
3 injection standard (low)
3 injection standard (low)
36
Uncertainty table CO2
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 002 rel 1 002 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 03 rel
Uncertainty table CO
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 007 rel 1 007 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 05 rel
37
Uncertainty table C3H8
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 010 rel 1 001 rel
Analysis normal 028 rel 1 028 rel
Coverage factor 2
Expanded uncertainty 06 rel
Optional
You may provide additional data like the raw measurement data information on your
measurement procedure chromatograms etc
38
Appendix 3 SPECIFICATION OF POTENTIAL UNCERTAINTY SOURCES
a Uncertainty related to the balance and the weights Resolution of balance Accuracy of balance including linearity Incorrect zero point Drift (thermal and time effects) Instability due to draught Location of cylinder on the balance pan Uncertainties in the weights used Buoyancy effects on the weights used
b Uncertainties related to the gas cylinder Mechanical handling of cylinder
Loss of metal paints or labels from surface of cylinder Loss of metal from threads of valvefitting Dirt on cylinder valves or associated fitting
Absorptiondesorption effects on the external cylinder surface Buoyancy effects on the cylinder itself
Cylinder temperature differs from surrounding air due to eg filling with gas Change of cylinder volume during filling Change of density of surrounding air due to changes in temperature air pressure humidity and carbon dioxide content
Uncertainty in determination of external cylinder volume c Uncertainties related to the component gases Residual gas in cylinder Leakage Leakage of air into the cylinder after evacuation
Leakage of gas from the cylinder valve during filling Escape of gas from cylinder into transport lines
Gas remaining in transfer system when weight loss method is used Absorptionreaction of components on internal cylinder surface Reaction between components Impurities in all the initial gases Insufficient homogenization Uncertainty of molecular mass d Uncertainties related to the analysis
Repeatability and selectivity of the analyzer Appropriateness of the calibration curve
39
MEASUREMENT REPORT - All Ukrainian State Research-Industrial Center of Standardization Metrology Certification and Protection of Consumers Ukraine
gas ndash helium flow rate 15 cm3min detector TCD tdetector = 250 ordmС toven = 70 ordmС It was automatic data collection
Measurement and Calibration Methods Laboratory Measurement method Type of calibration curve
GCFID (С3Н8) 3 points linear Ukrmetrteststandard GCTCD (СО СО2) 3 points linear
GCFID ndash gas-chromatographic with flame-ionization detector GCTCD - gas-chromatographic with thermal-conductivity detector
42
Calibration Standards
Calibration standards ndash primary standard gas mixtures (PSGM) used for measurements by comparison method
PSGM-1 Cylinder 0116
PSGM-2 Cylinder 0107
PSGM-3 Cylinder 0093 Composition
x u(x) x u(x) x u(x) СО 27874 00015 29899 00015 31891 00015 СО2 130187 00015 144456 00016 137016 00016 С3Н8 019003 000008 020017 000008 021013 000008 N2 balance balance balance
Note x ndash mole fraction u(x) ndash absolute standard uncertainty
It was used gravimetric method of preparation of PSGM Electronic balance КА-20-3 of Mettler Toledo max limit of weighing is 20 kg least
limit of weighing is 01 g standard deviation is 0006 g Analysis of purity of parent gases was carried out with usage of chromatographs
НР6890N with helium ndash ionization detector flame ndash ionization detector thermal ndash conductivity detector and mass ndash spectrometric detector as well аs gas analyzers GIAM-15M and Onix condensate-thermometer hygrometer TOROS-3-2B
Calculation of uncertainties was carried out according to ISO 6142-2003 Corrections of temperature pressure and humidity of environment were considered
in calculations according to ISO 6142-2003 (program of ISO-6142 2000-03-17 designer is NMi) Protocols and explanations are in Annex A
Instrument (Comparator) Calibration Calibration of comparator ndash gas chromatograph HP 6890 was carried out with usage
of PSGM Measurement sequence PSGM -1 х 3 PSGM -2 х 3 COOMET gas mixture х 3 PSGM -2 х 3 PSGM -3 х 3 It is necessary to use PSGM-2 repeatedly for estimation of reproducibility of results
Program B_LEAST recommended by ISO 6143-2003 was used for constructing the curve Mathematical model of calibration curve is linear one
Sample Handling The cylinder was kept for 24 hrs at a room where comparators were disposed This room is a thermostatic room with t = (20plusmn2) ordmС
43
A method of sample input to a comparator is a method with flow stabilization Uncertainty The following uncertainties were included to the budget of uncertainty - uncertainty of the balance - uncertainties of impurities in parent gases Contribution from other uncertainty sources was insignificant A cabin of the balance is thermostatically The balance is the one-pan balance
Air transfer is absent in the cabin of the balance Drift of the balance is absent for PSGM preparation
Contribution from other uncertainty sources was considered in software according to ISO 6142-2003
Uncertainties related to the analysis (comparison) were considered in software according to ISO 6143-2003 and enclosed in Annex B
Uncertainty table СО2
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas mixture
B 001 1 001
Analysis A B 008 1 008
Coverage factor 2 Expanded uncertainty 002sdot10-2 molmol Uncertainty table СО
Protocols of analysis (comparison) in accordance with ISO 6143-2003
57
Explanation of protocols of comparison
Chapter I ldquoThe calibration data set isrdquo contains columns 1 mole fraction of a component 2 absolute standard uncertainty of mole fraction of a component 3 a signal of a comparator 4 absolute standard uncertainty of a comparator signal
Chapter II ldquoResults of ISO 6143 methodrdquo contains parameters of a calibration curve including its
uncertainty
Chapter ІІІ ldquoPart II Processing of datardquo contains columns
1 calc x - the results of comparison mole fraction of a component 2 u(x) - absolute standard uncertainty of mole fraction of a component 3 response y - a signal of a comparator 4 u(y) - absolute standard uncertainty of a comparator signal
58
СО2 - measurement 1 Data setCO2_21 The calibration data set is 1302E+01 1510E-03 1022E+04 1820E+00 1370E+01 1560E-03 1077E+04 2730E+00 1445E+01 1620E-03 1135E+04 5900E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 20331E-02 12711E-03 12573E-01 11653E-05 -14638E-06 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 10548E-02 12722E-03 31762E-02 28898E-06 -91698E-08 Remaining SSD is 74346 Weighted distances x-value x-dist y-dist 100E+00 130E+01 490E-01 -755E-01 200E+00 137E+01 -103E+00 228E+00 300E+00 144E+01 539E-01 -250E-01 Goodness-of-fit measure 22837 Parameter set 1 1054788657490729E-2 1272208026684145E-3 3176237146276368E-2 2889798108124711E-6 -
9169821653851327E-8 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_21c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13577E+01 25542E-03 10664E+04 15200E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 547E-06 328E-06 316E-06 784E-06 286E-06 652E-06 Linear model Parameters for the fit were (b0 b1) 10548E-02 12722E-03
59
СО2 - measurement 2
Data setCO2_20 The calibration data set is 1302E+01 1512E-03 1021E+04 4723E+00 1370E+01 1563E-03 1075E+04 1600E+00 1445E+01 1620E-03 1133E+04 7300E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -38760E-02 12784E-03 26817E-02 24890E-06 -66689E-08 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -62452E-02 12805E-03 47930E-02 43243E-06 -20716E-07 Remaining SSD is 03231 Weighted distances x-value x-dist y-dist 100E+00 130E+01 107E-01 -415E-01 200E+00 137E+01 -212E-01 283E-01 300E+00 144E+01 104E-01 -584E-02 Goodness-of-fit measure 04155 Parameter set 1 -6245240430658412E-2 1280492624666799E-3 4792952200361109E-2 4324266278840409E-6 -
2071623966851869E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_20c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13594E+01 10290E-02 10665E+04 78300E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 121E-05 683E-06 651E-06 315E-05 560E-06 106E-04 Linear model Parameters for the fit were (b0 b1) -62452E-02 12805E-03
60
С3Н8 - measurement 1
Data setC3H8 The calibration data set is 1900E-01 7800E-05 9057E+03 1098E+01 2002E-01 7900E-05 9552E+03 8569E+00 2101E-01 7960E-05 1007E+04 4049E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10529E-02 19831E-05 34552E-03 36109E-07 -12465E-09 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11642E-02 19714E-05 23073E-03 23522E-07 -54231E-10 Remaining SSD is 19453 Weighted distances x-value x-dist y-dist 100E+00 190E-01 -239E-01 666E-01 200E+00 200E-01 487E-01 -104E+00 300E+00 210E-01 -247E-01 248E-01 Goodness-of-fit measure 10414 Parameter set 1 1164239985182795E-2 1971441115316992E-5 2307269625077337E-3 2352198415608386E-7 -
5423119774765299E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19837E-01 14840E-04 94718E+03 45610E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
16
Uncertainty table С3Н8 Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas
mixture
B 005 1 005
Analysis A B 0045 1 0045
Coverage factor 2 Expanded uncertainty 013
17
MEASUREMENT REPORT ndash Belorussian State Institute for Metrology Belarus (BelGIM)
I Results of experimental study
Laboratory Belarus BelGIM Section for physicochemical and optical measurements sector for standards and gas mixtures 8 Serova st Minsk Cylinder No 0128 9 dm3 aluminium NOMINAL COMPOSITION - Carbon dioxide 13middot10-2 - 14middot10-2 molmol - Carbon oxide 28middot10-2 - 32middot10-2 molmol - Propane 19middot10-4 - 21middot10-4molmol - Nitrogen Residual
Measurement No1 Date
Result (molmol)
x_
Standard deviation
S( x_
) rel
No of observations
n
Carbon dioxide 17062005 13567middot10-2 0096 6
Carbon oxide 17062005 2957middot10-2 014 6
Propane 17062005 1977middot10-4 015 6
Measurement No2 Date
Result (molmol)
x_
Standard deviation
S( x_
) rel
No of observations
n
Carbon dioxide 21062005 13564middot10-2 004 6
Carbon oxide 21062005 2957middot10-2 02 6
Propane 21062005 1979middot10-4 01 6
18
Measurement No3 Date
Result (molmol)
x_
Standard deviation
S( x_
) rel
No of observations
n
Carbon dioxide 23062005 13537middot10-2 007 6
Carbon oxide 23062005 2955middot10-2 01 6
Propane 23062005 1982middot10-4 01 6
Final results
Gas mixture Result
(molmol)
Coverage factor
Expanded uncertainty (molmol)
Carbon dioxide 136middot10-2 2 01 middot10-2
Carbon oxide 296middot10-2 2 002middot10-2
Propane 198middot10-4 2 02middot10-4
II Description of study Apparatus (principle of operation type configuration data collection etc)
Measurements were carried out using gas chromatograph Crystal 2000М (hereinafter
referred to as chromatograph) combined with thermal conductivity detector (hereinafter referred to as TCD) with detection limit of 510-9 gml for propane and flame-ionization detector (hereinafter referred to as FID) with detection limit of 510-12 gs for propane
Computers and software Chromatech Analytic version 121 were used to control chromatograph and collect and process chromatographical data
For the purpose of measurements the following auxiliary devices and materials were used
1 Two-position doser with 10 ports and with doses of 025 cm3 for FID channel and with doses of 025 cm3 for TCD channel (hereinafter referred to as doser)
2 Metallic packed column 3m х 3mm х 2mm - HayeSep N 80100 metallic packed column 1m х 4mm х 2mm-CaA 016025 (TCD channel) capillary column HP PLOTQ 30m х 0536mm (FID channel)
3 Aneroid BАММ-1 with a measurement range of 80-106 kPа and accuracy of plusmn 02 kPа
4 Mercurial thermometer ТL-4 with a measurement range of 0-50ordmС and scale division of 01ordmС
19
5 Fine adjustment valve (hereinafter referred to as FAV) provided to transport a gas sample into chromotograph and set to gas flow-rate of 10-15 mlmin
6 Foamy gas flow meter type YIRG - 2А accuracy of flow measurement plusmn 1 сm3min
7 Helium gas Type A according to TU 51-940-80 8 High purity hydrogen gas according to TU 301-07-27-90 9 Compressed air 10 Multicomponent calibration gas mixtures (hereinafter referred to as CGM)
produced and certified by gravimetric method
Calibration reference materials - calibration gas mixtures used for measurements 1 Quantitative composition of KGS is determined using gravimetric method defined in
ISO 61422001 by calculating weight of each component of a gas mixture The content of CGM components is expressed as a mole fraction Uncertainty of KGS composition is expressed as expanded uncertainty with coverage factor k = 2 Molar masses of components and their uncertainties are taken from ISO 149122003 Performance and metrological characteristics of the equipment used for gravimetric preparation of mixtures are given in Table 1
Table 1
Description of the equipment
Manufacturer Metrological characteristics
Mass-comparator balance type КА10-3Р
Mettler-Toledo
Switzerland
Maximum load 15 kg Scale division 1 mg Standard deviation 19 mg at load of 10 kg Operating temperature range +10divide30degС Maximum temperature change within 1 h plusmn05 degС
Gas mixer type USG 00001 BelGIM
Measurement range 000025 divide 100 МPa Accuracy class for manometers ndash 015 Accuracy class for vacuummeters ndash 025 Vacuummeter with pressure sensor for measuring the residual pressure before filling Residual pressure before filling of each component not more than 20 Pa
2 Purity analysis of primary gas standards
The purity analysis of primary gas standards is based on the information provided by the supplier or on the results of determination of impurity in pure gases using measurement procedure developed inside BelGIM
20
If an analytical method laid down in 43 of ISO 61422001 cannot be used for impurity determination mole fraction of an expected impurity is assumed to be half of the detection limit of the analytical method The content of the undetected impurity produces rectangular distribution
whereby its standard uncertainty is calculated as half of the detection limit divided by 3 The composition of the pure gases used for preparation of calibration mixtures is given
in Table 2 Table 2 - Metrological characteristics of pure gases
N2 999967 00005 Nitrogen Cylinder 40 dm3 Origin Russia O2 00033 00005 Propane Cylinder 2 dm3 Origin Russia
C3H8 9979 0017
3 After preparation of mixture the cylinder was maintained in laboratory room within
24 hours the mixture then was homogenized on the stand by rotating on the rollers within 4-5 hours The chromotograph for CGM was calibrated 2-3 days after its preparation
Calibration of the chromotograph
1 The chromotograph was calibrated using CGMs with composition identical to the analyzed sample The content of each component and its expanded uncertainty (k = 2) are given in Table 1 Table 1 - Calibrationе gas mixtures
2 Number of observations of each calibration sample- 3 Number of calibration samples - 3
3 The analytical function used for determination of the content of the analyzed sample components is as follows
x (y) =b1y+b0 (2) Where x ndash determined content molmol y - chromotograph response for the specific component b1- slope b0 - intercept 4 After completion of calibration the coefficients of analytical function were
calculated according to ISO 61432001 using generalized least-squares method Also the uncertainties of the intercept and slope and covariance between them were calculated After determination of parameters which are part of analytical function and which affect the uncertainty of measurements it was checked whether the analytical function is fit to the experimental data obtained in calibration and subsequently whether the analytical function is applicable
Results of calibration measurements coefficients of analytical function their uncertainties covariance and measure of goodness-of-fit Г (maximum value of the weighted differences of the experimental points and calculated points of the analytical function for each measurement run) are given in Tables 3 and 4 respectively Chromotograph operating conditions in calibration and analysis are given in Table 5
Table 3 - Results of experimental study
Date Component of
calibration mixture
Content x mole fraction
Expanded uncertainty
U(x) mole fraction
Mean of peak area y
mVs
Uncertainty )(yu
mVs
13374 0004 1279500 141 1389 0004 1329150 2899 CO2
12833 0004 1231000 849 2916 0005 404070 240
316 0005 437705 926 CO 2768 0004 383070 467
019 0002 3143200 4101
1706 2005
C3H8 0202 0002 3319150 2051
22
0181 0002 2948750 212 13374 0004 1269833 624
1389 0004 1321000 1272 CO2 12833 0004 1223900 1698
2916 0005 399490 612 316 0005 434010 863 CO
2768 0004 379660 410 019 0002 3157867 6772
0202 0002 3332400 3394
2106 2005
C3H8 0181 0002 2959900 4950
13374 0004 1277100 2152 1389 0004 1329900 2828 CO2
12833 0004 1229100 1980 2916 0005 400330 529
316 0005 434745 969 CO 2768 0004 379695 106
019 0002 3142433 9416 0202 0002 3321600 4101
2306 2005
C3H8 0181 0002 2961000 3111
According to ISO 61432003 calculation of the measure of goodness-of-fit Г is the maximum value of the weighed differences between the coordinates of measured and adjusted calibration points is an effective and simple method to test the compatibility of а prospective analytical function A function is admissible if Г le 2
minus
minus=
)(ˆ
)(ˆ
iii
iii
yuyy
xuxxΓ
(4) Where хi is the reference value of the content of calibration sample component
ix is the CGM component content obtained using the calculated analytical function
уi is the experimental response to the reference content of component iy is the response obtained in calculation of analytical function
u (хi) u (уi) are the uncertainties of reference contents and responses to these contents respectively
i is the number of calibration points i=1 3 This prerequisite is equivalent to the requirement that the curve of calculated response should cross each experimental calibration rectangular [хi plusmn 2u(хi) уi plusmn 2и(уi)] based on an expanded uncertainty U = ku with coverage factor k = 2 Table 4 Calculations of analytical function
Date Component Analytical function parameters
Uncertainty of analytical
function parameters
Covariance of
parameters Г
23
b1 b0 u(b1) u(b0) u(b0b1) 1706 11086E-
03 -81128E-
0119491E-
0524883E-
01 -48497E-06 10544
2106 10729E-03
-26126E-01
22698E-05
28930E-01 -65652E-06 19997
2306
CO2 10593E-
03 -17688E-
0135807E-
0545413E-
01 -16254E-05 10022
1706 71537E-04
26507E-02
14231E-05
57044E-02 -81115E-07 03017
2106 72346E-04
22401E-02
13819E-05
54490E-02 -75209E-07 05935
2306
CO 71321E-
04 60080E-
0212663E-
0549016E-
02 -62026E-07 01341
1706 56521E-06
13712E-02
38279E-07
12015E-02 -45937E-09 12991
2106 56295E-06
13707E-02
39247E-07
12379E-02 -48529E-09 12905
2306
C3H8 58258E-
06 80469E-
0340085E-
0712590E-
02 -50407E-09 08589
Two columns separated by switching device are located one after another in TCD
channel One column is intended for carbon dioxide heavy hydrocarbons and another column is intended for light gases Before the first switch the light gases including carbon oxide flow through the first column without being separated and remain in the second column The switch makes them locked in the second column The analysis of carbon dioxide is carried out up to the second switch Second switch makes the second column unlocked and carbon oxide is analyzed Third switch is required to allow propane escape from a column and prevent it from getting into a second column The analysis of the very propane is carried out using FID Time intervals between switches were selected experimentally when developing the analysis method Such analysis method makes it possible to analyze all three components per one sample inject
Table 5 - Chromotograph operating conditions in calibration and analysis Parameter of the operating conditions Thermostating temperature of TCD and FID degС 170
Temperature of separation columns degС
Program 60 degС within 9 min
than rise to 160 degС at 20degСmin
Rate of flow of carrier gas through TCD channel columns mlmin 15
Rate of flow of carrier gas through TCD comparison channel mlmin 15
Pressure in FID channel column kPa Program
24
80 to 100 Rise from the 1st s of
analysis at 2 kPamin
Flow-rate of hydrogen FID mlmin 20 Flow-rate of air FID mlmin 200 Temperature of switching device degС 65 Response time of switching device s 1 110 2 330 3 540
TCD FID Volume of injected analyzed gas cm3 025 025 Carrier gas Helium Duration of analysis min 17 Calculation of the content of comparison sample components and its uncertainty Results of comparison sample measurements are given in Table 6 Table 6 - Results of comparison sample measurements
1 The content of comparison sample component and its uncertainty were determined
using calculated analytical function according to ISO 61432001 as follows (5) Where G(y)=b1y+b0 is the calculated analytical function и(y) is the standard uncertainty of response y u2(bj) is the variance of analytical function parameter bj
u(bj bI) is the covariance of analytical function parameters bj bI N is the number of function coefficients N=2 j=0 1
sum sumsumminus
= +==
partpart
partpart
+
partpart
+
partpart
=1
0 1
2
2
0
22
)(2)()()(N
jIj
N
jI Ijj
N
j j
bbubG
bGbu
bGyu
yGxu
25
After substitution of analytical function (2) and transformations the expression takes form (5)
)(2)()()()()( 01122
0222
1 bbyubuybuyubxu +++= (6) The contents of comparison sample components under determination and their
uncertainties were calculated using B_LEAST a computer program recommended in ISO 6143 Calculations are summarized in Table 6
Table 6 Calculations of the content of comparison sample components and their
2 The final content of a component was determined as an arithmetiс mean from three measurements Final standard uncertainty was calculated using formula as follows
22
222)( Адаватмтемсериикал uuuuuxu ++++= (7)
Where ucal is the uncertainty of the component content produced by
calibration of chromotograph urun is the uncertainty of the component content produced by
change of chromotograph response in each measurement run ut is the uncertainty of the component content produced by
change of an ambient temperature upressure is the uncertainty of the component content produced by
change of atmospheric pressure u A is the standard uncertainty of three measurement runs
21 Uncertainty of the component content produced by calibration of chromotograph
This uncertainty is calculated using formula (6) but the first term of the sum ie
)()( 221 yub which represents the standard uncertainty of the chromotograph response in a
measurement run is not taken into account Calculations are summarized in Table 7
26
Table 7 Calculation of uncertainty produced by calibration of chromotograph
Date u(b1) u(b0) u(b0b1) x
molmol y Ucal molmol
Ucal rel
1706 19491E-05
24883E-01
-48497E-06
13567middot10-
2129698
3 0005middot1
0-2 003
2106 22698E-05
28930E-01
-65652E-06
13564middot10-
2 128855 0007middot1
0-2 005
2306
CO2
35807E-05
45413E-01
-16254E-05
135374middot10-2
1294633
0016middot10-2 012
1706 14231E-05
57044E-02
-81115E-07 2957middot10-2 409633
0003middot10-2 009
2106 13819E-05
54490E-02
-75209E-07
29577middot10-
2 405663 0003middot1
0-2 01
2306
CO
12663E-05
49016E-02
-62026E-07 2955middot10-2 405882
0003middot10-2 01
1706 38279E-07
12015E-02
-45937E-09 1977middot10-4
3255817
007middot10-
2 038
2106 39247E-07
12379E-02
-48529E-09 1980middot10-4
3273329
008middot10-
2 038
2306
C3H8
40085E-07
12590E-02
-50407E-09 1982middot10-4 32636
008middot10-
2 04 The total estimate of relative uncertainty produced by calibration of chromotograph was
calculated for each component as follows
3
3
1
2sum=
cali
cali
uu (8)
Where ucal i is the relative uncertainty produced by calibration of chromotograph and calculated for each measurement run
The calculations are summarized in Table 8
Table 8 Uncertainty produced by calibration of chromotograph
Component Ucal rel
CO2 008 CO 01
C3H8 04 22 Uncertainty of the component content produced by change of chromotograph response in each measurement run This uncertainty is calculated using the equation (6) whereby the first term of the sum
only ie )()( 221 yub which represents the standard uncertainty of the chromotograph
response in a measurement run is taken into account Calculations are summarized in Table 9
27
Table 9 Calculation of uncertainty produced by change of chromotograph response in each measurement run
The total estimate of relative uncertainty produced by change of chromotograph
response in each measurement run was calculated for each component as follows
3
3
1
2sum=
run
run
uu (9)
Where urun is the relative uncertainty produced by change of chromotograph response in each measurement run Calculations are summarized in Table 10
Table 10 Uncertainty produced by change of chromotograph response in each measurement
run
Component Urun rel
CO2 007 CO 015
C3H8 012 23 Uncertainty of the component content produced by change of temperature in a room
The recorded change of temperature in measurements is plusmn 05 degree The contribution of uncertainty type B (rectangular distribution) is estimated as follows
201003
12931
=sdotsdot=tu rel
28
24 Uncertainty of the component content produced by change of atmospheric pressure The recorded change of atmospheric pressure within three days was
05 kPа The contribution of uncertainty type B (rectangular distribution) is estimated as follows
2801003
13101
50=sdotsdot=pressureu rel
25 Standard deviation of 3 measurement runs Standard deviation is calculated as follows
isu p
A
2
= (10)
Where S2p is the group experimental variation
The group experimental variation is calculated as follows
(11)
Where si
2 is the experimental variation of measurement run i from independent repeated observations ni having freedom degrees
νi = n - 1 n=6 i= 3 Calculations are summarized in Table 11 Table 11 Calculations of standard uncertainty of 3 measurement runs
Date 2iS x
molmol 2iS
rel uA
rel
1706 2953E-05 13567middot10-2 000022
2106 588987E-06 13564middot10-2 0000043
2306
CO2 141137E-
05 135374middot10
-2 000010
0006
1706 225604E-06 2957middot10-2 0000077
2106 681346E-06 29577middot10-2 000023
2306
CO
175166E-06 2955middot10-2 0000060
0006
1706 C3H8 130158E-
08 1977middot10-4 00000066 0001
ss
p
i ii
N
ii
N2
2
1
1
= =
=
sum
sum
ν
ν
29
2106 44616E-09 1980middot10-4 00000023
2306
381032E-09 1982middot10-4 00000019
26 Total standard uncertainty
Uncertainty estimation СО2
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph ucal Normal 008 1 008
Change of temperature ut Rectangular 02 1 02 Change of atmospheric pressure upressure Rectangular 028 1 028
Changes of chromotograph response
urun Normal 007 1 007
Standard deviation of 3 runs uA Normal 0006 1 0006
Relative total standard uncertainty 036 Coverage factor k=2 Expanded uncertainty 01middot10-2 molmol Uncertainty estimation СО
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph ucal Normal 01 1 01 Change of temperature ut Rectangular 02 1 02 Change of atmospheric pressure upressure Rectangular 028 1 028 Changes of chromotograph response
urun Normal 015 1 015
Standard deviation of 3 runs uA Normal 0006 1 0006
Relative total standard uncertainty 039 Coverage factor k=2 Expanded uncertainty 002middot10-2 molmol Uncertainty estimation С3Н8
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph 04 Normal 04 1 008
30
Change of temperature 02 Rectangular 02 1 02 Change of atmospheric pressure 028 Rectangular 028 1 028
Changes of chromotograph response
012 Normal 012 1 007
Standard deviation of 3 runs 0001 Normal 0001 1 0006
Relative total standard uncertainty 054 Coverage factor k=2 Expanded uncertainty 02middot10-4 molmol
Sample handling
Period for exposure of cylinder to measurement conditions and method how to transport sample to the device
1 Stands for storing gas standard cylinders and calibration mixture cylinders and chromotograph are placed in a laboratory room which is not accessible to unauthorized persons The laboratory is equipped with air-conditioner to maintain required temperature and humidity on a continuous basis and some auxiliary measuring instruments as thermometer psychrometric hygrometer and aneroid to control temperature humidity and atmospheric inside the room
2 The comparison sample cylinder was stored in laboratory from the date of its
delivery to Minsk on 25042005 CGM cylinders are stored horizontally on racks and positioned vertically using special support when measurements are carried out
3 The analyzed gas sample is transported through the fine adjustment valve (FAV)
Conjunctions Cylinder - FAV FAV - tube tube - doser are made of metal and use adapters with spherical ends and bushes FAV is made of brass tube is made of copper and doser is made of duralumin
Instrument(s) (principles make type configuration data collection etc) For the analysis a GC were used with specifically applications For the determination of (Nitrogen (N2)) Carbon Dioxide (CO2) Carbon Monoxide (CO) and Propane (C3H8) balance GC Perkin Elmer AutoSystem XL (two channel system) with a stream selection valve for 4 streams and 2 gas sampling valves
Channel A for the determination of N2 CO and CO2 Carrier Gas Helium Columns Column system with two packed columns (6 ft x 18rdquo Porapak R 80100 mesh and 6 ft x 18rdquo Mol-Sieve 13X 80100 mesh) Oven Temperature 960 degC to 180 degC Detector micro-TCD Data Collection Total Chrom Workstation Channel B for the determination of C3H8 Carrier Gas Helium Columns Capillary column 50 m x 032 microm LP-SIL-8-CB Oven Temperature 60 degC to 180 degC Detector FID Data Collection Total Chrom Workstation
34
Calibration Standards
Calibration Standards for the measurements (preparation method purity analyses estimated uncertainty etc)
All standards were prepared individually according to ISO 6142 rdquoGas analysis - Preparation of calibration gases - Gravimetric Methodrdquo
Depending on the concentration of the components standards were prepared individually from pure gases or from pre-mixtures which were individually prepared from pure gases
The content of the impurities in all pure gases were determined before use by GC-DID GC-FID and or GC-TCD
After preparation the standards were verified by analytical comparisons against existing gravimetrically prepared standards Only when no significant difference between the analysed and the calculated gravimetric composition is found the ldquonew prepared candidate rdquo is accepted as a new standards
For the analysis of all components multi component standards with nitrogen as balance gas were used
Composition of calibrants BAM C49250-050722 Component Assigned value( x)
mmol mol Standard uncertainty (u(x)) relativ (k=2)
Calibration procedure (mathematical modelcalibration curve number and concentrations of standards measurement sequence temperaturepressure correction etc)
For the instrument calibration the bracketing technique was used The fraction of the current used standards deviated no more than +10rel and -10rel respectively from those of the sample
Measurement sequence
Sample Handling
How were the cylinders treated after arrival (eg stabilized) and how were samples transferred to the instrument (automatic high pressure mass-flow controller dilution etc) After heating (45 - 50 degC) the cylinder for 8 hours the cylinder were rolled about 16 hours before analysis was started Each cylinder was equipped with a pressure regulator that was purged three times by sequential evacuation and pressurisation with the gas mixture used Continous flow (2 ndash 3mlmin) through the sample loop
Uncertainty The specification of potential uncertainty sources is given in Annex 3
3 injection standard (high)
3 injection sample
3 injection standard (high)
3 injection sample
3 injection standard (low)
3 injection sample
3 injection standard (low)
3 injection standard (low)
36
Uncertainty table CO2
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 002 rel 1 002 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 03 rel
Uncertainty table CO
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 007 rel 1 007 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 05 rel
37
Uncertainty table C3H8
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 010 rel 1 001 rel
Analysis normal 028 rel 1 028 rel
Coverage factor 2
Expanded uncertainty 06 rel
Optional
You may provide additional data like the raw measurement data information on your
measurement procedure chromatograms etc
38
Appendix 3 SPECIFICATION OF POTENTIAL UNCERTAINTY SOURCES
a Uncertainty related to the balance and the weights Resolution of balance Accuracy of balance including linearity Incorrect zero point Drift (thermal and time effects) Instability due to draught Location of cylinder on the balance pan Uncertainties in the weights used Buoyancy effects on the weights used
b Uncertainties related to the gas cylinder Mechanical handling of cylinder
Loss of metal paints or labels from surface of cylinder Loss of metal from threads of valvefitting Dirt on cylinder valves or associated fitting
Absorptiondesorption effects on the external cylinder surface Buoyancy effects on the cylinder itself
Cylinder temperature differs from surrounding air due to eg filling with gas Change of cylinder volume during filling Change of density of surrounding air due to changes in temperature air pressure humidity and carbon dioxide content
Uncertainty in determination of external cylinder volume c Uncertainties related to the component gases Residual gas in cylinder Leakage Leakage of air into the cylinder after evacuation
Leakage of gas from the cylinder valve during filling Escape of gas from cylinder into transport lines
Gas remaining in transfer system when weight loss method is used Absorptionreaction of components on internal cylinder surface Reaction between components Impurities in all the initial gases Insufficient homogenization Uncertainty of molecular mass d Uncertainties related to the analysis
Repeatability and selectivity of the analyzer Appropriateness of the calibration curve
39
MEASUREMENT REPORT - All Ukrainian State Research-Industrial Center of Standardization Metrology Certification and Protection of Consumers Ukraine
gas ndash helium flow rate 15 cm3min detector TCD tdetector = 250 ordmС toven = 70 ordmС It was automatic data collection
Measurement and Calibration Methods Laboratory Measurement method Type of calibration curve
GCFID (С3Н8) 3 points linear Ukrmetrteststandard GCTCD (СО СО2) 3 points linear
GCFID ndash gas-chromatographic with flame-ionization detector GCTCD - gas-chromatographic with thermal-conductivity detector
42
Calibration Standards
Calibration standards ndash primary standard gas mixtures (PSGM) used for measurements by comparison method
PSGM-1 Cylinder 0116
PSGM-2 Cylinder 0107
PSGM-3 Cylinder 0093 Composition
x u(x) x u(x) x u(x) СО 27874 00015 29899 00015 31891 00015 СО2 130187 00015 144456 00016 137016 00016 С3Н8 019003 000008 020017 000008 021013 000008 N2 balance balance balance
Note x ndash mole fraction u(x) ndash absolute standard uncertainty
It was used gravimetric method of preparation of PSGM Electronic balance КА-20-3 of Mettler Toledo max limit of weighing is 20 kg least
limit of weighing is 01 g standard deviation is 0006 g Analysis of purity of parent gases was carried out with usage of chromatographs
НР6890N with helium ndash ionization detector flame ndash ionization detector thermal ndash conductivity detector and mass ndash spectrometric detector as well аs gas analyzers GIAM-15M and Onix condensate-thermometer hygrometer TOROS-3-2B
Calculation of uncertainties was carried out according to ISO 6142-2003 Corrections of temperature pressure and humidity of environment were considered
in calculations according to ISO 6142-2003 (program of ISO-6142 2000-03-17 designer is NMi) Protocols and explanations are in Annex A
Instrument (Comparator) Calibration Calibration of comparator ndash gas chromatograph HP 6890 was carried out with usage
of PSGM Measurement sequence PSGM -1 х 3 PSGM -2 х 3 COOMET gas mixture х 3 PSGM -2 х 3 PSGM -3 х 3 It is necessary to use PSGM-2 repeatedly for estimation of reproducibility of results
Program B_LEAST recommended by ISO 6143-2003 was used for constructing the curve Mathematical model of calibration curve is linear one
Sample Handling The cylinder was kept for 24 hrs at a room where comparators were disposed This room is a thermostatic room with t = (20plusmn2) ordmС
43
A method of sample input to a comparator is a method with flow stabilization Uncertainty The following uncertainties were included to the budget of uncertainty - uncertainty of the balance - uncertainties of impurities in parent gases Contribution from other uncertainty sources was insignificant A cabin of the balance is thermostatically The balance is the one-pan balance
Air transfer is absent in the cabin of the balance Drift of the balance is absent for PSGM preparation
Contribution from other uncertainty sources was considered in software according to ISO 6142-2003
Uncertainties related to the analysis (comparison) were considered in software according to ISO 6143-2003 and enclosed in Annex B
Uncertainty table СО2
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas mixture
B 001 1 001
Analysis A B 008 1 008
Coverage factor 2 Expanded uncertainty 002sdot10-2 molmol Uncertainty table СО
Protocols of analysis (comparison) in accordance with ISO 6143-2003
57
Explanation of protocols of comparison
Chapter I ldquoThe calibration data set isrdquo contains columns 1 mole fraction of a component 2 absolute standard uncertainty of mole fraction of a component 3 a signal of a comparator 4 absolute standard uncertainty of a comparator signal
Chapter II ldquoResults of ISO 6143 methodrdquo contains parameters of a calibration curve including its
uncertainty
Chapter ІІІ ldquoPart II Processing of datardquo contains columns
1 calc x - the results of comparison mole fraction of a component 2 u(x) - absolute standard uncertainty of mole fraction of a component 3 response y - a signal of a comparator 4 u(y) - absolute standard uncertainty of a comparator signal
58
СО2 - measurement 1 Data setCO2_21 The calibration data set is 1302E+01 1510E-03 1022E+04 1820E+00 1370E+01 1560E-03 1077E+04 2730E+00 1445E+01 1620E-03 1135E+04 5900E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 20331E-02 12711E-03 12573E-01 11653E-05 -14638E-06 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 10548E-02 12722E-03 31762E-02 28898E-06 -91698E-08 Remaining SSD is 74346 Weighted distances x-value x-dist y-dist 100E+00 130E+01 490E-01 -755E-01 200E+00 137E+01 -103E+00 228E+00 300E+00 144E+01 539E-01 -250E-01 Goodness-of-fit measure 22837 Parameter set 1 1054788657490729E-2 1272208026684145E-3 3176237146276368E-2 2889798108124711E-6 -
9169821653851327E-8 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_21c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13577E+01 25542E-03 10664E+04 15200E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 547E-06 328E-06 316E-06 784E-06 286E-06 652E-06 Linear model Parameters for the fit were (b0 b1) 10548E-02 12722E-03
59
СО2 - measurement 2
Data setCO2_20 The calibration data set is 1302E+01 1512E-03 1021E+04 4723E+00 1370E+01 1563E-03 1075E+04 1600E+00 1445E+01 1620E-03 1133E+04 7300E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -38760E-02 12784E-03 26817E-02 24890E-06 -66689E-08 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -62452E-02 12805E-03 47930E-02 43243E-06 -20716E-07 Remaining SSD is 03231 Weighted distances x-value x-dist y-dist 100E+00 130E+01 107E-01 -415E-01 200E+00 137E+01 -212E-01 283E-01 300E+00 144E+01 104E-01 -584E-02 Goodness-of-fit measure 04155 Parameter set 1 -6245240430658412E-2 1280492624666799E-3 4792952200361109E-2 4324266278840409E-6 -
2071623966851869E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_20c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13594E+01 10290E-02 10665E+04 78300E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 121E-05 683E-06 651E-06 315E-05 560E-06 106E-04 Linear model Parameters for the fit were (b0 b1) -62452E-02 12805E-03
60
С3Н8 - measurement 1
Data setC3H8 The calibration data set is 1900E-01 7800E-05 9057E+03 1098E+01 2002E-01 7900E-05 9552E+03 8569E+00 2101E-01 7960E-05 1007E+04 4049E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10529E-02 19831E-05 34552E-03 36109E-07 -12465E-09 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11642E-02 19714E-05 23073E-03 23522E-07 -54231E-10 Remaining SSD is 19453 Weighted distances x-value x-dist y-dist 100E+00 190E-01 -239E-01 666E-01 200E+00 200E-01 487E-01 -104E+00 300E+00 210E-01 -247E-01 248E-01 Goodness-of-fit measure 10414 Parameter set 1 1164239985182795E-2 1971441115316992E-5 2307269625077337E-3 2352198415608386E-7 -
5423119774765299E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19837E-01 14840E-04 94718E+03 45610E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
17
MEASUREMENT REPORT ndash Belorussian State Institute for Metrology Belarus (BelGIM)
I Results of experimental study
Laboratory Belarus BelGIM Section for physicochemical and optical measurements sector for standards and gas mixtures 8 Serova st Minsk Cylinder No 0128 9 dm3 aluminium NOMINAL COMPOSITION - Carbon dioxide 13middot10-2 - 14middot10-2 molmol - Carbon oxide 28middot10-2 - 32middot10-2 molmol - Propane 19middot10-4 - 21middot10-4molmol - Nitrogen Residual
Measurement No1 Date
Result (molmol)
x_
Standard deviation
S( x_
) rel
No of observations
n
Carbon dioxide 17062005 13567middot10-2 0096 6
Carbon oxide 17062005 2957middot10-2 014 6
Propane 17062005 1977middot10-4 015 6
Measurement No2 Date
Result (molmol)
x_
Standard deviation
S( x_
) rel
No of observations
n
Carbon dioxide 21062005 13564middot10-2 004 6
Carbon oxide 21062005 2957middot10-2 02 6
Propane 21062005 1979middot10-4 01 6
18
Measurement No3 Date
Result (molmol)
x_
Standard deviation
S( x_
) rel
No of observations
n
Carbon dioxide 23062005 13537middot10-2 007 6
Carbon oxide 23062005 2955middot10-2 01 6
Propane 23062005 1982middot10-4 01 6
Final results
Gas mixture Result
(molmol)
Coverage factor
Expanded uncertainty (molmol)
Carbon dioxide 136middot10-2 2 01 middot10-2
Carbon oxide 296middot10-2 2 002middot10-2
Propane 198middot10-4 2 02middot10-4
II Description of study Apparatus (principle of operation type configuration data collection etc)
Measurements were carried out using gas chromatograph Crystal 2000М (hereinafter
referred to as chromatograph) combined with thermal conductivity detector (hereinafter referred to as TCD) with detection limit of 510-9 gml for propane and flame-ionization detector (hereinafter referred to as FID) with detection limit of 510-12 gs for propane
Computers and software Chromatech Analytic version 121 were used to control chromatograph and collect and process chromatographical data
For the purpose of measurements the following auxiliary devices and materials were used
1 Two-position doser with 10 ports and with doses of 025 cm3 for FID channel and with doses of 025 cm3 for TCD channel (hereinafter referred to as doser)
2 Metallic packed column 3m х 3mm х 2mm - HayeSep N 80100 metallic packed column 1m х 4mm х 2mm-CaA 016025 (TCD channel) capillary column HP PLOTQ 30m х 0536mm (FID channel)
3 Aneroid BАММ-1 with a measurement range of 80-106 kPа and accuracy of plusmn 02 kPа
4 Mercurial thermometer ТL-4 with a measurement range of 0-50ordmС and scale division of 01ordmС
19
5 Fine adjustment valve (hereinafter referred to as FAV) provided to transport a gas sample into chromotograph and set to gas flow-rate of 10-15 mlmin
6 Foamy gas flow meter type YIRG - 2А accuracy of flow measurement plusmn 1 сm3min
7 Helium gas Type A according to TU 51-940-80 8 High purity hydrogen gas according to TU 301-07-27-90 9 Compressed air 10 Multicomponent calibration gas mixtures (hereinafter referred to as CGM)
produced and certified by gravimetric method
Calibration reference materials - calibration gas mixtures used for measurements 1 Quantitative composition of KGS is determined using gravimetric method defined in
ISO 61422001 by calculating weight of each component of a gas mixture The content of CGM components is expressed as a mole fraction Uncertainty of KGS composition is expressed as expanded uncertainty with coverage factor k = 2 Molar masses of components and their uncertainties are taken from ISO 149122003 Performance and metrological characteristics of the equipment used for gravimetric preparation of mixtures are given in Table 1
Table 1
Description of the equipment
Manufacturer Metrological characteristics
Mass-comparator balance type КА10-3Р
Mettler-Toledo
Switzerland
Maximum load 15 kg Scale division 1 mg Standard deviation 19 mg at load of 10 kg Operating temperature range +10divide30degС Maximum temperature change within 1 h plusmn05 degС
Gas mixer type USG 00001 BelGIM
Measurement range 000025 divide 100 МPa Accuracy class for manometers ndash 015 Accuracy class for vacuummeters ndash 025 Vacuummeter with pressure sensor for measuring the residual pressure before filling Residual pressure before filling of each component not more than 20 Pa
2 Purity analysis of primary gas standards
The purity analysis of primary gas standards is based on the information provided by the supplier or on the results of determination of impurity in pure gases using measurement procedure developed inside BelGIM
20
If an analytical method laid down in 43 of ISO 61422001 cannot be used for impurity determination mole fraction of an expected impurity is assumed to be half of the detection limit of the analytical method The content of the undetected impurity produces rectangular distribution
whereby its standard uncertainty is calculated as half of the detection limit divided by 3 The composition of the pure gases used for preparation of calibration mixtures is given
in Table 2 Table 2 - Metrological characteristics of pure gases
N2 999967 00005 Nitrogen Cylinder 40 dm3 Origin Russia O2 00033 00005 Propane Cylinder 2 dm3 Origin Russia
C3H8 9979 0017
3 After preparation of mixture the cylinder was maintained in laboratory room within
24 hours the mixture then was homogenized on the stand by rotating on the rollers within 4-5 hours The chromotograph for CGM was calibrated 2-3 days after its preparation
Calibration of the chromotograph
1 The chromotograph was calibrated using CGMs with composition identical to the analyzed sample The content of each component and its expanded uncertainty (k = 2) are given in Table 1 Table 1 - Calibrationе gas mixtures
2 Number of observations of each calibration sample- 3 Number of calibration samples - 3
3 The analytical function used for determination of the content of the analyzed sample components is as follows
x (y) =b1y+b0 (2) Where x ndash determined content molmol y - chromotograph response for the specific component b1- slope b0 - intercept 4 After completion of calibration the coefficients of analytical function were
calculated according to ISO 61432001 using generalized least-squares method Also the uncertainties of the intercept and slope and covariance between them were calculated After determination of parameters which are part of analytical function and which affect the uncertainty of measurements it was checked whether the analytical function is fit to the experimental data obtained in calibration and subsequently whether the analytical function is applicable
Results of calibration measurements coefficients of analytical function their uncertainties covariance and measure of goodness-of-fit Г (maximum value of the weighted differences of the experimental points and calculated points of the analytical function for each measurement run) are given in Tables 3 and 4 respectively Chromotograph operating conditions in calibration and analysis are given in Table 5
Table 3 - Results of experimental study
Date Component of
calibration mixture
Content x mole fraction
Expanded uncertainty
U(x) mole fraction
Mean of peak area y
mVs
Uncertainty )(yu
mVs
13374 0004 1279500 141 1389 0004 1329150 2899 CO2
12833 0004 1231000 849 2916 0005 404070 240
316 0005 437705 926 CO 2768 0004 383070 467
019 0002 3143200 4101
1706 2005
C3H8 0202 0002 3319150 2051
22
0181 0002 2948750 212 13374 0004 1269833 624
1389 0004 1321000 1272 CO2 12833 0004 1223900 1698
2916 0005 399490 612 316 0005 434010 863 CO
2768 0004 379660 410 019 0002 3157867 6772
0202 0002 3332400 3394
2106 2005
C3H8 0181 0002 2959900 4950
13374 0004 1277100 2152 1389 0004 1329900 2828 CO2
12833 0004 1229100 1980 2916 0005 400330 529
316 0005 434745 969 CO 2768 0004 379695 106
019 0002 3142433 9416 0202 0002 3321600 4101
2306 2005
C3H8 0181 0002 2961000 3111
According to ISO 61432003 calculation of the measure of goodness-of-fit Г is the maximum value of the weighed differences between the coordinates of measured and adjusted calibration points is an effective and simple method to test the compatibility of а prospective analytical function A function is admissible if Г le 2
minus
minus=
)(ˆ
)(ˆ
iii
iii
yuyy
xuxxΓ
(4) Where хi is the reference value of the content of calibration sample component
ix is the CGM component content obtained using the calculated analytical function
уi is the experimental response to the reference content of component iy is the response obtained in calculation of analytical function
u (хi) u (уi) are the uncertainties of reference contents and responses to these contents respectively
i is the number of calibration points i=1 3 This prerequisite is equivalent to the requirement that the curve of calculated response should cross each experimental calibration rectangular [хi plusmn 2u(хi) уi plusmn 2и(уi)] based on an expanded uncertainty U = ku with coverage factor k = 2 Table 4 Calculations of analytical function
Date Component Analytical function parameters
Uncertainty of analytical
function parameters
Covariance of
parameters Г
23
b1 b0 u(b1) u(b0) u(b0b1) 1706 11086E-
03 -81128E-
0119491E-
0524883E-
01 -48497E-06 10544
2106 10729E-03
-26126E-01
22698E-05
28930E-01 -65652E-06 19997
2306
CO2 10593E-
03 -17688E-
0135807E-
0545413E-
01 -16254E-05 10022
1706 71537E-04
26507E-02
14231E-05
57044E-02 -81115E-07 03017
2106 72346E-04
22401E-02
13819E-05
54490E-02 -75209E-07 05935
2306
CO 71321E-
04 60080E-
0212663E-
0549016E-
02 -62026E-07 01341
1706 56521E-06
13712E-02
38279E-07
12015E-02 -45937E-09 12991
2106 56295E-06
13707E-02
39247E-07
12379E-02 -48529E-09 12905
2306
C3H8 58258E-
06 80469E-
0340085E-
0712590E-
02 -50407E-09 08589
Two columns separated by switching device are located one after another in TCD
channel One column is intended for carbon dioxide heavy hydrocarbons and another column is intended for light gases Before the first switch the light gases including carbon oxide flow through the first column without being separated and remain in the second column The switch makes them locked in the second column The analysis of carbon dioxide is carried out up to the second switch Second switch makes the second column unlocked and carbon oxide is analyzed Third switch is required to allow propane escape from a column and prevent it from getting into a second column The analysis of the very propane is carried out using FID Time intervals between switches were selected experimentally when developing the analysis method Such analysis method makes it possible to analyze all three components per one sample inject
Table 5 - Chromotograph operating conditions in calibration and analysis Parameter of the operating conditions Thermostating temperature of TCD and FID degС 170
Temperature of separation columns degС
Program 60 degС within 9 min
than rise to 160 degС at 20degСmin
Rate of flow of carrier gas through TCD channel columns mlmin 15
Rate of flow of carrier gas through TCD comparison channel mlmin 15
Pressure in FID channel column kPa Program
24
80 to 100 Rise from the 1st s of
analysis at 2 kPamin
Flow-rate of hydrogen FID mlmin 20 Flow-rate of air FID mlmin 200 Temperature of switching device degС 65 Response time of switching device s 1 110 2 330 3 540
TCD FID Volume of injected analyzed gas cm3 025 025 Carrier gas Helium Duration of analysis min 17 Calculation of the content of comparison sample components and its uncertainty Results of comparison sample measurements are given in Table 6 Table 6 - Results of comparison sample measurements
1 The content of comparison sample component and its uncertainty were determined
using calculated analytical function according to ISO 61432001 as follows (5) Where G(y)=b1y+b0 is the calculated analytical function и(y) is the standard uncertainty of response y u2(bj) is the variance of analytical function parameter bj
u(bj bI) is the covariance of analytical function parameters bj bI N is the number of function coefficients N=2 j=0 1
sum sumsumminus
= +==
partpart
partpart
+
partpart
+
partpart
=1
0 1
2
2
0
22
)(2)()()(N
jIj
N
jI Ijj
N
j j
bbubG
bGbu
bGyu
yGxu
25
After substitution of analytical function (2) and transformations the expression takes form (5)
)(2)()()()()( 01122
0222
1 bbyubuybuyubxu +++= (6) The contents of comparison sample components under determination and their
uncertainties were calculated using B_LEAST a computer program recommended in ISO 6143 Calculations are summarized in Table 6
Table 6 Calculations of the content of comparison sample components and their
2 The final content of a component was determined as an arithmetiс mean from three measurements Final standard uncertainty was calculated using formula as follows
22
222)( Адаватмтемсериикал uuuuuxu ++++= (7)
Where ucal is the uncertainty of the component content produced by
calibration of chromotograph urun is the uncertainty of the component content produced by
change of chromotograph response in each measurement run ut is the uncertainty of the component content produced by
change of an ambient temperature upressure is the uncertainty of the component content produced by
change of atmospheric pressure u A is the standard uncertainty of three measurement runs
21 Uncertainty of the component content produced by calibration of chromotograph
This uncertainty is calculated using formula (6) but the first term of the sum ie
)()( 221 yub which represents the standard uncertainty of the chromotograph response in a
measurement run is not taken into account Calculations are summarized in Table 7
26
Table 7 Calculation of uncertainty produced by calibration of chromotograph
Date u(b1) u(b0) u(b0b1) x
molmol y Ucal molmol
Ucal rel
1706 19491E-05
24883E-01
-48497E-06
13567middot10-
2129698
3 0005middot1
0-2 003
2106 22698E-05
28930E-01
-65652E-06
13564middot10-
2 128855 0007middot1
0-2 005
2306
CO2
35807E-05
45413E-01
-16254E-05
135374middot10-2
1294633
0016middot10-2 012
1706 14231E-05
57044E-02
-81115E-07 2957middot10-2 409633
0003middot10-2 009
2106 13819E-05
54490E-02
-75209E-07
29577middot10-
2 405663 0003middot1
0-2 01
2306
CO
12663E-05
49016E-02
-62026E-07 2955middot10-2 405882
0003middot10-2 01
1706 38279E-07
12015E-02
-45937E-09 1977middot10-4
3255817
007middot10-
2 038
2106 39247E-07
12379E-02
-48529E-09 1980middot10-4
3273329
008middot10-
2 038
2306
C3H8
40085E-07
12590E-02
-50407E-09 1982middot10-4 32636
008middot10-
2 04 The total estimate of relative uncertainty produced by calibration of chromotograph was
calculated for each component as follows
3
3
1
2sum=
cali
cali
uu (8)
Where ucal i is the relative uncertainty produced by calibration of chromotograph and calculated for each measurement run
The calculations are summarized in Table 8
Table 8 Uncertainty produced by calibration of chromotograph
Component Ucal rel
CO2 008 CO 01
C3H8 04 22 Uncertainty of the component content produced by change of chromotograph response in each measurement run This uncertainty is calculated using the equation (6) whereby the first term of the sum
only ie )()( 221 yub which represents the standard uncertainty of the chromotograph
response in a measurement run is taken into account Calculations are summarized in Table 9
27
Table 9 Calculation of uncertainty produced by change of chromotograph response in each measurement run
The total estimate of relative uncertainty produced by change of chromotograph
response in each measurement run was calculated for each component as follows
3
3
1
2sum=
run
run
uu (9)
Where urun is the relative uncertainty produced by change of chromotograph response in each measurement run Calculations are summarized in Table 10
Table 10 Uncertainty produced by change of chromotograph response in each measurement
run
Component Urun rel
CO2 007 CO 015
C3H8 012 23 Uncertainty of the component content produced by change of temperature in a room
The recorded change of temperature in measurements is plusmn 05 degree The contribution of uncertainty type B (rectangular distribution) is estimated as follows
201003
12931
=sdotsdot=tu rel
28
24 Uncertainty of the component content produced by change of atmospheric pressure The recorded change of atmospheric pressure within three days was
05 kPа The contribution of uncertainty type B (rectangular distribution) is estimated as follows
2801003
13101
50=sdotsdot=pressureu rel
25 Standard deviation of 3 measurement runs Standard deviation is calculated as follows
isu p
A
2
= (10)
Where S2p is the group experimental variation
The group experimental variation is calculated as follows
(11)
Where si
2 is the experimental variation of measurement run i from independent repeated observations ni having freedom degrees
νi = n - 1 n=6 i= 3 Calculations are summarized in Table 11 Table 11 Calculations of standard uncertainty of 3 measurement runs
Date 2iS x
molmol 2iS
rel uA
rel
1706 2953E-05 13567middot10-2 000022
2106 588987E-06 13564middot10-2 0000043
2306
CO2 141137E-
05 135374middot10
-2 000010
0006
1706 225604E-06 2957middot10-2 0000077
2106 681346E-06 29577middot10-2 000023
2306
CO
175166E-06 2955middot10-2 0000060
0006
1706 C3H8 130158E-
08 1977middot10-4 00000066 0001
ss
p
i ii
N
ii
N2
2
1
1
= =
=
sum
sum
ν
ν
29
2106 44616E-09 1980middot10-4 00000023
2306
381032E-09 1982middot10-4 00000019
26 Total standard uncertainty
Uncertainty estimation СО2
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph ucal Normal 008 1 008
Change of temperature ut Rectangular 02 1 02 Change of atmospheric pressure upressure Rectangular 028 1 028
Changes of chromotograph response
urun Normal 007 1 007
Standard deviation of 3 runs uA Normal 0006 1 0006
Relative total standard uncertainty 036 Coverage factor k=2 Expanded uncertainty 01middot10-2 molmol Uncertainty estimation СО
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph ucal Normal 01 1 01 Change of temperature ut Rectangular 02 1 02 Change of atmospheric pressure upressure Rectangular 028 1 028 Changes of chromotograph response
urun Normal 015 1 015
Standard deviation of 3 runs uA Normal 0006 1 0006
Relative total standard uncertainty 039 Coverage factor k=2 Expanded uncertainty 002middot10-2 molmol Uncertainty estimation С3Н8
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph 04 Normal 04 1 008
30
Change of temperature 02 Rectangular 02 1 02 Change of atmospheric pressure 028 Rectangular 028 1 028
Changes of chromotograph response
012 Normal 012 1 007
Standard deviation of 3 runs 0001 Normal 0001 1 0006
Relative total standard uncertainty 054 Coverage factor k=2 Expanded uncertainty 02middot10-4 molmol
Sample handling
Period for exposure of cylinder to measurement conditions and method how to transport sample to the device
1 Stands for storing gas standard cylinders and calibration mixture cylinders and chromotograph are placed in a laboratory room which is not accessible to unauthorized persons The laboratory is equipped with air-conditioner to maintain required temperature and humidity on a continuous basis and some auxiliary measuring instruments as thermometer psychrometric hygrometer and aneroid to control temperature humidity and atmospheric inside the room
2 The comparison sample cylinder was stored in laboratory from the date of its
delivery to Minsk on 25042005 CGM cylinders are stored horizontally on racks and positioned vertically using special support when measurements are carried out
3 The analyzed gas sample is transported through the fine adjustment valve (FAV)
Conjunctions Cylinder - FAV FAV - tube tube - doser are made of metal and use adapters with spherical ends and bushes FAV is made of brass tube is made of copper and doser is made of duralumin
Instrument(s) (principles make type configuration data collection etc) For the analysis a GC were used with specifically applications For the determination of (Nitrogen (N2)) Carbon Dioxide (CO2) Carbon Monoxide (CO) and Propane (C3H8) balance GC Perkin Elmer AutoSystem XL (two channel system) with a stream selection valve for 4 streams and 2 gas sampling valves
Channel A for the determination of N2 CO and CO2 Carrier Gas Helium Columns Column system with two packed columns (6 ft x 18rdquo Porapak R 80100 mesh and 6 ft x 18rdquo Mol-Sieve 13X 80100 mesh) Oven Temperature 960 degC to 180 degC Detector micro-TCD Data Collection Total Chrom Workstation Channel B for the determination of C3H8 Carrier Gas Helium Columns Capillary column 50 m x 032 microm LP-SIL-8-CB Oven Temperature 60 degC to 180 degC Detector FID Data Collection Total Chrom Workstation
34
Calibration Standards
Calibration Standards for the measurements (preparation method purity analyses estimated uncertainty etc)
All standards were prepared individually according to ISO 6142 rdquoGas analysis - Preparation of calibration gases - Gravimetric Methodrdquo
Depending on the concentration of the components standards were prepared individually from pure gases or from pre-mixtures which were individually prepared from pure gases
The content of the impurities in all pure gases were determined before use by GC-DID GC-FID and or GC-TCD
After preparation the standards were verified by analytical comparisons against existing gravimetrically prepared standards Only when no significant difference between the analysed and the calculated gravimetric composition is found the ldquonew prepared candidate rdquo is accepted as a new standards
For the analysis of all components multi component standards with nitrogen as balance gas were used
Composition of calibrants BAM C49250-050722 Component Assigned value( x)
mmol mol Standard uncertainty (u(x)) relativ (k=2)
Calibration procedure (mathematical modelcalibration curve number and concentrations of standards measurement sequence temperaturepressure correction etc)
For the instrument calibration the bracketing technique was used The fraction of the current used standards deviated no more than +10rel and -10rel respectively from those of the sample
Measurement sequence
Sample Handling
How were the cylinders treated after arrival (eg stabilized) and how were samples transferred to the instrument (automatic high pressure mass-flow controller dilution etc) After heating (45 - 50 degC) the cylinder for 8 hours the cylinder were rolled about 16 hours before analysis was started Each cylinder was equipped with a pressure regulator that was purged three times by sequential evacuation and pressurisation with the gas mixture used Continous flow (2 ndash 3mlmin) through the sample loop
Uncertainty The specification of potential uncertainty sources is given in Annex 3
3 injection standard (high)
3 injection sample
3 injection standard (high)
3 injection sample
3 injection standard (low)
3 injection sample
3 injection standard (low)
3 injection standard (low)
36
Uncertainty table CO2
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 002 rel 1 002 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 03 rel
Uncertainty table CO
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 007 rel 1 007 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 05 rel
37
Uncertainty table C3H8
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 010 rel 1 001 rel
Analysis normal 028 rel 1 028 rel
Coverage factor 2
Expanded uncertainty 06 rel
Optional
You may provide additional data like the raw measurement data information on your
measurement procedure chromatograms etc
38
Appendix 3 SPECIFICATION OF POTENTIAL UNCERTAINTY SOURCES
a Uncertainty related to the balance and the weights Resolution of balance Accuracy of balance including linearity Incorrect zero point Drift (thermal and time effects) Instability due to draught Location of cylinder on the balance pan Uncertainties in the weights used Buoyancy effects on the weights used
b Uncertainties related to the gas cylinder Mechanical handling of cylinder
Loss of metal paints or labels from surface of cylinder Loss of metal from threads of valvefitting Dirt on cylinder valves or associated fitting
Absorptiondesorption effects on the external cylinder surface Buoyancy effects on the cylinder itself
Cylinder temperature differs from surrounding air due to eg filling with gas Change of cylinder volume during filling Change of density of surrounding air due to changes in temperature air pressure humidity and carbon dioxide content
Uncertainty in determination of external cylinder volume c Uncertainties related to the component gases Residual gas in cylinder Leakage Leakage of air into the cylinder after evacuation
Leakage of gas from the cylinder valve during filling Escape of gas from cylinder into transport lines
Gas remaining in transfer system when weight loss method is used Absorptionreaction of components on internal cylinder surface Reaction between components Impurities in all the initial gases Insufficient homogenization Uncertainty of molecular mass d Uncertainties related to the analysis
Repeatability and selectivity of the analyzer Appropriateness of the calibration curve
39
MEASUREMENT REPORT - All Ukrainian State Research-Industrial Center of Standardization Metrology Certification and Protection of Consumers Ukraine
gas ndash helium flow rate 15 cm3min detector TCD tdetector = 250 ordmС toven = 70 ordmС It was automatic data collection
Measurement and Calibration Methods Laboratory Measurement method Type of calibration curve
GCFID (С3Н8) 3 points linear Ukrmetrteststandard GCTCD (СО СО2) 3 points linear
GCFID ndash gas-chromatographic with flame-ionization detector GCTCD - gas-chromatographic with thermal-conductivity detector
42
Calibration Standards
Calibration standards ndash primary standard gas mixtures (PSGM) used for measurements by comparison method
PSGM-1 Cylinder 0116
PSGM-2 Cylinder 0107
PSGM-3 Cylinder 0093 Composition
x u(x) x u(x) x u(x) СО 27874 00015 29899 00015 31891 00015 СО2 130187 00015 144456 00016 137016 00016 С3Н8 019003 000008 020017 000008 021013 000008 N2 balance balance balance
Note x ndash mole fraction u(x) ndash absolute standard uncertainty
It was used gravimetric method of preparation of PSGM Electronic balance КА-20-3 of Mettler Toledo max limit of weighing is 20 kg least
limit of weighing is 01 g standard deviation is 0006 g Analysis of purity of parent gases was carried out with usage of chromatographs
НР6890N with helium ndash ionization detector flame ndash ionization detector thermal ndash conductivity detector and mass ndash spectrometric detector as well аs gas analyzers GIAM-15M and Onix condensate-thermometer hygrometer TOROS-3-2B
Calculation of uncertainties was carried out according to ISO 6142-2003 Corrections of temperature pressure and humidity of environment were considered
in calculations according to ISO 6142-2003 (program of ISO-6142 2000-03-17 designer is NMi) Protocols and explanations are in Annex A
Instrument (Comparator) Calibration Calibration of comparator ndash gas chromatograph HP 6890 was carried out with usage
of PSGM Measurement sequence PSGM -1 х 3 PSGM -2 х 3 COOMET gas mixture х 3 PSGM -2 х 3 PSGM -3 х 3 It is necessary to use PSGM-2 repeatedly for estimation of reproducibility of results
Program B_LEAST recommended by ISO 6143-2003 was used for constructing the curve Mathematical model of calibration curve is linear one
Sample Handling The cylinder was kept for 24 hrs at a room where comparators were disposed This room is a thermostatic room with t = (20plusmn2) ordmС
43
A method of sample input to a comparator is a method with flow stabilization Uncertainty The following uncertainties were included to the budget of uncertainty - uncertainty of the balance - uncertainties of impurities in parent gases Contribution from other uncertainty sources was insignificant A cabin of the balance is thermostatically The balance is the one-pan balance
Air transfer is absent in the cabin of the balance Drift of the balance is absent for PSGM preparation
Contribution from other uncertainty sources was considered in software according to ISO 6142-2003
Uncertainties related to the analysis (comparison) were considered in software according to ISO 6143-2003 and enclosed in Annex B
Uncertainty table СО2
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas mixture
B 001 1 001
Analysis A B 008 1 008
Coverage factor 2 Expanded uncertainty 002sdot10-2 molmol Uncertainty table СО
Protocols of analysis (comparison) in accordance with ISO 6143-2003
57
Explanation of protocols of comparison
Chapter I ldquoThe calibration data set isrdquo contains columns 1 mole fraction of a component 2 absolute standard uncertainty of mole fraction of a component 3 a signal of a comparator 4 absolute standard uncertainty of a comparator signal
Chapter II ldquoResults of ISO 6143 methodrdquo contains parameters of a calibration curve including its
uncertainty
Chapter ІІІ ldquoPart II Processing of datardquo contains columns
1 calc x - the results of comparison mole fraction of a component 2 u(x) - absolute standard uncertainty of mole fraction of a component 3 response y - a signal of a comparator 4 u(y) - absolute standard uncertainty of a comparator signal
58
СО2 - measurement 1 Data setCO2_21 The calibration data set is 1302E+01 1510E-03 1022E+04 1820E+00 1370E+01 1560E-03 1077E+04 2730E+00 1445E+01 1620E-03 1135E+04 5900E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 20331E-02 12711E-03 12573E-01 11653E-05 -14638E-06 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 10548E-02 12722E-03 31762E-02 28898E-06 -91698E-08 Remaining SSD is 74346 Weighted distances x-value x-dist y-dist 100E+00 130E+01 490E-01 -755E-01 200E+00 137E+01 -103E+00 228E+00 300E+00 144E+01 539E-01 -250E-01 Goodness-of-fit measure 22837 Parameter set 1 1054788657490729E-2 1272208026684145E-3 3176237146276368E-2 2889798108124711E-6 -
9169821653851327E-8 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_21c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13577E+01 25542E-03 10664E+04 15200E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 547E-06 328E-06 316E-06 784E-06 286E-06 652E-06 Linear model Parameters for the fit were (b0 b1) 10548E-02 12722E-03
59
СО2 - measurement 2
Data setCO2_20 The calibration data set is 1302E+01 1512E-03 1021E+04 4723E+00 1370E+01 1563E-03 1075E+04 1600E+00 1445E+01 1620E-03 1133E+04 7300E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -38760E-02 12784E-03 26817E-02 24890E-06 -66689E-08 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -62452E-02 12805E-03 47930E-02 43243E-06 -20716E-07 Remaining SSD is 03231 Weighted distances x-value x-dist y-dist 100E+00 130E+01 107E-01 -415E-01 200E+00 137E+01 -212E-01 283E-01 300E+00 144E+01 104E-01 -584E-02 Goodness-of-fit measure 04155 Parameter set 1 -6245240430658412E-2 1280492624666799E-3 4792952200361109E-2 4324266278840409E-6 -
2071623966851869E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_20c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13594E+01 10290E-02 10665E+04 78300E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 121E-05 683E-06 651E-06 315E-05 560E-06 106E-04 Linear model Parameters for the fit were (b0 b1) -62452E-02 12805E-03
60
С3Н8 - measurement 1
Data setC3H8 The calibration data set is 1900E-01 7800E-05 9057E+03 1098E+01 2002E-01 7900E-05 9552E+03 8569E+00 2101E-01 7960E-05 1007E+04 4049E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10529E-02 19831E-05 34552E-03 36109E-07 -12465E-09 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11642E-02 19714E-05 23073E-03 23522E-07 -54231E-10 Remaining SSD is 19453 Weighted distances x-value x-dist y-dist 100E+00 190E-01 -239E-01 666E-01 200E+00 200E-01 487E-01 -104E+00 300E+00 210E-01 -247E-01 248E-01 Goodness-of-fit measure 10414 Parameter set 1 1164239985182795E-2 1971441115316992E-5 2307269625077337E-3 2352198415608386E-7 -
5423119774765299E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19837E-01 14840E-04 94718E+03 45610E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
18
Measurement No3 Date
Result (molmol)
x_
Standard deviation
S( x_
) rel
No of observations
n
Carbon dioxide 23062005 13537middot10-2 007 6
Carbon oxide 23062005 2955middot10-2 01 6
Propane 23062005 1982middot10-4 01 6
Final results
Gas mixture Result
(molmol)
Coverage factor
Expanded uncertainty (molmol)
Carbon dioxide 136middot10-2 2 01 middot10-2
Carbon oxide 296middot10-2 2 002middot10-2
Propane 198middot10-4 2 02middot10-4
II Description of study Apparatus (principle of operation type configuration data collection etc)
Measurements were carried out using gas chromatograph Crystal 2000М (hereinafter
referred to as chromatograph) combined with thermal conductivity detector (hereinafter referred to as TCD) with detection limit of 510-9 gml for propane and flame-ionization detector (hereinafter referred to as FID) with detection limit of 510-12 gs for propane
Computers and software Chromatech Analytic version 121 were used to control chromatograph and collect and process chromatographical data
For the purpose of measurements the following auxiliary devices and materials were used
1 Two-position doser with 10 ports and with doses of 025 cm3 for FID channel and with doses of 025 cm3 for TCD channel (hereinafter referred to as doser)
2 Metallic packed column 3m х 3mm х 2mm - HayeSep N 80100 metallic packed column 1m х 4mm х 2mm-CaA 016025 (TCD channel) capillary column HP PLOTQ 30m х 0536mm (FID channel)
3 Aneroid BАММ-1 with a measurement range of 80-106 kPа and accuracy of plusmn 02 kPа
4 Mercurial thermometer ТL-4 with a measurement range of 0-50ordmС and scale division of 01ordmС
19
5 Fine adjustment valve (hereinafter referred to as FAV) provided to transport a gas sample into chromotograph and set to gas flow-rate of 10-15 mlmin
6 Foamy gas flow meter type YIRG - 2А accuracy of flow measurement plusmn 1 сm3min
7 Helium gas Type A according to TU 51-940-80 8 High purity hydrogen gas according to TU 301-07-27-90 9 Compressed air 10 Multicomponent calibration gas mixtures (hereinafter referred to as CGM)
produced and certified by gravimetric method
Calibration reference materials - calibration gas mixtures used for measurements 1 Quantitative composition of KGS is determined using gravimetric method defined in
ISO 61422001 by calculating weight of each component of a gas mixture The content of CGM components is expressed as a mole fraction Uncertainty of KGS composition is expressed as expanded uncertainty with coverage factor k = 2 Molar masses of components and their uncertainties are taken from ISO 149122003 Performance and metrological characteristics of the equipment used for gravimetric preparation of mixtures are given in Table 1
Table 1
Description of the equipment
Manufacturer Metrological characteristics
Mass-comparator balance type КА10-3Р
Mettler-Toledo
Switzerland
Maximum load 15 kg Scale division 1 mg Standard deviation 19 mg at load of 10 kg Operating temperature range +10divide30degС Maximum temperature change within 1 h plusmn05 degС
Gas mixer type USG 00001 BelGIM
Measurement range 000025 divide 100 МPa Accuracy class for manometers ndash 015 Accuracy class for vacuummeters ndash 025 Vacuummeter with pressure sensor for measuring the residual pressure before filling Residual pressure before filling of each component not more than 20 Pa
2 Purity analysis of primary gas standards
The purity analysis of primary gas standards is based on the information provided by the supplier or on the results of determination of impurity in pure gases using measurement procedure developed inside BelGIM
20
If an analytical method laid down in 43 of ISO 61422001 cannot be used for impurity determination mole fraction of an expected impurity is assumed to be half of the detection limit of the analytical method The content of the undetected impurity produces rectangular distribution
whereby its standard uncertainty is calculated as half of the detection limit divided by 3 The composition of the pure gases used for preparation of calibration mixtures is given
in Table 2 Table 2 - Metrological characteristics of pure gases
N2 999967 00005 Nitrogen Cylinder 40 dm3 Origin Russia O2 00033 00005 Propane Cylinder 2 dm3 Origin Russia
C3H8 9979 0017
3 After preparation of mixture the cylinder was maintained in laboratory room within
24 hours the mixture then was homogenized on the stand by rotating on the rollers within 4-5 hours The chromotograph for CGM was calibrated 2-3 days after its preparation
Calibration of the chromotograph
1 The chromotograph was calibrated using CGMs with composition identical to the analyzed sample The content of each component and its expanded uncertainty (k = 2) are given in Table 1 Table 1 - Calibrationе gas mixtures
2 Number of observations of each calibration sample- 3 Number of calibration samples - 3
3 The analytical function used for determination of the content of the analyzed sample components is as follows
x (y) =b1y+b0 (2) Where x ndash determined content molmol y - chromotograph response for the specific component b1- slope b0 - intercept 4 After completion of calibration the coefficients of analytical function were
calculated according to ISO 61432001 using generalized least-squares method Also the uncertainties of the intercept and slope and covariance between them were calculated After determination of parameters which are part of analytical function and which affect the uncertainty of measurements it was checked whether the analytical function is fit to the experimental data obtained in calibration and subsequently whether the analytical function is applicable
Results of calibration measurements coefficients of analytical function their uncertainties covariance and measure of goodness-of-fit Г (maximum value of the weighted differences of the experimental points and calculated points of the analytical function for each measurement run) are given in Tables 3 and 4 respectively Chromotograph operating conditions in calibration and analysis are given in Table 5
Table 3 - Results of experimental study
Date Component of
calibration mixture
Content x mole fraction
Expanded uncertainty
U(x) mole fraction
Mean of peak area y
mVs
Uncertainty )(yu
mVs
13374 0004 1279500 141 1389 0004 1329150 2899 CO2
12833 0004 1231000 849 2916 0005 404070 240
316 0005 437705 926 CO 2768 0004 383070 467
019 0002 3143200 4101
1706 2005
C3H8 0202 0002 3319150 2051
22
0181 0002 2948750 212 13374 0004 1269833 624
1389 0004 1321000 1272 CO2 12833 0004 1223900 1698
2916 0005 399490 612 316 0005 434010 863 CO
2768 0004 379660 410 019 0002 3157867 6772
0202 0002 3332400 3394
2106 2005
C3H8 0181 0002 2959900 4950
13374 0004 1277100 2152 1389 0004 1329900 2828 CO2
12833 0004 1229100 1980 2916 0005 400330 529
316 0005 434745 969 CO 2768 0004 379695 106
019 0002 3142433 9416 0202 0002 3321600 4101
2306 2005
C3H8 0181 0002 2961000 3111
According to ISO 61432003 calculation of the measure of goodness-of-fit Г is the maximum value of the weighed differences between the coordinates of measured and adjusted calibration points is an effective and simple method to test the compatibility of а prospective analytical function A function is admissible if Г le 2
minus
minus=
)(ˆ
)(ˆ
iii
iii
yuyy
xuxxΓ
(4) Where хi is the reference value of the content of calibration sample component
ix is the CGM component content obtained using the calculated analytical function
уi is the experimental response to the reference content of component iy is the response obtained in calculation of analytical function
u (хi) u (уi) are the uncertainties of reference contents and responses to these contents respectively
i is the number of calibration points i=1 3 This prerequisite is equivalent to the requirement that the curve of calculated response should cross each experimental calibration rectangular [хi plusmn 2u(хi) уi plusmn 2и(уi)] based on an expanded uncertainty U = ku with coverage factor k = 2 Table 4 Calculations of analytical function
Date Component Analytical function parameters
Uncertainty of analytical
function parameters
Covariance of
parameters Г
23
b1 b0 u(b1) u(b0) u(b0b1) 1706 11086E-
03 -81128E-
0119491E-
0524883E-
01 -48497E-06 10544
2106 10729E-03
-26126E-01
22698E-05
28930E-01 -65652E-06 19997
2306
CO2 10593E-
03 -17688E-
0135807E-
0545413E-
01 -16254E-05 10022
1706 71537E-04
26507E-02
14231E-05
57044E-02 -81115E-07 03017
2106 72346E-04
22401E-02
13819E-05
54490E-02 -75209E-07 05935
2306
CO 71321E-
04 60080E-
0212663E-
0549016E-
02 -62026E-07 01341
1706 56521E-06
13712E-02
38279E-07
12015E-02 -45937E-09 12991
2106 56295E-06
13707E-02
39247E-07
12379E-02 -48529E-09 12905
2306
C3H8 58258E-
06 80469E-
0340085E-
0712590E-
02 -50407E-09 08589
Two columns separated by switching device are located one after another in TCD
channel One column is intended for carbon dioxide heavy hydrocarbons and another column is intended for light gases Before the first switch the light gases including carbon oxide flow through the first column without being separated and remain in the second column The switch makes them locked in the second column The analysis of carbon dioxide is carried out up to the second switch Second switch makes the second column unlocked and carbon oxide is analyzed Third switch is required to allow propane escape from a column and prevent it from getting into a second column The analysis of the very propane is carried out using FID Time intervals between switches were selected experimentally when developing the analysis method Such analysis method makes it possible to analyze all three components per one sample inject
Table 5 - Chromotograph operating conditions in calibration and analysis Parameter of the operating conditions Thermostating temperature of TCD and FID degС 170
Temperature of separation columns degС
Program 60 degС within 9 min
than rise to 160 degС at 20degСmin
Rate of flow of carrier gas through TCD channel columns mlmin 15
Rate of flow of carrier gas through TCD comparison channel mlmin 15
Pressure in FID channel column kPa Program
24
80 to 100 Rise from the 1st s of
analysis at 2 kPamin
Flow-rate of hydrogen FID mlmin 20 Flow-rate of air FID mlmin 200 Temperature of switching device degС 65 Response time of switching device s 1 110 2 330 3 540
TCD FID Volume of injected analyzed gas cm3 025 025 Carrier gas Helium Duration of analysis min 17 Calculation of the content of comparison sample components and its uncertainty Results of comparison sample measurements are given in Table 6 Table 6 - Results of comparison sample measurements
1 The content of comparison sample component and its uncertainty were determined
using calculated analytical function according to ISO 61432001 as follows (5) Where G(y)=b1y+b0 is the calculated analytical function и(y) is the standard uncertainty of response y u2(bj) is the variance of analytical function parameter bj
u(bj bI) is the covariance of analytical function parameters bj bI N is the number of function coefficients N=2 j=0 1
sum sumsumminus
= +==
partpart
partpart
+
partpart
+
partpart
=1
0 1
2
2
0
22
)(2)()()(N
jIj
N
jI Ijj
N
j j
bbubG
bGbu
bGyu
yGxu
25
After substitution of analytical function (2) and transformations the expression takes form (5)
)(2)()()()()( 01122
0222
1 bbyubuybuyubxu +++= (6) The contents of comparison sample components under determination and their
uncertainties were calculated using B_LEAST a computer program recommended in ISO 6143 Calculations are summarized in Table 6
Table 6 Calculations of the content of comparison sample components and their
2 The final content of a component was determined as an arithmetiс mean from three measurements Final standard uncertainty was calculated using formula as follows
22
222)( Адаватмтемсериикал uuuuuxu ++++= (7)
Where ucal is the uncertainty of the component content produced by
calibration of chromotograph urun is the uncertainty of the component content produced by
change of chromotograph response in each measurement run ut is the uncertainty of the component content produced by
change of an ambient temperature upressure is the uncertainty of the component content produced by
change of atmospheric pressure u A is the standard uncertainty of three measurement runs
21 Uncertainty of the component content produced by calibration of chromotograph
This uncertainty is calculated using formula (6) but the first term of the sum ie
)()( 221 yub which represents the standard uncertainty of the chromotograph response in a
measurement run is not taken into account Calculations are summarized in Table 7
26
Table 7 Calculation of uncertainty produced by calibration of chromotograph
Date u(b1) u(b0) u(b0b1) x
molmol y Ucal molmol
Ucal rel
1706 19491E-05
24883E-01
-48497E-06
13567middot10-
2129698
3 0005middot1
0-2 003
2106 22698E-05
28930E-01
-65652E-06
13564middot10-
2 128855 0007middot1
0-2 005
2306
CO2
35807E-05
45413E-01
-16254E-05
135374middot10-2
1294633
0016middot10-2 012
1706 14231E-05
57044E-02
-81115E-07 2957middot10-2 409633
0003middot10-2 009
2106 13819E-05
54490E-02
-75209E-07
29577middot10-
2 405663 0003middot1
0-2 01
2306
CO
12663E-05
49016E-02
-62026E-07 2955middot10-2 405882
0003middot10-2 01
1706 38279E-07
12015E-02
-45937E-09 1977middot10-4
3255817
007middot10-
2 038
2106 39247E-07
12379E-02
-48529E-09 1980middot10-4
3273329
008middot10-
2 038
2306
C3H8
40085E-07
12590E-02
-50407E-09 1982middot10-4 32636
008middot10-
2 04 The total estimate of relative uncertainty produced by calibration of chromotograph was
calculated for each component as follows
3
3
1
2sum=
cali
cali
uu (8)
Where ucal i is the relative uncertainty produced by calibration of chromotograph and calculated for each measurement run
The calculations are summarized in Table 8
Table 8 Uncertainty produced by calibration of chromotograph
Component Ucal rel
CO2 008 CO 01
C3H8 04 22 Uncertainty of the component content produced by change of chromotograph response in each measurement run This uncertainty is calculated using the equation (6) whereby the first term of the sum
only ie )()( 221 yub which represents the standard uncertainty of the chromotograph
response in a measurement run is taken into account Calculations are summarized in Table 9
27
Table 9 Calculation of uncertainty produced by change of chromotograph response in each measurement run
The total estimate of relative uncertainty produced by change of chromotograph
response in each measurement run was calculated for each component as follows
3
3
1
2sum=
run
run
uu (9)
Where urun is the relative uncertainty produced by change of chromotograph response in each measurement run Calculations are summarized in Table 10
Table 10 Uncertainty produced by change of chromotograph response in each measurement
run
Component Urun rel
CO2 007 CO 015
C3H8 012 23 Uncertainty of the component content produced by change of temperature in a room
The recorded change of temperature in measurements is plusmn 05 degree The contribution of uncertainty type B (rectangular distribution) is estimated as follows
201003
12931
=sdotsdot=tu rel
28
24 Uncertainty of the component content produced by change of atmospheric pressure The recorded change of atmospheric pressure within three days was
05 kPа The contribution of uncertainty type B (rectangular distribution) is estimated as follows
2801003
13101
50=sdotsdot=pressureu rel
25 Standard deviation of 3 measurement runs Standard deviation is calculated as follows
isu p
A
2
= (10)
Where S2p is the group experimental variation
The group experimental variation is calculated as follows
(11)
Where si
2 is the experimental variation of measurement run i from independent repeated observations ni having freedom degrees
νi = n - 1 n=6 i= 3 Calculations are summarized in Table 11 Table 11 Calculations of standard uncertainty of 3 measurement runs
Date 2iS x
molmol 2iS
rel uA
rel
1706 2953E-05 13567middot10-2 000022
2106 588987E-06 13564middot10-2 0000043
2306
CO2 141137E-
05 135374middot10
-2 000010
0006
1706 225604E-06 2957middot10-2 0000077
2106 681346E-06 29577middot10-2 000023
2306
CO
175166E-06 2955middot10-2 0000060
0006
1706 C3H8 130158E-
08 1977middot10-4 00000066 0001
ss
p
i ii
N
ii
N2
2
1
1
= =
=
sum
sum
ν
ν
29
2106 44616E-09 1980middot10-4 00000023
2306
381032E-09 1982middot10-4 00000019
26 Total standard uncertainty
Uncertainty estimation СО2
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph ucal Normal 008 1 008
Change of temperature ut Rectangular 02 1 02 Change of atmospheric pressure upressure Rectangular 028 1 028
Changes of chromotograph response
urun Normal 007 1 007
Standard deviation of 3 runs uA Normal 0006 1 0006
Relative total standard uncertainty 036 Coverage factor k=2 Expanded uncertainty 01middot10-2 molmol Uncertainty estimation СО
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph ucal Normal 01 1 01 Change of temperature ut Rectangular 02 1 02 Change of atmospheric pressure upressure Rectangular 028 1 028 Changes of chromotograph response
urun Normal 015 1 015
Standard deviation of 3 runs uA Normal 0006 1 0006
Relative total standard uncertainty 039 Coverage factor k=2 Expanded uncertainty 002middot10-2 molmol Uncertainty estimation С3Н8
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph 04 Normal 04 1 008
30
Change of temperature 02 Rectangular 02 1 02 Change of atmospheric pressure 028 Rectangular 028 1 028
Changes of chromotograph response
012 Normal 012 1 007
Standard deviation of 3 runs 0001 Normal 0001 1 0006
Relative total standard uncertainty 054 Coverage factor k=2 Expanded uncertainty 02middot10-4 molmol
Sample handling
Period for exposure of cylinder to measurement conditions and method how to transport sample to the device
1 Stands for storing gas standard cylinders and calibration mixture cylinders and chromotograph are placed in a laboratory room which is not accessible to unauthorized persons The laboratory is equipped with air-conditioner to maintain required temperature and humidity on a continuous basis and some auxiliary measuring instruments as thermometer psychrometric hygrometer and aneroid to control temperature humidity and atmospheric inside the room
2 The comparison sample cylinder was stored in laboratory from the date of its
delivery to Minsk on 25042005 CGM cylinders are stored horizontally on racks and positioned vertically using special support when measurements are carried out
3 The analyzed gas sample is transported through the fine adjustment valve (FAV)
Conjunctions Cylinder - FAV FAV - tube tube - doser are made of metal and use adapters with spherical ends and bushes FAV is made of brass tube is made of copper and doser is made of duralumin
Instrument(s) (principles make type configuration data collection etc) For the analysis a GC were used with specifically applications For the determination of (Nitrogen (N2)) Carbon Dioxide (CO2) Carbon Monoxide (CO) and Propane (C3H8) balance GC Perkin Elmer AutoSystem XL (two channel system) with a stream selection valve for 4 streams and 2 gas sampling valves
Channel A for the determination of N2 CO and CO2 Carrier Gas Helium Columns Column system with two packed columns (6 ft x 18rdquo Porapak R 80100 mesh and 6 ft x 18rdquo Mol-Sieve 13X 80100 mesh) Oven Temperature 960 degC to 180 degC Detector micro-TCD Data Collection Total Chrom Workstation Channel B for the determination of C3H8 Carrier Gas Helium Columns Capillary column 50 m x 032 microm LP-SIL-8-CB Oven Temperature 60 degC to 180 degC Detector FID Data Collection Total Chrom Workstation
34
Calibration Standards
Calibration Standards for the measurements (preparation method purity analyses estimated uncertainty etc)
All standards were prepared individually according to ISO 6142 rdquoGas analysis - Preparation of calibration gases - Gravimetric Methodrdquo
Depending on the concentration of the components standards were prepared individually from pure gases or from pre-mixtures which were individually prepared from pure gases
The content of the impurities in all pure gases were determined before use by GC-DID GC-FID and or GC-TCD
After preparation the standards were verified by analytical comparisons against existing gravimetrically prepared standards Only when no significant difference between the analysed and the calculated gravimetric composition is found the ldquonew prepared candidate rdquo is accepted as a new standards
For the analysis of all components multi component standards with nitrogen as balance gas were used
Composition of calibrants BAM C49250-050722 Component Assigned value( x)
mmol mol Standard uncertainty (u(x)) relativ (k=2)
Calibration procedure (mathematical modelcalibration curve number and concentrations of standards measurement sequence temperaturepressure correction etc)
For the instrument calibration the bracketing technique was used The fraction of the current used standards deviated no more than +10rel and -10rel respectively from those of the sample
Measurement sequence
Sample Handling
How were the cylinders treated after arrival (eg stabilized) and how were samples transferred to the instrument (automatic high pressure mass-flow controller dilution etc) After heating (45 - 50 degC) the cylinder for 8 hours the cylinder were rolled about 16 hours before analysis was started Each cylinder was equipped with a pressure regulator that was purged three times by sequential evacuation and pressurisation with the gas mixture used Continous flow (2 ndash 3mlmin) through the sample loop
Uncertainty The specification of potential uncertainty sources is given in Annex 3
3 injection standard (high)
3 injection sample
3 injection standard (high)
3 injection sample
3 injection standard (low)
3 injection sample
3 injection standard (low)
3 injection standard (low)
36
Uncertainty table CO2
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 002 rel 1 002 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 03 rel
Uncertainty table CO
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 007 rel 1 007 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 05 rel
37
Uncertainty table C3H8
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 010 rel 1 001 rel
Analysis normal 028 rel 1 028 rel
Coverage factor 2
Expanded uncertainty 06 rel
Optional
You may provide additional data like the raw measurement data information on your
measurement procedure chromatograms etc
38
Appendix 3 SPECIFICATION OF POTENTIAL UNCERTAINTY SOURCES
a Uncertainty related to the balance and the weights Resolution of balance Accuracy of balance including linearity Incorrect zero point Drift (thermal and time effects) Instability due to draught Location of cylinder on the balance pan Uncertainties in the weights used Buoyancy effects on the weights used
b Uncertainties related to the gas cylinder Mechanical handling of cylinder
Loss of metal paints or labels from surface of cylinder Loss of metal from threads of valvefitting Dirt on cylinder valves or associated fitting
Absorptiondesorption effects on the external cylinder surface Buoyancy effects on the cylinder itself
Cylinder temperature differs from surrounding air due to eg filling with gas Change of cylinder volume during filling Change of density of surrounding air due to changes in temperature air pressure humidity and carbon dioxide content
Uncertainty in determination of external cylinder volume c Uncertainties related to the component gases Residual gas in cylinder Leakage Leakage of air into the cylinder after evacuation
Leakage of gas from the cylinder valve during filling Escape of gas from cylinder into transport lines
Gas remaining in transfer system when weight loss method is used Absorptionreaction of components on internal cylinder surface Reaction between components Impurities in all the initial gases Insufficient homogenization Uncertainty of molecular mass d Uncertainties related to the analysis
Repeatability and selectivity of the analyzer Appropriateness of the calibration curve
39
MEASUREMENT REPORT - All Ukrainian State Research-Industrial Center of Standardization Metrology Certification and Protection of Consumers Ukraine
gas ndash helium flow rate 15 cm3min detector TCD tdetector = 250 ordmС toven = 70 ordmС It was automatic data collection
Measurement and Calibration Methods Laboratory Measurement method Type of calibration curve
GCFID (С3Н8) 3 points linear Ukrmetrteststandard GCTCD (СО СО2) 3 points linear
GCFID ndash gas-chromatographic with flame-ionization detector GCTCD - gas-chromatographic with thermal-conductivity detector
42
Calibration Standards
Calibration standards ndash primary standard gas mixtures (PSGM) used for measurements by comparison method
PSGM-1 Cylinder 0116
PSGM-2 Cylinder 0107
PSGM-3 Cylinder 0093 Composition
x u(x) x u(x) x u(x) СО 27874 00015 29899 00015 31891 00015 СО2 130187 00015 144456 00016 137016 00016 С3Н8 019003 000008 020017 000008 021013 000008 N2 balance balance balance
Note x ndash mole fraction u(x) ndash absolute standard uncertainty
It was used gravimetric method of preparation of PSGM Electronic balance КА-20-3 of Mettler Toledo max limit of weighing is 20 kg least
limit of weighing is 01 g standard deviation is 0006 g Analysis of purity of parent gases was carried out with usage of chromatographs
НР6890N with helium ndash ionization detector flame ndash ionization detector thermal ndash conductivity detector and mass ndash spectrometric detector as well аs gas analyzers GIAM-15M and Onix condensate-thermometer hygrometer TOROS-3-2B
Calculation of uncertainties was carried out according to ISO 6142-2003 Corrections of temperature pressure and humidity of environment were considered
in calculations according to ISO 6142-2003 (program of ISO-6142 2000-03-17 designer is NMi) Protocols and explanations are in Annex A
Instrument (Comparator) Calibration Calibration of comparator ndash gas chromatograph HP 6890 was carried out with usage
of PSGM Measurement sequence PSGM -1 х 3 PSGM -2 х 3 COOMET gas mixture х 3 PSGM -2 х 3 PSGM -3 х 3 It is necessary to use PSGM-2 repeatedly for estimation of reproducibility of results
Program B_LEAST recommended by ISO 6143-2003 was used for constructing the curve Mathematical model of calibration curve is linear one
Sample Handling The cylinder was kept for 24 hrs at a room where comparators were disposed This room is a thermostatic room with t = (20plusmn2) ordmС
43
A method of sample input to a comparator is a method with flow stabilization Uncertainty The following uncertainties were included to the budget of uncertainty - uncertainty of the balance - uncertainties of impurities in parent gases Contribution from other uncertainty sources was insignificant A cabin of the balance is thermostatically The balance is the one-pan balance
Air transfer is absent in the cabin of the balance Drift of the balance is absent for PSGM preparation
Contribution from other uncertainty sources was considered in software according to ISO 6142-2003
Uncertainties related to the analysis (comparison) were considered in software according to ISO 6143-2003 and enclosed in Annex B
Uncertainty table СО2
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas mixture
B 001 1 001
Analysis A B 008 1 008
Coverage factor 2 Expanded uncertainty 002sdot10-2 molmol Uncertainty table СО
Protocols of analysis (comparison) in accordance with ISO 6143-2003
57
Explanation of protocols of comparison
Chapter I ldquoThe calibration data set isrdquo contains columns 1 mole fraction of a component 2 absolute standard uncertainty of mole fraction of a component 3 a signal of a comparator 4 absolute standard uncertainty of a comparator signal
Chapter II ldquoResults of ISO 6143 methodrdquo contains parameters of a calibration curve including its
uncertainty
Chapter ІІІ ldquoPart II Processing of datardquo contains columns
1 calc x - the results of comparison mole fraction of a component 2 u(x) - absolute standard uncertainty of mole fraction of a component 3 response y - a signal of a comparator 4 u(y) - absolute standard uncertainty of a comparator signal
58
СО2 - measurement 1 Data setCO2_21 The calibration data set is 1302E+01 1510E-03 1022E+04 1820E+00 1370E+01 1560E-03 1077E+04 2730E+00 1445E+01 1620E-03 1135E+04 5900E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 20331E-02 12711E-03 12573E-01 11653E-05 -14638E-06 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 10548E-02 12722E-03 31762E-02 28898E-06 -91698E-08 Remaining SSD is 74346 Weighted distances x-value x-dist y-dist 100E+00 130E+01 490E-01 -755E-01 200E+00 137E+01 -103E+00 228E+00 300E+00 144E+01 539E-01 -250E-01 Goodness-of-fit measure 22837 Parameter set 1 1054788657490729E-2 1272208026684145E-3 3176237146276368E-2 2889798108124711E-6 -
9169821653851327E-8 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_21c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13577E+01 25542E-03 10664E+04 15200E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 547E-06 328E-06 316E-06 784E-06 286E-06 652E-06 Linear model Parameters for the fit were (b0 b1) 10548E-02 12722E-03
59
СО2 - measurement 2
Data setCO2_20 The calibration data set is 1302E+01 1512E-03 1021E+04 4723E+00 1370E+01 1563E-03 1075E+04 1600E+00 1445E+01 1620E-03 1133E+04 7300E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -38760E-02 12784E-03 26817E-02 24890E-06 -66689E-08 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -62452E-02 12805E-03 47930E-02 43243E-06 -20716E-07 Remaining SSD is 03231 Weighted distances x-value x-dist y-dist 100E+00 130E+01 107E-01 -415E-01 200E+00 137E+01 -212E-01 283E-01 300E+00 144E+01 104E-01 -584E-02 Goodness-of-fit measure 04155 Parameter set 1 -6245240430658412E-2 1280492624666799E-3 4792952200361109E-2 4324266278840409E-6 -
2071623966851869E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_20c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13594E+01 10290E-02 10665E+04 78300E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 121E-05 683E-06 651E-06 315E-05 560E-06 106E-04 Linear model Parameters for the fit were (b0 b1) -62452E-02 12805E-03
60
С3Н8 - measurement 1
Data setC3H8 The calibration data set is 1900E-01 7800E-05 9057E+03 1098E+01 2002E-01 7900E-05 9552E+03 8569E+00 2101E-01 7960E-05 1007E+04 4049E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10529E-02 19831E-05 34552E-03 36109E-07 -12465E-09 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11642E-02 19714E-05 23073E-03 23522E-07 -54231E-10 Remaining SSD is 19453 Weighted distances x-value x-dist y-dist 100E+00 190E-01 -239E-01 666E-01 200E+00 200E-01 487E-01 -104E+00 300E+00 210E-01 -247E-01 248E-01 Goodness-of-fit measure 10414 Parameter set 1 1164239985182795E-2 1971441115316992E-5 2307269625077337E-3 2352198415608386E-7 -
5423119774765299E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19837E-01 14840E-04 94718E+03 45610E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
19
5 Fine adjustment valve (hereinafter referred to as FAV) provided to transport a gas sample into chromotograph and set to gas flow-rate of 10-15 mlmin
6 Foamy gas flow meter type YIRG - 2А accuracy of flow measurement plusmn 1 сm3min
7 Helium gas Type A according to TU 51-940-80 8 High purity hydrogen gas according to TU 301-07-27-90 9 Compressed air 10 Multicomponent calibration gas mixtures (hereinafter referred to as CGM)
produced and certified by gravimetric method
Calibration reference materials - calibration gas mixtures used for measurements 1 Quantitative composition of KGS is determined using gravimetric method defined in
ISO 61422001 by calculating weight of each component of a gas mixture The content of CGM components is expressed as a mole fraction Uncertainty of KGS composition is expressed as expanded uncertainty with coverage factor k = 2 Molar masses of components and their uncertainties are taken from ISO 149122003 Performance and metrological characteristics of the equipment used for gravimetric preparation of mixtures are given in Table 1
Table 1
Description of the equipment
Manufacturer Metrological characteristics
Mass-comparator balance type КА10-3Р
Mettler-Toledo
Switzerland
Maximum load 15 kg Scale division 1 mg Standard deviation 19 mg at load of 10 kg Operating temperature range +10divide30degС Maximum temperature change within 1 h plusmn05 degС
Gas mixer type USG 00001 BelGIM
Measurement range 000025 divide 100 МPa Accuracy class for manometers ndash 015 Accuracy class for vacuummeters ndash 025 Vacuummeter with pressure sensor for measuring the residual pressure before filling Residual pressure before filling of each component not more than 20 Pa
2 Purity analysis of primary gas standards
The purity analysis of primary gas standards is based on the information provided by the supplier or on the results of determination of impurity in pure gases using measurement procedure developed inside BelGIM
20
If an analytical method laid down in 43 of ISO 61422001 cannot be used for impurity determination mole fraction of an expected impurity is assumed to be half of the detection limit of the analytical method The content of the undetected impurity produces rectangular distribution
whereby its standard uncertainty is calculated as half of the detection limit divided by 3 The composition of the pure gases used for preparation of calibration mixtures is given
in Table 2 Table 2 - Metrological characteristics of pure gases
N2 999967 00005 Nitrogen Cylinder 40 dm3 Origin Russia O2 00033 00005 Propane Cylinder 2 dm3 Origin Russia
C3H8 9979 0017
3 After preparation of mixture the cylinder was maintained in laboratory room within
24 hours the mixture then was homogenized on the stand by rotating on the rollers within 4-5 hours The chromotograph for CGM was calibrated 2-3 days after its preparation
Calibration of the chromotograph
1 The chromotograph was calibrated using CGMs with composition identical to the analyzed sample The content of each component and its expanded uncertainty (k = 2) are given in Table 1 Table 1 - Calibrationе gas mixtures
2 Number of observations of each calibration sample- 3 Number of calibration samples - 3
3 The analytical function used for determination of the content of the analyzed sample components is as follows
x (y) =b1y+b0 (2) Where x ndash determined content molmol y - chromotograph response for the specific component b1- slope b0 - intercept 4 After completion of calibration the coefficients of analytical function were
calculated according to ISO 61432001 using generalized least-squares method Also the uncertainties of the intercept and slope and covariance between them were calculated After determination of parameters which are part of analytical function and which affect the uncertainty of measurements it was checked whether the analytical function is fit to the experimental data obtained in calibration and subsequently whether the analytical function is applicable
Results of calibration measurements coefficients of analytical function their uncertainties covariance and measure of goodness-of-fit Г (maximum value of the weighted differences of the experimental points and calculated points of the analytical function for each measurement run) are given in Tables 3 and 4 respectively Chromotograph operating conditions in calibration and analysis are given in Table 5
Table 3 - Results of experimental study
Date Component of
calibration mixture
Content x mole fraction
Expanded uncertainty
U(x) mole fraction
Mean of peak area y
mVs
Uncertainty )(yu
mVs
13374 0004 1279500 141 1389 0004 1329150 2899 CO2
12833 0004 1231000 849 2916 0005 404070 240
316 0005 437705 926 CO 2768 0004 383070 467
019 0002 3143200 4101
1706 2005
C3H8 0202 0002 3319150 2051
22
0181 0002 2948750 212 13374 0004 1269833 624
1389 0004 1321000 1272 CO2 12833 0004 1223900 1698
2916 0005 399490 612 316 0005 434010 863 CO
2768 0004 379660 410 019 0002 3157867 6772
0202 0002 3332400 3394
2106 2005
C3H8 0181 0002 2959900 4950
13374 0004 1277100 2152 1389 0004 1329900 2828 CO2
12833 0004 1229100 1980 2916 0005 400330 529
316 0005 434745 969 CO 2768 0004 379695 106
019 0002 3142433 9416 0202 0002 3321600 4101
2306 2005
C3H8 0181 0002 2961000 3111
According to ISO 61432003 calculation of the measure of goodness-of-fit Г is the maximum value of the weighed differences between the coordinates of measured and adjusted calibration points is an effective and simple method to test the compatibility of а prospective analytical function A function is admissible if Г le 2
minus
minus=
)(ˆ
)(ˆ
iii
iii
yuyy
xuxxΓ
(4) Where хi is the reference value of the content of calibration sample component
ix is the CGM component content obtained using the calculated analytical function
уi is the experimental response to the reference content of component iy is the response obtained in calculation of analytical function
u (хi) u (уi) are the uncertainties of reference contents and responses to these contents respectively
i is the number of calibration points i=1 3 This prerequisite is equivalent to the requirement that the curve of calculated response should cross each experimental calibration rectangular [хi plusmn 2u(хi) уi plusmn 2и(уi)] based on an expanded uncertainty U = ku with coverage factor k = 2 Table 4 Calculations of analytical function
Date Component Analytical function parameters
Uncertainty of analytical
function parameters
Covariance of
parameters Г
23
b1 b0 u(b1) u(b0) u(b0b1) 1706 11086E-
03 -81128E-
0119491E-
0524883E-
01 -48497E-06 10544
2106 10729E-03
-26126E-01
22698E-05
28930E-01 -65652E-06 19997
2306
CO2 10593E-
03 -17688E-
0135807E-
0545413E-
01 -16254E-05 10022
1706 71537E-04
26507E-02
14231E-05
57044E-02 -81115E-07 03017
2106 72346E-04
22401E-02
13819E-05
54490E-02 -75209E-07 05935
2306
CO 71321E-
04 60080E-
0212663E-
0549016E-
02 -62026E-07 01341
1706 56521E-06
13712E-02
38279E-07
12015E-02 -45937E-09 12991
2106 56295E-06
13707E-02
39247E-07
12379E-02 -48529E-09 12905
2306
C3H8 58258E-
06 80469E-
0340085E-
0712590E-
02 -50407E-09 08589
Two columns separated by switching device are located one after another in TCD
channel One column is intended for carbon dioxide heavy hydrocarbons and another column is intended for light gases Before the first switch the light gases including carbon oxide flow through the first column without being separated and remain in the second column The switch makes them locked in the second column The analysis of carbon dioxide is carried out up to the second switch Second switch makes the second column unlocked and carbon oxide is analyzed Third switch is required to allow propane escape from a column and prevent it from getting into a second column The analysis of the very propane is carried out using FID Time intervals between switches were selected experimentally when developing the analysis method Such analysis method makes it possible to analyze all three components per one sample inject
Table 5 - Chromotograph operating conditions in calibration and analysis Parameter of the operating conditions Thermostating temperature of TCD and FID degС 170
Temperature of separation columns degС
Program 60 degС within 9 min
than rise to 160 degС at 20degСmin
Rate of flow of carrier gas through TCD channel columns mlmin 15
Rate of flow of carrier gas through TCD comparison channel mlmin 15
Pressure in FID channel column kPa Program
24
80 to 100 Rise from the 1st s of
analysis at 2 kPamin
Flow-rate of hydrogen FID mlmin 20 Flow-rate of air FID mlmin 200 Temperature of switching device degС 65 Response time of switching device s 1 110 2 330 3 540
TCD FID Volume of injected analyzed gas cm3 025 025 Carrier gas Helium Duration of analysis min 17 Calculation of the content of comparison sample components and its uncertainty Results of comparison sample measurements are given in Table 6 Table 6 - Results of comparison sample measurements
1 The content of comparison sample component and its uncertainty were determined
using calculated analytical function according to ISO 61432001 as follows (5) Where G(y)=b1y+b0 is the calculated analytical function и(y) is the standard uncertainty of response y u2(bj) is the variance of analytical function parameter bj
u(bj bI) is the covariance of analytical function parameters bj bI N is the number of function coefficients N=2 j=0 1
sum sumsumminus
= +==
partpart
partpart
+
partpart
+
partpart
=1
0 1
2
2
0
22
)(2)()()(N
jIj
N
jI Ijj
N
j j
bbubG
bGbu
bGyu
yGxu
25
After substitution of analytical function (2) and transformations the expression takes form (5)
)(2)()()()()( 01122
0222
1 bbyubuybuyubxu +++= (6) The contents of comparison sample components under determination and their
uncertainties were calculated using B_LEAST a computer program recommended in ISO 6143 Calculations are summarized in Table 6
Table 6 Calculations of the content of comparison sample components and their
2 The final content of a component was determined as an arithmetiс mean from three measurements Final standard uncertainty was calculated using formula as follows
22
222)( Адаватмтемсериикал uuuuuxu ++++= (7)
Where ucal is the uncertainty of the component content produced by
calibration of chromotograph urun is the uncertainty of the component content produced by
change of chromotograph response in each measurement run ut is the uncertainty of the component content produced by
change of an ambient temperature upressure is the uncertainty of the component content produced by
change of atmospheric pressure u A is the standard uncertainty of three measurement runs
21 Uncertainty of the component content produced by calibration of chromotograph
This uncertainty is calculated using formula (6) but the first term of the sum ie
)()( 221 yub which represents the standard uncertainty of the chromotograph response in a
measurement run is not taken into account Calculations are summarized in Table 7
26
Table 7 Calculation of uncertainty produced by calibration of chromotograph
Date u(b1) u(b0) u(b0b1) x
molmol y Ucal molmol
Ucal rel
1706 19491E-05
24883E-01
-48497E-06
13567middot10-
2129698
3 0005middot1
0-2 003
2106 22698E-05
28930E-01
-65652E-06
13564middot10-
2 128855 0007middot1
0-2 005
2306
CO2
35807E-05
45413E-01
-16254E-05
135374middot10-2
1294633
0016middot10-2 012
1706 14231E-05
57044E-02
-81115E-07 2957middot10-2 409633
0003middot10-2 009
2106 13819E-05
54490E-02
-75209E-07
29577middot10-
2 405663 0003middot1
0-2 01
2306
CO
12663E-05
49016E-02
-62026E-07 2955middot10-2 405882
0003middot10-2 01
1706 38279E-07
12015E-02
-45937E-09 1977middot10-4
3255817
007middot10-
2 038
2106 39247E-07
12379E-02
-48529E-09 1980middot10-4
3273329
008middot10-
2 038
2306
C3H8
40085E-07
12590E-02
-50407E-09 1982middot10-4 32636
008middot10-
2 04 The total estimate of relative uncertainty produced by calibration of chromotograph was
calculated for each component as follows
3
3
1
2sum=
cali
cali
uu (8)
Where ucal i is the relative uncertainty produced by calibration of chromotograph and calculated for each measurement run
The calculations are summarized in Table 8
Table 8 Uncertainty produced by calibration of chromotograph
Component Ucal rel
CO2 008 CO 01
C3H8 04 22 Uncertainty of the component content produced by change of chromotograph response in each measurement run This uncertainty is calculated using the equation (6) whereby the first term of the sum
only ie )()( 221 yub which represents the standard uncertainty of the chromotograph
response in a measurement run is taken into account Calculations are summarized in Table 9
27
Table 9 Calculation of uncertainty produced by change of chromotograph response in each measurement run
The total estimate of relative uncertainty produced by change of chromotograph
response in each measurement run was calculated for each component as follows
3
3
1
2sum=
run
run
uu (9)
Where urun is the relative uncertainty produced by change of chromotograph response in each measurement run Calculations are summarized in Table 10
Table 10 Uncertainty produced by change of chromotograph response in each measurement
run
Component Urun rel
CO2 007 CO 015
C3H8 012 23 Uncertainty of the component content produced by change of temperature in a room
The recorded change of temperature in measurements is plusmn 05 degree The contribution of uncertainty type B (rectangular distribution) is estimated as follows
201003
12931
=sdotsdot=tu rel
28
24 Uncertainty of the component content produced by change of atmospheric pressure The recorded change of atmospheric pressure within three days was
05 kPа The contribution of uncertainty type B (rectangular distribution) is estimated as follows
2801003
13101
50=sdotsdot=pressureu rel
25 Standard deviation of 3 measurement runs Standard deviation is calculated as follows
isu p
A
2
= (10)
Where S2p is the group experimental variation
The group experimental variation is calculated as follows
(11)
Where si
2 is the experimental variation of measurement run i from independent repeated observations ni having freedom degrees
νi = n - 1 n=6 i= 3 Calculations are summarized in Table 11 Table 11 Calculations of standard uncertainty of 3 measurement runs
Date 2iS x
molmol 2iS
rel uA
rel
1706 2953E-05 13567middot10-2 000022
2106 588987E-06 13564middot10-2 0000043
2306
CO2 141137E-
05 135374middot10
-2 000010
0006
1706 225604E-06 2957middot10-2 0000077
2106 681346E-06 29577middot10-2 000023
2306
CO
175166E-06 2955middot10-2 0000060
0006
1706 C3H8 130158E-
08 1977middot10-4 00000066 0001
ss
p
i ii
N
ii
N2
2
1
1
= =
=
sum
sum
ν
ν
29
2106 44616E-09 1980middot10-4 00000023
2306
381032E-09 1982middot10-4 00000019
26 Total standard uncertainty
Uncertainty estimation СО2
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph ucal Normal 008 1 008
Change of temperature ut Rectangular 02 1 02 Change of atmospheric pressure upressure Rectangular 028 1 028
Changes of chromotograph response
urun Normal 007 1 007
Standard deviation of 3 runs uA Normal 0006 1 0006
Relative total standard uncertainty 036 Coverage factor k=2 Expanded uncertainty 01middot10-2 molmol Uncertainty estimation СО
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph ucal Normal 01 1 01 Change of temperature ut Rectangular 02 1 02 Change of atmospheric pressure upressure Rectangular 028 1 028 Changes of chromotograph response
urun Normal 015 1 015
Standard deviation of 3 runs uA Normal 0006 1 0006
Relative total standard uncertainty 039 Coverage factor k=2 Expanded uncertainty 002middot10-2 molmol Uncertainty estimation С3Н8
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph 04 Normal 04 1 008
30
Change of temperature 02 Rectangular 02 1 02 Change of atmospheric pressure 028 Rectangular 028 1 028
Changes of chromotograph response
012 Normal 012 1 007
Standard deviation of 3 runs 0001 Normal 0001 1 0006
Relative total standard uncertainty 054 Coverage factor k=2 Expanded uncertainty 02middot10-4 molmol
Sample handling
Period for exposure of cylinder to measurement conditions and method how to transport sample to the device
1 Stands for storing gas standard cylinders and calibration mixture cylinders and chromotograph are placed in a laboratory room which is not accessible to unauthorized persons The laboratory is equipped with air-conditioner to maintain required temperature and humidity on a continuous basis and some auxiliary measuring instruments as thermometer psychrometric hygrometer and aneroid to control temperature humidity and atmospheric inside the room
2 The comparison sample cylinder was stored in laboratory from the date of its
delivery to Minsk on 25042005 CGM cylinders are stored horizontally on racks and positioned vertically using special support when measurements are carried out
3 The analyzed gas sample is transported through the fine adjustment valve (FAV)
Conjunctions Cylinder - FAV FAV - tube tube - doser are made of metal and use adapters with spherical ends and bushes FAV is made of brass tube is made of copper and doser is made of duralumin
Instrument(s) (principles make type configuration data collection etc) For the analysis a GC were used with specifically applications For the determination of (Nitrogen (N2)) Carbon Dioxide (CO2) Carbon Monoxide (CO) and Propane (C3H8) balance GC Perkin Elmer AutoSystem XL (two channel system) with a stream selection valve for 4 streams and 2 gas sampling valves
Channel A for the determination of N2 CO and CO2 Carrier Gas Helium Columns Column system with two packed columns (6 ft x 18rdquo Porapak R 80100 mesh and 6 ft x 18rdquo Mol-Sieve 13X 80100 mesh) Oven Temperature 960 degC to 180 degC Detector micro-TCD Data Collection Total Chrom Workstation Channel B for the determination of C3H8 Carrier Gas Helium Columns Capillary column 50 m x 032 microm LP-SIL-8-CB Oven Temperature 60 degC to 180 degC Detector FID Data Collection Total Chrom Workstation
34
Calibration Standards
Calibration Standards for the measurements (preparation method purity analyses estimated uncertainty etc)
All standards were prepared individually according to ISO 6142 rdquoGas analysis - Preparation of calibration gases - Gravimetric Methodrdquo
Depending on the concentration of the components standards were prepared individually from pure gases or from pre-mixtures which were individually prepared from pure gases
The content of the impurities in all pure gases were determined before use by GC-DID GC-FID and or GC-TCD
After preparation the standards were verified by analytical comparisons against existing gravimetrically prepared standards Only when no significant difference between the analysed and the calculated gravimetric composition is found the ldquonew prepared candidate rdquo is accepted as a new standards
For the analysis of all components multi component standards with nitrogen as balance gas were used
Composition of calibrants BAM C49250-050722 Component Assigned value( x)
mmol mol Standard uncertainty (u(x)) relativ (k=2)
Calibration procedure (mathematical modelcalibration curve number and concentrations of standards measurement sequence temperaturepressure correction etc)
For the instrument calibration the bracketing technique was used The fraction of the current used standards deviated no more than +10rel and -10rel respectively from those of the sample
Measurement sequence
Sample Handling
How were the cylinders treated after arrival (eg stabilized) and how were samples transferred to the instrument (automatic high pressure mass-flow controller dilution etc) After heating (45 - 50 degC) the cylinder for 8 hours the cylinder were rolled about 16 hours before analysis was started Each cylinder was equipped with a pressure regulator that was purged three times by sequential evacuation and pressurisation with the gas mixture used Continous flow (2 ndash 3mlmin) through the sample loop
Uncertainty The specification of potential uncertainty sources is given in Annex 3
3 injection standard (high)
3 injection sample
3 injection standard (high)
3 injection sample
3 injection standard (low)
3 injection sample
3 injection standard (low)
3 injection standard (low)
36
Uncertainty table CO2
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 002 rel 1 002 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 03 rel
Uncertainty table CO
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 007 rel 1 007 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 05 rel
37
Uncertainty table C3H8
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 010 rel 1 001 rel
Analysis normal 028 rel 1 028 rel
Coverage factor 2
Expanded uncertainty 06 rel
Optional
You may provide additional data like the raw measurement data information on your
measurement procedure chromatograms etc
38
Appendix 3 SPECIFICATION OF POTENTIAL UNCERTAINTY SOURCES
a Uncertainty related to the balance and the weights Resolution of balance Accuracy of balance including linearity Incorrect zero point Drift (thermal and time effects) Instability due to draught Location of cylinder on the balance pan Uncertainties in the weights used Buoyancy effects on the weights used
b Uncertainties related to the gas cylinder Mechanical handling of cylinder
Loss of metal paints or labels from surface of cylinder Loss of metal from threads of valvefitting Dirt on cylinder valves or associated fitting
Absorptiondesorption effects on the external cylinder surface Buoyancy effects on the cylinder itself
Cylinder temperature differs from surrounding air due to eg filling with gas Change of cylinder volume during filling Change of density of surrounding air due to changes in temperature air pressure humidity and carbon dioxide content
Uncertainty in determination of external cylinder volume c Uncertainties related to the component gases Residual gas in cylinder Leakage Leakage of air into the cylinder after evacuation
Leakage of gas from the cylinder valve during filling Escape of gas from cylinder into transport lines
Gas remaining in transfer system when weight loss method is used Absorptionreaction of components on internal cylinder surface Reaction between components Impurities in all the initial gases Insufficient homogenization Uncertainty of molecular mass d Uncertainties related to the analysis
Repeatability and selectivity of the analyzer Appropriateness of the calibration curve
39
MEASUREMENT REPORT - All Ukrainian State Research-Industrial Center of Standardization Metrology Certification and Protection of Consumers Ukraine
gas ndash helium flow rate 15 cm3min detector TCD tdetector = 250 ordmС toven = 70 ordmС It was automatic data collection
Measurement and Calibration Methods Laboratory Measurement method Type of calibration curve
GCFID (С3Н8) 3 points linear Ukrmetrteststandard GCTCD (СО СО2) 3 points linear
GCFID ndash gas-chromatographic with flame-ionization detector GCTCD - gas-chromatographic with thermal-conductivity detector
42
Calibration Standards
Calibration standards ndash primary standard gas mixtures (PSGM) used for measurements by comparison method
PSGM-1 Cylinder 0116
PSGM-2 Cylinder 0107
PSGM-3 Cylinder 0093 Composition
x u(x) x u(x) x u(x) СО 27874 00015 29899 00015 31891 00015 СО2 130187 00015 144456 00016 137016 00016 С3Н8 019003 000008 020017 000008 021013 000008 N2 balance balance balance
Note x ndash mole fraction u(x) ndash absolute standard uncertainty
It was used gravimetric method of preparation of PSGM Electronic balance КА-20-3 of Mettler Toledo max limit of weighing is 20 kg least
limit of weighing is 01 g standard deviation is 0006 g Analysis of purity of parent gases was carried out with usage of chromatographs
НР6890N with helium ndash ionization detector flame ndash ionization detector thermal ndash conductivity detector and mass ndash spectrometric detector as well аs gas analyzers GIAM-15M and Onix condensate-thermometer hygrometer TOROS-3-2B
Calculation of uncertainties was carried out according to ISO 6142-2003 Corrections of temperature pressure and humidity of environment were considered
in calculations according to ISO 6142-2003 (program of ISO-6142 2000-03-17 designer is NMi) Protocols and explanations are in Annex A
Instrument (Comparator) Calibration Calibration of comparator ndash gas chromatograph HP 6890 was carried out with usage
of PSGM Measurement sequence PSGM -1 х 3 PSGM -2 х 3 COOMET gas mixture х 3 PSGM -2 х 3 PSGM -3 х 3 It is necessary to use PSGM-2 repeatedly for estimation of reproducibility of results
Program B_LEAST recommended by ISO 6143-2003 was used for constructing the curve Mathematical model of calibration curve is linear one
Sample Handling The cylinder was kept for 24 hrs at a room where comparators were disposed This room is a thermostatic room with t = (20plusmn2) ordmС
43
A method of sample input to a comparator is a method with flow stabilization Uncertainty The following uncertainties were included to the budget of uncertainty - uncertainty of the balance - uncertainties of impurities in parent gases Contribution from other uncertainty sources was insignificant A cabin of the balance is thermostatically The balance is the one-pan balance
Air transfer is absent in the cabin of the balance Drift of the balance is absent for PSGM preparation
Contribution from other uncertainty sources was considered in software according to ISO 6142-2003
Uncertainties related to the analysis (comparison) were considered in software according to ISO 6143-2003 and enclosed in Annex B
Uncertainty table СО2
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas mixture
B 001 1 001
Analysis A B 008 1 008
Coverage factor 2 Expanded uncertainty 002sdot10-2 molmol Uncertainty table СО
Protocols of analysis (comparison) in accordance with ISO 6143-2003
57
Explanation of protocols of comparison
Chapter I ldquoThe calibration data set isrdquo contains columns 1 mole fraction of a component 2 absolute standard uncertainty of mole fraction of a component 3 a signal of a comparator 4 absolute standard uncertainty of a comparator signal
Chapter II ldquoResults of ISO 6143 methodrdquo contains parameters of a calibration curve including its
uncertainty
Chapter ІІІ ldquoPart II Processing of datardquo contains columns
1 calc x - the results of comparison mole fraction of a component 2 u(x) - absolute standard uncertainty of mole fraction of a component 3 response y - a signal of a comparator 4 u(y) - absolute standard uncertainty of a comparator signal
58
СО2 - measurement 1 Data setCO2_21 The calibration data set is 1302E+01 1510E-03 1022E+04 1820E+00 1370E+01 1560E-03 1077E+04 2730E+00 1445E+01 1620E-03 1135E+04 5900E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 20331E-02 12711E-03 12573E-01 11653E-05 -14638E-06 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 10548E-02 12722E-03 31762E-02 28898E-06 -91698E-08 Remaining SSD is 74346 Weighted distances x-value x-dist y-dist 100E+00 130E+01 490E-01 -755E-01 200E+00 137E+01 -103E+00 228E+00 300E+00 144E+01 539E-01 -250E-01 Goodness-of-fit measure 22837 Parameter set 1 1054788657490729E-2 1272208026684145E-3 3176237146276368E-2 2889798108124711E-6 -
9169821653851327E-8 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_21c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13577E+01 25542E-03 10664E+04 15200E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 547E-06 328E-06 316E-06 784E-06 286E-06 652E-06 Linear model Parameters for the fit were (b0 b1) 10548E-02 12722E-03
59
СО2 - measurement 2
Data setCO2_20 The calibration data set is 1302E+01 1512E-03 1021E+04 4723E+00 1370E+01 1563E-03 1075E+04 1600E+00 1445E+01 1620E-03 1133E+04 7300E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -38760E-02 12784E-03 26817E-02 24890E-06 -66689E-08 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -62452E-02 12805E-03 47930E-02 43243E-06 -20716E-07 Remaining SSD is 03231 Weighted distances x-value x-dist y-dist 100E+00 130E+01 107E-01 -415E-01 200E+00 137E+01 -212E-01 283E-01 300E+00 144E+01 104E-01 -584E-02 Goodness-of-fit measure 04155 Parameter set 1 -6245240430658412E-2 1280492624666799E-3 4792952200361109E-2 4324266278840409E-6 -
2071623966851869E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_20c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13594E+01 10290E-02 10665E+04 78300E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 121E-05 683E-06 651E-06 315E-05 560E-06 106E-04 Linear model Parameters for the fit were (b0 b1) -62452E-02 12805E-03
60
С3Н8 - measurement 1
Data setC3H8 The calibration data set is 1900E-01 7800E-05 9057E+03 1098E+01 2002E-01 7900E-05 9552E+03 8569E+00 2101E-01 7960E-05 1007E+04 4049E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10529E-02 19831E-05 34552E-03 36109E-07 -12465E-09 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11642E-02 19714E-05 23073E-03 23522E-07 -54231E-10 Remaining SSD is 19453 Weighted distances x-value x-dist y-dist 100E+00 190E-01 -239E-01 666E-01 200E+00 200E-01 487E-01 -104E+00 300E+00 210E-01 -247E-01 248E-01 Goodness-of-fit measure 10414 Parameter set 1 1164239985182795E-2 1971441115316992E-5 2307269625077337E-3 2352198415608386E-7 -
5423119774765299E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19837E-01 14840E-04 94718E+03 45610E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
20
If an analytical method laid down in 43 of ISO 61422001 cannot be used for impurity determination mole fraction of an expected impurity is assumed to be half of the detection limit of the analytical method The content of the undetected impurity produces rectangular distribution
whereby its standard uncertainty is calculated as half of the detection limit divided by 3 The composition of the pure gases used for preparation of calibration mixtures is given
in Table 2 Table 2 - Metrological characteristics of pure gases
N2 999967 00005 Nitrogen Cylinder 40 dm3 Origin Russia O2 00033 00005 Propane Cylinder 2 dm3 Origin Russia
C3H8 9979 0017
3 After preparation of mixture the cylinder was maintained in laboratory room within
24 hours the mixture then was homogenized on the stand by rotating on the rollers within 4-5 hours The chromotograph for CGM was calibrated 2-3 days after its preparation
Calibration of the chromotograph
1 The chromotograph was calibrated using CGMs with composition identical to the analyzed sample The content of each component and its expanded uncertainty (k = 2) are given in Table 1 Table 1 - Calibrationе gas mixtures
2 Number of observations of each calibration sample- 3 Number of calibration samples - 3
3 The analytical function used for determination of the content of the analyzed sample components is as follows
x (y) =b1y+b0 (2) Where x ndash determined content molmol y - chromotograph response for the specific component b1- slope b0 - intercept 4 After completion of calibration the coefficients of analytical function were
calculated according to ISO 61432001 using generalized least-squares method Also the uncertainties of the intercept and slope and covariance between them were calculated After determination of parameters which are part of analytical function and which affect the uncertainty of measurements it was checked whether the analytical function is fit to the experimental data obtained in calibration and subsequently whether the analytical function is applicable
Results of calibration measurements coefficients of analytical function their uncertainties covariance and measure of goodness-of-fit Г (maximum value of the weighted differences of the experimental points and calculated points of the analytical function for each measurement run) are given in Tables 3 and 4 respectively Chromotograph operating conditions in calibration and analysis are given in Table 5
Table 3 - Results of experimental study
Date Component of
calibration mixture
Content x mole fraction
Expanded uncertainty
U(x) mole fraction
Mean of peak area y
mVs
Uncertainty )(yu
mVs
13374 0004 1279500 141 1389 0004 1329150 2899 CO2
12833 0004 1231000 849 2916 0005 404070 240
316 0005 437705 926 CO 2768 0004 383070 467
019 0002 3143200 4101
1706 2005
C3H8 0202 0002 3319150 2051
22
0181 0002 2948750 212 13374 0004 1269833 624
1389 0004 1321000 1272 CO2 12833 0004 1223900 1698
2916 0005 399490 612 316 0005 434010 863 CO
2768 0004 379660 410 019 0002 3157867 6772
0202 0002 3332400 3394
2106 2005
C3H8 0181 0002 2959900 4950
13374 0004 1277100 2152 1389 0004 1329900 2828 CO2
12833 0004 1229100 1980 2916 0005 400330 529
316 0005 434745 969 CO 2768 0004 379695 106
019 0002 3142433 9416 0202 0002 3321600 4101
2306 2005
C3H8 0181 0002 2961000 3111
According to ISO 61432003 calculation of the measure of goodness-of-fit Г is the maximum value of the weighed differences between the coordinates of measured and adjusted calibration points is an effective and simple method to test the compatibility of а prospective analytical function A function is admissible if Г le 2
minus
minus=
)(ˆ
)(ˆ
iii
iii
yuyy
xuxxΓ
(4) Where хi is the reference value of the content of calibration sample component
ix is the CGM component content obtained using the calculated analytical function
уi is the experimental response to the reference content of component iy is the response obtained in calculation of analytical function
u (хi) u (уi) are the uncertainties of reference contents and responses to these contents respectively
i is the number of calibration points i=1 3 This prerequisite is equivalent to the requirement that the curve of calculated response should cross each experimental calibration rectangular [хi plusmn 2u(хi) уi plusmn 2и(уi)] based on an expanded uncertainty U = ku with coverage factor k = 2 Table 4 Calculations of analytical function
Date Component Analytical function parameters
Uncertainty of analytical
function parameters
Covariance of
parameters Г
23
b1 b0 u(b1) u(b0) u(b0b1) 1706 11086E-
03 -81128E-
0119491E-
0524883E-
01 -48497E-06 10544
2106 10729E-03
-26126E-01
22698E-05
28930E-01 -65652E-06 19997
2306
CO2 10593E-
03 -17688E-
0135807E-
0545413E-
01 -16254E-05 10022
1706 71537E-04
26507E-02
14231E-05
57044E-02 -81115E-07 03017
2106 72346E-04
22401E-02
13819E-05
54490E-02 -75209E-07 05935
2306
CO 71321E-
04 60080E-
0212663E-
0549016E-
02 -62026E-07 01341
1706 56521E-06
13712E-02
38279E-07
12015E-02 -45937E-09 12991
2106 56295E-06
13707E-02
39247E-07
12379E-02 -48529E-09 12905
2306
C3H8 58258E-
06 80469E-
0340085E-
0712590E-
02 -50407E-09 08589
Two columns separated by switching device are located one after another in TCD
channel One column is intended for carbon dioxide heavy hydrocarbons and another column is intended for light gases Before the first switch the light gases including carbon oxide flow through the first column without being separated and remain in the second column The switch makes them locked in the second column The analysis of carbon dioxide is carried out up to the second switch Second switch makes the second column unlocked and carbon oxide is analyzed Third switch is required to allow propane escape from a column and prevent it from getting into a second column The analysis of the very propane is carried out using FID Time intervals between switches were selected experimentally when developing the analysis method Such analysis method makes it possible to analyze all three components per one sample inject
Table 5 - Chromotograph operating conditions in calibration and analysis Parameter of the operating conditions Thermostating temperature of TCD and FID degС 170
Temperature of separation columns degС
Program 60 degС within 9 min
than rise to 160 degС at 20degСmin
Rate of flow of carrier gas through TCD channel columns mlmin 15
Rate of flow of carrier gas through TCD comparison channel mlmin 15
Pressure in FID channel column kPa Program
24
80 to 100 Rise from the 1st s of
analysis at 2 kPamin
Flow-rate of hydrogen FID mlmin 20 Flow-rate of air FID mlmin 200 Temperature of switching device degС 65 Response time of switching device s 1 110 2 330 3 540
TCD FID Volume of injected analyzed gas cm3 025 025 Carrier gas Helium Duration of analysis min 17 Calculation of the content of comparison sample components and its uncertainty Results of comparison sample measurements are given in Table 6 Table 6 - Results of comparison sample measurements
1 The content of comparison sample component and its uncertainty were determined
using calculated analytical function according to ISO 61432001 as follows (5) Where G(y)=b1y+b0 is the calculated analytical function и(y) is the standard uncertainty of response y u2(bj) is the variance of analytical function parameter bj
u(bj bI) is the covariance of analytical function parameters bj bI N is the number of function coefficients N=2 j=0 1
sum sumsumminus
= +==
partpart
partpart
+
partpart
+
partpart
=1
0 1
2
2
0
22
)(2)()()(N
jIj
N
jI Ijj
N
j j
bbubG
bGbu
bGyu
yGxu
25
After substitution of analytical function (2) and transformations the expression takes form (5)
)(2)()()()()( 01122
0222
1 bbyubuybuyubxu +++= (6) The contents of comparison sample components under determination and their
uncertainties were calculated using B_LEAST a computer program recommended in ISO 6143 Calculations are summarized in Table 6
Table 6 Calculations of the content of comparison sample components and their
2 The final content of a component was determined as an arithmetiс mean from three measurements Final standard uncertainty was calculated using formula as follows
22
222)( Адаватмтемсериикал uuuuuxu ++++= (7)
Where ucal is the uncertainty of the component content produced by
calibration of chromotograph urun is the uncertainty of the component content produced by
change of chromotograph response in each measurement run ut is the uncertainty of the component content produced by
change of an ambient temperature upressure is the uncertainty of the component content produced by
change of atmospheric pressure u A is the standard uncertainty of three measurement runs
21 Uncertainty of the component content produced by calibration of chromotograph
This uncertainty is calculated using formula (6) but the first term of the sum ie
)()( 221 yub which represents the standard uncertainty of the chromotograph response in a
measurement run is not taken into account Calculations are summarized in Table 7
26
Table 7 Calculation of uncertainty produced by calibration of chromotograph
Date u(b1) u(b0) u(b0b1) x
molmol y Ucal molmol
Ucal rel
1706 19491E-05
24883E-01
-48497E-06
13567middot10-
2129698
3 0005middot1
0-2 003
2106 22698E-05
28930E-01
-65652E-06
13564middot10-
2 128855 0007middot1
0-2 005
2306
CO2
35807E-05
45413E-01
-16254E-05
135374middot10-2
1294633
0016middot10-2 012
1706 14231E-05
57044E-02
-81115E-07 2957middot10-2 409633
0003middot10-2 009
2106 13819E-05
54490E-02
-75209E-07
29577middot10-
2 405663 0003middot1
0-2 01
2306
CO
12663E-05
49016E-02
-62026E-07 2955middot10-2 405882
0003middot10-2 01
1706 38279E-07
12015E-02
-45937E-09 1977middot10-4
3255817
007middot10-
2 038
2106 39247E-07
12379E-02
-48529E-09 1980middot10-4
3273329
008middot10-
2 038
2306
C3H8
40085E-07
12590E-02
-50407E-09 1982middot10-4 32636
008middot10-
2 04 The total estimate of relative uncertainty produced by calibration of chromotograph was
calculated for each component as follows
3
3
1
2sum=
cali
cali
uu (8)
Where ucal i is the relative uncertainty produced by calibration of chromotograph and calculated for each measurement run
The calculations are summarized in Table 8
Table 8 Uncertainty produced by calibration of chromotograph
Component Ucal rel
CO2 008 CO 01
C3H8 04 22 Uncertainty of the component content produced by change of chromotograph response in each measurement run This uncertainty is calculated using the equation (6) whereby the first term of the sum
only ie )()( 221 yub which represents the standard uncertainty of the chromotograph
response in a measurement run is taken into account Calculations are summarized in Table 9
27
Table 9 Calculation of uncertainty produced by change of chromotograph response in each measurement run
The total estimate of relative uncertainty produced by change of chromotograph
response in each measurement run was calculated for each component as follows
3
3
1
2sum=
run
run
uu (9)
Where urun is the relative uncertainty produced by change of chromotograph response in each measurement run Calculations are summarized in Table 10
Table 10 Uncertainty produced by change of chromotograph response in each measurement
run
Component Urun rel
CO2 007 CO 015
C3H8 012 23 Uncertainty of the component content produced by change of temperature in a room
The recorded change of temperature in measurements is plusmn 05 degree The contribution of uncertainty type B (rectangular distribution) is estimated as follows
201003
12931
=sdotsdot=tu rel
28
24 Uncertainty of the component content produced by change of atmospheric pressure The recorded change of atmospheric pressure within three days was
05 kPа The contribution of uncertainty type B (rectangular distribution) is estimated as follows
2801003
13101
50=sdotsdot=pressureu rel
25 Standard deviation of 3 measurement runs Standard deviation is calculated as follows
isu p
A
2
= (10)
Where S2p is the group experimental variation
The group experimental variation is calculated as follows
(11)
Where si
2 is the experimental variation of measurement run i from independent repeated observations ni having freedom degrees
νi = n - 1 n=6 i= 3 Calculations are summarized in Table 11 Table 11 Calculations of standard uncertainty of 3 measurement runs
Date 2iS x
molmol 2iS
rel uA
rel
1706 2953E-05 13567middot10-2 000022
2106 588987E-06 13564middot10-2 0000043
2306
CO2 141137E-
05 135374middot10
-2 000010
0006
1706 225604E-06 2957middot10-2 0000077
2106 681346E-06 29577middot10-2 000023
2306
CO
175166E-06 2955middot10-2 0000060
0006
1706 C3H8 130158E-
08 1977middot10-4 00000066 0001
ss
p
i ii
N
ii
N2
2
1
1
= =
=
sum
sum
ν
ν
29
2106 44616E-09 1980middot10-4 00000023
2306
381032E-09 1982middot10-4 00000019
26 Total standard uncertainty
Uncertainty estimation СО2
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph ucal Normal 008 1 008
Change of temperature ut Rectangular 02 1 02 Change of atmospheric pressure upressure Rectangular 028 1 028
Changes of chromotograph response
urun Normal 007 1 007
Standard deviation of 3 runs uA Normal 0006 1 0006
Relative total standard uncertainty 036 Coverage factor k=2 Expanded uncertainty 01middot10-2 molmol Uncertainty estimation СО
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph ucal Normal 01 1 01 Change of temperature ut Rectangular 02 1 02 Change of atmospheric pressure upressure Rectangular 028 1 028 Changes of chromotograph response
urun Normal 015 1 015
Standard deviation of 3 runs uA Normal 0006 1 0006
Relative total standard uncertainty 039 Coverage factor k=2 Expanded uncertainty 002middot10-2 molmol Uncertainty estimation С3Н8
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph 04 Normal 04 1 008
30
Change of temperature 02 Rectangular 02 1 02 Change of atmospheric pressure 028 Rectangular 028 1 028
Changes of chromotograph response
012 Normal 012 1 007
Standard deviation of 3 runs 0001 Normal 0001 1 0006
Relative total standard uncertainty 054 Coverage factor k=2 Expanded uncertainty 02middot10-4 molmol
Sample handling
Period for exposure of cylinder to measurement conditions and method how to transport sample to the device
1 Stands for storing gas standard cylinders and calibration mixture cylinders and chromotograph are placed in a laboratory room which is not accessible to unauthorized persons The laboratory is equipped with air-conditioner to maintain required temperature and humidity on a continuous basis and some auxiliary measuring instruments as thermometer psychrometric hygrometer and aneroid to control temperature humidity and atmospheric inside the room
2 The comparison sample cylinder was stored in laboratory from the date of its
delivery to Minsk on 25042005 CGM cylinders are stored horizontally on racks and positioned vertically using special support when measurements are carried out
3 The analyzed gas sample is transported through the fine adjustment valve (FAV)
Conjunctions Cylinder - FAV FAV - tube tube - doser are made of metal and use adapters with spherical ends and bushes FAV is made of brass tube is made of copper and doser is made of duralumin
Instrument(s) (principles make type configuration data collection etc) For the analysis a GC were used with specifically applications For the determination of (Nitrogen (N2)) Carbon Dioxide (CO2) Carbon Monoxide (CO) and Propane (C3H8) balance GC Perkin Elmer AutoSystem XL (two channel system) with a stream selection valve for 4 streams and 2 gas sampling valves
Channel A for the determination of N2 CO and CO2 Carrier Gas Helium Columns Column system with two packed columns (6 ft x 18rdquo Porapak R 80100 mesh and 6 ft x 18rdquo Mol-Sieve 13X 80100 mesh) Oven Temperature 960 degC to 180 degC Detector micro-TCD Data Collection Total Chrom Workstation Channel B for the determination of C3H8 Carrier Gas Helium Columns Capillary column 50 m x 032 microm LP-SIL-8-CB Oven Temperature 60 degC to 180 degC Detector FID Data Collection Total Chrom Workstation
34
Calibration Standards
Calibration Standards for the measurements (preparation method purity analyses estimated uncertainty etc)
All standards were prepared individually according to ISO 6142 rdquoGas analysis - Preparation of calibration gases - Gravimetric Methodrdquo
Depending on the concentration of the components standards were prepared individually from pure gases or from pre-mixtures which were individually prepared from pure gases
The content of the impurities in all pure gases were determined before use by GC-DID GC-FID and or GC-TCD
After preparation the standards were verified by analytical comparisons against existing gravimetrically prepared standards Only when no significant difference between the analysed and the calculated gravimetric composition is found the ldquonew prepared candidate rdquo is accepted as a new standards
For the analysis of all components multi component standards with nitrogen as balance gas were used
Composition of calibrants BAM C49250-050722 Component Assigned value( x)
mmol mol Standard uncertainty (u(x)) relativ (k=2)
Calibration procedure (mathematical modelcalibration curve number and concentrations of standards measurement sequence temperaturepressure correction etc)
For the instrument calibration the bracketing technique was used The fraction of the current used standards deviated no more than +10rel and -10rel respectively from those of the sample
Measurement sequence
Sample Handling
How were the cylinders treated after arrival (eg stabilized) and how were samples transferred to the instrument (automatic high pressure mass-flow controller dilution etc) After heating (45 - 50 degC) the cylinder for 8 hours the cylinder were rolled about 16 hours before analysis was started Each cylinder was equipped with a pressure regulator that was purged three times by sequential evacuation and pressurisation with the gas mixture used Continous flow (2 ndash 3mlmin) through the sample loop
Uncertainty The specification of potential uncertainty sources is given in Annex 3
3 injection standard (high)
3 injection sample
3 injection standard (high)
3 injection sample
3 injection standard (low)
3 injection sample
3 injection standard (low)
3 injection standard (low)
36
Uncertainty table CO2
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 002 rel 1 002 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 03 rel
Uncertainty table CO
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 007 rel 1 007 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 05 rel
37
Uncertainty table C3H8
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 010 rel 1 001 rel
Analysis normal 028 rel 1 028 rel
Coverage factor 2
Expanded uncertainty 06 rel
Optional
You may provide additional data like the raw measurement data information on your
measurement procedure chromatograms etc
38
Appendix 3 SPECIFICATION OF POTENTIAL UNCERTAINTY SOURCES
a Uncertainty related to the balance and the weights Resolution of balance Accuracy of balance including linearity Incorrect zero point Drift (thermal and time effects) Instability due to draught Location of cylinder on the balance pan Uncertainties in the weights used Buoyancy effects on the weights used
b Uncertainties related to the gas cylinder Mechanical handling of cylinder
Loss of metal paints or labels from surface of cylinder Loss of metal from threads of valvefitting Dirt on cylinder valves or associated fitting
Absorptiondesorption effects on the external cylinder surface Buoyancy effects on the cylinder itself
Cylinder temperature differs from surrounding air due to eg filling with gas Change of cylinder volume during filling Change of density of surrounding air due to changes in temperature air pressure humidity and carbon dioxide content
Uncertainty in determination of external cylinder volume c Uncertainties related to the component gases Residual gas in cylinder Leakage Leakage of air into the cylinder after evacuation
Leakage of gas from the cylinder valve during filling Escape of gas from cylinder into transport lines
Gas remaining in transfer system when weight loss method is used Absorptionreaction of components on internal cylinder surface Reaction between components Impurities in all the initial gases Insufficient homogenization Uncertainty of molecular mass d Uncertainties related to the analysis
Repeatability and selectivity of the analyzer Appropriateness of the calibration curve
39
MEASUREMENT REPORT - All Ukrainian State Research-Industrial Center of Standardization Metrology Certification and Protection of Consumers Ukraine
gas ndash helium flow rate 15 cm3min detector TCD tdetector = 250 ordmС toven = 70 ordmС It was automatic data collection
Measurement and Calibration Methods Laboratory Measurement method Type of calibration curve
GCFID (С3Н8) 3 points linear Ukrmetrteststandard GCTCD (СО СО2) 3 points linear
GCFID ndash gas-chromatographic with flame-ionization detector GCTCD - gas-chromatographic with thermal-conductivity detector
42
Calibration Standards
Calibration standards ndash primary standard gas mixtures (PSGM) used for measurements by comparison method
PSGM-1 Cylinder 0116
PSGM-2 Cylinder 0107
PSGM-3 Cylinder 0093 Composition
x u(x) x u(x) x u(x) СО 27874 00015 29899 00015 31891 00015 СО2 130187 00015 144456 00016 137016 00016 С3Н8 019003 000008 020017 000008 021013 000008 N2 balance balance balance
Note x ndash mole fraction u(x) ndash absolute standard uncertainty
It was used gravimetric method of preparation of PSGM Electronic balance КА-20-3 of Mettler Toledo max limit of weighing is 20 kg least
limit of weighing is 01 g standard deviation is 0006 g Analysis of purity of parent gases was carried out with usage of chromatographs
НР6890N with helium ndash ionization detector flame ndash ionization detector thermal ndash conductivity detector and mass ndash spectrometric detector as well аs gas analyzers GIAM-15M and Onix condensate-thermometer hygrometer TOROS-3-2B
Calculation of uncertainties was carried out according to ISO 6142-2003 Corrections of temperature pressure and humidity of environment were considered
in calculations according to ISO 6142-2003 (program of ISO-6142 2000-03-17 designer is NMi) Protocols and explanations are in Annex A
Instrument (Comparator) Calibration Calibration of comparator ndash gas chromatograph HP 6890 was carried out with usage
of PSGM Measurement sequence PSGM -1 х 3 PSGM -2 х 3 COOMET gas mixture х 3 PSGM -2 х 3 PSGM -3 х 3 It is necessary to use PSGM-2 repeatedly for estimation of reproducibility of results
Program B_LEAST recommended by ISO 6143-2003 was used for constructing the curve Mathematical model of calibration curve is linear one
Sample Handling The cylinder was kept for 24 hrs at a room where comparators were disposed This room is a thermostatic room with t = (20plusmn2) ordmС
43
A method of sample input to a comparator is a method with flow stabilization Uncertainty The following uncertainties were included to the budget of uncertainty - uncertainty of the balance - uncertainties of impurities in parent gases Contribution from other uncertainty sources was insignificant A cabin of the balance is thermostatically The balance is the one-pan balance
Air transfer is absent in the cabin of the balance Drift of the balance is absent for PSGM preparation
Contribution from other uncertainty sources was considered in software according to ISO 6142-2003
Uncertainties related to the analysis (comparison) were considered in software according to ISO 6143-2003 and enclosed in Annex B
Uncertainty table СО2
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas mixture
B 001 1 001
Analysis A B 008 1 008
Coverage factor 2 Expanded uncertainty 002sdot10-2 molmol Uncertainty table СО
Protocols of analysis (comparison) in accordance with ISO 6143-2003
57
Explanation of protocols of comparison
Chapter I ldquoThe calibration data set isrdquo contains columns 1 mole fraction of a component 2 absolute standard uncertainty of mole fraction of a component 3 a signal of a comparator 4 absolute standard uncertainty of a comparator signal
Chapter II ldquoResults of ISO 6143 methodrdquo contains parameters of a calibration curve including its
uncertainty
Chapter ІІІ ldquoPart II Processing of datardquo contains columns
1 calc x - the results of comparison mole fraction of a component 2 u(x) - absolute standard uncertainty of mole fraction of a component 3 response y - a signal of a comparator 4 u(y) - absolute standard uncertainty of a comparator signal
58
СО2 - measurement 1 Data setCO2_21 The calibration data set is 1302E+01 1510E-03 1022E+04 1820E+00 1370E+01 1560E-03 1077E+04 2730E+00 1445E+01 1620E-03 1135E+04 5900E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 20331E-02 12711E-03 12573E-01 11653E-05 -14638E-06 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 10548E-02 12722E-03 31762E-02 28898E-06 -91698E-08 Remaining SSD is 74346 Weighted distances x-value x-dist y-dist 100E+00 130E+01 490E-01 -755E-01 200E+00 137E+01 -103E+00 228E+00 300E+00 144E+01 539E-01 -250E-01 Goodness-of-fit measure 22837 Parameter set 1 1054788657490729E-2 1272208026684145E-3 3176237146276368E-2 2889798108124711E-6 -
9169821653851327E-8 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_21c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13577E+01 25542E-03 10664E+04 15200E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 547E-06 328E-06 316E-06 784E-06 286E-06 652E-06 Linear model Parameters for the fit were (b0 b1) 10548E-02 12722E-03
59
СО2 - measurement 2
Data setCO2_20 The calibration data set is 1302E+01 1512E-03 1021E+04 4723E+00 1370E+01 1563E-03 1075E+04 1600E+00 1445E+01 1620E-03 1133E+04 7300E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -38760E-02 12784E-03 26817E-02 24890E-06 -66689E-08 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -62452E-02 12805E-03 47930E-02 43243E-06 -20716E-07 Remaining SSD is 03231 Weighted distances x-value x-dist y-dist 100E+00 130E+01 107E-01 -415E-01 200E+00 137E+01 -212E-01 283E-01 300E+00 144E+01 104E-01 -584E-02 Goodness-of-fit measure 04155 Parameter set 1 -6245240430658412E-2 1280492624666799E-3 4792952200361109E-2 4324266278840409E-6 -
2071623966851869E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_20c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13594E+01 10290E-02 10665E+04 78300E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 121E-05 683E-06 651E-06 315E-05 560E-06 106E-04 Linear model Parameters for the fit were (b0 b1) -62452E-02 12805E-03
60
С3Н8 - measurement 1
Data setC3H8 The calibration data set is 1900E-01 7800E-05 9057E+03 1098E+01 2002E-01 7900E-05 9552E+03 8569E+00 2101E-01 7960E-05 1007E+04 4049E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10529E-02 19831E-05 34552E-03 36109E-07 -12465E-09 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11642E-02 19714E-05 23073E-03 23522E-07 -54231E-10 Remaining SSD is 19453 Weighted distances x-value x-dist y-dist 100E+00 190E-01 -239E-01 666E-01 200E+00 200E-01 487E-01 -104E+00 300E+00 210E-01 -247E-01 248E-01 Goodness-of-fit measure 10414 Parameter set 1 1164239985182795E-2 1971441115316992E-5 2307269625077337E-3 2352198415608386E-7 -
5423119774765299E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19837E-01 14840E-04 94718E+03 45610E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
2 Number of observations of each calibration sample- 3 Number of calibration samples - 3
3 The analytical function used for determination of the content of the analyzed sample components is as follows
x (y) =b1y+b0 (2) Where x ndash determined content molmol y - chromotograph response for the specific component b1- slope b0 - intercept 4 After completion of calibration the coefficients of analytical function were
calculated according to ISO 61432001 using generalized least-squares method Also the uncertainties of the intercept and slope and covariance between them were calculated After determination of parameters which are part of analytical function and which affect the uncertainty of measurements it was checked whether the analytical function is fit to the experimental data obtained in calibration and subsequently whether the analytical function is applicable
Results of calibration measurements coefficients of analytical function their uncertainties covariance and measure of goodness-of-fit Г (maximum value of the weighted differences of the experimental points and calculated points of the analytical function for each measurement run) are given in Tables 3 and 4 respectively Chromotograph operating conditions in calibration and analysis are given in Table 5
Table 3 - Results of experimental study
Date Component of
calibration mixture
Content x mole fraction
Expanded uncertainty
U(x) mole fraction
Mean of peak area y
mVs
Uncertainty )(yu
mVs
13374 0004 1279500 141 1389 0004 1329150 2899 CO2
12833 0004 1231000 849 2916 0005 404070 240
316 0005 437705 926 CO 2768 0004 383070 467
019 0002 3143200 4101
1706 2005
C3H8 0202 0002 3319150 2051
22
0181 0002 2948750 212 13374 0004 1269833 624
1389 0004 1321000 1272 CO2 12833 0004 1223900 1698
2916 0005 399490 612 316 0005 434010 863 CO
2768 0004 379660 410 019 0002 3157867 6772
0202 0002 3332400 3394
2106 2005
C3H8 0181 0002 2959900 4950
13374 0004 1277100 2152 1389 0004 1329900 2828 CO2
12833 0004 1229100 1980 2916 0005 400330 529
316 0005 434745 969 CO 2768 0004 379695 106
019 0002 3142433 9416 0202 0002 3321600 4101
2306 2005
C3H8 0181 0002 2961000 3111
According to ISO 61432003 calculation of the measure of goodness-of-fit Г is the maximum value of the weighed differences between the coordinates of measured and adjusted calibration points is an effective and simple method to test the compatibility of а prospective analytical function A function is admissible if Г le 2
minus
minus=
)(ˆ
)(ˆ
iii
iii
yuyy
xuxxΓ
(4) Where хi is the reference value of the content of calibration sample component
ix is the CGM component content obtained using the calculated analytical function
уi is the experimental response to the reference content of component iy is the response obtained in calculation of analytical function
u (хi) u (уi) are the uncertainties of reference contents and responses to these contents respectively
i is the number of calibration points i=1 3 This prerequisite is equivalent to the requirement that the curve of calculated response should cross each experimental calibration rectangular [хi plusmn 2u(хi) уi plusmn 2и(уi)] based on an expanded uncertainty U = ku with coverage factor k = 2 Table 4 Calculations of analytical function
Date Component Analytical function parameters
Uncertainty of analytical
function parameters
Covariance of
parameters Г
23
b1 b0 u(b1) u(b0) u(b0b1) 1706 11086E-
03 -81128E-
0119491E-
0524883E-
01 -48497E-06 10544
2106 10729E-03
-26126E-01
22698E-05
28930E-01 -65652E-06 19997
2306
CO2 10593E-
03 -17688E-
0135807E-
0545413E-
01 -16254E-05 10022
1706 71537E-04
26507E-02
14231E-05
57044E-02 -81115E-07 03017
2106 72346E-04
22401E-02
13819E-05
54490E-02 -75209E-07 05935
2306
CO 71321E-
04 60080E-
0212663E-
0549016E-
02 -62026E-07 01341
1706 56521E-06
13712E-02
38279E-07
12015E-02 -45937E-09 12991
2106 56295E-06
13707E-02
39247E-07
12379E-02 -48529E-09 12905
2306
C3H8 58258E-
06 80469E-
0340085E-
0712590E-
02 -50407E-09 08589
Two columns separated by switching device are located one after another in TCD
channel One column is intended for carbon dioxide heavy hydrocarbons and another column is intended for light gases Before the first switch the light gases including carbon oxide flow through the first column without being separated and remain in the second column The switch makes them locked in the second column The analysis of carbon dioxide is carried out up to the second switch Second switch makes the second column unlocked and carbon oxide is analyzed Third switch is required to allow propane escape from a column and prevent it from getting into a second column The analysis of the very propane is carried out using FID Time intervals between switches were selected experimentally when developing the analysis method Such analysis method makes it possible to analyze all three components per one sample inject
Table 5 - Chromotograph operating conditions in calibration and analysis Parameter of the operating conditions Thermostating temperature of TCD and FID degС 170
Temperature of separation columns degС
Program 60 degС within 9 min
than rise to 160 degС at 20degСmin
Rate of flow of carrier gas through TCD channel columns mlmin 15
Rate of flow of carrier gas through TCD comparison channel mlmin 15
Pressure in FID channel column kPa Program
24
80 to 100 Rise from the 1st s of
analysis at 2 kPamin
Flow-rate of hydrogen FID mlmin 20 Flow-rate of air FID mlmin 200 Temperature of switching device degС 65 Response time of switching device s 1 110 2 330 3 540
TCD FID Volume of injected analyzed gas cm3 025 025 Carrier gas Helium Duration of analysis min 17 Calculation of the content of comparison sample components and its uncertainty Results of comparison sample measurements are given in Table 6 Table 6 - Results of comparison sample measurements
1 The content of comparison sample component and its uncertainty were determined
using calculated analytical function according to ISO 61432001 as follows (5) Where G(y)=b1y+b0 is the calculated analytical function и(y) is the standard uncertainty of response y u2(bj) is the variance of analytical function parameter bj
u(bj bI) is the covariance of analytical function parameters bj bI N is the number of function coefficients N=2 j=0 1
sum sumsumminus
= +==
partpart
partpart
+
partpart
+
partpart
=1
0 1
2
2
0
22
)(2)()()(N
jIj
N
jI Ijj
N
j j
bbubG
bGbu
bGyu
yGxu
25
After substitution of analytical function (2) and transformations the expression takes form (5)
)(2)()()()()( 01122
0222
1 bbyubuybuyubxu +++= (6) The contents of comparison sample components under determination and their
uncertainties were calculated using B_LEAST a computer program recommended in ISO 6143 Calculations are summarized in Table 6
Table 6 Calculations of the content of comparison sample components and their
2 The final content of a component was determined as an arithmetiс mean from three measurements Final standard uncertainty was calculated using formula as follows
22
222)( Адаватмтемсериикал uuuuuxu ++++= (7)
Where ucal is the uncertainty of the component content produced by
calibration of chromotograph urun is the uncertainty of the component content produced by
change of chromotograph response in each measurement run ut is the uncertainty of the component content produced by
change of an ambient temperature upressure is the uncertainty of the component content produced by
change of atmospheric pressure u A is the standard uncertainty of three measurement runs
21 Uncertainty of the component content produced by calibration of chromotograph
This uncertainty is calculated using formula (6) but the first term of the sum ie
)()( 221 yub which represents the standard uncertainty of the chromotograph response in a
measurement run is not taken into account Calculations are summarized in Table 7
26
Table 7 Calculation of uncertainty produced by calibration of chromotograph
Date u(b1) u(b0) u(b0b1) x
molmol y Ucal molmol
Ucal rel
1706 19491E-05
24883E-01
-48497E-06
13567middot10-
2129698
3 0005middot1
0-2 003
2106 22698E-05
28930E-01
-65652E-06
13564middot10-
2 128855 0007middot1
0-2 005
2306
CO2
35807E-05
45413E-01
-16254E-05
135374middot10-2
1294633
0016middot10-2 012
1706 14231E-05
57044E-02
-81115E-07 2957middot10-2 409633
0003middot10-2 009
2106 13819E-05
54490E-02
-75209E-07
29577middot10-
2 405663 0003middot1
0-2 01
2306
CO
12663E-05
49016E-02
-62026E-07 2955middot10-2 405882
0003middot10-2 01
1706 38279E-07
12015E-02
-45937E-09 1977middot10-4
3255817
007middot10-
2 038
2106 39247E-07
12379E-02
-48529E-09 1980middot10-4
3273329
008middot10-
2 038
2306
C3H8
40085E-07
12590E-02
-50407E-09 1982middot10-4 32636
008middot10-
2 04 The total estimate of relative uncertainty produced by calibration of chromotograph was
calculated for each component as follows
3
3
1
2sum=
cali
cali
uu (8)
Where ucal i is the relative uncertainty produced by calibration of chromotograph and calculated for each measurement run
The calculations are summarized in Table 8
Table 8 Uncertainty produced by calibration of chromotograph
Component Ucal rel
CO2 008 CO 01
C3H8 04 22 Uncertainty of the component content produced by change of chromotograph response in each measurement run This uncertainty is calculated using the equation (6) whereby the first term of the sum
only ie )()( 221 yub which represents the standard uncertainty of the chromotograph
response in a measurement run is taken into account Calculations are summarized in Table 9
27
Table 9 Calculation of uncertainty produced by change of chromotograph response in each measurement run
The total estimate of relative uncertainty produced by change of chromotograph
response in each measurement run was calculated for each component as follows
3
3
1
2sum=
run
run
uu (9)
Where urun is the relative uncertainty produced by change of chromotograph response in each measurement run Calculations are summarized in Table 10
Table 10 Uncertainty produced by change of chromotograph response in each measurement
run
Component Urun rel
CO2 007 CO 015
C3H8 012 23 Uncertainty of the component content produced by change of temperature in a room
The recorded change of temperature in measurements is plusmn 05 degree The contribution of uncertainty type B (rectangular distribution) is estimated as follows
201003
12931
=sdotsdot=tu rel
28
24 Uncertainty of the component content produced by change of atmospheric pressure The recorded change of atmospheric pressure within three days was
05 kPа The contribution of uncertainty type B (rectangular distribution) is estimated as follows
2801003
13101
50=sdotsdot=pressureu rel
25 Standard deviation of 3 measurement runs Standard deviation is calculated as follows
isu p
A
2
= (10)
Where S2p is the group experimental variation
The group experimental variation is calculated as follows
(11)
Where si
2 is the experimental variation of measurement run i from independent repeated observations ni having freedom degrees
νi = n - 1 n=6 i= 3 Calculations are summarized in Table 11 Table 11 Calculations of standard uncertainty of 3 measurement runs
Date 2iS x
molmol 2iS
rel uA
rel
1706 2953E-05 13567middot10-2 000022
2106 588987E-06 13564middot10-2 0000043
2306
CO2 141137E-
05 135374middot10
-2 000010
0006
1706 225604E-06 2957middot10-2 0000077
2106 681346E-06 29577middot10-2 000023
2306
CO
175166E-06 2955middot10-2 0000060
0006
1706 C3H8 130158E-
08 1977middot10-4 00000066 0001
ss
p
i ii
N
ii
N2
2
1
1
= =
=
sum
sum
ν
ν
29
2106 44616E-09 1980middot10-4 00000023
2306
381032E-09 1982middot10-4 00000019
26 Total standard uncertainty
Uncertainty estimation СО2
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph ucal Normal 008 1 008
Change of temperature ut Rectangular 02 1 02 Change of atmospheric pressure upressure Rectangular 028 1 028
Changes of chromotograph response
urun Normal 007 1 007
Standard deviation of 3 runs uA Normal 0006 1 0006
Relative total standard uncertainty 036 Coverage factor k=2 Expanded uncertainty 01middot10-2 molmol Uncertainty estimation СО
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph ucal Normal 01 1 01 Change of temperature ut Rectangular 02 1 02 Change of atmospheric pressure upressure Rectangular 028 1 028 Changes of chromotograph response
urun Normal 015 1 015
Standard deviation of 3 runs uA Normal 0006 1 0006
Relative total standard uncertainty 039 Coverage factor k=2 Expanded uncertainty 002middot10-2 molmol Uncertainty estimation С3Н8
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph 04 Normal 04 1 008
30
Change of temperature 02 Rectangular 02 1 02 Change of atmospheric pressure 028 Rectangular 028 1 028
Changes of chromotograph response
012 Normal 012 1 007
Standard deviation of 3 runs 0001 Normal 0001 1 0006
Relative total standard uncertainty 054 Coverage factor k=2 Expanded uncertainty 02middot10-4 molmol
Sample handling
Period for exposure of cylinder to measurement conditions and method how to transport sample to the device
1 Stands for storing gas standard cylinders and calibration mixture cylinders and chromotograph are placed in a laboratory room which is not accessible to unauthorized persons The laboratory is equipped with air-conditioner to maintain required temperature and humidity on a continuous basis and some auxiliary measuring instruments as thermometer psychrometric hygrometer and aneroid to control temperature humidity and atmospheric inside the room
2 The comparison sample cylinder was stored in laboratory from the date of its
delivery to Minsk on 25042005 CGM cylinders are stored horizontally on racks and positioned vertically using special support when measurements are carried out
3 The analyzed gas sample is transported through the fine adjustment valve (FAV)
Conjunctions Cylinder - FAV FAV - tube tube - doser are made of metal and use adapters with spherical ends and bushes FAV is made of brass tube is made of copper and doser is made of duralumin
Instrument(s) (principles make type configuration data collection etc) For the analysis a GC were used with specifically applications For the determination of (Nitrogen (N2)) Carbon Dioxide (CO2) Carbon Monoxide (CO) and Propane (C3H8) balance GC Perkin Elmer AutoSystem XL (two channel system) with a stream selection valve for 4 streams and 2 gas sampling valves
Channel A for the determination of N2 CO and CO2 Carrier Gas Helium Columns Column system with two packed columns (6 ft x 18rdquo Porapak R 80100 mesh and 6 ft x 18rdquo Mol-Sieve 13X 80100 mesh) Oven Temperature 960 degC to 180 degC Detector micro-TCD Data Collection Total Chrom Workstation Channel B for the determination of C3H8 Carrier Gas Helium Columns Capillary column 50 m x 032 microm LP-SIL-8-CB Oven Temperature 60 degC to 180 degC Detector FID Data Collection Total Chrom Workstation
34
Calibration Standards
Calibration Standards for the measurements (preparation method purity analyses estimated uncertainty etc)
All standards were prepared individually according to ISO 6142 rdquoGas analysis - Preparation of calibration gases - Gravimetric Methodrdquo
Depending on the concentration of the components standards were prepared individually from pure gases or from pre-mixtures which were individually prepared from pure gases
The content of the impurities in all pure gases were determined before use by GC-DID GC-FID and or GC-TCD
After preparation the standards were verified by analytical comparisons against existing gravimetrically prepared standards Only when no significant difference between the analysed and the calculated gravimetric composition is found the ldquonew prepared candidate rdquo is accepted as a new standards
For the analysis of all components multi component standards with nitrogen as balance gas were used
Composition of calibrants BAM C49250-050722 Component Assigned value( x)
mmol mol Standard uncertainty (u(x)) relativ (k=2)
Calibration procedure (mathematical modelcalibration curve number and concentrations of standards measurement sequence temperaturepressure correction etc)
For the instrument calibration the bracketing technique was used The fraction of the current used standards deviated no more than +10rel and -10rel respectively from those of the sample
Measurement sequence
Sample Handling
How were the cylinders treated after arrival (eg stabilized) and how were samples transferred to the instrument (automatic high pressure mass-flow controller dilution etc) After heating (45 - 50 degC) the cylinder for 8 hours the cylinder were rolled about 16 hours before analysis was started Each cylinder was equipped with a pressure regulator that was purged three times by sequential evacuation and pressurisation with the gas mixture used Continous flow (2 ndash 3mlmin) through the sample loop
Uncertainty The specification of potential uncertainty sources is given in Annex 3
3 injection standard (high)
3 injection sample
3 injection standard (high)
3 injection sample
3 injection standard (low)
3 injection sample
3 injection standard (low)
3 injection standard (low)
36
Uncertainty table CO2
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 002 rel 1 002 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 03 rel
Uncertainty table CO
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 007 rel 1 007 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 05 rel
37
Uncertainty table C3H8
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 010 rel 1 001 rel
Analysis normal 028 rel 1 028 rel
Coverage factor 2
Expanded uncertainty 06 rel
Optional
You may provide additional data like the raw measurement data information on your
measurement procedure chromatograms etc
38
Appendix 3 SPECIFICATION OF POTENTIAL UNCERTAINTY SOURCES
a Uncertainty related to the balance and the weights Resolution of balance Accuracy of balance including linearity Incorrect zero point Drift (thermal and time effects) Instability due to draught Location of cylinder on the balance pan Uncertainties in the weights used Buoyancy effects on the weights used
b Uncertainties related to the gas cylinder Mechanical handling of cylinder
Loss of metal paints or labels from surface of cylinder Loss of metal from threads of valvefitting Dirt on cylinder valves or associated fitting
Absorptiondesorption effects on the external cylinder surface Buoyancy effects on the cylinder itself
Cylinder temperature differs from surrounding air due to eg filling with gas Change of cylinder volume during filling Change of density of surrounding air due to changes in temperature air pressure humidity and carbon dioxide content
Uncertainty in determination of external cylinder volume c Uncertainties related to the component gases Residual gas in cylinder Leakage Leakage of air into the cylinder after evacuation
Leakage of gas from the cylinder valve during filling Escape of gas from cylinder into transport lines
Gas remaining in transfer system when weight loss method is used Absorptionreaction of components on internal cylinder surface Reaction between components Impurities in all the initial gases Insufficient homogenization Uncertainty of molecular mass d Uncertainties related to the analysis
Repeatability and selectivity of the analyzer Appropriateness of the calibration curve
39
MEASUREMENT REPORT - All Ukrainian State Research-Industrial Center of Standardization Metrology Certification and Protection of Consumers Ukraine
gas ndash helium flow rate 15 cm3min detector TCD tdetector = 250 ordmС toven = 70 ordmС It was automatic data collection
Measurement and Calibration Methods Laboratory Measurement method Type of calibration curve
GCFID (С3Н8) 3 points linear Ukrmetrteststandard GCTCD (СО СО2) 3 points linear
GCFID ndash gas-chromatographic with flame-ionization detector GCTCD - gas-chromatographic with thermal-conductivity detector
42
Calibration Standards
Calibration standards ndash primary standard gas mixtures (PSGM) used for measurements by comparison method
PSGM-1 Cylinder 0116
PSGM-2 Cylinder 0107
PSGM-3 Cylinder 0093 Composition
x u(x) x u(x) x u(x) СО 27874 00015 29899 00015 31891 00015 СО2 130187 00015 144456 00016 137016 00016 С3Н8 019003 000008 020017 000008 021013 000008 N2 balance balance balance
Note x ndash mole fraction u(x) ndash absolute standard uncertainty
It was used gravimetric method of preparation of PSGM Electronic balance КА-20-3 of Mettler Toledo max limit of weighing is 20 kg least
limit of weighing is 01 g standard deviation is 0006 g Analysis of purity of parent gases was carried out with usage of chromatographs
НР6890N with helium ndash ionization detector flame ndash ionization detector thermal ndash conductivity detector and mass ndash spectrometric detector as well аs gas analyzers GIAM-15M and Onix condensate-thermometer hygrometer TOROS-3-2B
Calculation of uncertainties was carried out according to ISO 6142-2003 Corrections of temperature pressure and humidity of environment were considered
in calculations according to ISO 6142-2003 (program of ISO-6142 2000-03-17 designer is NMi) Protocols and explanations are in Annex A
Instrument (Comparator) Calibration Calibration of comparator ndash gas chromatograph HP 6890 was carried out with usage
of PSGM Measurement sequence PSGM -1 х 3 PSGM -2 х 3 COOMET gas mixture х 3 PSGM -2 х 3 PSGM -3 х 3 It is necessary to use PSGM-2 repeatedly for estimation of reproducibility of results
Program B_LEAST recommended by ISO 6143-2003 was used for constructing the curve Mathematical model of calibration curve is linear one
Sample Handling The cylinder was kept for 24 hrs at a room where comparators were disposed This room is a thermostatic room with t = (20plusmn2) ordmС
43
A method of sample input to a comparator is a method with flow stabilization Uncertainty The following uncertainties were included to the budget of uncertainty - uncertainty of the balance - uncertainties of impurities in parent gases Contribution from other uncertainty sources was insignificant A cabin of the balance is thermostatically The balance is the one-pan balance
Air transfer is absent in the cabin of the balance Drift of the balance is absent for PSGM preparation
Contribution from other uncertainty sources was considered in software according to ISO 6142-2003
Uncertainties related to the analysis (comparison) were considered in software according to ISO 6143-2003 and enclosed in Annex B
Uncertainty table СО2
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas mixture
B 001 1 001
Analysis A B 008 1 008
Coverage factor 2 Expanded uncertainty 002sdot10-2 molmol Uncertainty table СО
Protocols of analysis (comparison) in accordance with ISO 6143-2003
57
Explanation of protocols of comparison
Chapter I ldquoThe calibration data set isrdquo contains columns 1 mole fraction of a component 2 absolute standard uncertainty of mole fraction of a component 3 a signal of a comparator 4 absolute standard uncertainty of a comparator signal
Chapter II ldquoResults of ISO 6143 methodrdquo contains parameters of a calibration curve including its
uncertainty
Chapter ІІІ ldquoPart II Processing of datardquo contains columns
1 calc x - the results of comparison mole fraction of a component 2 u(x) - absolute standard uncertainty of mole fraction of a component 3 response y - a signal of a comparator 4 u(y) - absolute standard uncertainty of a comparator signal
58
СО2 - measurement 1 Data setCO2_21 The calibration data set is 1302E+01 1510E-03 1022E+04 1820E+00 1370E+01 1560E-03 1077E+04 2730E+00 1445E+01 1620E-03 1135E+04 5900E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 20331E-02 12711E-03 12573E-01 11653E-05 -14638E-06 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 10548E-02 12722E-03 31762E-02 28898E-06 -91698E-08 Remaining SSD is 74346 Weighted distances x-value x-dist y-dist 100E+00 130E+01 490E-01 -755E-01 200E+00 137E+01 -103E+00 228E+00 300E+00 144E+01 539E-01 -250E-01 Goodness-of-fit measure 22837 Parameter set 1 1054788657490729E-2 1272208026684145E-3 3176237146276368E-2 2889798108124711E-6 -
9169821653851327E-8 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_21c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13577E+01 25542E-03 10664E+04 15200E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 547E-06 328E-06 316E-06 784E-06 286E-06 652E-06 Linear model Parameters for the fit were (b0 b1) 10548E-02 12722E-03
59
СО2 - measurement 2
Data setCO2_20 The calibration data set is 1302E+01 1512E-03 1021E+04 4723E+00 1370E+01 1563E-03 1075E+04 1600E+00 1445E+01 1620E-03 1133E+04 7300E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -38760E-02 12784E-03 26817E-02 24890E-06 -66689E-08 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -62452E-02 12805E-03 47930E-02 43243E-06 -20716E-07 Remaining SSD is 03231 Weighted distances x-value x-dist y-dist 100E+00 130E+01 107E-01 -415E-01 200E+00 137E+01 -212E-01 283E-01 300E+00 144E+01 104E-01 -584E-02 Goodness-of-fit measure 04155 Parameter set 1 -6245240430658412E-2 1280492624666799E-3 4792952200361109E-2 4324266278840409E-6 -
2071623966851869E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_20c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13594E+01 10290E-02 10665E+04 78300E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 121E-05 683E-06 651E-06 315E-05 560E-06 106E-04 Linear model Parameters for the fit were (b0 b1) -62452E-02 12805E-03
60
С3Н8 - measurement 1
Data setC3H8 The calibration data set is 1900E-01 7800E-05 9057E+03 1098E+01 2002E-01 7900E-05 9552E+03 8569E+00 2101E-01 7960E-05 1007E+04 4049E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10529E-02 19831E-05 34552E-03 36109E-07 -12465E-09 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11642E-02 19714E-05 23073E-03 23522E-07 -54231E-10 Remaining SSD is 19453 Weighted distances x-value x-dist y-dist 100E+00 190E-01 -239E-01 666E-01 200E+00 200E-01 487E-01 -104E+00 300E+00 210E-01 -247E-01 248E-01 Goodness-of-fit measure 10414 Parameter set 1 1164239985182795E-2 1971441115316992E-5 2307269625077337E-3 2352198415608386E-7 -
5423119774765299E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19837E-01 14840E-04 94718E+03 45610E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
22
0181 0002 2948750 212 13374 0004 1269833 624
1389 0004 1321000 1272 CO2 12833 0004 1223900 1698
2916 0005 399490 612 316 0005 434010 863 CO
2768 0004 379660 410 019 0002 3157867 6772
0202 0002 3332400 3394
2106 2005
C3H8 0181 0002 2959900 4950
13374 0004 1277100 2152 1389 0004 1329900 2828 CO2
12833 0004 1229100 1980 2916 0005 400330 529
316 0005 434745 969 CO 2768 0004 379695 106
019 0002 3142433 9416 0202 0002 3321600 4101
2306 2005
C3H8 0181 0002 2961000 3111
According to ISO 61432003 calculation of the measure of goodness-of-fit Г is the maximum value of the weighed differences between the coordinates of measured and adjusted calibration points is an effective and simple method to test the compatibility of а prospective analytical function A function is admissible if Г le 2
minus
minus=
)(ˆ
)(ˆ
iii
iii
yuyy
xuxxΓ
(4) Where хi is the reference value of the content of calibration sample component
ix is the CGM component content obtained using the calculated analytical function
уi is the experimental response to the reference content of component iy is the response obtained in calculation of analytical function
u (хi) u (уi) are the uncertainties of reference contents and responses to these contents respectively
i is the number of calibration points i=1 3 This prerequisite is equivalent to the requirement that the curve of calculated response should cross each experimental calibration rectangular [хi plusmn 2u(хi) уi plusmn 2и(уi)] based on an expanded uncertainty U = ku with coverage factor k = 2 Table 4 Calculations of analytical function
Date Component Analytical function parameters
Uncertainty of analytical
function parameters
Covariance of
parameters Г
23
b1 b0 u(b1) u(b0) u(b0b1) 1706 11086E-
03 -81128E-
0119491E-
0524883E-
01 -48497E-06 10544
2106 10729E-03
-26126E-01
22698E-05
28930E-01 -65652E-06 19997
2306
CO2 10593E-
03 -17688E-
0135807E-
0545413E-
01 -16254E-05 10022
1706 71537E-04
26507E-02
14231E-05
57044E-02 -81115E-07 03017
2106 72346E-04
22401E-02
13819E-05
54490E-02 -75209E-07 05935
2306
CO 71321E-
04 60080E-
0212663E-
0549016E-
02 -62026E-07 01341
1706 56521E-06
13712E-02
38279E-07
12015E-02 -45937E-09 12991
2106 56295E-06
13707E-02
39247E-07
12379E-02 -48529E-09 12905
2306
C3H8 58258E-
06 80469E-
0340085E-
0712590E-
02 -50407E-09 08589
Two columns separated by switching device are located one after another in TCD
channel One column is intended for carbon dioxide heavy hydrocarbons and another column is intended for light gases Before the first switch the light gases including carbon oxide flow through the first column without being separated and remain in the second column The switch makes them locked in the second column The analysis of carbon dioxide is carried out up to the second switch Second switch makes the second column unlocked and carbon oxide is analyzed Third switch is required to allow propane escape from a column and prevent it from getting into a second column The analysis of the very propane is carried out using FID Time intervals between switches were selected experimentally when developing the analysis method Such analysis method makes it possible to analyze all three components per one sample inject
Table 5 - Chromotograph operating conditions in calibration and analysis Parameter of the operating conditions Thermostating temperature of TCD and FID degС 170
Temperature of separation columns degС
Program 60 degС within 9 min
than rise to 160 degС at 20degСmin
Rate of flow of carrier gas through TCD channel columns mlmin 15
Rate of flow of carrier gas through TCD comparison channel mlmin 15
Pressure in FID channel column kPa Program
24
80 to 100 Rise from the 1st s of
analysis at 2 kPamin
Flow-rate of hydrogen FID mlmin 20 Flow-rate of air FID mlmin 200 Temperature of switching device degС 65 Response time of switching device s 1 110 2 330 3 540
TCD FID Volume of injected analyzed gas cm3 025 025 Carrier gas Helium Duration of analysis min 17 Calculation of the content of comparison sample components and its uncertainty Results of comparison sample measurements are given in Table 6 Table 6 - Results of comparison sample measurements
1 The content of comparison sample component and its uncertainty were determined
using calculated analytical function according to ISO 61432001 as follows (5) Where G(y)=b1y+b0 is the calculated analytical function и(y) is the standard uncertainty of response y u2(bj) is the variance of analytical function parameter bj
u(bj bI) is the covariance of analytical function parameters bj bI N is the number of function coefficients N=2 j=0 1
sum sumsumminus
= +==
partpart
partpart
+
partpart
+
partpart
=1
0 1
2
2
0
22
)(2)()()(N
jIj
N
jI Ijj
N
j j
bbubG
bGbu
bGyu
yGxu
25
After substitution of analytical function (2) and transformations the expression takes form (5)
)(2)()()()()( 01122
0222
1 bbyubuybuyubxu +++= (6) The contents of comparison sample components under determination and their
uncertainties were calculated using B_LEAST a computer program recommended in ISO 6143 Calculations are summarized in Table 6
Table 6 Calculations of the content of comparison sample components and their
2 The final content of a component was determined as an arithmetiс mean from three measurements Final standard uncertainty was calculated using formula as follows
22
222)( Адаватмтемсериикал uuuuuxu ++++= (7)
Where ucal is the uncertainty of the component content produced by
calibration of chromotograph urun is the uncertainty of the component content produced by
change of chromotograph response in each measurement run ut is the uncertainty of the component content produced by
change of an ambient temperature upressure is the uncertainty of the component content produced by
change of atmospheric pressure u A is the standard uncertainty of three measurement runs
21 Uncertainty of the component content produced by calibration of chromotograph
This uncertainty is calculated using formula (6) but the first term of the sum ie
)()( 221 yub which represents the standard uncertainty of the chromotograph response in a
measurement run is not taken into account Calculations are summarized in Table 7
26
Table 7 Calculation of uncertainty produced by calibration of chromotograph
Date u(b1) u(b0) u(b0b1) x
molmol y Ucal molmol
Ucal rel
1706 19491E-05
24883E-01
-48497E-06
13567middot10-
2129698
3 0005middot1
0-2 003
2106 22698E-05
28930E-01
-65652E-06
13564middot10-
2 128855 0007middot1
0-2 005
2306
CO2
35807E-05
45413E-01
-16254E-05
135374middot10-2
1294633
0016middot10-2 012
1706 14231E-05
57044E-02
-81115E-07 2957middot10-2 409633
0003middot10-2 009
2106 13819E-05
54490E-02
-75209E-07
29577middot10-
2 405663 0003middot1
0-2 01
2306
CO
12663E-05
49016E-02
-62026E-07 2955middot10-2 405882
0003middot10-2 01
1706 38279E-07
12015E-02
-45937E-09 1977middot10-4
3255817
007middot10-
2 038
2106 39247E-07
12379E-02
-48529E-09 1980middot10-4
3273329
008middot10-
2 038
2306
C3H8
40085E-07
12590E-02
-50407E-09 1982middot10-4 32636
008middot10-
2 04 The total estimate of relative uncertainty produced by calibration of chromotograph was
calculated for each component as follows
3
3
1
2sum=
cali
cali
uu (8)
Where ucal i is the relative uncertainty produced by calibration of chromotograph and calculated for each measurement run
The calculations are summarized in Table 8
Table 8 Uncertainty produced by calibration of chromotograph
Component Ucal rel
CO2 008 CO 01
C3H8 04 22 Uncertainty of the component content produced by change of chromotograph response in each measurement run This uncertainty is calculated using the equation (6) whereby the first term of the sum
only ie )()( 221 yub which represents the standard uncertainty of the chromotograph
response in a measurement run is taken into account Calculations are summarized in Table 9
27
Table 9 Calculation of uncertainty produced by change of chromotograph response in each measurement run
The total estimate of relative uncertainty produced by change of chromotograph
response in each measurement run was calculated for each component as follows
3
3
1
2sum=
run
run
uu (9)
Where urun is the relative uncertainty produced by change of chromotograph response in each measurement run Calculations are summarized in Table 10
Table 10 Uncertainty produced by change of chromotograph response in each measurement
run
Component Urun rel
CO2 007 CO 015
C3H8 012 23 Uncertainty of the component content produced by change of temperature in a room
The recorded change of temperature in measurements is plusmn 05 degree The contribution of uncertainty type B (rectangular distribution) is estimated as follows
201003
12931
=sdotsdot=tu rel
28
24 Uncertainty of the component content produced by change of atmospheric pressure The recorded change of atmospheric pressure within three days was
05 kPа The contribution of uncertainty type B (rectangular distribution) is estimated as follows
2801003
13101
50=sdotsdot=pressureu rel
25 Standard deviation of 3 measurement runs Standard deviation is calculated as follows
isu p
A
2
= (10)
Where S2p is the group experimental variation
The group experimental variation is calculated as follows
(11)
Where si
2 is the experimental variation of measurement run i from independent repeated observations ni having freedom degrees
νi = n - 1 n=6 i= 3 Calculations are summarized in Table 11 Table 11 Calculations of standard uncertainty of 3 measurement runs
Date 2iS x
molmol 2iS
rel uA
rel
1706 2953E-05 13567middot10-2 000022
2106 588987E-06 13564middot10-2 0000043
2306
CO2 141137E-
05 135374middot10
-2 000010
0006
1706 225604E-06 2957middot10-2 0000077
2106 681346E-06 29577middot10-2 000023
2306
CO
175166E-06 2955middot10-2 0000060
0006
1706 C3H8 130158E-
08 1977middot10-4 00000066 0001
ss
p
i ii
N
ii
N2
2
1
1
= =
=
sum
sum
ν
ν
29
2106 44616E-09 1980middot10-4 00000023
2306
381032E-09 1982middot10-4 00000019
26 Total standard uncertainty
Uncertainty estimation СО2
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph ucal Normal 008 1 008
Change of temperature ut Rectangular 02 1 02 Change of atmospheric pressure upressure Rectangular 028 1 028
Changes of chromotograph response
urun Normal 007 1 007
Standard deviation of 3 runs uA Normal 0006 1 0006
Relative total standard uncertainty 036 Coverage factor k=2 Expanded uncertainty 01middot10-2 molmol Uncertainty estimation СО
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph ucal Normal 01 1 01 Change of temperature ut Rectangular 02 1 02 Change of atmospheric pressure upressure Rectangular 028 1 028 Changes of chromotograph response
urun Normal 015 1 015
Standard deviation of 3 runs uA Normal 0006 1 0006
Relative total standard uncertainty 039 Coverage factor k=2 Expanded uncertainty 002middot10-2 molmol Uncertainty estimation С3Н8
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph 04 Normal 04 1 008
30
Change of temperature 02 Rectangular 02 1 02 Change of atmospheric pressure 028 Rectangular 028 1 028
Changes of chromotograph response
012 Normal 012 1 007
Standard deviation of 3 runs 0001 Normal 0001 1 0006
Relative total standard uncertainty 054 Coverage factor k=2 Expanded uncertainty 02middot10-4 molmol
Sample handling
Period for exposure of cylinder to measurement conditions and method how to transport sample to the device
1 Stands for storing gas standard cylinders and calibration mixture cylinders and chromotograph are placed in a laboratory room which is not accessible to unauthorized persons The laboratory is equipped with air-conditioner to maintain required temperature and humidity on a continuous basis and some auxiliary measuring instruments as thermometer psychrometric hygrometer and aneroid to control temperature humidity and atmospheric inside the room
2 The comparison sample cylinder was stored in laboratory from the date of its
delivery to Minsk on 25042005 CGM cylinders are stored horizontally on racks and positioned vertically using special support when measurements are carried out
3 The analyzed gas sample is transported through the fine adjustment valve (FAV)
Conjunctions Cylinder - FAV FAV - tube tube - doser are made of metal and use adapters with spherical ends and bushes FAV is made of brass tube is made of copper and doser is made of duralumin
Instrument(s) (principles make type configuration data collection etc) For the analysis a GC were used with specifically applications For the determination of (Nitrogen (N2)) Carbon Dioxide (CO2) Carbon Monoxide (CO) and Propane (C3H8) balance GC Perkin Elmer AutoSystem XL (two channel system) with a stream selection valve for 4 streams and 2 gas sampling valves
Channel A for the determination of N2 CO and CO2 Carrier Gas Helium Columns Column system with two packed columns (6 ft x 18rdquo Porapak R 80100 mesh and 6 ft x 18rdquo Mol-Sieve 13X 80100 mesh) Oven Temperature 960 degC to 180 degC Detector micro-TCD Data Collection Total Chrom Workstation Channel B for the determination of C3H8 Carrier Gas Helium Columns Capillary column 50 m x 032 microm LP-SIL-8-CB Oven Temperature 60 degC to 180 degC Detector FID Data Collection Total Chrom Workstation
34
Calibration Standards
Calibration Standards for the measurements (preparation method purity analyses estimated uncertainty etc)
All standards were prepared individually according to ISO 6142 rdquoGas analysis - Preparation of calibration gases - Gravimetric Methodrdquo
Depending on the concentration of the components standards were prepared individually from pure gases or from pre-mixtures which were individually prepared from pure gases
The content of the impurities in all pure gases were determined before use by GC-DID GC-FID and or GC-TCD
After preparation the standards were verified by analytical comparisons against existing gravimetrically prepared standards Only when no significant difference between the analysed and the calculated gravimetric composition is found the ldquonew prepared candidate rdquo is accepted as a new standards
For the analysis of all components multi component standards with nitrogen as balance gas were used
Composition of calibrants BAM C49250-050722 Component Assigned value( x)
mmol mol Standard uncertainty (u(x)) relativ (k=2)
Calibration procedure (mathematical modelcalibration curve number and concentrations of standards measurement sequence temperaturepressure correction etc)
For the instrument calibration the bracketing technique was used The fraction of the current used standards deviated no more than +10rel and -10rel respectively from those of the sample
Measurement sequence
Sample Handling
How were the cylinders treated after arrival (eg stabilized) and how were samples transferred to the instrument (automatic high pressure mass-flow controller dilution etc) After heating (45 - 50 degC) the cylinder for 8 hours the cylinder were rolled about 16 hours before analysis was started Each cylinder was equipped with a pressure regulator that was purged three times by sequential evacuation and pressurisation with the gas mixture used Continous flow (2 ndash 3mlmin) through the sample loop
Uncertainty The specification of potential uncertainty sources is given in Annex 3
3 injection standard (high)
3 injection sample
3 injection standard (high)
3 injection sample
3 injection standard (low)
3 injection sample
3 injection standard (low)
3 injection standard (low)
36
Uncertainty table CO2
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 002 rel 1 002 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 03 rel
Uncertainty table CO
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 007 rel 1 007 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 05 rel
37
Uncertainty table C3H8
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 010 rel 1 001 rel
Analysis normal 028 rel 1 028 rel
Coverage factor 2
Expanded uncertainty 06 rel
Optional
You may provide additional data like the raw measurement data information on your
measurement procedure chromatograms etc
38
Appendix 3 SPECIFICATION OF POTENTIAL UNCERTAINTY SOURCES
a Uncertainty related to the balance and the weights Resolution of balance Accuracy of balance including linearity Incorrect zero point Drift (thermal and time effects) Instability due to draught Location of cylinder on the balance pan Uncertainties in the weights used Buoyancy effects on the weights used
b Uncertainties related to the gas cylinder Mechanical handling of cylinder
Loss of metal paints or labels from surface of cylinder Loss of metal from threads of valvefitting Dirt on cylinder valves or associated fitting
Absorptiondesorption effects on the external cylinder surface Buoyancy effects on the cylinder itself
Cylinder temperature differs from surrounding air due to eg filling with gas Change of cylinder volume during filling Change of density of surrounding air due to changes in temperature air pressure humidity and carbon dioxide content
Uncertainty in determination of external cylinder volume c Uncertainties related to the component gases Residual gas in cylinder Leakage Leakage of air into the cylinder after evacuation
Leakage of gas from the cylinder valve during filling Escape of gas from cylinder into transport lines
Gas remaining in transfer system when weight loss method is used Absorptionreaction of components on internal cylinder surface Reaction between components Impurities in all the initial gases Insufficient homogenization Uncertainty of molecular mass d Uncertainties related to the analysis
Repeatability and selectivity of the analyzer Appropriateness of the calibration curve
39
MEASUREMENT REPORT - All Ukrainian State Research-Industrial Center of Standardization Metrology Certification and Protection of Consumers Ukraine
gas ndash helium flow rate 15 cm3min detector TCD tdetector = 250 ordmС toven = 70 ordmС It was automatic data collection
Measurement and Calibration Methods Laboratory Measurement method Type of calibration curve
GCFID (С3Н8) 3 points linear Ukrmetrteststandard GCTCD (СО СО2) 3 points linear
GCFID ndash gas-chromatographic with flame-ionization detector GCTCD - gas-chromatographic with thermal-conductivity detector
42
Calibration Standards
Calibration standards ndash primary standard gas mixtures (PSGM) used for measurements by comparison method
PSGM-1 Cylinder 0116
PSGM-2 Cylinder 0107
PSGM-3 Cylinder 0093 Composition
x u(x) x u(x) x u(x) СО 27874 00015 29899 00015 31891 00015 СО2 130187 00015 144456 00016 137016 00016 С3Н8 019003 000008 020017 000008 021013 000008 N2 balance balance balance
Note x ndash mole fraction u(x) ndash absolute standard uncertainty
It was used gravimetric method of preparation of PSGM Electronic balance КА-20-3 of Mettler Toledo max limit of weighing is 20 kg least
limit of weighing is 01 g standard deviation is 0006 g Analysis of purity of parent gases was carried out with usage of chromatographs
НР6890N with helium ndash ionization detector flame ndash ionization detector thermal ndash conductivity detector and mass ndash spectrometric detector as well аs gas analyzers GIAM-15M and Onix condensate-thermometer hygrometer TOROS-3-2B
Calculation of uncertainties was carried out according to ISO 6142-2003 Corrections of temperature pressure and humidity of environment were considered
in calculations according to ISO 6142-2003 (program of ISO-6142 2000-03-17 designer is NMi) Protocols and explanations are in Annex A
Instrument (Comparator) Calibration Calibration of comparator ndash gas chromatograph HP 6890 was carried out with usage
of PSGM Measurement sequence PSGM -1 х 3 PSGM -2 х 3 COOMET gas mixture х 3 PSGM -2 х 3 PSGM -3 х 3 It is necessary to use PSGM-2 repeatedly for estimation of reproducibility of results
Program B_LEAST recommended by ISO 6143-2003 was used for constructing the curve Mathematical model of calibration curve is linear one
Sample Handling The cylinder was kept for 24 hrs at a room where comparators were disposed This room is a thermostatic room with t = (20plusmn2) ordmС
43
A method of sample input to a comparator is a method with flow stabilization Uncertainty The following uncertainties were included to the budget of uncertainty - uncertainty of the balance - uncertainties of impurities in parent gases Contribution from other uncertainty sources was insignificant A cabin of the balance is thermostatically The balance is the one-pan balance
Air transfer is absent in the cabin of the balance Drift of the balance is absent for PSGM preparation
Contribution from other uncertainty sources was considered in software according to ISO 6142-2003
Uncertainties related to the analysis (comparison) were considered in software according to ISO 6143-2003 and enclosed in Annex B
Uncertainty table СО2
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas mixture
B 001 1 001
Analysis A B 008 1 008
Coverage factor 2 Expanded uncertainty 002sdot10-2 molmol Uncertainty table СО
Protocols of analysis (comparison) in accordance with ISO 6143-2003
57
Explanation of protocols of comparison
Chapter I ldquoThe calibration data set isrdquo contains columns 1 mole fraction of a component 2 absolute standard uncertainty of mole fraction of a component 3 a signal of a comparator 4 absolute standard uncertainty of a comparator signal
Chapter II ldquoResults of ISO 6143 methodrdquo contains parameters of a calibration curve including its
uncertainty
Chapter ІІІ ldquoPart II Processing of datardquo contains columns
1 calc x - the results of comparison mole fraction of a component 2 u(x) - absolute standard uncertainty of mole fraction of a component 3 response y - a signal of a comparator 4 u(y) - absolute standard uncertainty of a comparator signal
58
СО2 - measurement 1 Data setCO2_21 The calibration data set is 1302E+01 1510E-03 1022E+04 1820E+00 1370E+01 1560E-03 1077E+04 2730E+00 1445E+01 1620E-03 1135E+04 5900E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 20331E-02 12711E-03 12573E-01 11653E-05 -14638E-06 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 10548E-02 12722E-03 31762E-02 28898E-06 -91698E-08 Remaining SSD is 74346 Weighted distances x-value x-dist y-dist 100E+00 130E+01 490E-01 -755E-01 200E+00 137E+01 -103E+00 228E+00 300E+00 144E+01 539E-01 -250E-01 Goodness-of-fit measure 22837 Parameter set 1 1054788657490729E-2 1272208026684145E-3 3176237146276368E-2 2889798108124711E-6 -
9169821653851327E-8 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_21c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13577E+01 25542E-03 10664E+04 15200E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 547E-06 328E-06 316E-06 784E-06 286E-06 652E-06 Linear model Parameters for the fit were (b0 b1) 10548E-02 12722E-03
59
СО2 - measurement 2
Data setCO2_20 The calibration data set is 1302E+01 1512E-03 1021E+04 4723E+00 1370E+01 1563E-03 1075E+04 1600E+00 1445E+01 1620E-03 1133E+04 7300E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -38760E-02 12784E-03 26817E-02 24890E-06 -66689E-08 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -62452E-02 12805E-03 47930E-02 43243E-06 -20716E-07 Remaining SSD is 03231 Weighted distances x-value x-dist y-dist 100E+00 130E+01 107E-01 -415E-01 200E+00 137E+01 -212E-01 283E-01 300E+00 144E+01 104E-01 -584E-02 Goodness-of-fit measure 04155 Parameter set 1 -6245240430658412E-2 1280492624666799E-3 4792952200361109E-2 4324266278840409E-6 -
2071623966851869E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_20c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13594E+01 10290E-02 10665E+04 78300E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 121E-05 683E-06 651E-06 315E-05 560E-06 106E-04 Linear model Parameters for the fit were (b0 b1) -62452E-02 12805E-03
60
С3Н8 - measurement 1
Data setC3H8 The calibration data set is 1900E-01 7800E-05 9057E+03 1098E+01 2002E-01 7900E-05 9552E+03 8569E+00 2101E-01 7960E-05 1007E+04 4049E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10529E-02 19831E-05 34552E-03 36109E-07 -12465E-09 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11642E-02 19714E-05 23073E-03 23522E-07 -54231E-10 Remaining SSD is 19453 Weighted distances x-value x-dist y-dist 100E+00 190E-01 -239E-01 666E-01 200E+00 200E-01 487E-01 -104E+00 300E+00 210E-01 -247E-01 248E-01 Goodness-of-fit measure 10414 Parameter set 1 1164239985182795E-2 1971441115316992E-5 2307269625077337E-3 2352198415608386E-7 -
5423119774765299E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19837E-01 14840E-04 94718E+03 45610E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
23
b1 b0 u(b1) u(b0) u(b0b1) 1706 11086E-
03 -81128E-
0119491E-
0524883E-
01 -48497E-06 10544
2106 10729E-03
-26126E-01
22698E-05
28930E-01 -65652E-06 19997
2306
CO2 10593E-
03 -17688E-
0135807E-
0545413E-
01 -16254E-05 10022
1706 71537E-04
26507E-02
14231E-05
57044E-02 -81115E-07 03017
2106 72346E-04
22401E-02
13819E-05
54490E-02 -75209E-07 05935
2306
CO 71321E-
04 60080E-
0212663E-
0549016E-
02 -62026E-07 01341
1706 56521E-06
13712E-02
38279E-07
12015E-02 -45937E-09 12991
2106 56295E-06
13707E-02
39247E-07
12379E-02 -48529E-09 12905
2306
C3H8 58258E-
06 80469E-
0340085E-
0712590E-
02 -50407E-09 08589
Two columns separated by switching device are located one after another in TCD
channel One column is intended for carbon dioxide heavy hydrocarbons and another column is intended for light gases Before the first switch the light gases including carbon oxide flow through the first column without being separated and remain in the second column The switch makes them locked in the second column The analysis of carbon dioxide is carried out up to the second switch Second switch makes the second column unlocked and carbon oxide is analyzed Third switch is required to allow propane escape from a column and prevent it from getting into a second column The analysis of the very propane is carried out using FID Time intervals between switches were selected experimentally when developing the analysis method Such analysis method makes it possible to analyze all three components per one sample inject
Table 5 - Chromotograph operating conditions in calibration and analysis Parameter of the operating conditions Thermostating temperature of TCD and FID degС 170
Temperature of separation columns degС
Program 60 degС within 9 min
than rise to 160 degС at 20degСmin
Rate of flow of carrier gas through TCD channel columns mlmin 15
Rate of flow of carrier gas through TCD comparison channel mlmin 15
Pressure in FID channel column kPa Program
24
80 to 100 Rise from the 1st s of
analysis at 2 kPamin
Flow-rate of hydrogen FID mlmin 20 Flow-rate of air FID mlmin 200 Temperature of switching device degС 65 Response time of switching device s 1 110 2 330 3 540
TCD FID Volume of injected analyzed gas cm3 025 025 Carrier gas Helium Duration of analysis min 17 Calculation of the content of comparison sample components and its uncertainty Results of comparison sample measurements are given in Table 6 Table 6 - Results of comparison sample measurements
1 The content of comparison sample component and its uncertainty were determined
using calculated analytical function according to ISO 61432001 as follows (5) Where G(y)=b1y+b0 is the calculated analytical function и(y) is the standard uncertainty of response y u2(bj) is the variance of analytical function parameter bj
u(bj bI) is the covariance of analytical function parameters bj bI N is the number of function coefficients N=2 j=0 1
sum sumsumminus
= +==
partpart
partpart
+
partpart
+
partpart
=1
0 1
2
2
0
22
)(2)()()(N
jIj
N
jI Ijj
N
j j
bbubG
bGbu
bGyu
yGxu
25
After substitution of analytical function (2) and transformations the expression takes form (5)
)(2)()()()()( 01122
0222
1 bbyubuybuyubxu +++= (6) The contents of comparison sample components under determination and their
uncertainties were calculated using B_LEAST a computer program recommended in ISO 6143 Calculations are summarized in Table 6
Table 6 Calculations of the content of comparison sample components and their
2 The final content of a component was determined as an arithmetiс mean from three measurements Final standard uncertainty was calculated using formula as follows
22
222)( Адаватмтемсериикал uuuuuxu ++++= (7)
Where ucal is the uncertainty of the component content produced by
calibration of chromotograph urun is the uncertainty of the component content produced by
change of chromotograph response in each measurement run ut is the uncertainty of the component content produced by
change of an ambient temperature upressure is the uncertainty of the component content produced by
change of atmospheric pressure u A is the standard uncertainty of three measurement runs
21 Uncertainty of the component content produced by calibration of chromotograph
This uncertainty is calculated using formula (6) but the first term of the sum ie
)()( 221 yub which represents the standard uncertainty of the chromotograph response in a
measurement run is not taken into account Calculations are summarized in Table 7
26
Table 7 Calculation of uncertainty produced by calibration of chromotograph
Date u(b1) u(b0) u(b0b1) x
molmol y Ucal molmol
Ucal rel
1706 19491E-05
24883E-01
-48497E-06
13567middot10-
2129698
3 0005middot1
0-2 003
2106 22698E-05
28930E-01
-65652E-06
13564middot10-
2 128855 0007middot1
0-2 005
2306
CO2
35807E-05
45413E-01
-16254E-05
135374middot10-2
1294633
0016middot10-2 012
1706 14231E-05
57044E-02
-81115E-07 2957middot10-2 409633
0003middot10-2 009
2106 13819E-05
54490E-02
-75209E-07
29577middot10-
2 405663 0003middot1
0-2 01
2306
CO
12663E-05
49016E-02
-62026E-07 2955middot10-2 405882
0003middot10-2 01
1706 38279E-07
12015E-02
-45937E-09 1977middot10-4
3255817
007middot10-
2 038
2106 39247E-07
12379E-02
-48529E-09 1980middot10-4
3273329
008middot10-
2 038
2306
C3H8
40085E-07
12590E-02
-50407E-09 1982middot10-4 32636
008middot10-
2 04 The total estimate of relative uncertainty produced by calibration of chromotograph was
calculated for each component as follows
3
3
1
2sum=
cali
cali
uu (8)
Where ucal i is the relative uncertainty produced by calibration of chromotograph and calculated for each measurement run
The calculations are summarized in Table 8
Table 8 Uncertainty produced by calibration of chromotograph
Component Ucal rel
CO2 008 CO 01
C3H8 04 22 Uncertainty of the component content produced by change of chromotograph response in each measurement run This uncertainty is calculated using the equation (6) whereby the first term of the sum
only ie )()( 221 yub which represents the standard uncertainty of the chromotograph
response in a measurement run is taken into account Calculations are summarized in Table 9
27
Table 9 Calculation of uncertainty produced by change of chromotograph response in each measurement run
The total estimate of relative uncertainty produced by change of chromotograph
response in each measurement run was calculated for each component as follows
3
3
1
2sum=
run
run
uu (9)
Where urun is the relative uncertainty produced by change of chromotograph response in each measurement run Calculations are summarized in Table 10
Table 10 Uncertainty produced by change of chromotograph response in each measurement
run
Component Urun rel
CO2 007 CO 015
C3H8 012 23 Uncertainty of the component content produced by change of temperature in a room
The recorded change of temperature in measurements is plusmn 05 degree The contribution of uncertainty type B (rectangular distribution) is estimated as follows
201003
12931
=sdotsdot=tu rel
28
24 Uncertainty of the component content produced by change of atmospheric pressure The recorded change of atmospheric pressure within three days was
05 kPа The contribution of uncertainty type B (rectangular distribution) is estimated as follows
2801003
13101
50=sdotsdot=pressureu rel
25 Standard deviation of 3 measurement runs Standard deviation is calculated as follows
isu p
A
2
= (10)
Where S2p is the group experimental variation
The group experimental variation is calculated as follows
(11)
Where si
2 is the experimental variation of measurement run i from independent repeated observations ni having freedom degrees
νi = n - 1 n=6 i= 3 Calculations are summarized in Table 11 Table 11 Calculations of standard uncertainty of 3 measurement runs
Date 2iS x
molmol 2iS
rel uA
rel
1706 2953E-05 13567middot10-2 000022
2106 588987E-06 13564middot10-2 0000043
2306
CO2 141137E-
05 135374middot10
-2 000010
0006
1706 225604E-06 2957middot10-2 0000077
2106 681346E-06 29577middot10-2 000023
2306
CO
175166E-06 2955middot10-2 0000060
0006
1706 C3H8 130158E-
08 1977middot10-4 00000066 0001
ss
p
i ii
N
ii
N2
2
1
1
= =
=
sum
sum
ν
ν
29
2106 44616E-09 1980middot10-4 00000023
2306
381032E-09 1982middot10-4 00000019
26 Total standard uncertainty
Uncertainty estimation СО2
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph ucal Normal 008 1 008
Change of temperature ut Rectangular 02 1 02 Change of atmospheric pressure upressure Rectangular 028 1 028
Changes of chromotograph response
urun Normal 007 1 007
Standard deviation of 3 runs uA Normal 0006 1 0006
Relative total standard uncertainty 036 Coverage factor k=2 Expanded uncertainty 01middot10-2 molmol Uncertainty estimation СО
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph ucal Normal 01 1 01 Change of temperature ut Rectangular 02 1 02 Change of atmospheric pressure upressure Rectangular 028 1 028 Changes of chromotograph response
urun Normal 015 1 015
Standard deviation of 3 runs uA Normal 0006 1 0006
Relative total standard uncertainty 039 Coverage factor k=2 Expanded uncertainty 002middot10-2 molmol Uncertainty estimation С3Н8
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph 04 Normal 04 1 008
30
Change of temperature 02 Rectangular 02 1 02 Change of atmospheric pressure 028 Rectangular 028 1 028
Changes of chromotograph response
012 Normal 012 1 007
Standard deviation of 3 runs 0001 Normal 0001 1 0006
Relative total standard uncertainty 054 Coverage factor k=2 Expanded uncertainty 02middot10-4 molmol
Sample handling
Period for exposure of cylinder to measurement conditions and method how to transport sample to the device
1 Stands for storing gas standard cylinders and calibration mixture cylinders and chromotograph are placed in a laboratory room which is not accessible to unauthorized persons The laboratory is equipped with air-conditioner to maintain required temperature and humidity on a continuous basis and some auxiliary measuring instruments as thermometer psychrometric hygrometer and aneroid to control temperature humidity and atmospheric inside the room
2 The comparison sample cylinder was stored in laboratory from the date of its
delivery to Minsk on 25042005 CGM cylinders are stored horizontally on racks and positioned vertically using special support when measurements are carried out
3 The analyzed gas sample is transported through the fine adjustment valve (FAV)
Conjunctions Cylinder - FAV FAV - tube tube - doser are made of metal and use adapters with spherical ends and bushes FAV is made of brass tube is made of copper and doser is made of duralumin
Instrument(s) (principles make type configuration data collection etc) For the analysis a GC were used with specifically applications For the determination of (Nitrogen (N2)) Carbon Dioxide (CO2) Carbon Monoxide (CO) and Propane (C3H8) balance GC Perkin Elmer AutoSystem XL (two channel system) with a stream selection valve for 4 streams and 2 gas sampling valves
Channel A for the determination of N2 CO and CO2 Carrier Gas Helium Columns Column system with two packed columns (6 ft x 18rdquo Porapak R 80100 mesh and 6 ft x 18rdquo Mol-Sieve 13X 80100 mesh) Oven Temperature 960 degC to 180 degC Detector micro-TCD Data Collection Total Chrom Workstation Channel B for the determination of C3H8 Carrier Gas Helium Columns Capillary column 50 m x 032 microm LP-SIL-8-CB Oven Temperature 60 degC to 180 degC Detector FID Data Collection Total Chrom Workstation
34
Calibration Standards
Calibration Standards for the measurements (preparation method purity analyses estimated uncertainty etc)
All standards were prepared individually according to ISO 6142 rdquoGas analysis - Preparation of calibration gases - Gravimetric Methodrdquo
Depending on the concentration of the components standards were prepared individually from pure gases or from pre-mixtures which were individually prepared from pure gases
The content of the impurities in all pure gases were determined before use by GC-DID GC-FID and or GC-TCD
After preparation the standards were verified by analytical comparisons against existing gravimetrically prepared standards Only when no significant difference between the analysed and the calculated gravimetric composition is found the ldquonew prepared candidate rdquo is accepted as a new standards
For the analysis of all components multi component standards with nitrogen as balance gas were used
Composition of calibrants BAM C49250-050722 Component Assigned value( x)
mmol mol Standard uncertainty (u(x)) relativ (k=2)
Calibration procedure (mathematical modelcalibration curve number and concentrations of standards measurement sequence temperaturepressure correction etc)
For the instrument calibration the bracketing technique was used The fraction of the current used standards deviated no more than +10rel and -10rel respectively from those of the sample
Measurement sequence
Sample Handling
How were the cylinders treated after arrival (eg stabilized) and how were samples transferred to the instrument (automatic high pressure mass-flow controller dilution etc) After heating (45 - 50 degC) the cylinder for 8 hours the cylinder were rolled about 16 hours before analysis was started Each cylinder was equipped with a pressure regulator that was purged three times by sequential evacuation and pressurisation with the gas mixture used Continous flow (2 ndash 3mlmin) through the sample loop
Uncertainty The specification of potential uncertainty sources is given in Annex 3
3 injection standard (high)
3 injection sample
3 injection standard (high)
3 injection sample
3 injection standard (low)
3 injection sample
3 injection standard (low)
3 injection standard (low)
36
Uncertainty table CO2
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 002 rel 1 002 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 03 rel
Uncertainty table CO
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 007 rel 1 007 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 05 rel
37
Uncertainty table C3H8
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 010 rel 1 001 rel
Analysis normal 028 rel 1 028 rel
Coverage factor 2
Expanded uncertainty 06 rel
Optional
You may provide additional data like the raw measurement data information on your
measurement procedure chromatograms etc
38
Appendix 3 SPECIFICATION OF POTENTIAL UNCERTAINTY SOURCES
a Uncertainty related to the balance and the weights Resolution of balance Accuracy of balance including linearity Incorrect zero point Drift (thermal and time effects) Instability due to draught Location of cylinder on the balance pan Uncertainties in the weights used Buoyancy effects on the weights used
b Uncertainties related to the gas cylinder Mechanical handling of cylinder
Loss of metal paints or labels from surface of cylinder Loss of metal from threads of valvefitting Dirt on cylinder valves or associated fitting
Absorptiondesorption effects on the external cylinder surface Buoyancy effects on the cylinder itself
Cylinder temperature differs from surrounding air due to eg filling with gas Change of cylinder volume during filling Change of density of surrounding air due to changes in temperature air pressure humidity and carbon dioxide content
Uncertainty in determination of external cylinder volume c Uncertainties related to the component gases Residual gas in cylinder Leakage Leakage of air into the cylinder after evacuation
Leakage of gas from the cylinder valve during filling Escape of gas from cylinder into transport lines
Gas remaining in transfer system when weight loss method is used Absorptionreaction of components on internal cylinder surface Reaction between components Impurities in all the initial gases Insufficient homogenization Uncertainty of molecular mass d Uncertainties related to the analysis
Repeatability and selectivity of the analyzer Appropriateness of the calibration curve
39
MEASUREMENT REPORT - All Ukrainian State Research-Industrial Center of Standardization Metrology Certification and Protection of Consumers Ukraine
gas ndash helium flow rate 15 cm3min detector TCD tdetector = 250 ordmС toven = 70 ordmС It was automatic data collection
Measurement and Calibration Methods Laboratory Measurement method Type of calibration curve
GCFID (С3Н8) 3 points linear Ukrmetrteststandard GCTCD (СО СО2) 3 points linear
GCFID ndash gas-chromatographic with flame-ionization detector GCTCD - gas-chromatographic with thermal-conductivity detector
42
Calibration Standards
Calibration standards ndash primary standard gas mixtures (PSGM) used for measurements by comparison method
PSGM-1 Cylinder 0116
PSGM-2 Cylinder 0107
PSGM-3 Cylinder 0093 Composition
x u(x) x u(x) x u(x) СО 27874 00015 29899 00015 31891 00015 СО2 130187 00015 144456 00016 137016 00016 С3Н8 019003 000008 020017 000008 021013 000008 N2 balance balance balance
Note x ndash mole fraction u(x) ndash absolute standard uncertainty
It was used gravimetric method of preparation of PSGM Electronic balance КА-20-3 of Mettler Toledo max limit of weighing is 20 kg least
limit of weighing is 01 g standard deviation is 0006 g Analysis of purity of parent gases was carried out with usage of chromatographs
НР6890N with helium ndash ionization detector flame ndash ionization detector thermal ndash conductivity detector and mass ndash spectrometric detector as well аs gas analyzers GIAM-15M and Onix condensate-thermometer hygrometer TOROS-3-2B
Calculation of uncertainties was carried out according to ISO 6142-2003 Corrections of temperature pressure and humidity of environment were considered
in calculations according to ISO 6142-2003 (program of ISO-6142 2000-03-17 designer is NMi) Protocols and explanations are in Annex A
Instrument (Comparator) Calibration Calibration of comparator ndash gas chromatograph HP 6890 was carried out with usage
of PSGM Measurement sequence PSGM -1 х 3 PSGM -2 х 3 COOMET gas mixture х 3 PSGM -2 х 3 PSGM -3 х 3 It is necessary to use PSGM-2 repeatedly for estimation of reproducibility of results
Program B_LEAST recommended by ISO 6143-2003 was used for constructing the curve Mathematical model of calibration curve is linear one
Sample Handling The cylinder was kept for 24 hrs at a room where comparators were disposed This room is a thermostatic room with t = (20plusmn2) ordmС
43
A method of sample input to a comparator is a method with flow stabilization Uncertainty The following uncertainties were included to the budget of uncertainty - uncertainty of the balance - uncertainties of impurities in parent gases Contribution from other uncertainty sources was insignificant A cabin of the balance is thermostatically The balance is the one-pan balance
Air transfer is absent in the cabin of the balance Drift of the balance is absent for PSGM preparation
Contribution from other uncertainty sources was considered in software according to ISO 6142-2003
Uncertainties related to the analysis (comparison) were considered in software according to ISO 6143-2003 and enclosed in Annex B
Uncertainty table СО2
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas mixture
B 001 1 001
Analysis A B 008 1 008
Coverage factor 2 Expanded uncertainty 002sdot10-2 molmol Uncertainty table СО
Protocols of analysis (comparison) in accordance with ISO 6143-2003
57
Explanation of protocols of comparison
Chapter I ldquoThe calibration data set isrdquo contains columns 1 mole fraction of a component 2 absolute standard uncertainty of mole fraction of a component 3 a signal of a comparator 4 absolute standard uncertainty of a comparator signal
Chapter II ldquoResults of ISO 6143 methodrdquo contains parameters of a calibration curve including its
uncertainty
Chapter ІІІ ldquoPart II Processing of datardquo contains columns
1 calc x - the results of comparison mole fraction of a component 2 u(x) - absolute standard uncertainty of mole fraction of a component 3 response y - a signal of a comparator 4 u(y) - absolute standard uncertainty of a comparator signal
58
СО2 - measurement 1 Data setCO2_21 The calibration data set is 1302E+01 1510E-03 1022E+04 1820E+00 1370E+01 1560E-03 1077E+04 2730E+00 1445E+01 1620E-03 1135E+04 5900E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 20331E-02 12711E-03 12573E-01 11653E-05 -14638E-06 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 10548E-02 12722E-03 31762E-02 28898E-06 -91698E-08 Remaining SSD is 74346 Weighted distances x-value x-dist y-dist 100E+00 130E+01 490E-01 -755E-01 200E+00 137E+01 -103E+00 228E+00 300E+00 144E+01 539E-01 -250E-01 Goodness-of-fit measure 22837 Parameter set 1 1054788657490729E-2 1272208026684145E-3 3176237146276368E-2 2889798108124711E-6 -
9169821653851327E-8 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_21c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13577E+01 25542E-03 10664E+04 15200E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 547E-06 328E-06 316E-06 784E-06 286E-06 652E-06 Linear model Parameters for the fit were (b0 b1) 10548E-02 12722E-03
59
СО2 - measurement 2
Data setCO2_20 The calibration data set is 1302E+01 1512E-03 1021E+04 4723E+00 1370E+01 1563E-03 1075E+04 1600E+00 1445E+01 1620E-03 1133E+04 7300E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -38760E-02 12784E-03 26817E-02 24890E-06 -66689E-08 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -62452E-02 12805E-03 47930E-02 43243E-06 -20716E-07 Remaining SSD is 03231 Weighted distances x-value x-dist y-dist 100E+00 130E+01 107E-01 -415E-01 200E+00 137E+01 -212E-01 283E-01 300E+00 144E+01 104E-01 -584E-02 Goodness-of-fit measure 04155 Parameter set 1 -6245240430658412E-2 1280492624666799E-3 4792952200361109E-2 4324266278840409E-6 -
2071623966851869E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_20c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13594E+01 10290E-02 10665E+04 78300E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 121E-05 683E-06 651E-06 315E-05 560E-06 106E-04 Linear model Parameters for the fit were (b0 b1) -62452E-02 12805E-03
60
С3Н8 - measurement 1
Data setC3H8 The calibration data set is 1900E-01 7800E-05 9057E+03 1098E+01 2002E-01 7900E-05 9552E+03 8569E+00 2101E-01 7960E-05 1007E+04 4049E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10529E-02 19831E-05 34552E-03 36109E-07 -12465E-09 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11642E-02 19714E-05 23073E-03 23522E-07 -54231E-10 Remaining SSD is 19453 Weighted distances x-value x-dist y-dist 100E+00 190E-01 -239E-01 666E-01 200E+00 200E-01 487E-01 -104E+00 300E+00 210E-01 -247E-01 248E-01 Goodness-of-fit measure 10414 Parameter set 1 1164239985182795E-2 1971441115316992E-5 2307269625077337E-3 2352198415608386E-7 -
5423119774765299E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19837E-01 14840E-04 94718E+03 45610E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
24
80 to 100 Rise from the 1st s of
analysis at 2 kPamin
Flow-rate of hydrogen FID mlmin 20 Flow-rate of air FID mlmin 200 Temperature of switching device degС 65 Response time of switching device s 1 110 2 330 3 540
TCD FID Volume of injected analyzed gas cm3 025 025 Carrier gas Helium Duration of analysis min 17 Calculation of the content of comparison sample components and its uncertainty Results of comparison sample measurements are given in Table 6 Table 6 - Results of comparison sample measurements
1 The content of comparison sample component and its uncertainty were determined
using calculated analytical function according to ISO 61432001 as follows (5) Where G(y)=b1y+b0 is the calculated analytical function и(y) is the standard uncertainty of response y u2(bj) is the variance of analytical function parameter bj
u(bj bI) is the covariance of analytical function parameters bj bI N is the number of function coefficients N=2 j=0 1
sum sumsumminus
= +==
partpart
partpart
+
partpart
+
partpart
=1
0 1
2
2
0
22
)(2)()()(N
jIj
N
jI Ijj
N
j j
bbubG
bGbu
bGyu
yGxu
25
After substitution of analytical function (2) and transformations the expression takes form (5)
)(2)()()()()( 01122
0222
1 bbyubuybuyubxu +++= (6) The contents of comparison sample components under determination and their
uncertainties were calculated using B_LEAST a computer program recommended in ISO 6143 Calculations are summarized in Table 6
Table 6 Calculations of the content of comparison sample components and their
2 The final content of a component was determined as an arithmetiс mean from three measurements Final standard uncertainty was calculated using formula as follows
22
222)( Адаватмтемсериикал uuuuuxu ++++= (7)
Where ucal is the uncertainty of the component content produced by
calibration of chromotograph urun is the uncertainty of the component content produced by
change of chromotograph response in each measurement run ut is the uncertainty of the component content produced by
change of an ambient temperature upressure is the uncertainty of the component content produced by
change of atmospheric pressure u A is the standard uncertainty of three measurement runs
21 Uncertainty of the component content produced by calibration of chromotograph
This uncertainty is calculated using formula (6) but the first term of the sum ie
)()( 221 yub which represents the standard uncertainty of the chromotograph response in a
measurement run is not taken into account Calculations are summarized in Table 7
26
Table 7 Calculation of uncertainty produced by calibration of chromotograph
Date u(b1) u(b0) u(b0b1) x
molmol y Ucal molmol
Ucal rel
1706 19491E-05
24883E-01
-48497E-06
13567middot10-
2129698
3 0005middot1
0-2 003
2106 22698E-05
28930E-01
-65652E-06
13564middot10-
2 128855 0007middot1
0-2 005
2306
CO2
35807E-05
45413E-01
-16254E-05
135374middot10-2
1294633
0016middot10-2 012
1706 14231E-05
57044E-02
-81115E-07 2957middot10-2 409633
0003middot10-2 009
2106 13819E-05
54490E-02
-75209E-07
29577middot10-
2 405663 0003middot1
0-2 01
2306
CO
12663E-05
49016E-02
-62026E-07 2955middot10-2 405882
0003middot10-2 01
1706 38279E-07
12015E-02
-45937E-09 1977middot10-4
3255817
007middot10-
2 038
2106 39247E-07
12379E-02
-48529E-09 1980middot10-4
3273329
008middot10-
2 038
2306
C3H8
40085E-07
12590E-02
-50407E-09 1982middot10-4 32636
008middot10-
2 04 The total estimate of relative uncertainty produced by calibration of chromotograph was
calculated for each component as follows
3
3
1
2sum=
cali
cali
uu (8)
Where ucal i is the relative uncertainty produced by calibration of chromotograph and calculated for each measurement run
The calculations are summarized in Table 8
Table 8 Uncertainty produced by calibration of chromotograph
Component Ucal rel
CO2 008 CO 01
C3H8 04 22 Uncertainty of the component content produced by change of chromotograph response in each measurement run This uncertainty is calculated using the equation (6) whereby the first term of the sum
only ie )()( 221 yub which represents the standard uncertainty of the chromotograph
response in a measurement run is taken into account Calculations are summarized in Table 9
27
Table 9 Calculation of uncertainty produced by change of chromotograph response in each measurement run
The total estimate of relative uncertainty produced by change of chromotograph
response in each measurement run was calculated for each component as follows
3
3
1
2sum=
run
run
uu (9)
Where urun is the relative uncertainty produced by change of chromotograph response in each measurement run Calculations are summarized in Table 10
Table 10 Uncertainty produced by change of chromotograph response in each measurement
run
Component Urun rel
CO2 007 CO 015
C3H8 012 23 Uncertainty of the component content produced by change of temperature in a room
The recorded change of temperature in measurements is plusmn 05 degree The contribution of uncertainty type B (rectangular distribution) is estimated as follows
201003
12931
=sdotsdot=tu rel
28
24 Uncertainty of the component content produced by change of atmospheric pressure The recorded change of atmospheric pressure within three days was
05 kPа The contribution of uncertainty type B (rectangular distribution) is estimated as follows
2801003
13101
50=sdotsdot=pressureu rel
25 Standard deviation of 3 measurement runs Standard deviation is calculated as follows
isu p
A
2
= (10)
Where S2p is the group experimental variation
The group experimental variation is calculated as follows
(11)
Where si
2 is the experimental variation of measurement run i from independent repeated observations ni having freedom degrees
νi = n - 1 n=6 i= 3 Calculations are summarized in Table 11 Table 11 Calculations of standard uncertainty of 3 measurement runs
Date 2iS x
molmol 2iS
rel uA
rel
1706 2953E-05 13567middot10-2 000022
2106 588987E-06 13564middot10-2 0000043
2306
CO2 141137E-
05 135374middot10
-2 000010
0006
1706 225604E-06 2957middot10-2 0000077
2106 681346E-06 29577middot10-2 000023
2306
CO
175166E-06 2955middot10-2 0000060
0006
1706 C3H8 130158E-
08 1977middot10-4 00000066 0001
ss
p
i ii
N
ii
N2
2
1
1
= =
=
sum
sum
ν
ν
29
2106 44616E-09 1980middot10-4 00000023
2306
381032E-09 1982middot10-4 00000019
26 Total standard uncertainty
Uncertainty estimation СО2
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph ucal Normal 008 1 008
Change of temperature ut Rectangular 02 1 02 Change of atmospheric pressure upressure Rectangular 028 1 028
Changes of chromotograph response
urun Normal 007 1 007
Standard deviation of 3 runs uA Normal 0006 1 0006
Relative total standard uncertainty 036 Coverage factor k=2 Expanded uncertainty 01middot10-2 molmol Uncertainty estimation СО
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph ucal Normal 01 1 01 Change of temperature ut Rectangular 02 1 02 Change of atmospheric pressure upressure Rectangular 028 1 028 Changes of chromotograph response
urun Normal 015 1 015
Standard deviation of 3 runs uA Normal 0006 1 0006
Relative total standard uncertainty 039 Coverage factor k=2 Expanded uncertainty 002middot10-2 molmol Uncertainty estimation С3Н8
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph 04 Normal 04 1 008
30
Change of temperature 02 Rectangular 02 1 02 Change of atmospheric pressure 028 Rectangular 028 1 028
Changes of chromotograph response
012 Normal 012 1 007
Standard deviation of 3 runs 0001 Normal 0001 1 0006
Relative total standard uncertainty 054 Coverage factor k=2 Expanded uncertainty 02middot10-4 molmol
Sample handling
Period for exposure of cylinder to measurement conditions and method how to transport sample to the device
1 Stands for storing gas standard cylinders and calibration mixture cylinders and chromotograph are placed in a laboratory room which is not accessible to unauthorized persons The laboratory is equipped with air-conditioner to maintain required temperature and humidity on a continuous basis and some auxiliary measuring instruments as thermometer psychrometric hygrometer and aneroid to control temperature humidity and atmospheric inside the room
2 The comparison sample cylinder was stored in laboratory from the date of its
delivery to Minsk on 25042005 CGM cylinders are stored horizontally on racks and positioned vertically using special support when measurements are carried out
3 The analyzed gas sample is transported through the fine adjustment valve (FAV)
Conjunctions Cylinder - FAV FAV - tube tube - doser are made of metal and use adapters with spherical ends and bushes FAV is made of brass tube is made of copper and doser is made of duralumin
Instrument(s) (principles make type configuration data collection etc) For the analysis a GC were used with specifically applications For the determination of (Nitrogen (N2)) Carbon Dioxide (CO2) Carbon Monoxide (CO) and Propane (C3H8) balance GC Perkin Elmer AutoSystem XL (two channel system) with a stream selection valve for 4 streams and 2 gas sampling valves
Channel A for the determination of N2 CO and CO2 Carrier Gas Helium Columns Column system with two packed columns (6 ft x 18rdquo Porapak R 80100 mesh and 6 ft x 18rdquo Mol-Sieve 13X 80100 mesh) Oven Temperature 960 degC to 180 degC Detector micro-TCD Data Collection Total Chrom Workstation Channel B for the determination of C3H8 Carrier Gas Helium Columns Capillary column 50 m x 032 microm LP-SIL-8-CB Oven Temperature 60 degC to 180 degC Detector FID Data Collection Total Chrom Workstation
34
Calibration Standards
Calibration Standards for the measurements (preparation method purity analyses estimated uncertainty etc)
All standards were prepared individually according to ISO 6142 rdquoGas analysis - Preparation of calibration gases - Gravimetric Methodrdquo
Depending on the concentration of the components standards were prepared individually from pure gases or from pre-mixtures which were individually prepared from pure gases
The content of the impurities in all pure gases were determined before use by GC-DID GC-FID and or GC-TCD
After preparation the standards were verified by analytical comparisons against existing gravimetrically prepared standards Only when no significant difference between the analysed and the calculated gravimetric composition is found the ldquonew prepared candidate rdquo is accepted as a new standards
For the analysis of all components multi component standards with nitrogen as balance gas were used
Composition of calibrants BAM C49250-050722 Component Assigned value( x)
mmol mol Standard uncertainty (u(x)) relativ (k=2)
Calibration procedure (mathematical modelcalibration curve number and concentrations of standards measurement sequence temperaturepressure correction etc)
For the instrument calibration the bracketing technique was used The fraction of the current used standards deviated no more than +10rel and -10rel respectively from those of the sample
Measurement sequence
Sample Handling
How were the cylinders treated after arrival (eg stabilized) and how were samples transferred to the instrument (automatic high pressure mass-flow controller dilution etc) After heating (45 - 50 degC) the cylinder for 8 hours the cylinder were rolled about 16 hours before analysis was started Each cylinder was equipped with a pressure regulator that was purged three times by sequential evacuation and pressurisation with the gas mixture used Continous flow (2 ndash 3mlmin) through the sample loop
Uncertainty The specification of potential uncertainty sources is given in Annex 3
3 injection standard (high)
3 injection sample
3 injection standard (high)
3 injection sample
3 injection standard (low)
3 injection sample
3 injection standard (low)
3 injection standard (low)
36
Uncertainty table CO2
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 002 rel 1 002 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 03 rel
Uncertainty table CO
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 007 rel 1 007 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 05 rel
37
Uncertainty table C3H8
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 010 rel 1 001 rel
Analysis normal 028 rel 1 028 rel
Coverage factor 2
Expanded uncertainty 06 rel
Optional
You may provide additional data like the raw measurement data information on your
measurement procedure chromatograms etc
38
Appendix 3 SPECIFICATION OF POTENTIAL UNCERTAINTY SOURCES
a Uncertainty related to the balance and the weights Resolution of balance Accuracy of balance including linearity Incorrect zero point Drift (thermal and time effects) Instability due to draught Location of cylinder on the balance pan Uncertainties in the weights used Buoyancy effects on the weights used
b Uncertainties related to the gas cylinder Mechanical handling of cylinder
Loss of metal paints or labels from surface of cylinder Loss of metal from threads of valvefitting Dirt on cylinder valves or associated fitting
Absorptiondesorption effects on the external cylinder surface Buoyancy effects on the cylinder itself
Cylinder temperature differs from surrounding air due to eg filling with gas Change of cylinder volume during filling Change of density of surrounding air due to changes in temperature air pressure humidity and carbon dioxide content
Uncertainty in determination of external cylinder volume c Uncertainties related to the component gases Residual gas in cylinder Leakage Leakage of air into the cylinder after evacuation
Leakage of gas from the cylinder valve during filling Escape of gas from cylinder into transport lines
Gas remaining in transfer system when weight loss method is used Absorptionreaction of components on internal cylinder surface Reaction between components Impurities in all the initial gases Insufficient homogenization Uncertainty of molecular mass d Uncertainties related to the analysis
Repeatability and selectivity of the analyzer Appropriateness of the calibration curve
39
MEASUREMENT REPORT - All Ukrainian State Research-Industrial Center of Standardization Metrology Certification and Protection of Consumers Ukraine
gas ndash helium flow rate 15 cm3min detector TCD tdetector = 250 ordmС toven = 70 ordmС It was automatic data collection
Measurement and Calibration Methods Laboratory Measurement method Type of calibration curve
GCFID (С3Н8) 3 points linear Ukrmetrteststandard GCTCD (СО СО2) 3 points linear
GCFID ndash gas-chromatographic with flame-ionization detector GCTCD - gas-chromatographic with thermal-conductivity detector
42
Calibration Standards
Calibration standards ndash primary standard gas mixtures (PSGM) used for measurements by comparison method
PSGM-1 Cylinder 0116
PSGM-2 Cylinder 0107
PSGM-3 Cylinder 0093 Composition
x u(x) x u(x) x u(x) СО 27874 00015 29899 00015 31891 00015 СО2 130187 00015 144456 00016 137016 00016 С3Н8 019003 000008 020017 000008 021013 000008 N2 balance balance balance
Note x ndash mole fraction u(x) ndash absolute standard uncertainty
It was used gravimetric method of preparation of PSGM Electronic balance КА-20-3 of Mettler Toledo max limit of weighing is 20 kg least
limit of weighing is 01 g standard deviation is 0006 g Analysis of purity of parent gases was carried out with usage of chromatographs
НР6890N with helium ndash ionization detector flame ndash ionization detector thermal ndash conductivity detector and mass ndash spectrometric detector as well аs gas analyzers GIAM-15M and Onix condensate-thermometer hygrometer TOROS-3-2B
Calculation of uncertainties was carried out according to ISO 6142-2003 Corrections of temperature pressure and humidity of environment were considered
in calculations according to ISO 6142-2003 (program of ISO-6142 2000-03-17 designer is NMi) Protocols and explanations are in Annex A
Instrument (Comparator) Calibration Calibration of comparator ndash gas chromatograph HP 6890 was carried out with usage
of PSGM Measurement sequence PSGM -1 х 3 PSGM -2 х 3 COOMET gas mixture х 3 PSGM -2 х 3 PSGM -3 х 3 It is necessary to use PSGM-2 repeatedly for estimation of reproducibility of results
Program B_LEAST recommended by ISO 6143-2003 was used for constructing the curve Mathematical model of calibration curve is linear one
Sample Handling The cylinder was kept for 24 hrs at a room where comparators were disposed This room is a thermostatic room with t = (20plusmn2) ordmС
43
A method of sample input to a comparator is a method with flow stabilization Uncertainty The following uncertainties were included to the budget of uncertainty - uncertainty of the balance - uncertainties of impurities in parent gases Contribution from other uncertainty sources was insignificant A cabin of the balance is thermostatically The balance is the one-pan balance
Air transfer is absent in the cabin of the balance Drift of the balance is absent for PSGM preparation
Contribution from other uncertainty sources was considered in software according to ISO 6142-2003
Uncertainties related to the analysis (comparison) were considered in software according to ISO 6143-2003 and enclosed in Annex B
Uncertainty table СО2
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas mixture
B 001 1 001
Analysis A B 008 1 008
Coverage factor 2 Expanded uncertainty 002sdot10-2 molmol Uncertainty table СО
Protocols of analysis (comparison) in accordance with ISO 6143-2003
57
Explanation of protocols of comparison
Chapter I ldquoThe calibration data set isrdquo contains columns 1 mole fraction of a component 2 absolute standard uncertainty of mole fraction of a component 3 a signal of a comparator 4 absolute standard uncertainty of a comparator signal
Chapter II ldquoResults of ISO 6143 methodrdquo contains parameters of a calibration curve including its
uncertainty
Chapter ІІІ ldquoPart II Processing of datardquo contains columns
1 calc x - the results of comparison mole fraction of a component 2 u(x) - absolute standard uncertainty of mole fraction of a component 3 response y - a signal of a comparator 4 u(y) - absolute standard uncertainty of a comparator signal
58
СО2 - measurement 1 Data setCO2_21 The calibration data set is 1302E+01 1510E-03 1022E+04 1820E+00 1370E+01 1560E-03 1077E+04 2730E+00 1445E+01 1620E-03 1135E+04 5900E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 20331E-02 12711E-03 12573E-01 11653E-05 -14638E-06 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 10548E-02 12722E-03 31762E-02 28898E-06 -91698E-08 Remaining SSD is 74346 Weighted distances x-value x-dist y-dist 100E+00 130E+01 490E-01 -755E-01 200E+00 137E+01 -103E+00 228E+00 300E+00 144E+01 539E-01 -250E-01 Goodness-of-fit measure 22837 Parameter set 1 1054788657490729E-2 1272208026684145E-3 3176237146276368E-2 2889798108124711E-6 -
9169821653851327E-8 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_21c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13577E+01 25542E-03 10664E+04 15200E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 547E-06 328E-06 316E-06 784E-06 286E-06 652E-06 Linear model Parameters for the fit were (b0 b1) 10548E-02 12722E-03
59
СО2 - measurement 2
Data setCO2_20 The calibration data set is 1302E+01 1512E-03 1021E+04 4723E+00 1370E+01 1563E-03 1075E+04 1600E+00 1445E+01 1620E-03 1133E+04 7300E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -38760E-02 12784E-03 26817E-02 24890E-06 -66689E-08 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -62452E-02 12805E-03 47930E-02 43243E-06 -20716E-07 Remaining SSD is 03231 Weighted distances x-value x-dist y-dist 100E+00 130E+01 107E-01 -415E-01 200E+00 137E+01 -212E-01 283E-01 300E+00 144E+01 104E-01 -584E-02 Goodness-of-fit measure 04155 Parameter set 1 -6245240430658412E-2 1280492624666799E-3 4792952200361109E-2 4324266278840409E-6 -
2071623966851869E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_20c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13594E+01 10290E-02 10665E+04 78300E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 121E-05 683E-06 651E-06 315E-05 560E-06 106E-04 Linear model Parameters for the fit were (b0 b1) -62452E-02 12805E-03
60
С3Н8 - measurement 1
Data setC3H8 The calibration data set is 1900E-01 7800E-05 9057E+03 1098E+01 2002E-01 7900E-05 9552E+03 8569E+00 2101E-01 7960E-05 1007E+04 4049E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10529E-02 19831E-05 34552E-03 36109E-07 -12465E-09 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11642E-02 19714E-05 23073E-03 23522E-07 -54231E-10 Remaining SSD is 19453 Weighted distances x-value x-dist y-dist 100E+00 190E-01 -239E-01 666E-01 200E+00 200E-01 487E-01 -104E+00 300E+00 210E-01 -247E-01 248E-01 Goodness-of-fit measure 10414 Parameter set 1 1164239985182795E-2 1971441115316992E-5 2307269625077337E-3 2352198415608386E-7 -
5423119774765299E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19837E-01 14840E-04 94718E+03 45610E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
25
After substitution of analytical function (2) and transformations the expression takes form (5)
)(2)()()()()( 01122
0222
1 bbyubuybuyubxu +++= (6) The contents of comparison sample components under determination and their
uncertainties were calculated using B_LEAST a computer program recommended in ISO 6143 Calculations are summarized in Table 6
Table 6 Calculations of the content of comparison sample components and their
2 The final content of a component was determined as an arithmetiс mean from three measurements Final standard uncertainty was calculated using formula as follows
22
222)( Адаватмтемсериикал uuuuuxu ++++= (7)
Where ucal is the uncertainty of the component content produced by
calibration of chromotograph urun is the uncertainty of the component content produced by
change of chromotograph response in each measurement run ut is the uncertainty of the component content produced by
change of an ambient temperature upressure is the uncertainty of the component content produced by
change of atmospheric pressure u A is the standard uncertainty of three measurement runs
21 Uncertainty of the component content produced by calibration of chromotograph
This uncertainty is calculated using formula (6) but the first term of the sum ie
)()( 221 yub which represents the standard uncertainty of the chromotograph response in a
measurement run is not taken into account Calculations are summarized in Table 7
26
Table 7 Calculation of uncertainty produced by calibration of chromotograph
Date u(b1) u(b0) u(b0b1) x
molmol y Ucal molmol
Ucal rel
1706 19491E-05
24883E-01
-48497E-06
13567middot10-
2129698
3 0005middot1
0-2 003
2106 22698E-05
28930E-01
-65652E-06
13564middot10-
2 128855 0007middot1
0-2 005
2306
CO2
35807E-05
45413E-01
-16254E-05
135374middot10-2
1294633
0016middot10-2 012
1706 14231E-05
57044E-02
-81115E-07 2957middot10-2 409633
0003middot10-2 009
2106 13819E-05
54490E-02
-75209E-07
29577middot10-
2 405663 0003middot1
0-2 01
2306
CO
12663E-05
49016E-02
-62026E-07 2955middot10-2 405882
0003middot10-2 01
1706 38279E-07
12015E-02
-45937E-09 1977middot10-4
3255817
007middot10-
2 038
2106 39247E-07
12379E-02
-48529E-09 1980middot10-4
3273329
008middot10-
2 038
2306
C3H8
40085E-07
12590E-02
-50407E-09 1982middot10-4 32636
008middot10-
2 04 The total estimate of relative uncertainty produced by calibration of chromotograph was
calculated for each component as follows
3
3
1
2sum=
cali
cali
uu (8)
Where ucal i is the relative uncertainty produced by calibration of chromotograph and calculated for each measurement run
The calculations are summarized in Table 8
Table 8 Uncertainty produced by calibration of chromotograph
Component Ucal rel
CO2 008 CO 01
C3H8 04 22 Uncertainty of the component content produced by change of chromotograph response in each measurement run This uncertainty is calculated using the equation (6) whereby the first term of the sum
only ie )()( 221 yub which represents the standard uncertainty of the chromotograph
response in a measurement run is taken into account Calculations are summarized in Table 9
27
Table 9 Calculation of uncertainty produced by change of chromotograph response in each measurement run
The total estimate of relative uncertainty produced by change of chromotograph
response in each measurement run was calculated for each component as follows
3
3
1
2sum=
run
run
uu (9)
Where urun is the relative uncertainty produced by change of chromotograph response in each measurement run Calculations are summarized in Table 10
Table 10 Uncertainty produced by change of chromotograph response in each measurement
run
Component Urun rel
CO2 007 CO 015
C3H8 012 23 Uncertainty of the component content produced by change of temperature in a room
The recorded change of temperature in measurements is plusmn 05 degree The contribution of uncertainty type B (rectangular distribution) is estimated as follows
201003
12931
=sdotsdot=tu rel
28
24 Uncertainty of the component content produced by change of atmospheric pressure The recorded change of atmospheric pressure within three days was
05 kPа The contribution of uncertainty type B (rectangular distribution) is estimated as follows
2801003
13101
50=sdotsdot=pressureu rel
25 Standard deviation of 3 measurement runs Standard deviation is calculated as follows
isu p
A
2
= (10)
Where S2p is the group experimental variation
The group experimental variation is calculated as follows
(11)
Where si
2 is the experimental variation of measurement run i from independent repeated observations ni having freedom degrees
νi = n - 1 n=6 i= 3 Calculations are summarized in Table 11 Table 11 Calculations of standard uncertainty of 3 measurement runs
Date 2iS x
molmol 2iS
rel uA
rel
1706 2953E-05 13567middot10-2 000022
2106 588987E-06 13564middot10-2 0000043
2306
CO2 141137E-
05 135374middot10
-2 000010
0006
1706 225604E-06 2957middot10-2 0000077
2106 681346E-06 29577middot10-2 000023
2306
CO
175166E-06 2955middot10-2 0000060
0006
1706 C3H8 130158E-
08 1977middot10-4 00000066 0001
ss
p
i ii
N
ii
N2
2
1
1
= =
=
sum
sum
ν
ν
29
2106 44616E-09 1980middot10-4 00000023
2306
381032E-09 1982middot10-4 00000019
26 Total standard uncertainty
Uncertainty estimation СО2
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph ucal Normal 008 1 008
Change of temperature ut Rectangular 02 1 02 Change of atmospheric pressure upressure Rectangular 028 1 028
Changes of chromotograph response
urun Normal 007 1 007
Standard deviation of 3 runs uA Normal 0006 1 0006
Relative total standard uncertainty 036 Coverage factor k=2 Expanded uncertainty 01middot10-2 molmol Uncertainty estimation СО
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph ucal Normal 01 1 01 Change of temperature ut Rectangular 02 1 02 Change of atmospheric pressure upressure Rectangular 028 1 028 Changes of chromotograph response
urun Normal 015 1 015
Standard deviation of 3 runs uA Normal 0006 1 0006
Relative total standard uncertainty 039 Coverage factor k=2 Expanded uncertainty 002middot10-2 molmol Uncertainty estimation С3Н8
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph 04 Normal 04 1 008
30
Change of temperature 02 Rectangular 02 1 02 Change of atmospheric pressure 028 Rectangular 028 1 028
Changes of chromotograph response
012 Normal 012 1 007
Standard deviation of 3 runs 0001 Normal 0001 1 0006
Relative total standard uncertainty 054 Coverage factor k=2 Expanded uncertainty 02middot10-4 molmol
Sample handling
Period for exposure of cylinder to measurement conditions and method how to transport sample to the device
1 Stands for storing gas standard cylinders and calibration mixture cylinders and chromotograph are placed in a laboratory room which is not accessible to unauthorized persons The laboratory is equipped with air-conditioner to maintain required temperature and humidity on a continuous basis and some auxiliary measuring instruments as thermometer psychrometric hygrometer and aneroid to control temperature humidity and atmospheric inside the room
2 The comparison sample cylinder was stored in laboratory from the date of its
delivery to Minsk on 25042005 CGM cylinders are stored horizontally on racks and positioned vertically using special support when measurements are carried out
3 The analyzed gas sample is transported through the fine adjustment valve (FAV)
Conjunctions Cylinder - FAV FAV - tube tube - doser are made of metal and use adapters with spherical ends and bushes FAV is made of brass tube is made of copper and doser is made of duralumin
Instrument(s) (principles make type configuration data collection etc) For the analysis a GC were used with specifically applications For the determination of (Nitrogen (N2)) Carbon Dioxide (CO2) Carbon Monoxide (CO) and Propane (C3H8) balance GC Perkin Elmer AutoSystem XL (two channel system) with a stream selection valve for 4 streams and 2 gas sampling valves
Channel A for the determination of N2 CO and CO2 Carrier Gas Helium Columns Column system with two packed columns (6 ft x 18rdquo Porapak R 80100 mesh and 6 ft x 18rdquo Mol-Sieve 13X 80100 mesh) Oven Temperature 960 degC to 180 degC Detector micro-TCD Data Collection Total Chrom Workstation Channel B for the determination of C3H8 Carrier Gas Helium Columns Capillary column 50 m x 032 microm LP-SIL-8-CB Oven Temperature 60 degC to 180 degC Detector FID Data Collection Total Chrom Workstation
34
Calibration Standards
Calibration Standards for the measurements (preparation method purity analyses estimated uncertainty etc)
All standards were prepared individually according to ISO 6142 rdquoGas analysis - Preparation of calibration gases - Gravimetric Methodrdquo
Depending on the concentration of the components standards were prepared individually from pure gases or from pre-mixtures which were individually prepared from pure gases
The content of the impurities in all pure gases were determined before use by GC-DID GC-FID and or GC-TCD
After preparation the standards were verified by analytical comparisons against existing gravimetrically prepared standards Only when no significant difference between the analysed and the calculated gravimetric composition is found the ldquonew prepared candidate rdquo is accepted as a new standards
For the analysis of all components multi component standards with nitrogen as balance gas were used
Composition of calibrants BAM C49250-050722 Component Assigned value( x)
mmol mol Standard uncertainty (u(x)) relativ (k=2)
Calibration procedure (mathematical modelcalibration curve number and concentrations of standards measurement sequence temperaturepressure correction etc)
For the instrument calibration the bracketing technique was used The fraction of the current used standards deviated no more than +10rel and -10rel respectively from those of the sample
Measurement sequence
Sample Handling
How were the cylinders treated after arrival (eg stabilized) and how were samples transferred to the instrument (automatic high pressure mass-flow controller dilution etc) After heating (45 - 50 degC) the cylinder for 8 hours the cylinder were rolled about 16 hours before analysis was started Each cylinder was equipped with a pressure regulator that was purged three times by sequential evacuation and pressurisation with the gas mixture used Continous flow (2 ndash 3mlmin) through the sample loop
Uncertainty The specification of potential uncertainty sources is given in Annex 3
3 injection standard (high)
3 injection sample
3 injection standard (high)
3 injection sample
3 injection standard (low)
3 injection sample
3 injection standard (low)
3 injection standard (low)
36
Uncertainty table CO2
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 002 rel 1 002 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 03 rel
Uncertainty table CO
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 007 rel 1 007 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 05 rel
37
Uncertainty table C3H8
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 010 rel 1 001 rel
Analysis normal 028 rel 1 028 rel
Coverage factor 2
Expanded uncertainty 06 rel
Optional
You may provide additional data like the raw measurement data information on your
measurement procedure chromatograms etc
38
Appendix 3 SPECIFICATION OF POTENTIAL UNCERTAINTY SOURCES
a Uncertainty related to the balance and the weights Resolution of balance Accuracy of balance including linearity Incorrect zero point Drift (thermal and time effects) Instability due to draught Location of cylinder on the balance pan Uncertainties in the weights used Buoyancy effects on the weights used
b Uncertainties related to the gas cylinder Mechanical handling of cylinder
Loss of metal paints or labels from surface of cylinder Loss of metal from threads of valvefitting Dirt on cylinder valves or associated fitting
Absorptiondesorption effects on the external cylinder surface Buoyancy effects on the cylinder itself
Cylinder temperature differs from surrounding air due to eg filling with gas Change of cylinder volume during filling Change of density of surrounding air due to changes in temperature air pressure humidity and carbon dioxide content
Uncertainty in determination of external cylinder volume c Uncertainties related to the component gases Residual gas in cylinder Leakage Leakage of air into the cylinder after evacuation
Leakage of gas from the cylinder valve during filling Escape of gas from cylinder into transport lines
Gas remaining in transfer system when weight loss method is used Absorptionreaction of components on internal cylinder surface Reaction between components Impurities in all the initial gases Insufficient homogenization Uncertainty of molecular mass d Uncertainties related to the analysis
Repeatability and selectivity of the analyzer Appropriateness of the calibration curve
39
MEASUREMENT REPORT - All Ukrainian State Research-Industrial Center of Standardization Metrology Certification and Protection of Consumers Ukraine
gas ndash helium flow rate 15 cm3min detector TCD tdetector = 250 ordmС toven = 70 ordmС It was automatic data collection
Measurement and Calibration Methods Laboratory Measurement method Type of calibration curve
GCFID (С3Н8) 3 points linear Ukrmetrteststandard GCTCD (СО СО2) 3 points linear
GCFID ndash gas-chromatographic with flame-ionization detector GCTCD - gas-chromatographic with thermal-conductivity detector
42
Calibration Standards
Calibration standards ndash primary standard gas mixtures (PSGM) used for measurements by comparison method
PSGM-1 Cylinder 0116
PSGM-2 Cylinder 0107
PSGM-3 Cylinder 0093 Composition
x u(x) x u(x) x u(x) СО 27874 00015 29899 00015 31891 00015 СО2 130187 00015 144456 00016 137016 00016 С3Н8 019003 000008 020017 000008 021013 000008 N2 balance balance balance
Note x ndash mole fraction u(x) ndash absolute standard uncertainty
It was used gravimetric method of preparation of PSGM Electronic balance КА-20-3 of Mettler Toledo max limit of weighing is 20 kg least
limit of weighing is 01 g standard deviation is 0006 g Analysis of purity of parent gases was carried out with usage of chromatographs
НР6890N with helium ndash ionization detector flame ndash ionization detector thermal ndash conductivity detector and mass ndash spectrometric detector as well аs gas analyzers GIAM-15M and Onix condensate-thermometer hygrometer TOROS-3-2B
Calculation of uncertainties was carried out according to ISO 6142-2003 Corrections of temperature pressure and humidity of environment were considered
in calculations according to ISO 6142-2003 (program of ISO-6142 2000-03-17 designer is NMi) Protocols and explanations are in Annex A
Instrument (Comparator) Calibration Calibration of comparator ndash gas chromatograph HP 6890 was carried out with usage
of PSGM Measurement sequence PSGM -1 х 3 PSGM -2 х 3 COOMET gas mixture х 3 PSGM -2 х 3 PSGM -3 х 3 It is necessary to use PSGM-2 repeatedly for estimation of reproducibility of results
Program B_LEAST recommended by ISO 6143-2003 was used for constructing the curve Mathematical model of calibration curve is linear one
Sample Handling The cylinder was kept for 24 hrs at a room where comparators were disposed This room is a thermostatic room with t = (20plusmn2) ordmС
43
A method of sample input to a comparator is a method with flow stabilization Uncertainty The following uncertainties were included to the budget of uncertainty - uncertainty of the balance - uncertainties of impurities in parent gases Contribution from other uncertainty sources was insignificant A cabin of the balance is thermostatically The balance is the one-pan balance
Air transfer is absent in the cabin of the balance Drift of the balance is absent for PSGM preparation
Contribution from other uncertainty sources was considered in software according to ISO 6142-2003
Uncertainties related to the analysis (comparison) were considered in software according to ISO 6143-2003 and enclosed in Annex B
Uncertainty table СО2
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas mixture
B 001 1 001
Analysis A B 008 1 008
Coverage factor 2 Expanded uncertainty 002sdot10-2 molmol Uncertainty table СО
Protocols of analysis (comparison) in accordance with ISO 6143-2003
57
Explanation of protocols of comparison
Chapter I ldquoThe calibration data set isrdquo contains columns 1 mole fraction of a component 2 absolute standard uncertainty of mole fraction of a component 3 a signal of a comparator 4 absolute standard uncertainty of a comparator signal
Chapter II ldquoResults of ISO 6143 methodrdquo contains parameters of a calibration curve including its
uncertainty
Chapter ІІІ ldquoPart II Processing of datardquo contains columns
1 calc x - the results of comparison mole fraction of a component 2 u(x) - absolute standard uncertainty of mole fraction of a component 3 response y - a signal of a comparator 4 u(y) - absolute standard uncertainty of a comparator signal
58
СО2 - measurement 1 Data setCO2_21 The calibration data set is 1302E+01 1510E-03 1022E+04 1820E+00 1370E+01 1560E-03 1077E+04 2730E+00 1445E+01 1620E-03 1135E+04 5900E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 20331E-02 12711E-03 12573E-01 11653E-05 -14638E-06 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 10548E-02 12722E-03 31762E-02 28898E-06 -91698E-08 Remaining SSD is 74346 Weighted distances x-value x-dist y-dist 100E+00 130E+01 490E-01 -755E-01 200E+00 137E+01 -103E+00 228E+00 300E+00 144E+01 539E-01 -250E-01 Goodness-of-fit measure 22837 Parameter set 1 1054788657490729E-2 1272208026684145E-3 3176237146276368E-2 2889798108124711E-6 -
9169821653851327E-8 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_21c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13577E+01 25542E-03 10664E+04 15200E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 547E-06 328E-06 316E-06 784E-06 286E-06 652E-06 Linear model Parameters for the fit were (b0 b1) 10548E-02 12722E-03
59
СО2 - measurement 2
Data setCO2_20 The calibration data set is 1302E+01 1512E-03 1021E+04 4723E+00 1370E+01 1563E-03 1075E+04 1600E+00 1445E+01 1620E-03 1133E+04 7300E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -38760E-02 12784E-03 26817E-02 24890E-06 -66689E-08 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -62452E-02 12805E-03 47930E-02 43243E-06 -20716E-07 Remaining SSD is 03231 Weighted distances x-value x-dist y-dist 100E+00 130E+01 107E-01 -415E-01 200E+00 137E+01 -212E-01 283E-01 300E+00 144E+01 104E-01 -584E-02 Goodness-of-fit measure 04155 Parameter set 1 -6245240430658412E-2 1280492624666799E-3 4792952200361109E-2 4324266278840409E-6 -
2071623966851869E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_20c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13594E+01 10290E-02 10665E+04 78300E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 121E-05 683E-06 651E-06 315E-05 560E-06 106E-04 Linear model Parameters for the fit were (b0 b1) -62452E-02 12805E-03
60
С3Н8 - measurement 1
Data setC3H8 The calibration data set is 1900E-01 7800E-05 9057E+03 1098E+01 2002E-01 7900E-05 9552E+03 8569E+00 2101E-01 7960E-05 1007E+04 4049E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10529E-02 19831E-05 34552E-03 36109E-07 -12465E-09 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11642E-02 19714E-05 23073E-03 23522E-07 -54231E-10 Remaining SSD is 19453 Weighted distances x-value x-dist y-dist 100E+00 190E-01 -239E-01 666E-01 200E+00 200E-01 487E-01 -104E+00 300E+00 210E-01 -247E-01 248E-01 Goodness-of-fit measure 10414 Parameter set 1 1164239985182795E-2 1971441115316992E-5 2307269625077337E-3 2352198415608386E-7 -
5423119774765299E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19837E-01 14840E-04 94718E+03 45610E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
26
Table 7 Calculation of uncertainty produced by calibration of chromotograph
Date u(b1) u(b0) u(b0b1) x
molmol y Ucal molmol
Ucal rel
1706 19491E-05
24883E-01
-48497E-06
13567middot10-
2129698
3 0005middot1
0-2 003
2106 22698E-05
28930E-01
-65652E-06
13564middot10-
2 128855 0007middot1
0-2 005
2306
CO2
35807E-05
45413E-01
-16254E-05
135374middot10-2
1294633
0016middot10-2 012
1706 14231E-05
57044E-02
-81115E-07 2957middot10-2 409633
0003middot10-2 009
2106 13819E-05
54490E-02
-75209E-07
29577middot10-
2 405663 0003middot1
0-2 01
2306
CO
12663E-05
49016E-02
-62026E-07 2955middot10-2 405882
0003middot10-2 01
1706 38279E-07
12015E-02
-45937E-09 1977middot10-4
3255817
007middot10-
2 038
2106 39247E-07
12379E-02
-48529E-09 1980middot10-4
3273329
008middot10-
2 038
2306
C3H8
40085E-07
12590E-02
-50407E-09 1982middot10-4 32636
008middot10-
2 04 The total estimate of relative uncertainty produced by calibration of chromotograph was
calculated for each component as follows
3
3
1
2sum=
cali
cali
uu (8)
Where ucal i is the relative uncertainty produced by calibration of chromotograph and calculated for each measurement run
The calculations are summarized in Table 8
Table 8 Uncertainty produced by calibration of chromotograph
Component Ucal rel
CO2 008 CO 01
C3H8 04 22 Uncertainty of the component content produced by change of chromotograph response in each measurement run This uncertainty is calculated using the equation (6) whereby the first term of the sum
only ie )()( 221 yub which represents the standard uncertainty of the chromotograph
response in a measurement run is taken into account Calculations are summarized in Table 9
27
Table 9 Calculation of uncertainty produced by change of chromotograph response in each measurement run
The total estimate of relative uncertainty produced by change of chromotograph
response in each measurement run was calculated for each component as follows
3
3
1
2sum=
run
run
uu (9)
Where urun is the relative uncertainty produced by change of chromotograph response in each measurement run Calculations are summarized in Table 10
Table 10 Uncertainty produced by change of chromotograph response in each measurement
run
Component Urun rel
CO2 007 CO 015
C3H8 012 23 Uncertainty of the component content produced by change of temperature in a room
The recorded change of temperature in measurements is plusmn 05 degree The contribution of uncertainty type B (rectangular distribution) is estimated as follows
201003
12931
=sdotsdot=tu rel
28
24 Uncertainty of the component content produced by change of atmospheric pressure The recorded change of atmospheric pressure within three days was
05 kPа The contribution of uncertainty type B (rectangular distribution) is estimated as follows
2801003
13101
50=sdotsdot=pressureu rel
25 Standard deviation of 3 measurement runs Standard deviation is calculated as follows
isu p
A
2
= (10)
Where S2p is the group experimental variation
The group experimental variation is calculated as follows
(11)
Where si
2 is the experimental variation of measurement run i from independent repeated observations ni having freedom degrees
νi = n - 1 n=6 i= 3 Calculations are summarized in Table 11 Table 11 Calculations of standard uncertainty of 3 measurement runs
Date 2iS x
molmol 2iS
rel uA
rel
1706 2953E-05 13567middot10-2 000022
2106 588987E-06 13564middot10-2 0000043
2306
CO2 141137E-
05 135374middot10
-2 000010
0006
1706 225604E-06 2957middot10-2 0000077
2106 681346E-06 29577middot10-2 000023
2306
CO
175166E-06 2955middot10-2 0000060
0006
1706 C3H8 130158E-
08 1977middot10-4 00000066 0001
ss
p
i ii
N
ii
N2
2
1
1
= =
=
sum
sum
ν
ν
29
2106 44616E-09 1980middot10-4 00000023
2306
381032E-09 1982middot10-4 00000019
26 Total standard uncertainty
Uncertainty estimation СО2
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph ucal Normal 008 1 008
Change of temperature ut Rectangular 02 1 02 Change of atmospheric pressure upressure Rectangular 028 1 028
Changes of chromotograph response
urun Normal 007 1 007
Standard deviation of 3 runs uA Normal 0006 1 0006
Relative total standard uncertainty 036 Coverage factor k=2 Expanded uncertainty 01middot10-2 molmol Uncertainty estimation СО
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph ucal Normal 01 1 01 Change of temperature ut Rectangular 02 1 02 Change of atmospheric pressure upressure Rectangular 028 1 028 Changes of chromotograph response
urun Normal 015 1 015
Standard deviation of 3 runs uA Normal 0006 1 0006
Relative total standard uncertainty 039 Coverage factor k=2 Expanded uncertainty 002middot10-2 molmol Uncertainty estimation С3Н8
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph 04 Normal 04 1 008
30
Change of temperature 02 Rectangular 02 1 02 Change of atmospheric pressure 028 Rectangular 028 1 028
Changes of chromotograph response
012 Normal 012 1 007
Standard deviation of 3 runs 0001 Normal 0001 1 0006
Relative total standard uncertainty 054 Coverage factor k=2 Expanded uncertainty 02middot10-4 molmol
Sample handling
Period for exposure of cylinder to measurement conditions and method how to transport sample to the device
1 Stands for storing gas standard cylinders and calibration mixture cylinders and chromotograph are placed in a laboratory room which is not accessible to unauthorized persons The laboratory is equipped with air-conditioner to maintain required temperature and humidity on a continuous basis and some auxiliary measuring instruments as thermometer psychrometric hygrometer and aneroid to control temperature humidity and atmospheric inside the room
2 The comparison sample cylinder was stored in laboratory from the date of its
delivery to Minsk on 25042005 CGM cylinders are stored horizontally on racks and positioned vertically using special support when measurements are carried out
3 The analyzed gas sample is transported through the fine adjustment valve (FAV)
Conjunctions Cylinder - FAV FAV - tube tube - doser are made of metal and use adapters with spherical ends and bushes FAV is made of brass tube is made of copper and doser is made of duralumin
Instrument(s) (principles make type configuration data collection etc) For the analysis a GC were used with specifically applications For the determination of (Nitrogen (N2)) Carbon Dioxide (CO2) Carbon Monoxide (CO) and Propane (C3H8) balance GC Perkin Elmer AutoSystem XL (two channel system) with a stream selection valve for 4 streams and 2 gas sampling valves
Channel A for the determination of N2 CO and CO2 Carrier Gas Helium Columns Column system with two packed columns (6 ft x 18rdquo Porapak R 80100 mesh and 6 ft x 18rdquo Mol-Sieve 13X 80100 mesh) Oven Temperature 960 degC to 180 degC Detector micro-TCD Data Collection Total Chrom Workstation Channel B for the determination of C3H8 Carrier Gas Helium Columns Capillary column 50 m x 032 microm LP-SIL-8-CB Oven Temperature 60 degC to 180 degC Detector FID Data Collection Total Chrom Workstation
34
Calibration Standards
Calibration Standards for the measurements (preparation method purity analyses estimated uncertainty etc)
All standards were prepared individually according to ISO 6142 rdquoGas analysis - Preparation of calibration gases - Gravimetric Methodrdquo
Depending on the concentration of the components standards were prepared individually from pure gases or from pre-mixtures which were individually prepared from pure gases
The content of the impurities in all pure gases were determined before use by GC-DID GC-FID and or GC-TCD
After preparation the standards were verified by analytical comparisons against existing gravimetrically prepared standards Only when no significant difference between the analysed and the calculated gravimetric composition is found the ldquonew prepared candidate rdquo is accepted as a new standards
For the analysis of all components multi component standards with nitrogen as balance gas were used
Composition of calibrants BAM C49250-050722 Component Assigned value( x)
mmol mol Standard uncertainty (u(x)) relativ (k=2)
Calibration procedure (mathematical modelcalibration curve number and concentrations of standards measurement sequence temperaturepressure correction etc)
For the instrument calibration the bracketing technique was used The fraction of the current used standards deviated no more than +10rel and -10rel respectively from those of the sample
Measurement sequence
Sample Handling
How were the cylinders treated after arrival (eg stabilized) and how were samples transferred to the instrument (automatic high pressure mass-flow controller dilution etc) After heating (45 - 50 degC) the cylinder for 8 hours the cylinder were rolled about 16 hours before analysis was started Each cylinder was equipped with a pressure regulator that was purged three times by sequential evacuation and pressurisation with the gas mixture used Continous flow (2 ndash 3mlmin) through the sample loop
Uncertainty The specification of potential uncertainty sources is given in Annex 3
3 injection standard (high)
3 injection sample
3 injection standard (high)
3 injection sample
3 injection standard (low)
3 injection sample
3 injection standard (low)
3 injection standard (low)
36
Uncertainty table CO2
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 002 rel 1 002 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 03 rel
Uncertainty table CO
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 007 rel 1 007 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 05 rel
37
Uncertainty table C3H8
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 010 rel 1 001 rel
Analysis normal 028 rel 1 028 rel
Coverage factor 2
Expanded uncertainty 06 rel
Optional
You may provide additional data like the raw measurement data information on your
measurement procedure chromatograms etc
38
Appendix 3 SPECIFICATION OF POTENTIAL UNCERTAINTY SOURCES
a Uncertainty related to the balance and the weights Resolution of balance Accuracy of balance including linearity Incorrect zero point Drift (thermal and time effects) Instability due to draught Location of cylinder on the balance pan Uncertainties in the weights used Buoyancy effects on the weights used
b Uncertainties related to the gas cylinder Mechanical handling of cylinder
Loss of metal paints or labels from surface of cylinder Loss of metal from threads of valvefitting Dirt on cylinder valves or associated fitting
Absorptiondesorption effects on the external cylinder surface Buoyancy effects on the cylinder itself
Cylinder temperature differs from surrounding air due to eg filling with gas Change of cylinder volume during filling Change of density of surrounding air due to changes in temperature air pressure humidity and carbon dioxide content
Uncertainty in determination of external cylinder volume c Uncertainties related to the component gases Residual gas in cylinder Leakage Leakage of air into the cylinder after evacuation
Leakage of gas from the cylinder valve during filling Escape of gas from cylinder into transport lines
Gas remaining in transfer system when weight loss method is used Absorptionreaction of components on internal cylinder surface Reaction between components Impurities in all the initial gases Insufficient homogenization Uncertainty of molecular mass d Uncertainties related to the analysis
Repeatability and selectivity of the analyzer Appropriateness of the calibration curve
39
MEASUREMENT REPORT - All Ukrainian State Research-Industrial Center of Standardization Metrology Certification and Protection of Consumers Ukraine
gas ndash helium flow rate 15 cm3min detector TCD tdetector = 250 ordmС toven = 70 ordmС It was automatic data collection
Measurement and Calibration Methods Laboratory Measurement method Type of calibration curve
GCFID (С3Н8) 3 points linear Ukrmetrteststandard GCTCD (СО СО2) 3 points linear
GCFID ndash gas-chromatographic with flame-ionization detector GCTCD - gas-chromatographic with thermal-conductivity detector
42
Calibration Standards
Calibration standards ndash primary standard gas mixtures (PSGM) used for measurements by comparison method
PSGM-1 Cylinder 0116
PSGM-2 Cylinder 0107
PSGM-3 Cylinder 0093 Composition
x u(x) x u(x) x u(x) СО 27874 00015 29899 00015 31891 00015 СО2 130187 00015 144456 00016 137016 00016 С3Н8 019003 000008 020017 000008 021013 000008 N2 balance balance balance
Note x ndash mole fraction u(x) ndash absolute standard uncertainty
It was used gravimetric method of preparation of PSGM Electronic balance КА-20-3 of Mettler Toledo max limit of weighing is 20 kg least
limit of weighing is 01 g standard deviation is 0006 g Analysis of purity of parent gases was carried out with usage of chromatographs
НР6890N with helium ndash ionization detector flame ndash ionization detector thermal ndash conductivity detector and mass ndash spectrometric detector as well аs gas analyzers GIAM-15M and Onix condensate-thermometer hygrometer TOROS-3-2B
Calculation of uncertainties was carried out according to ISO 6142-2003 Corrections of temperature pressure and humidity of environment were considered
in calculations according to ISO 6142-2003 (program of ISO-6142 2000-03-17 designer is NMi) Protocols and explanations are in Annex A
Instrument (Comparator) Calibration Calibration of comparator ndash gas chromatograph HP 6890 was carried out with usage
of PSGM Measurement sequence PSGM -1 х 3 PSGM -2 х 3 COOMET gas mixture х 3 PSGM -2 х 3 PSGM -3 х 3 It is necessary to use PSGM-2 repeatedly for estimation of reproducibility of results
Program B_LEAST recommended by ISO 6143-2003 was used for constructing the curve Mathematical model of calibration curve is linear one
Sample Handling The cylinder was kept for 24 hrs at a room where comparators were disposed This room is a thermostatic room with t = (20plusmn2) ordmС
43
A method of sample input to a comparator is a method with flow stabilization Uncertainty The following uncertainties were included to the budget of uncertainty - uncertainty of the balance - uncertainties of impurities in parent gases Contribution from other uncertainty sources was insignificant A cabin of the balance is thermostatically The balance is the one-pan balance
Air transfer is absent in the cabin of the balance Drift of the balance is absent for PSGM preparation
Contribution from other uncertainty sources was considered in software according to ISO 6142-2003
Uncertainties related to the analysis (comparison) were considered in software according to ISO 6143-2003 and enclosed in Annex B
Uncertainty table СО2
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas mixture
B 001 1 001
Analysis A B 008 1 008
Coverage factor 2 Expanded uncertainty 002sdot10-2 molmol Uncertainty table СО
Protocols of analysis (comparison) in accordance with ISO 6143-2003
57
Explanation of protocols of comparison
Chapter I ldquoThe calibration data set isrdquo contains columns 1 mole fraction of a component 2 absolute standard uncertainty of mole fraction of a component 3 a signal of a comparator 4 absolute standard uncertainty of a comparator signal
Chapter II ldquoResults of ISO 6143 methodrdquo contains parameters of a calibration curve including its
uncertainty
Chapter ІІІ ldquoPart II Processing of datardquo contains columns
1 calc x - the results of comparison mole fraction of a component 2 u(x) - absolute standard uncertainty of mole fraction of a component 3 response y - a signal of a comparator 4 u(y) - absolute standard uncertainty of a comparator signal
58
СО2 - measurement 1 Data setCO2_21 The calibration data set is 1302E+01 1510E-03 1022E+04 1820E+00 1370E+01 1560E-03 1077E+04 2730E+00 1445E+01 1620E-03 1135E+04 5900E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 20331E-02 12711E-03 12573E-01 11653E-05 -14638E-06 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 10548E-02 12722E-03 31762E-02 28898E-06 -91698E-08 Remaining SSD is 74346 Weighted distances x-value x-dist y-dist 100E+00 130E+01 490E-01 -755E-01 200E+00 137E+01 -103E+00 228E+00 300E+00 144E+01 539E-01 -250E-01 Goodness-of-fit measure 22837 Parameter set 1 1054788657490729E-2 1272208026684145E-3 3176237146276368E-2 2889798108124711E-6 -
9169821653851327E-8 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_21c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13577E+01 25542E-03 10664E+04 15200E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 547E-06 328E-06 316E-06 784E-06 286E-06 652E-06 Linear model Parameters for the fit were (b0 b1) 10548E-02 12722E-03
59
СО2 - measurement 2
Data setCO2_20 The calibration data set is 1302E+01 1512E-03 1021E+04 4723E+00 1370E+01 1563E-03 1075E+04 1600E+00 1445E+01 1620E-03 1133E+04 7300E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -38760E-02 12784E-03 26817E-02 24890E-06 -66689E-08 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -62452E-02 12805E-03 47930E-02 43243E-06 -20716E-07 Remaining SSD is 03231 Weighted distances x-value x-dist y-dist 100E+00 130E+01 107E-01 -415E-01 200E+00 137E+01 -212E-01 283E-01 300E+00 144E+01 104E-01 -584E-02 Goodness-of-fit measure 04155 Parameter set 1 -6245240430658412E-2 1280492624666799E-3 4792952200361109E-2 4324266278840409E-6 -
2071623966851869E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_20c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13594E+01 10290E-02 10665E+04 78300E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 121E-05 683E-06 651E-06 315E-05 560E-06 106E-04 Linear model Parameters for the fit were (b0 b1) -62452E-02 12805E-03
60
С3Н8 - measurement 1
Data setC3H8 The calibration data set is 1900E-01 7800E-05 9057E+03 1098E+01 2002E-01 7900E-05 9552E+03 8569E+00 2101E-01 7960E-05 1007E+04 4049E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10529E-02 19831E-05 34552E-03 36109E-07 -12465E-09 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11642E-02 19714E-05 23073E-03 23522E-07 -54231E-10 Remaining SSD is 19453 Weighted distances x-value x-dist y-dist 100E+00 190E-01 -239E-01 666E-01 200E+00 200E-01 487E-01 -104E+00 300E+00 210E-01 -247E-01 248E-01 Goodness-of-fit measure 10414 Parameter set 1 1164239985182795E-2 1971441115316992E-5 2307269625077337E-3 2352198415608386E-7 -
5423119774765299E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19837E-01 14840E-04 94718E+03 45610E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
27
Table 9 Calculation of uncertainty produced by change of chromotograph response in each measurement run
The total estimate of relative uncertainty produced by change of chromotograph
response in each measurement run was calculated for each component as follows
3
3
1
2sum=
run
run
uu (9)
Where urun is the relative uncertainty produced by change of chromotograph response in each measurement run Calculations are summarized in Table 10
Table 10 Uncertainty produced by change of chromotograph response in each measurement
run
Component Urun rel
CO2 007 CO 015
C3H8 012 23 Uncertainty of the component content produced by change of temperature in a room
The recorded change of temperature in measurements is plusmn 05 degree The contribution of uncertainty type B (rectangular distribution) is estimated as follows
201003
12931
=sdotsdot=tu rel
28
24 Uncertainty of the component content produced by change of atmospheric pressure The recorded change of atmospheric pressure within three days was
05 kPа The contribution of uncertainty type B (rectangular distribution) is estimated as follows
2801003
13101
50=sdotsdot=pressureu rel
25 Standard deviation of 3 measurement runs Standard deviation is calculated as follows
isu p
A
2
= (10)
Where S2p is the group experimental variation
The group experimental variation is calculated as follows
(11)
Where si
2 is the experimental variation of measurement run i from independent repeated observations ni having freedom degrees
νi = n - 1 n=6 i= 3 Calculations are summarized in Table 11 Table 11 Calculations of standard uncertainty of 3 measurement runs
Date 2iS x
molmol 2iS
rel uA
rel
1706 2953E-05 13567middot10-2 000022
2106 588987E-06 13564middot10-2 0000043
2306
CO2 141137E-
05 135374middot10
-2 000010
0006
1706 225604E-06 2957middot10-2 0000077
2106 681346E-06 29577middot10-2 000023
2306
CO
175166E-06 2955middot10-2 0000060
0006
1706 C3H8 130158E-
08 1977middot10-4 00000066 0001
ss
p
i ii
N
ii
N2
2
1
1
= =
=
sum
sum
ν
ν
29
2106 44616E-09 1980middot10-4 00000023
2306
381032E-09 1982middot10-4 00000019
26 Total standard uncertainty
Uncertainty estimation СО2
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph ucal Normal 008 1 008
Change of temperature ut Rectangular 02 1 02 Change of atmospheric pressure upressure Rectangular 028 1 028
Changes of chromotograph response
urun Normal 007 1 007
Standard deviation of 3 runs uA Normal 0006 1 0006
Relative total standard uncertainty 036 Coverage factor k=2 Expanded uncertainty 01middot10-2 molmol Uncertainty estimation СО
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph ucal Normal 01 1 01 Change of temperature ut Rectangular 02 1 02 Change of atmospheric pressure upressure Rectangular 028 1 028 Changes of chromotograph response
urun Normal 015 1 015
Standard deviation of 3 runs uA Normal 0006 1 0006
Relative total standard uncertainty 039 Coverage factor k=2 Expanded uncertainty 002middot10-2 molmol Uncertainty estimation С3Н8
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph 04 Normal 04 1 008
30
Change of temperature 02 Rectangular 02 1 02 Change of atmospheric pressure 028 Rectangular 028 1 028
Changes of chromotograph response
012 Normal 012 1 007
Standard deviation of 3 runs 0001 Normal 0001 1 0006
Relative total standard uncertainty 054 Coverage factor k=2 Expanded uncertainty 02middot10-4 molmol
Sample handling
Period for exposure of cylinder to measurement conditions and method how to transport sample to the device
1 Stands for storing gas standard cylinders and calibration mixture cylinders and chromotograph are placed in a laboratory room which is not accessible to unauthorized persons The laboratory is equipped with air-conditioner to maintain required temperature and humidity on a continuous basis and some auxiliary measuring instruments as thermometer psychrometric hygrometer and aneroid to control temperature humidity and atmospheric inside the room
2 The comparison sample cylinder was stored in laboratory from the date of its
delivery to Minsk on 25042005 CGM cylinders are stored horizontally on racks and positioned vertically using special support when measurements are carried out
3 The analyzed gas sample is transported through the fine adjustment valve (FAV)
Conjunctions Cylinder - FAV FAV - tube tube - doser are made of metal and use adapters with spherical ends and bushes FAV is made of brass tube is made of copper and doser is made of duralumin
Instrument(s) (principles make type configuration data collection etc) For the analysis a GC were used with specifically applications For the determination of (Nitrogen (N2)) Carbon Dioxide (CO2) Carbon Monoxide (CO) and Propane (C3H8) balance GC Perkin Elmer AutoSystem XL (two channel system) with a stream selection valve for 4 streams and 2 gas sampling valves
Channel A for the determination of N2 CO and CO2 Carrier Gas Helium Columns Column system with two packed columns (6 ft x 18rdquo Porapak R 80100 mesh and 6 ft x 18rdquo Mol-Sieve 13X 80100 mesh) Oven Temperature 960 degC to 180 degC Detector micro-TCD Data Collection Total Chrom Workstation Channel B for the determination of C3H8 Carrier Gas Helium Columns Capillary column 50 m x 032 microm LP-SIL-8-CB Oven Temperature 60 degC to 180 degC Detector FID Data Collection Total Chrom Workstation
34
Calibration Standards
Calibration Standards for the measurements (preparation method purity analyses estimated uncertainty etc)
All standards were prepared individually according to ISO 6142 rdquoGas analysis - Preparation of calibration gases - Gravimetric Methodrdquo
Depending on the concentration of the components standards were prepared individually from pure gases or from pre-mixtures which were individually prepared from pure gases
The content of the impurities in all pure gases were determined before use by GC-DID GC-FID and or GC-TCD
After preparation the standards were verified by analytical comparisons against existing gravimetrically prepared standards Only when no significant difference between the analysed and the calculated gravimetric composition is found the ldquonew prepared candidate rdquo is accepted as a new standards
For the analysis of all components multi component standards with nitrogen as balance gas were used
Composition of calibrants BAM C49250-050722 Component Assigned value( x)
mmol mol Standard uncertainty (u(x)) relativ (k=2)
Calibration procedure (mathematical modelcalibration curve number and concentrations of standards measurement sequence temperaturepressure correction etc)
For the instrument calibration the bracketing technique was used The fraction of the current used standards deviated no more than +10rel and -10rel respectively from those of the sample
Measurement sequence
Sample Handling
How were the cylinders treated after arrival (eg stabilized) and how were samples transferred to the instrument (automatic high pressure mass-flow controller dilution etc) After heating (45 - 50 degC) the cylinder for 8 hours the cylinder were rolled about 16 hours before analysis was started Each cylinder was equipped with a pressure regulator that was purged three times by sequential evacuation and pressurisation with the gas mixture used Continous flow (2 ndash 3mlmin) through the sample loop
Uncertainty The specification of potential uncertainty sources is given in Annex 3
3 injection standard (high)
3 injection sample
3 injection standard (high)
3 injection sample
3 injection standard (low)
3 injection sample
3 injection standard (low)
3 injection standard (low)
36
Uncertainty table CO2
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 002 rel 1 002 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 03 rel
Uncertainty table CO
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 007 rel 1 007 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 05 rel
37
Uncertainty table C3H8
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 010 rel 1 001 rel
Analysis normal 028 rel 1 028 rel
Coverage factor 2
Expanded uncertainty 06 rel
Optional
You may provide additional data like the raw measurement data information on your
measurement procedure chromatograms etc
38
Appendix 3 SPECIFICATION OF POTENTIAL UNCERTAINTY SOURCES
a Uncertainty related to the balance and the weights Resolution of balance Accuracy of balance including linearity Incorrect zero point Drift (thermal and time effects) Instability due to draught Location of cylinder on the balance pan Uncertainties in the weights used Buoyancy effects on the weights used
b Uncertainties related to the gas cylinder Mechanical handling of cylinder
Loss of metal paints or labels from surface of cylinder Loss of metal from threads of valvefitting Dirt on cylinder valves or associated fitting
Absorptiondesorption effects on the external cylinder surface Buoyancy effects on the cylinder itself
Cylinder temperature differs from surrounding air due to eg filling with gas Change of cylinder volume during filling Change of density of surrounding air due to changes in temperature air pressure humidity and carbon dioxide content
Uncertainty in determination of external cylinder volume c Uncertainties related to the component gases Residual gas in cylinder Leakage Leakage of air into the cylinder after evacuation
Leakage of gas from the cylinder valve during filling Escape of gas from cylinder into transport lines
Gas remaining in transfer system when weight loss method is used Absorptionreaction of components on internal cylinder surface Reaction between components Impurities in all the initial gases Insufficient homogenization Uncertainty of molecular mass d Uncertainties related to the analysis
Repeatability and selectivity of the analyzer Appropriateness of the calibration curve
39
MEASUREMENT REPORT - All Ukrainian State Research-Industrial Center of Standardization Metrology Certification and Protection of Consumers Ukraine
gas ndash helium flow rate 15 cm3min detector TCD tdetector = 250 ordmС toven = 70 ordmС It was automatic data collection
Measurement and Calibration Methods Laboratory Measurement method Type of calibration curve
GCFID (С3Н8) 3 points linear Ukrmetrteststandard GCTCD (СО СО2) 3 points linear
GCFID ndash gas-chromatographic with flame-ionization detector GCTCD - gas-chromatographic with thermal-conductivity detector
42
Calibration Standards
Calibration standards ndash primary standard gas mixtures (PSGM) used for measurements by comparison method
PSGM-1 Cylinder 0116
PSGM-2 Cylinder 0107
PSGM-3 Cylinder 0093 Composition
x u(x) x u(x) x u(x) СО 27874 00015 29899 00015 31891 00015 СО2 130187 00015 144456 00016 137016 00016 С3Н8 019003 000008 020017 000008 021013 000008 N2 balance balance balance
Note x ndash mole fraction u(x) ndash absolute standard uncertainty
It was used gravimetric method of preparation of PSGM Electronic balance КА-20-3 of Mettler Toledo max limit of weighing is 20 kg least
limit of weighing is 01 g standard deviation is 0006 g Analysis of purity of parent gases was carried out with usage of chromatographs
НР6890N with helium ndash ionization detector flame ndash ionization detector thermal ndash conductivity detector and mass ndash spectrometric detector as well аs gas analyzers GIAM-15M and Onix condensate-thermometer hygrometer TOROS-3-2B
Calculation of uncertainties was carried out according to ISO 6142-2003 Corrections of temperature pressure and humidity of environment were considered
in calculations according to ISO 6142-2003 (program of ISO-6142 2000-03-17 designer is NMi) Protocols and explanations are in Annex A
Instrument (Comparator) Calibration Calibration of comparator ndash gas chromatograph HP 6890 was carried out with usage
of PSGM Measurement sequence PSGM -1 х 3 PSGM -2 х 3 COOMET gas mixture х 3 PSGM -2 х 3 PSGM -3 х 3 It is necessary to use PSGM-2 repeatedly for estimation of reproducibility of results
Program B_LEAST recommended by ISO 6143-2003 was used for constructing the curve Mathematical model of calibration curve is linear one
Sample Handling The cylinder was kept for 24 hrs at a room where comparators were disposed This room is a thermostatic room with t = (20plusmn2) ordmС
43
A method of sample input to a comparator is a method with flow stabilization Uncertainty The following uncertainties were included to the budget of uncertainty - uncertainty of the balance - uncertainties of impurities in parent gases Contribution from other uncertainty sources was insignificant A cabin of the balance is thermostatically The balance is the one-pan balance
Air transfer is absent in the cabin of the balance Drift of the balance is absent for PSGM preparation
Contribution from other uncertainty sources was considered in software according to ISO 6142-2003
Uncertainties related to the analysis (comparison) were considered in software according to ISO 6143-2003 and enclosed in Annex B
Uncertainty table СО2
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas mixture
B 001 1 001
Analysis A B 008 1 008
Coverage factor 2 Expanded uncertainty 002sdot10-2 molmol Uncertainty table СО
Protocols of analysis (comparison) in accordance with ISO 6143-2003
57
Explanation of protocols of comparison
Chapter I ldquoThe calibration data set isrdquo contains columns 1 mole fraction of a component 2 absolute standard uncertainty of mole fraction of a component 3 a signal of a comparator 4 absolute standard uncertainty of a comparator signal
Chapter II ldquoResults of ISO 6143 methodrdquo contains parameters of a calibration curve including its
uncertainty
Chapter ІІІ ldquoPart II Processing of datardquo contains columns
1 calc x - the results of comparison mole fraction of a component 2 u(x) - absolute standard uncertainty of mole fraction of a component 3 response y - a signal of a comparator 4 u(y) - absolute standard uncertainty of a comparator signal
58
СО2 - measurement 1 Data setCO2_21 The calibration data set is 1302E+01 1510E-03 1022E+04 1820E+00 1370E+01 1560E-03 1077E+04 2730E+00 1445E+01 1620E-03 1135E+04 5900E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 20331E-02 12711E-03 12573E-01 11653E-05 -14638E-06 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 10548E-02 12722E-03 31762E-02 28898E-06 -91698E-08 Remaining SSD is 74346 Weighted distances x-value x-dist y-dist 100E+00 130E+01 490E-01 -755E-01 200E+00 137E+01 -103E+00 228E+00 300E+00 144E+01 539E-01 -250E-01 Goodness-of-fit measure 22837 Parameter set 1 1054788657490729E-2 1272208026684145E-3 3176237146276368E-2 2889798108124711E-6 -
9169821653851327E-8 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_21c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13577E+01 25542E-03 10664E+04 15200E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 547E-06 328E-06 316E-06 784E-06 286E-06 652E-06 Linear model Parameters for the fit were (b0 b1) 10548E-02 12722E-03
59
СО2 - measurement 2
Data setCO2_20 The calibration data set is 1302E+01 1512E-03 1021E+04 4723E+00 1370E+01 1563E-03 1075E+04 1600E+00 1445E+01 1620E-03 1133E+04 7300E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -38760E-02 12784E-03 26817E-02 24890E-06 -66689E-08 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -62452E-02 12805E-03 47930E-02 43243E-06 -20716E-07 Remaining SSD is 03231 Weighted distances x-value x-dist y-dist 100E+00 130E+01 107E-01 -415E-01 200E+00 137E+01 -212E-01 283E-01 300E+00 144E+01 104E-01 -584E-02 Goodness-of-fit measure 04155 Parameter set 1 -6245240430658412E-2 1280492624666799E-3 4792952200361109E-2 4324266278840409E-6 -
2071623966851869E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_20c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13594E+01 10290E-02 10665E+04 78300E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 121E-05 683E-06 651E-06 315E-05 560E-06 106E-04 Linear model Parameters for the fit were (b0 b1) -62452E-02 12805E-03
60
С3Н8 - measurement 1
Data setC3H8 The calibration data set is 1900E-01 7800E-05 9057E+03 1098E+01 2002E-01 7900E-05 9552E+03 8569E+00 2101E-01 7960E-05 1007E+04 4049E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10529E-02 19831E-05 34552E-03 36109E-07 -12465E-09 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11642E-02 19714E-05 23073E-03 23522E-07 -54231E-10 Remaining SSD is 19453 Weighted distances x-value x-dist y-dist 100E+00 190E-01 -239E-01 666E-01 200E+00 200E-01 487E-01 -104E+00 300E+00 210E-01 -247E-01 248E-01 Goodness-of-fit measure 10414 Parameter set 1 1164239985182795E-2 1971441115316992E-5 2307269625077337E-3 2352198415608386E-7 -
5423119774765299E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19837E-01 14840E-04 94718E+03 45610E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
28
24 Uncertainty of the component content produced by change of atmospheric pressure The recorded change of atmospheric pressure within three days was
05 kPа The contribution of uncertainty type B (rectangular distribution) is estimated as follows
2801003
13101
50=sdotsdot=pressureu rel
25 Standard deviation of 3 measurement runs Standard deviation is calculated as follows
isu p
A
2
= (10)
Where S2p is the group experimental variation
The group experimental variation is calculated as follows
(11)
Where si
2 is the experimental variation of measurement run i from independent repeated observations ni having freedom degrees
νi = n - 1 n=6 i= 3 Calculations are summarized in Table 11 Table 11 Calculations of standard uncertainty of 3 measurement runs
Date 2iS x
molmol 2iS
rel uA
rel
1706 2953E-05 13567middot10-2 000022
2106 588987E-06 13564middot10-2 0000043
2306
CO2 141137E-
05 135374middot10
-2 000010
0006
1706 225604E-06 2957middot10-2 0000077
2106 681346E-06 29577middot10-2 000023
2306
CO
175166E-06 2955middot10-2 0000060
0006
1706 C3H8 130158E-
08 1977middot10-4 00000066 0001
ss
p
i ii
N
ii
N2
2
1
1
= =
=
sum
sum
ν
ν
29
2106 44616E-09 1980middot10-4 00000023
2306
381032E-09 1982middot10-4 00000019
26 Total standard uncertainty
Uncertainty estimation СО2
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph ucal Normal 008 1 008
Change of temperature ut Rectangular 02 1 02 Change of atmospheric pressure upressure Rectangular 028 1 028
Changes of chromotograph response
urun Normal 007 1 007
Standard deviation of 3 runs uA Normal 0006 1 0006
Relative total standard uncertainty 036 Coverage factor k=2 Expanded uncertainty 01middot10-2 molmol Uncertainty estimation СО
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph ucal Normal 01 1 01 Change of temperature ut Rectangular 02 1 02 Change of atmospheric pressure upressure Rectangular 028 1 028 Changes of chromotograph response
urun Normal 015 1 015
Standard deviation of 3 runs uA Normal 0006 1 0006
Relative total standard uncertainty 039 Coverage factor k=2 Expanded uncertainty 002middot10-2 molmol Uncertainty estimation С3Н8
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph 04 Normal 04 1 008
30
Change of temperature 02 Rectangular 02 1 02 Change of atmospheric pressure 028 Rectangular 028 1 028
Changes of chromotograph response
012 Normal 012 1 007
Standard deviation of 3 runs 0001 Normal 0001 1 0006
Relative total standard uncertainty 054 Coverage factor k=2 Expanded uncertainty 02middot10-4 molmol
Sample handling
Period for exposure of cylinder to measurement conditions and method how to transport sample to the device
1 Stands for storing gas standard cylinders and calibration mixture cylinders and chromotograph are placed in a laboratory room which is not accessible to unauthorized persons The laboratory is equipped with air-conditioner to maintain required temperature and humidity on a continuous basis and some auxiliary measuring instruments as thermometer psychrometric hygrometer and aneroid to control temperature humidity and atmospheric inside the room
2 The comparison sample cylinder was stored in laboratory from the date of its
delivery to Minsk on 25042005 CGM cylinders are stored horizontally on racks and positioned vertically using special support when measurements are carried out
3 The analyzed gas sample is transported through the fine adjustment valve (FAV)
Conjunctions Cylinder - FAV FAV - tube tube - doser are made of metal and use adapters with spherical ends and bushes FAV is made of brass tube is made of copper and doser is made of duralumin
Instrument(s) (principles make type configuration data collection etc) For the analysis a GC were used with specifically applications For the determination of (Nitrogen (N2)) Carbon Dioxide (CO2) Carbon Monoxide (CO) and Propane (C3H8) balance GC Perkin Elmer AutoSystem XL (two channel system) with a stream selection valve for 4 streams and 2 gas sampling valves
Channel A for the determination of N2 CO and CO2 Carrier Gas Helium Columns Column system with two packed columns (6 ft x 18rdquo Porapak R 80100 mesh and 6 ft x 18rdquo Mol-Sieve 13X 80100 mesh) Oven Temperature 960 degC to 180 degC Detector micro-TCD Data Collection Total Chrom Workstation Channel B for the determination of C3H8 Carrier Gas Helium Columns Capillary column 50 m x 032 microm LP-SIL-8-CB Oven Temperature 60 degC to 180 degC Detector FID Data Collection Total Chrom Workstation
34
Calibration Standards
Calibration Standards for the measurements (preparation method purity analyses estimated uncertainty etc)
All standards were prepared individually according to ISO 6142 rdquoGas analysis - Preparation of calibration gases - Gravimetric Methodrdquo
Depending on the concentration of the components standards were prepared individually from pure gases or from pre-mixtures which were individually prepared from pure gases
The content of the impurities in all pure gases were determined before use by GC-DID GC-FID and or GC-TCD
After preparation the standards were verified by analytical comparisons against existing gravimetrically prepared standards Only when no significant difference between the analysed and the calculated gravimetric composition is found the ldquonew prepared candidate rdquo is accepted as a new standards
For the analysis of all components multi component standards with nitrogen as balance gas were used
Composition of calibrants BAM C49250-050722 Component Assigned value( x)
mmol mol Standard uncertainty (u(x)) relativ (k=2)
Calibration procedure (mathematical modelcalibration curve number and concentrations of standards measurement sequence temperaturepressure correction etc)
For the instrument calibration the bracketing technique was used The fraction of the current used standards deviated no more than +10rel and -10rel respectively from those of the sample
Measurement sequence
Sample Handling
How were the cylinders treated after arrival (eg stabilized) and how were samples transferred to the instrument (automatic high pressure mass-flow controller dilution etc) After heating (45 - 50 degC) the cylinder for 8 hours the cylinder were rolled about 16 hours before analysis was started Each cylinder was equipped with a pressure regulator that was purged three times by sequential evacuation and pressurisation with the gas mixture used Continous flow (2 ndash 3mlmin) through the sample loop
Uncertainty The specification of potential uncertainty sources is given in Annex 3
3 injection standard (high)
3 injection sample
3 injection standard (high)
3 injection sample
3 injection standard (low)
3 injection sample
3 injection standard (low)
3 injection standard (low)
36
Uncertainty table CO2
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 002 rel 1 002 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 03 rel
Uncertainty table CO
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 007 rel 1 007 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 05 rel
37
Uncertainty table C3H8
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 010 rel 1 001 rel
Analysis normal 028 rel 1 028 rel
Coverage factor 2
Expanded uncertainty 06 rel
Optional
You may provide additional data like the raw measurement data information on your
measurement procedure chromatograms etc
38
Appendix 3 SPECIFICATION OF POTENTIAL UNCERTAINTY SOURCES
a Uncertainty related to the balance and the weights Resolution of balance Accuracy of balance including linearity Incorrect zero point Drift (thermal and time effects) Instability due to draught Location of cylinder on the balance pan Uncertainties in the weights used Buoyancy effects on the weights used
b Uncertainties related to the gas cylinder Mechanical handling of cylinder
Loss of metal paints or labels from surface of cylinder Loss of metal from threads of valvefitting Dirt on cylinder valves or associated fitting
Absorptiondesorption effects on the external cylinder surface Buoyancy effects on the cylinder itself
Cylinder temperature differs from surrounding air due to eg filling with gas Change of cylinder volume during filling Change of density of surrounding air due to changes in temperature air pressure humidity and carbon dioxide content
Uncertainty in determination of external cylinder volume c Uncertainties related to the component gases Residual gas in cylinder Leakage Leakage of air into the cylinder after evacuation
Leakage of gas from the cylinder valve during filling Escape of gas from cylinder into transport lines
Gas remaining in transfer system when weight loss method is used Absorptionreaction of components on internal cylinder surface Reaction between components Impurities in all the initial gases Insufficient homogenization Uncertainty of molecular mass d Uncertainties related to the analysis
Repeatability and selectivity of the analyzer Appropriateness of the calibration curve
39
MEASUREMENT REPORT - All Ukrainian State Research-Industrial Center of Standardization Metrology Certification and Protection of Consumers Ukraine
gas ndash helium flow rate 15 cm3min detector TCD tdetector = 250 ordmС toven = 70 ordmС It was automatic data collection
Measurement and Calibration Methods Laboratory Measurement method Type of calibration curve
GCFID (С3Н8) 3 points linear Ukrmetrteststandard GCTCD (СО СО2) 3 points linear
GCFID ndash gas-chromatographic with flame-ionization detector GCTCD - gas-chromatographic with thermal-conductivity detector
42
Calibration Standards
Calibration standards ndash primary standard gas mixtures (PSGM) used for measurements by comparison method
PSGM-1 Cylinder 0116
PSGM-2 Cylinder 0107
PSGM-3 Cylinder 0093 Composition
x u(x) x u(x) x u(x) СО 27874 00015 29899 00015 31891 00015 СО2 130187 00015 144456 00016 137016 00016 С3Н8 019003 000008 020017 000008 021013 000008 N2 balance balance balance
Note x ndash mole fraction u(x) ndash absolute standard uncertainty
It was used gravimetric method of preparation of PSGM Electronic balance КА-20-3 of Mettler Toledo max limit of weighing is 20 kg least
limit of weighing is 01 g standard deviation is 0006 g Analysis of purity of parent gases was carried out with usage of chromatographs
НР6890N with helium ndash ionization detector flame ndash ionization detector thermal ndash conductivity detector and mass ndash spectrometric detector as well аs gas analyzers GIAM-15M and Onix condensate-thermometer hygrometer TOROS-3-2B
Calculation of uncertainties was carried out according to ISO 6142-2003 Corrections of temperature pressure and humidity of environment were considered
in calculations according to ISO 6142-2003 (program of ISO-6142 2000-03-17 designer is NMi) Protocols and explanations are in Annex A
Instrument (Comparator) Calibration Calibration of comparator ndash gas chromatograph HP 6890 was carried out with usage
of PSGM Measurement sequence PSGM -1 х 3 PSGM -2 х 3 COOMET gas mixture х 3 PSGM -2 х 3 PSGM -3 х 3 It is necessary to use PSGM-2 repeatedly for estimation of reproducibility of results
Program B_LEAST recommended by ISO 6143-2003 was used for constructing the curve Mathematical model of calibration curve is linear one
Sample Handling The cylinder was kept for 24 hrs at a room where comparators were disposed This room is a thermostatic room with t = (20plusmn2) ordmС
43
A method of sample input to a comparator is a method with flow stabilization Uncertainty The following uncertainties were included to the budget of uncertainty - uncertainty of the balance - uncertainties of impurities in parent gases Contribution from other uncertainty sources was insignificant A cabin of the balance is thermostatically The balance is the one-pan balance
Air transfer is absent in the cabin of the balance Drift of the balance is absent for PSGM preparation
Contribution from other uncertainty sources was considered in software according to ISO 6142-2003
Uncertainties related to the analysis (comparison) were considered in software according to ISO 6143-2003 and enclosed in Annex B
Uncertainty table СО2
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas mixture
B 001 1 001
Analysis A B 008 1 008
Coverage factor 2 Expanded uncertainty 002sdot10-2 molmol Uncertainty table СО
Protocols of analysis (comparison) in accordance with ISO 6143-2003
57
Explanation of protocols of comparison
Chapter I ldquoThe calibration data set isrdquo contains columns 1 mole fraction of a component 2 absolute standard uncertainty of mole fraction of a component 3 a signal of a comparator 4 absolute standard uncertainty of a comparator signal
Chapter II ldquoResults of ISO 6143 methodrdquo contains parameters of a calibration curve including its
uncertainty
Chapter ІІІ ldquoPart II Processing of datardquo contains columns
1 calc x - the results of comparison mole fraction of a component 2 u(x) - absolute standard uncertainty of mole fraction of a component 3 response y - a signal of a comparator 4 u(y) - absolute standard uncertainty of a comparator signal
58
СО2 - measurement 1 Data setCO2_21 The calibration data set is 1302E+01 1510E-03 1022E+04 1820E+00 1370E+01 1560E-03 1077E+04 2730E+00 1445E+01 1620E-03 1135E+04 5900E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 20331E-02 12711E-03 12573E-01 11653E-05 -14638E-06 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 10548E-02 12722E-03 31762E-02 28898E-06 -91698E-08 Remaining SSD is 74346 Weighted distances x-value x-dist y-dist 100E+00 130E+01 490E-01 -755E-01 200E+00 137E+01 -103E+00 228E+00 300E+00 144E+01 539E-01 -250E-01 Goodness-of-fit measure 22837 Parameter set 1 1054788657490729E-2 1272208026684145E-3 3176237146276368E-2 2889798108124711E-6 -
9169821653851327E-8 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_21c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13577E+01 25542E-03 10664E+04 15200E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 547E-06 328E-06 316E-06 784E-06 286E-06 652E-06 Linear model Parameters for the fit were (b0 b1) 10548E-02 12722E-03
59
СО2 - measurement 2
Data setCO2_20 The calibration data set is 1302E+01 1512E-03 1021E+04 4723E+00 1370E+01 1563E-03 1075E+04 1600E+00 1445E+01 1620E-03 1133E+04 7300E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -38760E-02 12784E-03 26817E-02 24890E-06 -66689E-08 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -62452E-02 12805E-03 47930E-02 43243E-06 -20716E-07 Remaining SSD is 03231 Weighted distances x-value x-dist y-dist 100E+00 130E+01 107E-01 -415E-01 200E+00 137E+01 -212E-01 283E-01 300E+00 144E+01 104E-01 -584E-02 Goodness-of-fit measure 04155 Parameter set 1 -6245240430658412E-2 1280492624666799E-3 4792952200361109E-2 4324266278840409E-6 -
2071623966851869E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_20c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13594E+01 10290E-02 10665E+04 78300E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 121E-05 683E-06 651E-06 315E-05 560E-06 106E-04 Linear model Parameters for the fit were (b0 b1) -62452E-02 12805E-03
60
С3Н8 - measurement 1
Data setC3H8 The calibration data set is 1900E-01 7800E-05 9057E+03 1098E+01 2002E-01 7900E-05 9552E+03 8569E+00 2101E-01 7960E-05 1007E+04 4049E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10529E-02 19831E-05 34552E-03 36109E-07 -12465E-09 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11642E-02 19714E-05 23073E-03 23522E-07 -54231E-10 Remaining SSD is 19453 Weighted distances x-value x-dist y-dist 100E+00 190E-01 -239E-01 666E-01 200E+00 200E-01 487E-01 -104E+00 300E+00 210E-01 -247E-01 248E-01 Goodness-of-fit measure 10414 Parameter set 1 1164239985182795E-2 1971441115316992E-5 2307269625077337E-3 2352198415608386E-7 -
5423119774765299E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19837E-01 14840E-04 94718E+03 45610E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
29
2106 44616E-09 1980middot10-4 00000023
2306
381032E-09 1982middot10-4 00000019
26 Total standard uncertainty
Uncertainty estimation СО2
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph ucal Normal 008 1 008
Change of temperature ut Rectangular 02 1 02 Change of atmospheric pressure upressure Rectangular 028 1 028
Changes of chromotograph response
urun Normal 007 1 007
Standard deviation of 3 runs uA Normal 0006 1 0006
Relative total standard uncertainty 036 Coverage factor k=2 Expanded uncertainty 01middot10-2 molmol Uncertainty estimation СО
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph ucal Normal 01 1 01 Change of temperature ut Rectangular 02 1 02 Change of atmospheric pressure upressure Rectangular 028 1 028 Changes of chromotograph response
urun Normal 015 1 015
Standard deviation of 3 runs uA Normal 0006 1 0006
Relative total standard uncertainty 039 Coverage factor k=2 Expanded uncertainty 002middot10-2 molmol Uncertainty estimation С3Н8
Source of uncertainty
Xj
Estimate xj
Prospective distribution
Standard uncertainty u(xj) rel
Sensitivity coefficient
cj
Contribution to standard uncertainty
uj(y) rel
Calibration of chromotograph 04 Normal 04 1 008
30
Change of temperature 02 Rectangular 02 1 02 Change of atmospheric pressure 028 Rectangular 028 1 028
Changes of chromotograph response
012 Normal 012 1 007
Standard deviation of 3 runs 0001 Normal 0001 1 0006
Relative total standard uncertainty 054 Coverage factor k=2 Expanded uncertainty 02middot10-4 molmol
Sample handling
Period for exposure of cylinder to measurement conditions and method how to transport sample to the device
1 Stands for storing gas standard cylinders and calibration mixture cylinders and chromotograph are placed in a laboratory room which is not accessible to unauthorized persons The laboratory is equipped with air-conditioner to maintain required temperature and humidity on a continuous basis and some auxiliary measuring instruments as thermometer psychrometric hygrometer and aneroid to control temperature humidity and atmospheric inside the room
2 The comparison sample cylinder was stored in laboratory from the date of its
delivery to Minsk on 25042005 CGM cylinders are stored horizontally on racks and positioned vertically using special support when measurements are carried out
3 The analyzed gas sample is transported through the fine adjustment valve (FAV)
Conjunctions Cylinder - FAV FAV - tube tube - doser are made of metal and use adapters with spherical ends and bushes FAV is made of brass tube is made of copper and doser is made of duralumin
Instrument(s) (principles make type configuration data collection etc) For the analysis a GC were used with specifically applications For the determination of (Nitrogen (N2)) Carbon Dioxide (CO2) Carbon Monoxide (CO) and Propane (C3H8) balance GC Perkin Elmer AutoSystem XL (two channel system) with a stream selection valve for 4 streams and 2 gas sampling valves
Channel A for the determination of N2 CO and CO2 Carrier Gas Helium Columns Column system with two packed columns (6 ft x 18rdquo Porapak R 80100 mesh and 6 ft x 18rdquo Mol-Sieve 13X 80100 mesh) Oven Temperature 960 degC to 180 degC Detector micro-TCD Data Collection Total Chrom Workstation Channel B for the determination of C3H8 Carrier Gas Helium Columns Capillary column 50 m x 032 microm LP-SIL-8-CB Oven Temperature 60 degC to 180 degC Detector FID Data Collection Total Chrom Workstation
34
Calibration Standards
Calibration Standards for the measurements (preparation method purity analyses estimated uncertainty etc)
All standards were prepared individually according to ISO 6142 rdquoGas analysis - Preparation of calibration gases - Gravimetric Methodrdquo
Depending on the concentration of the components standards were prepared individually from pure gases or from pre-mixtures which were individually prepared from pure gases
The content of the impurities in all pure gases were determined before use by GC-DID GC-FID and or GC-TCD
After preparation the standards were verified by analytical comparisons against existing gravimetrically prepared standards Only when no significant difference between the analysed and the calculated gravimetric composition is found the ldquonew prepared candidate rdquo is accepted as a new standards
For the analysis of all components multi component standards with nitrogen as balance gas were used
Composition of calibrants BAM C49250-050722 Component Assigned value( x)
mmol mol Standard uncertainty (u(x)) relativ (k=2)
Calibration procedure (mathematical modelcalibration curve number and concentrations of standards measurement sequence temperaturepressure correction etc)
For the instrument calibration the bracketing technique was used The fraction of the current used standards deviated no more than +10rel and -10rel respectively from those of the sample
Measurement sequence
Sample Handling
How were the cylinders treated after arrival (eg stabilized) and how were samples transferred to the instrument (automatic high pressure mass-flow controller dilution etc) After heating (45 - 50 degC) the cylinder for 8 hours the cylinder were rolled about 16 hours before analysis was started Each cylinder was equipped with a pressure regulator that was purged three times by sequential evacuation and pressurisation with the gas mixture used Continous flow (2 ndash 3mlmin) through the sample loop
Uncertainty The specification of potential uncertainty sources is given in Annex 3
3 injection standard (high)
3 injection sample
3 injection standard (high)
3 injection sample
3 injection standard (low)
3 injection sample
3 injection standard (low)
3 injection standard (low)
36
Uncertainty table CO2
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 002 rel 1 002 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 03 rel
Uncertainty table CO
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 007 rel 1 007 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 05 rel
37
Uncertainty table C3H8
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 010 rel 1 001 rel
Analysis normal 028 rel 1 028 rel
Coverage factor 2
Expanded uncertainty 06 rel
Optional
You may provide additional data like the raw measurement data information on your
measurement procedure chromatograms etc
38
Appendix 3 SPECIFICATION OF POTENTIAL UNCERTAINTY SOURCES
a Uncertainty related to the balance and the weights Resolution of balance Accuracy of balance including linearity Incorrect zero point Drift (thermal and time effects) Instability due to draught Location of cylinder on the balance pan Uncertainties in the weights used Buoyancy effects on the weights used
b Uncertainties related to the gas cylinder Mechanical handling of cylinder
Loss of metal paints or labels from surface of cylinder Loss of metal from threads of valvefitting Dirt on cylinder valves or associated fitting
Absorptiondesorption effects on the external cylinder surface Buoyancy effects on the cylinder itself
Cylinder temperature differs from surrounding air due to eg filling with gas Change of cylinder volume during filling Change of density of surrounding air due to changes in temperature air pressure humidity and carbon dioxide content
Uncertainty in determination of external cylinder volume c Uncertainties related to the component gases Residual gas in cylinder Leakage Leakage of air into the cylinder after evacuation
Leakage of gas from the cylinder valve during filling Escape of gas from cylinder into transport lines
Gas remaining in transfer system when weight loss method is used Absorptionreaction of components on internal cylinder surface Reaction between components Impurities in all the initial gases Insufficient homogenization Uncertainty of molecular mass d Uncertainties related to the analysis
Repeatability and selectivity of the analyzer Appropriateness of the calibration curve
39
MEASUREMENT REPORT - All Ukrainian State Research-Industrial Center of Standardization Metrology Certification and Protection of Consumers Ukraine
gas ndash helium flow rate 15 cm3min detector TCD tdetector = 250 ordmС toven = 70 ordmС It was automatic data collection
Measurement and Calibration Methods Laboratory Measurement method Type of calibration curve
GCFID (С3Н8) 3 points linear Ukrmetrteststandard GCTCD (СО СО2) 3 points linear
GCFID ndash gas-chromatographic with flame-ionization detector GCTCD - gas-chromatographic with thermal-conductivity detector
42
Calibration Standards
Calibration standards ndash primary standard gas mixtures (PSGM) used for measurements by comparison method
PSGM-1 Cylinder 0116
PSGM-2 Cylinder 0107
PSGM-3 Cylinder 0093 Composition
x u(x) x u(x) x u(x) СО 27874 00015 29899 00015 31891 00015 СО2 130187 00015 144456 00016 137016 00016 С3Н8 019003 000008 020017 000008 021013 000008 N2 balance balance balance
Note x ndash mole fraction u(x) ndash absolute standard uncertainty
It was used gravimetric method of preparation of PSGM Electronic balance КА-20-3 of Mettler Toledo max limit of weighing is 20 kg least
limit of weighing is 01 g standard deviation is 0006 g Analysis of purity of parent gases was carried out with usage of chromatographs
НР6890N with helium ndash ionization detector flame ndash ionization detector thermal ndash conductivity detector and mass ndash spectrometric detector as well аs gas analyzers GIAM-15M and Onix condensate-thermometer hygrometer TOROS-3-2B
Calculation of uncertainties was carried out according to ISO 6142-2003 Corrections of temperature pressure and humidity of environment were considered
in calculations according to ISO 6142-2003 (program of ISO-6142 2000-03-17 designer is NMi) Protocols and explanations are in Annex A
Instrument (Comparator) Calibration Calibration of comparator ndash gas chromatograph HP 6890 was carried out with usage
of PSGM Measurement sequence PSGM -1 х 3 PSGM -2 х 3 COOMET gas mixture х 3 PSGM -2 х 3 PSGM -3 х 3 It is necessary to use PSGM-2 repeatedly for estimation of reproducibility of results
Program B_LEAST recommended by ISO 6143-2003 was used for constructing the curve Mathematical model of calibration curve is linear one
Sample Handling The cylinder was kept for 24 hrs at a room where comparators were disposed This room is a thermostatic room with t = (20plusmn2) ordmС
43
A method of sample input to a comparator is a method with flow stabilization Uncertainty The following uncertainties were included to the budget of uncertainty - uncertainty of the balance - uncertainties of impurities in parent gases Contribution from other uncertainty sources was insignificant A cabin of the balance is thermostatically The balance is the one-pan balance
Air transfer is absent in the cabin of the balance Drift of the balance is absent for PSGM preparation
Contribution from other uncertainty sources was considered in software according to ISO 6142-2003
Uncertainties related to the analysis (comparison) were considered in software according to ISO 6143-2003 and enclosed in Annex B
Uncertainty table СО2
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas mixture
B 001 1 001
Analysis A B 008 1 008
Coverage factor 2 Expanded uncertainty 002sdot10-2 molmol Uncertainty table СО
Protocols of analysis (comparison) in accordance with ISO 6143-2003
57
Explanation of protocols of comparison
Chapter I ldquoThe calibration data set isrdquo contains columns 1 mole fraction of a component 2 absolute standard uncertainty of mole fraction of a component 3 a signal of a comparator 4 absolute standard uncertainty of a comparator signal
Chapter II ldquoResults of ISO 6143 methodrdquo contains parameters of a calibration curve including its
uncertainty
Chapter ІІІ ldquoPart II Processing of datardquo contains columns
1 calc x - the results of comparison mole fraction of a component 2 u(x) - absolute standard uncertainty of mole fraction of a component 3 response y - a signal of a comparator 4 u(y) - absolute standard uncertainty of a comparator signal
58
СО2 - measurement 1 Data setCO2_21 The calibration data set is 1302E+01 1510E-03 1022E+04 1820E+00 1370E+01 1560E-03 1077E+04 2730E+00 1445E+01 1620E-03 1135E+04 5900E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 20331E-02 12711E-03 12573E-01 11653E-05 -14638E-06 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 10548E-02 12722E-03 31762E-02 28898E-06 -91698E-08 Remaining SSD is 74346 Weighted distances x-value x-dist y-dist 100E+00 130E+01 490E-01 -755E-01 200E+00 137E+01 -103E+00 228E+00 300E+00 144E+01 539E-01 -250E-01 Goodness-of-fit measure 22837 Parameter set 1 1054788657490729E-2 1272208026684145E-3 3176237146276368E-2 2889798108124711E-6 -
9169821653851327E-8 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_21c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13577E+01 25542E-03 10664E+04 15200E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 547E-06 328E-06 316E-06 784E-06 286E-06 652E-06 Linear model Parameters for the fit were (b0 b1) 10548E-02 12722E-03
59
СО2 - measurement 2
Data setCO2_20 The calibration data set is 1302E+01 1512E-03 1021E+04 4723E+00 1370E+01 1563E-03 1075E+04 1600E+00 1445E+01 1620E-03 1133E+04 7300E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -38760E-02 12784E-03 26817E-02 24890E-06 -66689E-08 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -62452E-02 12805E-03 47930E-02 43243E-06 -20716E-07 Remaining SSD is 03231 Weighted distances x-value x-dist y-dist 100E+00 130E+01 107E-01 -415E-01 200E+00 137E+01 -212E-01 283E-01 300E+00 144E+01 104E-01 -584E-02 Goodness-of-fit measure 04155 Parameter set 1 -6245240430658412E-2 1280492624666799E-3 4792952200361109E-2 4324266278840409E-6 -
2071623966851869E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_20c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13594E+01 10290E-02 10665E+04 78300E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 121E-05 683E-06 651E-06 315E-05 560E-06 106E-04 Linear model Parameters for the fit were (b0 b1) -62452E-02 12805E-03
60
С3Н8 - measurement 1
Data setC3H8 The calibration data set is 1900E-01 7800E-05 9057E+03 1098E+01 2002E-01 7900E-05 9552E+03 8569E+00 2101E-01 7960E-05 1007E+04 4049E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10529E-02 19831E-05 34552E-03 36109E-07 -12465E-09 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11642E-02 19714E-05 23073E-03 23522E-07 -54231E-10 Remaining SSD is 19453 Weighted distances x-value x-dist y-dist 100E+00 190E-01 -239E-01 666E-01 200E+00 200E-01 487E-01 -104E+00 300E+00 210E-01 -247E-01 248E-01 Goodness-of-fit measure 10414 Parameter set 1 1164239985182795E-2 1971441115316992E-5 2307269625077337E-3 2352198415608386E-7 -
5423119774765299E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19837E-01 14840E-04 94718E+03 45610E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
30
Change of temperature 02 Rectangular 02 1 02 Change of atmospheric pressure 028 Rectangular 028 1 028
Changes of chromotograph response
012 Normal 012 1 007
Standard deviation of 3 runs 0001 Normal 0001 1 0006
Relative total standard uncertainty 054 Coverage factor k=2 Expanded uncertainty 02middot10-4 molmol
Sample handling
Period for exposure of cylinder to measurement conditions and method how to transport sample to the device
1 Stands for storing gas standard cylinders and calibration mixture cylinders and chromotograph are placed in a laboratory room which is not accessible to unauthorized persons The laboratory is equipped with air-conditioner to maintain required temperature and humidity on a continuous basis and some auxiliary measuring instruments as thermometer psychrometric hygrometer and aneroid to control temperature humidity and atmospheric inside the room
2 The comparison sample cylinder was stored in laboratory from the date of its
delivery to Minsk on 25042005 CGM cylinders are stored horizontally on racks and positioned vertically using special support when measurements are carried out
3 The analyzed gas sample is transported through the fine adjustment valve (FAV)
Conjunctions Cylinder - FAV FAV - tube tube - doser are made of metal and use adapters with spherical ends and bushes FAV is made of brass tube is made of copper and doser is made of duralumin
Instrument(s) (principles make type configuration data collection etc) For the analysis a GC were used with specifically applications For the determination of (Nitrogen (N2)) Carbon Dioxide (CO2) Carbon Monoxide (CO) and Propane (C3H8) balance GC Perkin Elmer AutoSystem XL (two channel system) with a stream selection valve for 4 streams and 2 gas sampling valves
Channel A for the determination of N2 CO and CO2 Carrier Gas Helium Columns Column system with two packed columns (6 ft x 18rdquo Porapak R 80100 mesh and 6 ft x 18rdquo Mol-Sieve 13X 80100 mesh) Oven Temperature 960 degC to 180 degC Detector micro-TCD Data Collection Total Chrom Workstation Channel B for the determination of C3H8 Carrier Gas Helium Columns Capillary column 50 m x 032 microm LP-SIL-8-CB Oven Temperature 60 degC to 180 degC Detector FID Data Collection Total Chrom Workstation
34
Calibration Standards
Calibration Standards for the measurements (preparation method purity analyses estimated uncertainty etc)
All standards were prepared individually according to ISO 6142 rdquoGas analysis - Preparation of calibration gases - Gravimetric Methodrdquo
Depending on the concentration of the components standards were prepared individually from pure gases or from pre-mixtures which were individually prepared from pure gases
The content of the impurities in all pure gases were determined before use by GC-DID GC-FID and or GC-TCD
After preparation the standards were verified by analytical comparisons against existing gravimetrically prepared standards Only when no significant difference between the analysed and the calculated gravimetric composition is found the ldquonew prepared candidate rdquo is accepted as a new standards
For the analysis of all components multi component standards with nitrogen as balance gas were used
Composition of calibrants BAM C49250-050722 Component Assigned value( x)
mmol mol Standard uncertainty (u(x)) relativ (k=2)
Calibration procedure (mathematical modelcalibration curve number and concentrations of standards measurement sequence temperaturepressure correction etc)
For the instrument calibration the bracketing technique was used The fraction of the current used standards deviated no more than +10rel and -10rel respectively from those of the sample
Measurement sequence
Sample Handling
How were the cylinders treated after arrival (eg stabilized) and how were samples transferred to the instrument (automatic high pressure mass-flow controller dilution etc) After heating (45 - 50 degC) the cylinder for 8 hours the cylinder were rolled about 16 hours before analysis was started Each cylinder was equipped with a pressure regulator that was purged three times by sequential evacuation and pressurisation with the gas mixture used Continous flow (2 ndash 3mlmin) through the sample loop
Uncertainty The specification of potential uncertainty sources is given in Annex 3
3 injection standard (high)
3 injection sample
3 injection standard (high)
3 injection sample
3 injection standard (low)
3 injection sample
3 injection standard (low)
3 injection standard (low)
36
Uncertainty table CO2
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 002 rel 1 002 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 03 rel
Uncertainty table CO
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 007 rel 1 007 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 05 rel
37
Uncertainty table C3H8
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 010 rel 1 001 rel
Analysis normal 028 rel 1 028 rel
Coverage factor 2
Expanded uncertainty 06 rel
Optional
You may provide additional data like the raw measurement data information on your
measurement procedure chromatograms etc
38
Appendix 3 SPECIFICATION OF POTENTIAL UNCERTAINTY SOURCES
a Uncertainty related to the balance and the weights Resolution of balance Accuracy of balance including linearity Incorrect zero point Drift (thermal and time effects) Instability due to draught Location of cylinder on the balance pan Uncertainties in the weights used Buoyancy effects on the weights used
b Uncertainties related to the gas cylinder Mechanical handling of cylinder
Loss of metal paints or labels from surface of cylinder Loss of metal from threads of valvefitting Dirt on cylinder valves or associated fitting
Absorptiondesorption effects on the external cylinder surface Buoyancy effects on the cylinder itself
Cylinder temperature differs from surrounding air due to eg filling with gas Change of cylinder volume during filling Change of density of surrounding air due to changes in temperature air pressure humidity and carbon dioxide content
Uncertainty in determination of external cylinder volume c Uncertainties related to the component gases Residual gas in cylinder Leakage Leakage of air into the cylinder after evacuation
Leakage of gas from the cylinder valve during filling Escape of gas from cylinder into transport lines
Gas remaining in transfer system when weight loss method is used Absorptionreaction of components on internal cylinder surface Reaction between components Impurities in all the initial gases Insufficient homogenization Uncertainty of molecular mass d Uncertainties related to the analysis
Repeatability and selectivity of the analyzer Appropriateness of the calibration curve
39
MEASUREMENT REPORT - All Ukrainian State Research-Industrial Center of Standardization Metrology Certification and Protection of Consumers Ukraine
gas ndash helium flow rate 15 cm3min detector TCD tdetector = 250 ordmС toven = 70 ordmС It was automatic data collection
Measurement and Calibration Methods Laboratory Measurement method Type of calibration curve
GCFID (С3Н8) 3 points linear Ukrmetrteststandard GCTCD (СО СО2) 3 points linear
GCFID ndash gas-chromatographic with flame-ionization detector GCTCD - gas-chromatographic with thermal-conductivity detector
42
Calibration Standards
Calibration standards ndash primary standard gas mixtures (PSGM) used for measurements by comparison method
PSGM-1 Cylinder 0116
PSGM-2 Cylinder 0107
PSGM-3 Cylinder 0093 Composition
x u(x) x u(x) x u(x) СО 27874 00015 29899 00015 31891 00015 СО2 130187 00015 144456 00016 137016 00016 С3Н8 019003 000008 020017 000008 021013 000008 N2 balance balance balance
Note x ndash mole fraction u(x) ndash absolute standard uncertainty
It was used gravimetric method of preparation of PSGM Electronic balance КА-20-3 of Mettler Toledo max limit of weighing is 20 kg least
limit of weighing is 01 g standard deviation is 0006 g Analysis of purity of parent gases was carried out with usage of chromatographs
НР6890N with helium ndash ionization detector flame ndash ionization detector thermal ndash conductivity detector and mass ndash spectrometric detector as well аs gas analyzers GIAM-15M and Onix condensate-thermometer hygrometer TOROS-3-2B
Calculation of uncertainties was carried out according to ISO 6142-2003 Corrections of temperature pressure and humidity of environment were considered
in calculations according to ISO 6142-2003 (program of ISO-6142 2000-03-17 designer is NMi) Protocols and explanations are in Annex A
Instrument (Comparator) Calibration Calibration of comparator ndash gas chromatograph HP 6890 was carried out with usage
of PSGM Measurement sequence PSGM -1 х 3 PSGM -2 х 3 COOMET gas mixture х 3 PSGM -2 х 3 PSGM -3 х 3 It is necessary to use PSGM-2 repeatedly for estimation of reproducibility of results
Program B_LEAST recommended by ISO 6143-2003 was used for constructing the curve Mathematical model of calibration curve is linear one
Sample Handling The cylinder was kept for 24 hrs at a room where comparators were disposed This room is a thermostatic room with t = (20plusmn2) ordmС
43
A method of sample input to a comparator is a method with flow stabilization Uncertainty The following uncertainties were included to the budget of uncertainty - uncertainty of the balance - uncertainties of impurities in parent gases Contribution from other uncertainty sources was insignificant A cabin of the balance is thermostatically The balance is the one-pan balance
Air transfer is absent in the cabin of the balance Drift of the balance is absent for PSGM preparation
Contribution from other uncertainty sources was considered in software according to ISO 6142-2003
Uncertainties related to the analysis (comparison) were considered in software according to ISO 6143-2003 and enclosed in Annex B
Uncertainty table СО2
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas mixture
B 001 1 001
Analysis A B 008 1 008
Coverage factor 2 Expanded uncertainty 002sdot10-2 molmol Uncertainty table СО
Protocols of analysis (comparison) in accordance with ISO 6143-2003
57
Explanation of protocols of comparison
Chapter I ldquoThe calibration data set isrdquo contains columns 1 mole fraction of a component 2 absolute standard uncertainty of mole fraction of a component 3 a signal of a comparator 4 absolute standard uncertainty of a comparator signal
Chapter II ldquoResults of ISO 6143 methodrdquo contains parameters of a calibration curve including its
uncertainty
Chapter ІІІ ldquoPart II Processing of datardquo contains columns
1 calc x - the results of comparison mole fraction of a component 2 u(x) - absolute standard uncertainty of mole fraction of a component 3 response y - a signal of a comparator 4 u(y) - absolute standard uncertainty of a comparator signal
58
СО2 - measurement 1 Data setCO2_21 The calibration data set is 1302E+01 1510E-03 1022E+04 1820E+00 1370E+01 1560E-03 1077E+04 2730E+00 1445E+01 1620E-03 1135E+04 5900E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 20331E-02 12711E-03 12573E-01 11653E-05 -14638E-06 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 10548E-02 12722E-03 31762E-02 28898E-06 -91698E-08 Remaining SSD is 74346 Weighted distances x-value x-dist y-dist 100E+00 130E+01 490E-01 -755E-01 200E+00 137E+01 -103E+00 228E+00 300E+00 144E+01 539E-01 -250E-01 Goodness-of-fit measure 22837 Parameter set 1 1054788657490729E-2 1272208026684145E-3 3176237146276368E-2 2889798108124711E-6 -
9169821653851327E-8 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_21c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13577E+01 25542E-03 10664E+04 15200E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 547E-06 328E-06 316E-06 784E-06 286E-06 652E-06 Linear model Parameters for the fit were (b0 b1) 10548E-02 12722E-03
59
СО2 - measurement 2
Data setCO2_20 The calibration data set is 1302E+01 1512E-03 1021E+04 4723E+00 1370E+01 1563E-03 1075E+04 1600E+00 1445E+01 1620E-03 1133E+04 7300E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -38760E-02 12784E-03 26817E-02 24890E-06 -66689E-08 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -62452E-02 12805E-03 47930E-02 43243E-06 -20716E-07 Remaining SSD is 03231 Weighted distances x-value x-dist y-dist 100E+00 130E+01 107E-01 -415E-01 200E+00 137E+01 -212E-01 283E-01 300E+00 144E+01 104E-01 -584E-02 Goodness-of-fit measure 04155 Parameter set 1 -6245240430658412E-2 1280492624666799E-3 4792952200361109E-2 4324266278840409E-6 -
2071623966851869E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_20c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13594E+01 10290E-02 10665E+04 78300E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 121E-05 683E-06 651E-06 315E-05 560E-06 106E-04 Linear model Parameters for the fit were (b0 b1) -62452E-02 12805E-03
60
С3Н8 - measurement 1
Data setC3H8 The calibration data set is 1900E-01 7800E-05 9057E+03 1098E+01 2002E-01 7900E-05 9552E+03 8569E+00 2101E-01 7960E-05 1007E+04 4049E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10529E-02 19831E-05 34552E-03 36109E-07 -12465E-09 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11642E-02 19714E-05 23073E-03 23522E-07 -54231E-10 Remaining SSD is 19453 Weighted distances x-value x-dist y-dist 100E+00 190E-01 -239E-01 666E-01 200E+00 200E-01 487E-01 -104E+00 300E+00 210E-01 -247E-01 248E-01 Goodness-of-fit measure 10414 Parameter set 1 1164239985182795E-2 1971441115316992E-5 2307269625077337E-3 2352198415608386E-7 -
5423119774765299E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19837E-01 14840E-04 94718E+03 45610E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
Instrument(s) (principles make type configuration data collection etc) For the analysis a GC were used with specifically applications For the determination of (Nitrogen (N2)) Carbon Dioxide (CO2) Carbon Monoxide (CO) and Propane (C3H8) balance GC Perkin Elmer AutoSystem XL (two channel system) with a stream selection valve for 4 streams and 2 gas sampling valves
Channel A for the determination of N2 CO and CO2 Carrier Gas Helium Columns Column system with two packed columns (6 ft x 18rdquo Porapak R 80100 mesh and 6 ft x 18rdquo Mol-Sieve 13X 80100 mesh) Oven Temperature 960 degC to 180 degC Detector micro-TCD Data Collection Total Chrom Workstation Channel B for the determination of C3H8 Carrier Gas Helium Columns Capillary column 50 m x 032 microm LP-SIL-8-CB Oven Temperature 60 degC to 180 degC Detector FID Data Collection Total Chrom Workstation
34
Calibration Standards
Calibration Standards for the measurements (preparation method purity analyses estimated uncertainty etc)
All standards were prepared individually according to ISO 6142 rdquoGas analysis - Preparation of calibration gases - Gravimetric Methodrdquo
Depending on the concentration of the components standards were prepared individually from pure gases or from pre-mixtures which were individually prepared from pure gases
The content of the impurities in all pure gases were determined before use by GC-DID GC-FID and or GC-TCD
After preparation the standards were verified by analytical comparisons against existing gravimetrically prepared standards Only when no significant difference between the analysed and the calculated gravimetric composition is found the ldquonew prepared candidate rdquo is accepted as a new standards
For the analysis of all components multi component standards with nitrogen as balance gas were used
Composition of calibrants BAM C49250-050722 Component Assigned value( x)
mmol mol Standard uncertainty (u(x)) relativ (k=2)
Calibration procedure (mathematical modelcalibration curve number and concentrations of standards measurement sequence temperaturepressure correction etc)
For the instrument calibration the bracketing technique was used The fraction of the current used standards deviated no more than +10rel and -10rel respectively from those of the sample
Measurement sequence
Sample Handling
How were the cylinders treated after arrival (eg stabilized) and how were samples transferred to the instrument (automatic high pressure mass-flow controller dilution etc) After heating (45 - 50 degC) the cylinder for 8 hours the cylinder were rolled about 16 hours before analysis was started Each cylinder was equipped with a pressure regulator that was purged three times by sequential evacuation and pressurisation with the gas mixture used Continous flow (2 ndash 3mlmin) through the sample loop
Uncertainty The specification of potential uncertainty sources is given in Annex 3
3 injection standard (high)
3 injection sample
3 injection standard (high)
3 injection sample
3 injection standard (low)
3 injection sample
3 injection standard (low)
3 injection standard (low)
36
Uncertainty table CO2
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 002 rel 1 002 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 03 rel
Uncertainty table CO
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 007 rel 1 007 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 05 rel
37
Uncertainty table C3H8
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 010 rel 1 001 rel
Analysis normal 028 rel 1 028 rel
Coverage factor 2
Expanded uncertainty 06 rel
Optional
You may provide additional data like the raw measurement data information on your
measurement procedure chromatograms etc
38
Appendix 3 SPECIFICATION OF POTENTIAL UNCERTAINTY SOURCES
a Uncertainty related to the balance and the weights Resolution of balance Accuracy of balance including linearity Incorrect zero point Drift (thermal and time effects) Instability due to draught Location of cylinder on the balance pan Uncertainties in the weights used Buoyancy effects on the weights used
b Uncertainties related to the gas cylinder Mechanical handling of cylinder
Loss of metal paints or labels from surface of cylinder Loss of metal from threads of valvefitting Dirt on cylinder valves or associated fitting
Absorptiondesorption effects on the external cylinder surface Buoyancy effects on the cylinder itself
Cylinder temperature differs from surrounding air due to eg filling with gas Change of cylinder volume during filling Change of density of surrounding air due to changes in temperature air pressure humidity and carbon dioxide content
Uncertainty in determination of external cylinder volume c Uncertainties related to the component gases Residual gas in cylinder Leakage Leakage of air into the cylinder after evacuation
Leakage of gas from the cylinder valve during filling Escape of gas from cylinder into transport lines
Gas remaining in transfer system when weight loss method is used Absorptionreaction of components on internal cylinder surface Reaction between components Impurities in all the initial gases Insufficient homogenization Uncertainty of molecular mass d Uncertainties related to the analysis
Repeatability and selectivity of the analyzer Appropriateness of the calibration curve
39
MEASUREMENT REPORT - All Ukrainian State Research-Industrial Center of Standardization Metrology Certification and Protection of Consumers Ukraine
gas ndash helium flow rate 15 cm3min detector TCD tdetector = 250 ordmС toven = 70 ordmС It was automatic data collection
Measurement and Calibration Methods Laboratory Measurement method Type of calibration curve
GCFID (С3Н8) 3 points linear Ukrmetrteststandard GCTCD (СО СО2) 3 points linear
GCFID ndash gas-chromatographic with flame-ionization detector GCTCD - gas-chromatographic with thermal-conductivity detector
42
Calibration Standards
Calibration standards ndash primary standard gas mixtures (PSGM) used for measurements by comparison method
PSGM-1 Cylinder 0116
PSGM-2 Cylinder 0107
PSGM-3 Cylinder 0093 Composition
x u(x) x u(x) x u(x) СО 27874 00015 29899 00015 31891 00015 СО2 130187 00015 144456 00016 137016 00016 С3Н8 019003 000008 020017 000008 021013 000008 N2 balance balance balance
Note x ndash mole fraction u(x) ndash absolute standard uncertainty
It was used gravimetric method of preparation of PSGM Electronic balance КА-20-3 of Mettler Toledo max limit of weighing is 20 kg least
limit of weighing is 01 g standard deviation is 0006 g Analysis of purity of parent gases was carried out with usage of chromatographs
НР6890N with helium ndash ionization detector flame ndash ionization detector thermal ndash conductivity detector and mass ndash spectrometric detector as well аs gas analyzers GIAM-15M and Onix condensate-thermometer hygrometer TOROS-3-2B
Calculation of uncertainties was carried out according to ISO 6142-2003 Corrections of temperature pressure and humidity of environment were considered
in calculations according to ISO 6142-2003 (program of ISO-6142 2000-03-17 designer is NMi) Protocols and explanations are in Annex A
Instrument (Comparator) Calibration Calibration of comparator ndash gas chromatograph HP 6890 was carried out with usage
of PSGM Measurement sequence PSGM -1 х 3 PSGM -2 х 3 COOMET gas mixture х 3 PSGM -2 х 3 PSGM -3 х 3 It is necessary to use PSGM-2 repeatedly for estimation of reproducibility of results
Program B_LEAST recommended by ISO 6143-2003 was used for constructing the curve Mathematical model of calibration curve is linear one
Sample Handling The cylinder was kept for 24 hrs at a room where comparators were disposed This room is a thermostatic room with t = (20plusmn2) ordmС
43
A method of sample input to a comparator is a method with flow stabilization Uncertainty The following uncertainties were included to the budget of uncertainty - uncertainty of the balance - uncertainties of impurities in parent gases Contribution from other uncertainty sources was insignificant A cabin of the balance is thermostatically The balance is the one-pan balance
Air transfer is absent in the cabin of the balance Drift of the balance is absent for PSGM preparation
Contribution from other uncertainty sources was considered in software according to ISO 6142-2003
Uncertainties related to the analysis (comparison) were considered in software according to ISO 6143-2003 and enclosed in Annex B
Uncertainty table СО2
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas mixture
B 001 1 001
Analysis A B 008 1 008
Coverage factor 2 Expanded uncertainty 002sdot10-2 molmol Uncertainty table СО
Protocols of analysis (comparison) in accordance with ISO 6143-2003
57
Explanation of protocols of comparison
Chapter I ldquoThe calibration data set isrdquo contains columns 1 mole fraction of a component 2 absolute standard uncertainty of mole fraction of a component 3 a signal of a comparator 4 absolute standard uncertainty of a comparator signal
Chapter II ldquoResults of ISO 6143 methodrdquo contains parameters of a calibration curve including its
uncertainty
Chapter ІІІ ldquoPart II Processing of datardquo contains columns
1 calc x - the results of comparison mole fraction of a component 2 u(x) - absolute standard uncertainty of mole fraction of a component 3 response y - a signal of a comparator 4 u(y) - absolute standard uncertainty of a comparator signal
58
СО2 - measurement 1 Data setCO2_21 The calibration data set is 1302E+01 1510E-03 1022E+04 1820E+00 1370E+01 1560E-03 1077E+04 2730E+00 1445E+01 1620E-03 1135E+04 5900E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 20331E-02 12711E-03 12573E-01 11653E-05 -14638E-06 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 10548E-02 12722E-03 31762E-02 28898E-06 -91698E-08 Remaining SSD is 74346 Weighted distances x-value x-dist y-dist 100E+00 130E+01 490E-01 -755E-01 200E+00 137E+01 -103E+00 228E+00 300E+00 144E+01 539E-01 -250E-01 Goodness-of-fit measure 22837 Parameter set 1 1054788657490729E-2 1272208026684145E-3 3176237146276368E-2 2889798108124711E-6 -
9169821653851327E-8 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_21c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13577E+01 25542E-03 10664E+04 15200E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 547E-06 328E-06 316E-06 784E-06 286E-06 652E-06 Linear model Parameters for the fit were (b0 b1) 10548E-02 12722E-03
59
СО2 - measurement 2
Data setCO2_20 The calibration data set is 1302E+01 1512E-03 1021E+04 4723E+00 1370E+01 1563E-03 1075E+04 1600E+00 1445E+01 1620E-03 1133E+04 7300E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -38760E-02 12784E-03 26817E-02 24890E-06 -66689E-08 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -62452E-02 12805E-03 47930E-02 43243E-06 -20716E-07 Remaining SSD is 03231 Weighted distances x-value x-dist y-dist 100E+00 130E+01 107E-01 -415E-01 200E+00 137E+01 -212E-01 283E-01 300E+00 144E+01 104E-01 -584E-02 Goodness-of-fit measure 04155 Parameter set 1 -6245240430658412E-2 1280492624666799E-3 4792952200361109E-2 4324266278840409E-6 -
2071623966851869E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_20c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13594E+01 10290E-02 10665E+04 78300E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 121E-05 683E-06 651E-06 315E-05 560E-06 106E-04 Linear model Parameters for the fit were (b0 b1) -62452E-02 12805E-03
60
С3Н8 - measurement 1
Data setC3H8 The calibration data set is 1900E-01 7800E-05 9057E+03 1098E+01 2002E-01 7900E-05 9552E+03 8569E+00 2101E-01 7960E-05 1007E+04 4049E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10529E-02 19831E-05 34552E-03 36109E-07 -12465E-09 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11642E-02 19714E-05 23073E-03 23522E-07 -54231E-10 Remaining SSD is 19453 Weighted distances x-value x-dist y-dist 100E+00 190E-01 -239E-01 666E-01 200E+00 200E-01 487E-01 -104E+00 300E+00 210E-01 -247E-01 248E-01 Goodness-of-fit measure 10414 Parameter set 1 1164239985182795E-2 1971441115316992E-5 2307269625077337E-3 2352198415608386E-7 -
5423119774765299E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19837E-01 14840E-04 94718E+03 45610E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
Instrument(s) (principles make type configuration data collection etc) For the analysis a GC were used with specifically applications For the determination of (Nitrogen (N2)) Carbon Dioxide (CO2) Carbon Monoxide (CO) and Propane (C3H8) balance GC Perkin Elmer AutoSystem XL (two channel system) with a stream selection valve for 4 streams and 2 gas sampling valves
Channel A for the determination of N2 CO and CO2 Carrier Gas Helium Columns Column system with two packed columns (6 ft x 18rdquo Porapak R 80100 mesh and 6 ft x 18rdquo Mol-Sieve 13X 80100 mesh) Oven Temperature 960 degC to 180 degC Detector micro-TCD Data Collection Total Chrom Workstation Channel B for the determination of C3H8 Carrier Gas Helium Columns Capillary column 50 m x 032 microm LP-SIL-8-CB Oven Temperature 60 degC to 180 degC Detector FID Data Collection Total Chrom Workstation
34
Calibration Standards
Calibration Standards for the measurements (preparation method purity analyses estimated uncertainty etc)
All standards were prepared individually according to ISO 6142 rdquoGas analysis - Preparation of calibration gases - Gravimetric Methodrdquo
Depending on the concentration of the components standards were prepared individually from pure gases or from pre-mixtures which were individually prepared from pure gases
The content of the impurities in all pure gases were determined before use by GC-DID GC-FID and or GC-TCD
After preparation the standards were verified by analytical comparisons against existing gravimetrically prepared standards Only when no significant difference between the analysed and the calculated gravimetric composition is found the ldquonew prepared candidate rdquo is accepted as a new standards
For the analysis of all components multi component standards with nitrogen as balance gas were used
Composition of calibrants BAM C49250-050722 Component Assigned value( x)
mmol mol Standard uncertainty (u(x)) relativ (k=2)
Calibration procedure (mathematical modelcalibration curve number and concentrations of standards measurement sequence temperaturepressure correction etc)
For the instrument calibration the bracketing technique was used The fraction of the current used standards deviated no more than +10rel and -10rel respectively from those of the sample
Measurement sequence
Sample Handling
How were the cylinders treated after arrival (eg stabilized) and how were samples transferred to the instrument (automatic high pressure mass-flow controller dilution etc) After heating (45 - 50 degC) the cylinder for 8 hours the cylinder were rolled about 16 hours before analysis was started Each cylinder was equipped with a pressure regulator that was purged three times by sequential evacuation and pressurisation with the gas mixture used Continous flow (2 ndash 3mlmin) through the sample loop
Uncertainty The specification of potential uncertainty sources is given in Annex 3
3 injection standard (high)
3 injection sample
3 injection standard (high)
3 injection sample
3 injection standard (low)
3 injection sample
3 injection standard (low)
3 injection standard (low)
36
Uncertainty table CO2
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 002 rel 1 002 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 03 rel
Uncertainty table CO
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 007 rel 1 007 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 05 rel
37
Uncertainty table C3H8
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 010 rel 1 001 rel
Analysis normal 028 rel 1 028 rel
Coverage factor 2
Expanded uncertainty 06 rel
Optional
You may provide additional data like the raw measurement data information on your
measurement procedure chromatograms etc
38
Appendix 3 SPECIFICATION OF POTENTIAL UNCERTAINTY SOURCES
a Uncertainty related to the balance and the weights Resolution of balance Accuracy of balance including linearity Incorrect zero point Drift (thermal and time effects) Instability due to draught Location of cylinder on the balance pan Uncertainties in the weights used Buoyancy effects on the weights used
b Uncertainties related to the gas cylinder Mechanical handling of cylinder
Loss of metal paints or labels from surface of cylinder Loss of metal from threads of valvefitting Dirt on cylinder valves or associated fitting
Absorptiondesorption effects on the external cylinder surface Buoyancy effects on the cylinder itself
Cylinder temperature differs from surrounding air due to eg filling with gas Change of cylinder volume during filling Change of density of surrounding air due to changes in temperature air pressure humidity and carbon dioxide content
Uncertainty in determination of external cylinder volume c Uncertainties related to the component gases Residual gas in cylinder Leakage Leakage of air into the cylinder after evacuation
Leakage of gas from the cylinder valve during filling Escape of gas from cylinder into transport lines
Gas remaining in transfer system when weight loss method is used Absorptionreaction of components on internal cylinder surface Reaction between components Impurities in all the initial gases Insufficient homogenization Uncertainty of molecular mass d Uncertainties related to the analysis
Repeatability and selectivity of the analyzer Appropriateness of the calibration curve
39
MEASUREMENT REPORT - All Ukrainian State Research-Industrial Center of Standardization Metrology Certification and Protection of Consumers Ukraine
gas ndash helium flow rate 15 cm3min detector TCD tdetector = 250 ordmС toven = 70 ordmС It was automatic data collection
Measurement and Calibration Methods Laboratory Measurement method Type of calibration curve
GCFID (С3Н8) 3 points linear Ukrmetrteststandard GCTCD (СО СО2) 3 points linear
GCFID ndash gas-chromatographic with flame-ionization detector GCTCD - gas-chromatographic with thermal-conductivity detector
42
Calibration Standards
Calibration standards ndash primary standard gas mixtures (PSGM) used for measurements by comparison method
PSGM-1 Cylinder 0116
PSGM-2 Cylinder 0107
PSGM-3 Cylinder 0093 Composition
x u(x) x u(x) x u(x) СО 27874 00015 29899 00015 31891 00015 СО2 130187 00015 144456 00016 137016 00016 С3Н8 019003 000008 020017 000008 021013 000008 N2 balance balance balance
Note x ndash mole fraction u(x) ndash absolute standard uncertainty
It was used gravimetric method of preparation of PSGM Electronic balance КА-20-3 of Mettler Toledo max limit of weighing is 20 kg least
limit of weighing is 01 g standard deviation is 0006 g Analysis of purity of parent gases was carried out with usage of chromatographs
НР6890N with helium ndash ionization detector flame ndash ionization detector thermal ndash conductivity detector and mass ndash spectrometric detector as well аs gas analyzers GIAM-15M and Onix condensate-thermometer hygrometer TOROS-3-2B
Calculation of uncertainties was carried out according to ISO 6142-2003 Corrections of temperature pressure and humidity of environment were considered
in calculations according to ISO 6142-2003 (program of ISO-6142 2000-03-17 designer is NMi) Protocols and explanations are in Annex A
Instrument (Comparator) Calibration Calibration of comparator ndash gas chromatograph HP 6890 was carried out with usage
of PSGM Measurement sequence PSGM -1 х 3 PSGM -2 х 3 COOMET gas mixture х 3 PSGM -2 х 3 PSGM -3 х 3 It is necessary to use PSGM-2 repeatedly for estimation of reproducibility of results
Program B_LEAST recommended by ISO 6143-2003 was used for constructing the curve Mathematical model of calibration curve is linear one
Sample Handling The cylinder was kept for 24 hrs at a room where comparators were disposed This room is a thermostatic room with t = (20plusmn2) ordmС
43
A method of sample input to a comparator is a method with flow stabilization Uncertainty The following uncertainties were included to the budget of uncertainty - uncertainty of the balance - uncertainties of impurities in parent gases Contribution from other uncertainty sources was insignificant A cabin of the balance is thermostatically The balance is the one-pan balance
Air transfer is absent in the cabin of the balance Drift of the balance is absent for PSGM preparation
Contribution from other uncertainty sources was considered in software according to ISO 6142-2003
Uncertainties related to the analysis (comparison) were considered in software according to ISO 6143-2003 and enclosed in Annex B
Uncertainty table СО2
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas mixture
B 001 1 001
Analysis A B 008 1 008
Coverage factor 2 Expanded uncertainty 002sdot10-2 molmol Uncertainty table СО
Protocols of analysis (comparison) in accordance with ISO 6143-2003
57
Explanation of protocols of comparison
Chapter I ldquoThe calibration data set isrdquo contains columns 1 mole fraction of a component 2 absolute standard uncertainty of mole fraction of a component 3 a signal of a comparator 4 absolute standard uncertainty of a comparator signal
Chapter II ldquoResults of ISO 6143 methodrdquo contains parameters of a calibration curve including its
uncertainty
Chapter ІІІ ldquoPart II Processing of datardquo contains columns
1 calc x - the results of comparison mole fraction of a component 2 u(x) - absolute standard uncertainty of mole fraction of a component 3 response y - a signal of a comparator 4 u(y) - absolute standard uncertainty of a comparator signal
58
СО2 - measurement 1 Data setCO2_21 The calibration data set is 1302E+01 1510E-03 1022E+04 1820E+00 1370E+01 1560E-03 1077E+04 2730E+00 1445E+01 1620E-03 1135E+04 5900E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 20331E-02 12711E-03 12573E-01 11653E-05 -14638E-06 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 10548E-02 12722E-03 31762E-02 28898E-06 -91698E-08 Remaining SSD is 74346 Weighted distances x-value x-dist y-dist 100E+00 130E+01 490E-01 -755E-01 200E+00 137E+01 -103E+00 228E+00 300E+00 144E+01 539E-01 -250E-01 Goodness-of-fit measure 22837 Parameter set 1 1054788657490729E-2 1272208026684145E-3 3176237146276368E-2 2889798108124711E-6 -
9169821653851327E-8 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_21c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13577E+01 25542E-03 10664E+04 15200E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 547E-06 328E-06 316E-06 784E-06 286E-06 652E-06 Linear model Parameters for the fit were (b0 b1) 10548E-02 12722E-03
59
СО2 - measurement 2
Data setCO2_20 The calibration data set is 1302E+01 1512E-03 1021E+04 4723E+00 1370E+01 1563E-03 1075E+04 1600E+00 1445E+01 1620E-03 1133E+04 7300E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -38760E-02 12784E-03 26817E-02 24890E-06 -66689E-08 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -62452E-02 12805E-03 47930E-02 43243E-06 -20716E-07 Remaining SSD is 03231 Weighted distances x-value x-dist y-dist 100E+00 130E+01 107E-01 -415E-01 200E+00 137E+01 -212E-01 283E-01 300E+00 144E+01 104E-01 -584E-02 Goodness-of-fit measure 04155 Parameter set 1 -6245240430658412E-2 1280492624666799E-3 4792952200361109E-2 4324266278840409E-6 -
2071623966851869E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_20c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13594E+01 10290E-02 10665E+04 78300E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 121E-05 683E-06 651E-06 315E-05 560E-06 106E-04 Linear model Parameters for the fit were (b0 b1) -62452E-02 12805E-03
60
С3Н8 - measurement 1
Data setC3H8 The calibration data set is 1900E-01 7800E-05 9057E+03 1098E+01 2002E-01 7900E-05 9552E+03 8569E+00 2101E-01 7960E-05 1007E+04 4049E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10529E-02 19831E-05 34552E-03 36109E-07 -12465E-09 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11642E-02 19714E-05 23073E-03 23522E-07 -54231E-10 Remaining SSD is 19453 Weighted distances x-value x-dist y-dist 100E+00 190E-01 -239E-01 666E-01 200E+00 200E-01 487E-01 -104E+00 300E+00 210E-01 -247E-01 248E-01 Goodness-of-fit measure 10414 Parameter set 1 1164239985182795E-2 1971441115316992E-5 2307269625077337E-3 2352198415608386E-7 -
5423119774765299E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19837E-01 14840E-04 94718E+03 45610E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
Instrument(s) (principles make type configuration data collection etc) For the analysis a GC were used with specifically applications For the determination of (Nitrogen (N2)) Carbon Dioxide (CO2) Carbon Monoxide (CO) and Propane (C3H8) balance GC Perkin Elmer AutoSystem XL (two channel system) with a stream selection valve for 4 streams and 2 gas sampling valves
Channel A for the determination of N2 CO and CO2 Carrier Gas Helium Columns Column system with two packed columns (6 ft x 18rdquo Porapak R 80100 mesh and 6 ft x 18rdquo Mol-Sieve 13X 80100 mesh) Oven Temperature 960 degC to 180 degC Detector micro-TCD Data Collection Total Chrom Workstation Channel B for the determination of C3H8 Carrier Gas Helium Columns Capillary column 50 m x 032 microm LP-SIL-8-CB Oven Temperature 60 degC to 180 degC Detector FID Data Collection Total Chrom Workstation
34
Calibration Standards
Calibration Standards for the measurements (preparation method purity analyses estimated uncertainty etc)
All standards were prepared individually according to ISO 6142 rdquoGas analysis - Preparation of calibration gases - Gravimetric Methodrdquo
Depending on the concentration of the components standards were prepared individually from pure gases or from pre-mixtures which were individually prepared from pure gases
The content of the impurities in all pure gases were determined before use by GC-DID GC-FID and or GC-TCD
After preparation the standards were verified by analytical comparisons against existing gravimetrically prepared standards Only when no significant difference between the analysed and the calculated gravimetric composition is found the ldquonew prepared candidate rdquo is accepted as a new standards
For the analysis of all components multi component standards with nitrogen as balance gas were used
Composition of calibrants BAM C49250-050722 Component Assigned value( x)
mmol mol Standard uncertainty (u(x)) relativ (k=2)
Calibration procedure (mathematical modelcalibration curve number and concentrations of standards measurement sequence temperaturepressure correction etc)
For the instrument calibration the bracketing technique was used The fraction of the current used standards deviated no more than +10rel and -10rel respectively from those of the sample
Measurement sequence
Sample Handling
How were the cylinders treated after arrival (eg stabilized) and how were samples transferred to the instrument (automatic high pressure mass-flow controller dilution etc) After heating (45 - 50 degC) the cylinder for 8 hours the cylinder were rolled about 16 hours before analysis was started Each cylinder was equipped with a pressure regulator that was purged three times by sequential evacuation and pressurisation with the gas mixture used Continous flow (2 ndash 3mlmin) through the sample loop
Uncertainty The specification of potential uncertainty sources is given in Annex 3
3 injection standard (high)
3 injection sample
3 injection standard (high)
3 injection sample
3 injection standard (low)
3 injection sample
3 injection standard (low)
3 injection standard (low)
36
Uncertainty table CO2
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 002 rel 1 002 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 03 rel
Uncertainty table CO
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 007 rel 1 007 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 05 rel
37
Uncertainty table C3H8
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 010 rel 1 001 rel
Analysis normal 028 rel 1 028 rel
Coverage factor 2
Expanded uncertainty 06 rel
Optional
You may provide additional data like the raw measurement data information on your
measurement procedure chromatograms etc
38
Appendix 3 SPECIFICATION OF POTENTIAL UNCERTAINTY SOURCES
a Uncertainty related to the balance and the weights Resolution of balance Accuracy of balance including linearity Incorrect zero point Drift (thermal and time effects) Instability due to draught Location of cylinder on the balance pan Uncertainties in the weights used Buoyancy effects on the weights used
b Uncertainties related to the gas cylinder Mechanical handling of cylinder
Loss of metal paints or labels from surface of cylinder Loss of metal from threads of valvefitting Dirt on cylinder valves or associated fitting
Absorptiondesorption effects on the external cylinder surface Buoyancy effects on the cylinder itself
Cylinder temperature differs from surrounding air due to eg filling with gas Change of cylinder volume during filling Change of density of surrounding air due to changes in temperature air pressure humidity and carbon dioxide content
Uncertainty in determination of external cylinder volume c Uncertainties related to the component gases Residual gas in cylinder Leakage Leakage of air into the cylinder after evacuation
Leakage of gas from the cylinder valve during filling Escape of gas from cylinder into transport lines
Gas remaining in transfer system when weight loss method is used Absorptionreaction of components on internal cylinder surface Reaction between components Impurities in all the initial gases Insufficient homogenization Uncertainty of molecular mass d Uncertainties related to the analysis
Repeatability and selectivity of the analyzer Appropriateness of the calibration curve
39
MEASUREMENT REPORT - All Ukrainian State Research-Industrial Center of Standardization Metrology Certification and Protection of Consumers Ukraine
gas ndash helium flow rate 15 cm3min detector TCD tdetector = 250 ordmС toven = 70 ordmС It was automatic data collection
Measurement and Calibration Methods Laboratory Measurement method Type of calibration curve
GCFID (С3Н8) 3 points linear Ukrmetrteststandard GCTCD (СО СО2) 3 points linear
GCFID ndash gas-chromatographic with flame-ionization detector GCTCD - gas-chromatographic with thermal-conductivity detector
42
Calibration Standards
Calibration standards ndash primary standard gas mixtures (PSGM) used for measurements by comparison method
PSGM-1 Cylinder 0116
PSGM-2 Cylinder 0107
PSGM-3 Cylinder 0093 Composition
x u(x) x u(x) x u(x) СО 27874 00015 29899 00015 31891 00015 СО2 130187 00015 144456 00016 137016 00016 С3Н8 019003 000008 020017 000008 021013 000008 N2 balance balance balance
Note x ndash mole fraction u(x) ndash absolute standard uncertainty
It was used gravimetric method of preparation of PSGM Electronic balance КА-20-3 of Mettler Toledo max limit of weighing is 20 kg least
limit of weighing is 01 g standard deviation is 0006 g Analysis of purity of parent gases was carried out with usage of chromatographs
НР6890N with helium ndash ionization detector flame ndash ionization detector thermal ndash conductivity detector and mass ndash spectrometric detector as well аs gas analyzers GIAM-15M and Onix condensate-thermometer hygrometer TOROS-3-2B
Calculation of uncertainties was carried out according to ISO 6142-2003 Corrections of temperature pressure and humidity of environment were considered
in calculations according to ISO 6142-2003 (program of ISO-6142 2000-03-17 designer is NMi) Protocols and explanations are in Annex A
Instrument (Comparator) Calibration Calibration of comparator ndash gas chromatograph HP 6890 was carried out with usage
of PSGM Measurement sequence PSGM -1 х 3 PSGM -2 х 3 COOMET gas mixture х 3 PSGM -2 х 3 PSGM -3 х 3 It is necessary to use PSGM-2 repeatedly for estimation of reproducibility of results
Program B_LEAST recommended by ISO 6143-2003 was used for constructing the curve Mathematical model of calibration curve is linear one
Sample Handling The cylinder was kept for 24 hrs at a room where comparators were disposed This room is a thermostatic room with t = (20plusmn2) ordmС
43
A method of sample input to a comparator is a method with flow stabilization Uncertainty The following uncertainties were included to the budget of uncertainty - uncertainty of the balance - uncertainties of impurities in parent gases Contribution from other uncertainty sources was insignificant A cabin of the balance is thermostatically The balance is the one-pan balance
Air transfer is absent in the cabin of the balance Drift of the balance is absent for PSGM preparation
Contribution from other uncertainty sources was considered in software according to ISO 6142-2003
Uncertainties related to the analysis (comparison) were considered in software according to ISO 6143-2003 and enclosed in Annex B
Uncertainty table СО2
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas mixture
B 001 1 001
Analysis A B 008 1 008
Coverage factor 2 Expanded uncertainty 002sdot10-2 molmol Uncertainty table СО
Protocols of analysis (comparison) in accordance with ISO 6143-2003
57
Explanation of protocols of comparison
Chapter I ldquoThe calibration data set isrdquo contains columns 1 mole fraction of a component 2 absolute standard uncertainty of mole fraction of a component 3 a signal of a comparator 4 absolute standard uncertainty of a comparator signal
Chapter II ldquoResults of ISO 6143 methodrdquo contains parameters of a calibration curve including its
uncertainty
Chapter ІІІ ldquoPart II Processing of datardquo contains columns
1 calc x - the results of comparison mole fraction of a component 2 u(x) - absolute standard uncertainty of mole fraction of a component 3 response y - a signal of a comparator 4 u(y) - absolute standard uncertainty of a comparator signal
58
СО2 - measurement 1 Data setCO2_21 The calibration data set is 1302E+01 1510E-03 1022E+04 1820E+00 1370E+01 1560E-03 1077E+04 2730E+00 1445E+01 1620E-03 1135E+04 5900E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 20331E-02 12711E-03 12573E-01 11653E-05 -14638E-06 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 10548E-02 12722E-03 31762E-02 28898E-06 -91698E-08 Remaining SSD is 74346 Weighted distances x-value x-dist y-dist 100E+00 130E+01 490E-01 -755E-01 200E+00 137E+01 -103E+00 228E+00 300E+00 144E+01 539E-01 -250E-01 Goodness-of-fit measure 22837 Parameter set 1 1054788657490729E-2 1272208026684145E-3 3176237146276368E-2 2889798108124711E-6 -
9169821653851327E-8 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_21c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13577E+01 25542E-03 10664E+04 15200E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 547E-06 328E-06 316E-06 784E-06 286E-06 652E-06 Linear model Parameters for the fit were (b0 b1) 10548E-02 12722E-03
59
СО2 - measurement 2
Data setCO2_20 The calibration data set is 1302E+01 1512E-03 1021E+04 4723E+00 1370E+01 1563E-03 1075E+04 1600E+00 1445E+01 1620E-03 1133E+04 7300E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -38760E-02 12784E-03 26817E-02 24890E-06 -66689E-08 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -62452E-02 12805E-03 47930E-02 43243E-06 -20716E-07 Remaining SSD is 03231 Weighted distances x-value x-dist y-dist 100E+00 130E+01 107E-01 -415E-01 200E+00 137E+01 -212E-01 283E-01 300E+00 144E+01 104E-01 -584E-02 Goodness-of-fit measure 04155 Parameter set 1 -6245240430658412E-2 1280492624666799E-3 4792952200361109E-2 4324266278840409E-6 -
2071623966851869E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_20c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13594E+01 10290E-02 10665E+04 78300E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 121E-05 683E-06 651E-06 315E-05 560E-06 106E-04 Linear model Parameters for the fit were (b0 b1) -62452E-02 12805E-03
60
С3Н8 - measurement 1
Data setC3H8 The calibration data set is 1900E-01 7800E-05 9057E+03 1098E+01 2002E-01 7900E-05 9552E+03 8569E+00 2101E-01 7960E-05 1007E+04 4049E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10529E-02 19831E-05 34552E-03 36109E-07 -12465E-09 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11642E-02 19714E-05 23073E-03 23522E-07 -54231E-10 Remaining SSD is 19453 Weighted distances x-value x-dist y-dist 100E+00 190E-01 -239E-01 666E-01 200E+00 200E-01 487E-01 -104E+00 300E+00 210E-01 -247E-01 248E-01 Goodness-of-fit measure 10414 Parameter set 1 1164239985182795E-2 1971441115316992E-5 2307269625077337E-3 2352198415608386E-7 -
5423119774765299E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19837E-01 14840E-04 94718E+03 45610E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
34
Calibration Standards
Calibration Standards for the measurements (preparation method purity analyses estimated uncertainty etc)
All standards were prepared individually according to ISO 6142 rdquoGas analysis - Preparation of calibration gases - Gravimetric Methodrdquo
Depending on the concentration of the components standards were prepared individually from pure gases or from pre-mixtures which were individually prepared from pure gases
The content of the impurities in all pure gases were determined before use by GC-DID GC-FID and or GC-TCD
After preparation the standards were verified by analytical comparisons against existing gravimetrically prepared standards Only when no significant difference between the analysed and the calculated gravimetric composition is found the ldquonew prepared candidate rdquo is accepted as a new standards
For the analysis of all components multi component standards with nitrogen as balance gas were used
Composition of calibrants BAM C49250-050722 Component Assigned value( x)
mmol mol Standard uncertainty (u(x)) relativ (k=2)
Calibration procedure (mathematical modelcalibration curve number and concentrations of standards measurement sequence temperaturepressure correction etc)
For the instrument calibration the bracketing technique was used The fraction of the current used standards deviated no more than +10rel and -10rel respectively from those of the sample
Measurement sequence
Sample Handling
How were the cylinders treated after arrival (eg stabilized) and how were samples transferred to the instrument (automatic high pressure mass-flow controller dilution etc) After heating (45 - 50 degC) the cylinder for 8 hours the cylinder were rolled about 16 hours before analysis was started Each cylinder was equipped with a pressure regulator that was purged three times by sequential evacuation and pressurisation with the gas mixture used Continous flow (2 ndash 3mlmin) through the sample loop
Uncertainty The specification of potential uncertainty sources is given in Annex 3
3 injection standard (high)
3 injection sample
3 injection standard (high)
3 injection sample
3 injection standard (low)
3 injection sample
3 injection standard (low)
3 injection standard (low)
36
Uncertainty table CO2
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 002 rel 1 002 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 03 rel
Uncertainty table CO
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 007 rel 1 007 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 05 rel
37
Uncertainty table C3H8
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 010 rel 1 001 rel
Analysis normal 028 rel 1 028 rel
Coverage factor 2
Expanded uncertainty 06 rel
Optional
You may provide additional data like the raw measurement data information on your
measurement procedure chromatograms etc
38
Appendix 3 SPECIFICATION OF POTENTIAL UNCERTAINTY SOURCES
a Uncertainty related to the balance and the weights Resolution of balance Accuracy of balance including linearity Incorrect zero point Drift (thermal and time effects) Instability due to draught Location of cylinder on the balance pan Uncertainties in the weights used Buoyancy effects on the weights used
b Uncertainties related to the gas cylinder Mechanical handling of cylinder
Loss of metal paints or labels from surface of cylinder Loss of metal from threads of valvefitting Dirt on cylinder valves or associated fitting
Absorptiondesorption effects on the external cylinder surface Buoyancy effects on the cylinder itself
Cylinder temperature differs from surrounding air due to eg filling with gas Change of cylinder volume during filling Change of density of surrounding air due to changes in temperature air pressure humidity and carbon dioxide content
Uncertainty in determination of external cylinder volume c Uncertainties related to the component gases Residual gas in cylinder Leakage Leakage of air into the cylinder after evacuation
Leakage of gas from the cylinder valve during filling Escape of gas from cylinder into transport lines
Gas remaining in transfer system when weight loss method is used Absorptionreaction of components on internal cylinder surface Reaction between components Impurities in all the initial gases Insufficient homogenization Uncertainty of molecular mass d Uncertainties related to the analysis
Repeatability and selectivity of the analyzer Appropriateness of the calibration curve
39
MEASUREMENT REPORT - All Ukrainian State Research-Industrial Center of Standardization Metrology Certification and Protection of Consumers Ukraine
gas ndash helium flow rate 15 cm3min detector TCD tdetector = 250 ordmС toven = 70 ordmС It was automatic data collection
Measurement and Calibration Methods Laboratory Measurement method Type of calibration curve
GCFID (С3Н8) 3 points linear Ukrmetrteststandard GCTCD (СО СО2) 3 points linear
GCFID ndash gas-chromatographic with flame-ionization detector GCTCD - gas-chromatographic with thermal-conductivity detector
42
Calibration Standards
Calibration standards ndash primary standard gas mixtures (PSGM) used for measurements by comparison method
PSGM-1 Cylinder 0116
PSGM-2 Cylinder 0107
PSGM-3 Cylinder 0093 Composition
x u(x) x u(x) x u(x) СО 27874 00015 29899 00015 31891 00015 СО2 130187 00015 144456 00016 137016 00016 С3Н8 019003 000008 020017 000008 021013 000008 N2 balance balance balance
Note x ndash mole fraction u(x) ndash absolute standard uncertainty
It was used gravimetric method of preparation of PSGM Electronic balance КА-20-3 of Mettler Toledo max limit of weighing is 20 kg least
limit of weighing is 01 g standard deviation is 0006 g Analysis of purity of parent gases was carried out with usage of chromatographs
НР6890N with helium ndash ionization detector flame ndash ionization detector thermal ndash conductivity detector and mass ndash spectrometric detector as well аs gas analyzers GIAM-15M and Onix condensate-thermometer hygrometer TOROS-3-2B
Calculation of uncertainties was carried out according to ISO 6142-2003 Corrections of temperature pressure and humidity of environment were considered
in calculations according to ISO 6142-2003 (program of ISO-6142 2000-03-17 designer is NMi) Protocols and explanations are in Annex A
Instrument (Comparator) Calibration Calibration of comparator ndash gas chromatograph HP 6890 was carried out with usage
of PSGM Measurement sequence PSGM -1 х 3 PSGM -2 х 3 COOMET gas mixture х 3 PSGM -2 х 3 PSGM -3 х 3 It is necessary to use PSGM-2 repeatedly for estimation of reproducibility of results
Program B_LEAST recommended by ISO 6143-2003 was used for constructing the curve Mathematical model of calibration curve is linear one
Sample Handling The cylinder was kept for 24 hrs at a room where comparators were disposed This room is a thermostatic room with t = (20plusmn2) ordmС
43
A method of sample input to a comparator is a method with flow stabilization Uncertainty The following uncertainties were included to the budget of uncertainty - uncertainty of the balance - uncertainties of impurities in parent gases Contribution from other uncertainty sources was insignificant A cabin of the balance is thermostatically The balance is the one-pan balance
Air transfer is absent in the cabin of the balance Drift of the balance is absent for PSGM preparation
Contribution from other uncertainty sources was considered in software according to ISO 6142-2003
Uncertainties related to the analysis (comparison) were considered in software according to ISO 6143-2003 and enclosed in Annex B
Uncertainty table СО2
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas mixture
B 001 1 001
Analysis A B 008 1 008
Coverage factor 2 Expanded uncertainty 002sdot10-2 molmol Uncertainty table СО
Protocols of analysis (comparison) in accordance with ISO 6143-2003
57
Explanation of protocols of comparison
Chapter I ldquoThe calibration data set isrdquo contains columns 1 mole fraction of a component 2 absolute standard uncertainty of mole fraction of a component 3 a signal of a comparator 4 absolute standard uncertainty of a comparator signal
Chapter II ldquoResults of ISO 6143 methodrdquo contains parameters of a calibration curve including its
uncertainty
Chapter ІІІ ldquoPart II Processing of datardquo contains columns
1 calc x - the results of comparison mole fraction of a component 2 u(x) - absolute standard uncertainty of mole fraction of a component 3 response y - a signal of a comparator 4 u(y) - absolute standard uncertainty of a comparator signal
58
СО2 - measurement 1 Data setCO2_21 The calibration data set is 1302E+01 1510E-03 1022E+04 1820E+00 1370E+01 1560E-03 1077E+04 2730E+00 1445E+01 1620E-03 1135E+04 5900E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 20331E-02 12711E-03 12573E-01 11653E-05 -14638E-06 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 10548E-02 12722E-03 31762E-02 28898E-06 -91698E-08 Remaining SSD is 74346 Weighted distances x-value x-dist y-dist 100E+00 130E+01 490E-01 -755E-01 200E+00 137E+01 -103E+00 228E+00 300E+00 144E+01 539E-01 -250E-01 Goodness-of-fit measure 22837 Parameter set 1 1054788657490729E-2 1272208026684145E-3 3176237146276368E-2 2889798108124711E-6 -
9169821653851327E-8 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_21c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13577E+01 25542E-03 10664E+04 15200E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 547E-06 328E-06 316E-06 784E-06 286E-06 652E-06 Linear model Parameters for the fit were (b0 b1) 10548E-02 12722E-03
59
СО2 - measurement 2
Data setCO2_20 The calibration data set is 1302E+01 1512E-03 1021E+04 4723E+00 1370E+01 1563E-03 1075E+04 1600E+00 1445E+01 1620E-03 1133E+04 7300E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -38760E-02 12784E-03 26817E-02 24890E-06 -66689E-08 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -62452E-02 12805E-03 47930E-02 43243E-06 -20716E-07 Remaining SSD is 03231 Weighted distances x-value x-dist y-dist 100E+00 130E+01 107E-01 -415E-01 200E+00 137E+01 -212E-01 283E-01 300E+00 144E+01 104E-01 -584E-02 Goodness-of-fit measure 04155 Parameter set 1 -6245240430658412E-2 1280492624666799E-3 4792952200361109E-2 4324266278840409E-6 -
2071623966851869E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_20c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13594E+01 10290E-02 10665E+04 78300E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 121E-05 683E-06 651E-06 315E-05 560E-06 106E-04 Linear model Parameters for the fit were (b0 b1) -62452E-02 12805E-03
60
С3Н8 - measurement 1
Data setC3H8 The calibration data set is 1900E-01 7800E-05 9057E+03 1098E+01 2002E-01 7900E-05 9552E+03 8569E+00 2101E-01 7960E-05 1007E+04 4049E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10529E-02 19831E-05 34552E-03 36109E-07 -12465E-09 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11642E-02 19714E-05 23073E-03 23522E-07 -54231E-10 Remaining SSD is 19453 Weighted distances x-value x-dist y-dist 100E+00 190E-01 -239E-01 666E-01 200E+00 200E-01 487E-01 -104E+00 300E+00 210E-01 -247E-01 248E-01 Goodness-of-fit measure 10414 Parameter set 1 1164239985182795E-2 1971441115316992E-5 2307269625077337E-3 2352198415608386E-7 -
5423119774765299E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19837E-01 14840E-04 94718E+03 45610E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
35
Instrument Calibration
Calibration procedure (mathematical modelcalibration curve number and concentrations of standards measurement sequence temperaturepressure correction etc)
For the instrument calibration the bracketing technique was used The fraction of the current used standards deviated no more than +10rel and -10rel respectively from those of the sample
Measurement sequence
Sample Handling
How were the cylinders treated after arrival (eg stabilized) and how were samples transferred to the instrument (automatic high pressure mass-flow controller dilution etc) After heating (45 - 50 degC) the cylinder for 8 hours the cylinder were rolled about 16 hours before analysis was started Each cylinder was equipped with a pressure regulator that was purged three times by sequential evacuation and pressurisation with the gas mixture used Continous flow (2 ndash 3mlmin) through the sample loop
Uncertainty The specification of potential uncertainty sources is given in Annex 3
3 injection standard (high)
3 injection sample
3 injection standard (high)
3 injection sample
3 injection standard (low)
3 injection sample
3 injection standard (low)
3 injection standard (low)
36
Uncertainty table CO2
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 002 rel 1 002 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 03 rel
Uncertainty table CO
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 007 rel 1 007 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 05 rel
37
Uncertainty table C3H8
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 010 rel 1 001 rel
Analysis normal 028 rel 1 028 rel
Coverage factor 2
Expanded uncertainty 06 rel
Optional
You may provide additional data like the raw measurement data information on your
measurement procedure chromatograms etc
38
Appendix 3 SPECIFICATION OF POTENTIAL UNCERTAINTY SOURCES
a Uncertainty related to the balance and the weights Resolution of balance Accuracy of balance including linearity Incorrect zero point Drift (thermal and time effects) Instability due to draught Location of cylinder on the balance pan Uncertainties in the weights used Buoyancy effects on the weights used
b Uncertainties related to the gas cylinder Mechanical handling of cylinder
Loss of metal paints or labels from surface of cylinder Loss of metal from threads of valvefitting Dirt on cylinder valves or associated fitting
Absorptiondesorption effects on the external cylinder surface Buoyancy effects on the cylinder itself
Cylinder temperature differs from surrounding air due to eg filling with gas Change of cylinder volume during filling Change of density of surrounding air due to changes in temperature air pressure humidity and carbon dioxide content
Uncertainty in determination of external cylinder volume c Uncertainties related to the component gases Residual gas in cylinder Leakage Leakage of air into the cylinder after evacuation
Leakage of gas from the cylinder valve during filling Escape of gas from cylinder into transport lines
Gas remaining in transfer system when weight loss method is used Absorptionreaction of components on internal cylinder surface Reaction between components Impurities in all the initial gases Insufficient homogenization Uncertainty of molecular mass d Uncertainties related to the analysis
Repeatability and selectivity of the analyzer Appropriateness of the calibration curve
39
MEASUREMENT REPORT - All Ukrainian State Research-Industrial Center of Standardization Metrology Certification and Protection of Consumers Ukraine
gas ndash helium flow rate 15 cm3min detector TCD tdetector = 250 ordmС toven = 70 ordmС It was automatic data collection
Measurement and Calibration Methods Laboratory Measurement method Type of calibration curve
GCFID (С3Н8) 3 points linear Ukrmetrteststandard GCTCD (СО СО2) 3 points linear
GCFID ndash gas-chromatographic with flame-ionization detector GCTCD - gas-chromatographic with thermal-conductivity detector
42
Calibration Standards
Calibration standards ndash primary standard gas mixtures (PSGM) used for measurements by comparison method
PSGM-1 Cylinder 0116
PSGM-2 Cylinder 0107
PSGM-3 Cylinder 0093 Composition
x u(x) x u(x) x u(x) СО 27874 00015 29899 00015 31891 00015 СО2 130187 00015 144456 00016 137016 00016 С3Н8 019003 000008 020017 000008 021013 000008 N2 balance balance balance
Note x ndash mole fraction u(x) ndash absolute standard uncertainty
It was used gravimetric method of preparation of PSGM Electronic balance КА-20-3 of Mettler Toledo max limit of weighing is 20 kg least
limit of weighing is 01 g standard deviation is 0006 g Analysis of purity of parent gases was carried out with usage of chromatographs
НР6890N with helium ndash ionization detector flame ndash ionization detector thermal ndash conductivity detector and mass ndash spectrometric detector as well аs gas analyzers GIAM-15M and Onix condensate-thermometer hygrometer TOROS-3-2B
Calculation of uncertainties was carried out according to ISO 6142-2003 Corrections of temperature pressure and humidity of environment were considered
in calculations according to ISO 6142-2003 (program of ISO-6142 2000-03-17 designer is NMi) Protocols and explanations are in Annex A
Instrument (Comparator) Calibration Calibration of comparator ndash gas chromatograph HP 6890 was carried out with usage
of PSGM Measurement sequence PSGM -1 х 3 PSGM -2 х 3 COOMET gas mixture х 3 PSGM -2 х 3 PSGM -3 х 3 It is necessary to use PSGM-2 repeatedly for estimation of reproducibility of results
Program B_LEAST recommended by ISO 6143-2003 was used for constructing the curve Mathematical model of calibration curve is linear one
Sample Handling The cylinder was kept for 24 hrs at a room where comparators were disposed This room is a thermostatic room with t = (20plusmn2) ordmС
43
A method of sample input to a comparator is a method with flow stabilization Uncertainty The following uncertainties were included to the budget of uncertainty - uncertainty of the balance - uncertainties of impurities in parent gases Contribution from other uncertainty sources was insignificant A cabin of the balance is thermostatically The balance is the one-pan balance
Air transfer is absent in the cabin of the balance Drift of the balance is absent for PSGM preparation
Contribution from other uncertainty sources was considered in software according to ISO 6142-2003
Uncertainties related to the analysis (comparison) were considered in software according to ISO 6143-2003 and enclosed in Annex B
Uncertainty table СО2
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas mixture
B 001 1 001
Analysis A B 008 1 008
Coverage factor 2 Expanded uncertainty 002sdot10-2 molmol Uncertainty table СО
Protocols of analysis (comparison) in accordance with ISO 6143-2003
57
Explanation of protocols of comparison
Chapter I ldquoThe calibration data set isrdquo contains columns 1 mole fraction of a component 2 absolute standard uncertainty of mole fraction of a component 3 a signal of a comparator 4 absolute standard uncertainty of a comparator signal
Chapter II ldquoResults of ISO 6143 methodrdquo contains parameters of a calibration curve including its
uncertainty
Chapter ІІІ ldquoPart II Processing of datardquo contains columns
1 calc x - the results of comparison mole fraction of a component 2 u(x) - absolute standard uncertainty of mole fraction of a component 3 response y - a signal of a comparator 4 u(y) - absolute standard uncertainty of a comparator signal
58
СО2 - measurement 1 Data setCO2_21 The calibration data set is 1302E+01 1510E-03 1022E+04 1820E+00 1370E+01 1560E-03 1077E+04 2730E+00 1445E+01 1620E-03 1135E+04 5900E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 20331E-02 12711E-03 12573E-01 11653E-05 -14638E-06 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 10548E-02 12722E-03 31762E-02 28898E-06 -91698E-08 Remaining SSD is 74346 Weighted distances x-value x-dist y-dist 100E+00 130E+01 490E-01 -755E-01 200E+00 137E+01 -103E+00 228E+00 300E+00 144E+01 539E-01 -250E-01 Goodness-of-fit measure 22837 Parameter set 1 1054788657490729E-2 1272208026684145E-3 3176237146276368E-2 2889798108124711E-6 -
9169821653851327E-8 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_21c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13577E+01 25542E-03 10664E+04 15200E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 547E-06 328E-06 316E-06 784E-06 286E-06 652E-06 Linear model Parameters for the fit were (b0 b1) 10548E-02 12722E-03
59
СО2 - measurement 2
Data setCO2_20 The calibration data set is 1302E+01 1512E-03 1021E+04 4723E+00 1370E+01 1563E-03 1075E+04 1600E+00 1445E+01 1620E-03 1133E+04 7300E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -38760E-02 12784E-03 26817E-02 24890E-06 -66689E-08 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -62452E-02 12805E-03 47930E-02 43243E-06 -20716E-07 Remaining SSD is 03231 Weighted distances x-value x-dist y-dist 100E+00 130E+01 107E-01 -415E-01 200E+00 137E+01 -212E-01 283E-01 300E+00 144E+01 104E-01 -584E-02 Goodness-of-fit measure 04155 Parameter set 1 -6245240430658412E-2 1280492624666799E-3 4792952200361109E-2 4324266278840409E-6 -
2071623966851869E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_20c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13594E+01 10290E-02 10665E+04 78300E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 121E-05 683E-06 651E-06 315E-05 560E-06 106E-04 Linear model Parameters for the fit were (b0 b1) -62452E-02 12805E-03
60
С3Н8 - measurement 1
Data setC3H8 The calibration data set is 1900E-01 7800E-05 9057E+03 1098E+01 2002E-01 7900E-05 9552E+03 8569E+00 2101E-01 7960E-05 1007E+04 4049E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10529E-02 19831E-05 34552E-03 36109E-07 -12465E-09 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11642E-02 19714E-05 23073E-03 23522E-07 -54231E-10 Remaining SSD is 19453 Weighted distances x-value x-dist y-dist 100E+00 190E-01 -239E-01 666E-01 200E+00 200E-01 487E-01 -104E+00 300E+00 210E-01 -247E-01 248E-01 Goodness-of-fit measure 10414 Parameter set 1 1164239985182795E-2 1971441115316992E-5 2307269625077337E-3 2352198415608386E-7 -
5423119774765299E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19837E-01 14840E-04 94718E+03 45610E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
36
Uncertainty table CO2
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 002 rel 1 002 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 03 rel
Uncertainty table CO
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 007 rel 1 007 rel
Analysis normal 025 rel 1 025 rel
Coverage factor 2
Expanded uncertainty 05 rel
37
Uncertainty table C3H8
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 010 rel 1 001 rel
Analysis normal 028 rel 1 028 rel
Coverage factor 2
Expanded uncertainty 06 rel
Optional
You may provide additional data like the raw measurement data information on your
measurement procedure chromatograms etc
38
Appendix 3 SPECIFICATION OF POTENTIAL UNCERTAINTY SOURCES
a Uncertainty related to the balance and the weights Resolution of balance Accuracy of balance including linearity Incorrect zero point Drift (thermal and time effects) Instability due to draught Location of cylinder on the balance pan Uncertainties in the weights used Buoyancy effects on the weights used
b Uncertainties related to the gas cylinder Mechanical handling of cylinder
Loss of metal paints or labels from surface of cylinder Loss of metal from threads of valvefitting Dirt on cylinder valves or associated fitting
Absorptiondesorption effects on the external cylinder surface Buoyancy effects on the cylinder itself
Cylinder temperature differs from surrounding air due to eg filling with gas Change of cylinder volume during filling Change of density of surrounding air due to changes in temperature air pressure humidity and carbon dioxide content
Uncertainty in determination of external cylinder volume c Uncertainties related to the component gases Residual gas in cylinder Leakage Leakage of air into the cylinder after evacuation
Leakage of gas from the cylinder valve during filling Escape of gas from cylinder into transport lines
Gas remaining in transfer system when weight loss method is used Absorptionreaction of components on internal cylinder surface Reaction between components Impurities in all the initial gases Insufficient homogenization Uncertainty of molecular mass d Uncertainties related to the analysis
Repeatability and selectivity of the analyzer Appropriateness of the calibration curve
39
MEASUREMENT REPORT - All Ukrainian State Research-Industrial Center of Standardization Metrology Certification and Protection of Consumers Ukraine
gas ndash helium flow rate 15 cm3min detector TCD tdetector = 250 ordmС toven = 70 ordmС It was automatic data collection
Measurement and Calibration Methods Laboratory Measurement method Type of calibration curve
GCFID (С3Н8) 3 points linear Ukrmetrteststandard GCTCD (СО СО2) 3 points linear
GCFID ndash gas-chromatographic with flame-ionization detector GCTCD - gas-chromatographic with thermal-conductivity detector
42
Calibration Standards
Calibration standards ndash primary standard gas mixtures (PSGM) used for measurements by comparison method
PSGM-1 Cylinder 0116
PSGM-2 Cylinder 0107
PSGM-3 Cylinder 0093 Composition
x u(x) x u(x) x u(x) СО 27874 00015 29899 00015 31891 00015 СО2 130187 00015 144456 00016 137016 00016 С3Н8 019003 000008 020017 000008 021013 000008 N2 balance balance balance
Note x ndash mole fraction u(x) ndash absolute standard uncertainty
It was used gravimetric method of preparation of PSGM Electronic balance КА-20-3 of Mettler Toledo max limit of weighing is 20 kg least
limit of weighing is 01 g standard deviation is 0006 g Analysis of purity of parent gases was carried out with usage of chromatographs
НР6890N with helium ndash ionization detector flame ndash ionization detector thermal ndash conductivity detector and mass ndash spectrometric detector as well аs gas analyzers GIAM-15M and Onix condensate-thermometer hygrometer TOROS-3-2B
Calculation of uncertainties was carried out according to ISO 6142-2003 Corrections of temperature pressure and humidity of environment were considered
in calculations according to ISO 6142-2003 (program of ISO-6142 2000-03-17 designer is NMi) Protocols and explanations are in Annex A
Instrument (Comparator) Calibration Calibration of comparator ndash gas chromatograph HP 6890 was carried out with usage
of PSGM Measurement sequence PSGM -1 х 3 PSGM -2 х 3 COOMET gas mixture х 3 PSGM -2 х 3 PSGM -3 х 3 It is necessary to use PSGM-2 repeatedly for estimation of reproducibility of results
Program B_LEAST recommended by ISO 6143-2003 was used for constructing the curve Mathematical model of calibration curve is linear one
Sample Handling The cylinder was kept for 24 hrs at a room where comparators were disposed This room is a thermostatic room with t = (20plusmn2) ordmС
43
A method of sample input to a comparator is a method with flow stabilization Uncertainty The following uncertainties were included to the budget of uncertainty - uncertainty of the balance - uncertainties of impurities in parent gases Contribution from other uncertainty sources was insignificant A cabin of the balance is thermostatically The balance is the one-pan balance
Air transfer is absent in the cabin of the balance Drift of the balance is absent for PSGM preparation
Contribution from other uncertainty sources was considered in software according to ISO 6142-2003
Uncertainties related to the analysis (comparison) were considered in software according to ISO 6143-2003 and enclosed in Annex B
Uncertainty table СО2
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas mixture
B 001 1 001
Analysis A B 008 1 008
Coverage factor 2 Expanded uncertainty 002sdot10-2 molmol Uncertainty table СО
Protocols of analysis (comparison) in accordance with ISO 6143-2003
57
Explanation of protocols of comparison
Chapter I ldquoThe calibration data set isrdquo contains columns 1 mole fraction of a component 2 absolute standard uncertainty of mole fraction of a component 3 a signal of a comparator 4 absolute standard uncertainty of a comparator signal
Chapter II ldquoResults of ISO 6143 methodrdquo contains parameters of a calibration curve including its
uncertainty
Chapter ІІІ ldquoPart II Processing of datardquo contains columns
1 calc x - the results of comparison mole fraction of a component 2 u(x) - absolute standard uncertainty of mole fraction of a component 3 response y - a signal of a comparator 4 u(y) - absolute standard uncertainty of a comparator signal
58
СО2 - measurement 1 Data setCO2_21 The calibration data set is 1302E+01 1510E-03 1022E+04 1820E+00 1370E+01 1560E-03 1077E+04 2730E+00 1445E+01 1620E-03 1135E+04 5900E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 20331E-02 12711E-03 12573E-01 11653E-05 -14638E-06 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 10548E-02 12722E-03 31762E-02 28898E-06 -91698E-08 Remaining SSD is 74346 Weighted distances x-value x-dist y-dist 100E+00 130E+01 490E-01 -755E-01 200E+00 137E+01 -103E+00 228E+00 300E+00 144E+01 539E-01 -250E-01 Goodness-of-fit measure 22837 Parameter set 1 1054788657490729E-2 1272208026684145E-3 3176237146276368E-2 2889798108124711E-6 -
9169821653851327E-8 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_21c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13577E+01 25542E-03 10664E+04 15200E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 547E-06 328E-06 316E-06 784E-06 286E-06 652E-06 Linear model Parameters for the fit were (b0 b1) 10548E-02 12722E-03
59
СО2 - measurement 2
Data setCO2_20 The calibration data set is 1302E+01 1512E-03 1021E+04 4723E+00 1370E+01 1563E-03 1075E+04 1600E+00 1445E+01 1620E-03 1133E+04 7300E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -38760E-02 12784E-03 26817E-02 24890E-06 -66689E-08 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -62452E-02 12805E-03 47930E-02 43243E-06 -20716E-07 Remaining SSD is 03231 Weighted distances x-value x-dist y-dist 100E+00 130E+01 107E-01 -415E-01 200E+00 137E+01 -212E-01 283E-01 300E+00 144E+01 104E-01 -584E-02 Goodness-of-fit measure 04155 Parameter set 1 -6245240430658412E-2 1280492624666799E-3 4792952200361109E-2 4324266278840409E-6 -
2071623966851869E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_20c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13594E+01 10290E-02 10665E+04 78300E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 121E-05 683E-06 651E-06 315E-05 560E-06 106E-04 Linear model Parameters for the fit were (b0 b1) -62452E-02 12805E-03
60
С3Н8 - measurement 1
Data setC3H8 The calibration data set is 1900E-01 7800E-05 9057E+03 1098E+01 2002E-01 7900E-05 9552E+03 8569E+00 2101E-01 7960E-05 1007E+04 4049E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10529E-02 19831E-05 34552E-03 36109E-07 -12465E-09 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11642E-02 19714E-05 23073E-03 23522E-07 -54231E-10 Remaining SSD is 19453 Weighted distances x-value x-dist y-dist 100E+00 190E-01 -239E-01 666E-01 200E+00 200E-01 487E-01 -104E+00 300E+00 210E-01 -247E-01 248E-01 Goodness-of-fit measure 10414 Parameter set 1 1164239985182795E-2 1971441115316992E-5 2307269625077337E-3 2352198415608386E-7 -
5423119774765299E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19837E-01 14840E-04 94718E+03 45610E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
37
Uncertainty table C3H8
Uncertainty source
Xi
Estimate
xi
Assumed distribution
Standard uncertainty
u(xi)
( k = 2)
Sensitivity coefficient
ci
Contribution to standard uncertainty
ui(y) (k = 2)
Calibration gas
mixture
normal 010 rel 1 001 rel
Analysis normal 028 rel 1 028 rel
Coverage factor 2
Expanded uncertainty 06 rel
Optional
You may provide additional data like the raw measurement data information on your
measurement procedure chromatograms etc
38
Appendix 3 SPECIFICATION OF POTENTIAL UNCERTAINTY SOURCES
a Uncertainty related to the balance and the weights Resolution of balance Accuracy of balance including linearity Incorrect zero point Drift (thermal and time effects) Instability due to draught Location of cylinder on the balance pan Uncertainties in the weights used Buoyancy effects on the weights used
b Uncertainties related to the gas cylinder Mechanical handling of cylinder
Loss of metal paints or labels from surface of cylinder Loss of metal from threads of valvefitting Dirt on cylinder valves or associated fitting
Absorptiondesorption effects on the external cylinder surface Buoyancy effects on the cylinder itself
Cylinder temperature differs from surrounding air due to eg filling with gas Change of cylinder volume during filling Change of density of surrounding air due to changes in temperature air pressure humidity and carbon dioxide content
Uncertainty in determination of external cylinder volume c Uncertainties related to the component gases Residual gas in cylinder Leakage Leakage of air into the cylinder after evacuation
Leakage of gas from the cylinder valve during filling Escape of gas from cylinder into transport lines
Gas remaining in transfer system when weight loss method is used Absorptionreaction of components on internal cylinder surface Reaction between components Impurities in all the initial gases Insufficient homogenization Uncertainty of molecular mass d Uncertainties related to the analysis
Repeatability and selectivity of the analyzer Appropriateness of the calibration curve
39
MEASUREMENT REPORT - All Ukrainian State Research-Industrial Center of Standardization Metrology Certification and Protection of Consumers Ukraine
gas ndash helium flow rate 15 cm3min detector TCD tdetector = 250 ordmС toven = 70 ordmС It was automatic data collection
Measurement and Calibration Methods Laboratory Measurement method Type of calibration curve
GCFID (С3Н8) 3 points linear Ukrmetrteststandard GCTCD (СО СО2) 3 points linear
GCFID ndash gas-chromatographic with flame-ionization detector GCTCD - gas-chromatographic with thermal-conductivity detector
42
Calibration Standards
Calibration standards ndash primary standard gas mixtures (PSGM) used for measurements by comparison method
PSGM-1 Cylinder 0116
PSGM-2 Cylinder 0107
PSGM-3 Cylinder 0093 Composition
x u(x) x u(x) x u(x) СО 27874 00015 29899 00015 31891 00015 СО2 130187 00015 144456 00016 137016 00016 С3Н8 019003 000008 020017 000008 021013 000008 N2 balance balance balance
Note x ndash mole fraction u(x) ndash absolute standard uncertainty
It was used gravimetric method of preparation of PSGM Electronic balance КА-20-3 of Mettler Toledo max limit of weighing is 20 kg least
limit of weighing is 01 g standard deviation is 0006 g Analysis of purity of parent gases was carried out with usage of chromatographs
НР6890N with helium ndash ionization detector flame ndash ionization detector thermal ndash conductivity detector and mass ndash spectrometric detector as well аs gas analyzers GIAM-15M and Onix condensate-thermometer hygrometer TOROS-3-2B
Calculation of uncertainties was carried out according to ISO 6142-2003 Corrections of temperature pressure and humidity of environment were considered
in calculations according to ISO 6142-2003 (program of ISO-6142 2000-03-17 designer is NMi) Protocols and explanations are in Annex A
Instrument (Comparator) Calibration Calibration of comparator ndash gas chromatograph HP 6890 was carried out with usage
of PSGM Measurement sequence PSGM -1 х 3 PSGM -2 х 3 COOMET gas mixture х 3 PSGM -2 х 3 PSGM -3 х 3 It is necessary to use PSGM-2 repeatedly for estimation of reproducibility of results
Program B_LEAST recommended by ISO 6143-2003 was used for constructing the curve Mathematical model of calibration curve is linear one
Sample Handling The cylinder was kept for 24 hrs at a room where comparators were disposed This room is a thermostatic room with t = (20plusmn2) ordmС
43
A method of sample input to a comparator is a method with flow stabilization Uncertainty The following uncertainties were included to the budget of uncertainty - uncertainty of the balance - uncertainties of impurities in parent gases Contribution from other uncertainty sources was insignificant A cabin of the balance is thermostatically The balance is the one-pan balance
Air transfer is absent in the cabin of the balance Drift of the balance is absent for PSGM preparation
Contribution from other uncertainty sources was considered in software according to ISO 6142-2003
Uncertainties related to the analysis (comparison) were considered in software according to ISO 6143-2003 and enclosed in Annex B
Uncertainty table СО2
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas mixture
B 001 1 001
Analysis A B 008 1 008
Coverage factor 2 Expanded uncertainty 002sdot10-2 molmol Uncertainty table СО
Protocols of analysis (comparison) in accordance with ISO 6143-2003
57
Explanation of protocols of comparison
Chapter I ldquoThe calibration data set isrdquo contains columns 1 mole fraction of a component 2 absolute standard uncertainty of mole fraction of a component 3 a signal of a comparator 4 absolute standard uncertainty of a comparator signal
Chapter II ldquoResults of ISO 6143 methodrdquo contains parameters of a calibration curve including its
uncertainty
Chapter ІІІ ldquoPart II Processing of datardquo contains columns
1 calc x - the results of comparison mole fraction of a component 2 u(x) - absolute standard uncertainty of mole fraction of a component 3 response y - a signal of a comparator 4 u(y) - absolute standard uncertainty of a comparator signal
58
СО2 - measurement 1 Data setCO2_21 The calibration data set is 1302E+01 1510E-03 1022E+04 1820E+00 1370E+01 1560E-03 1077E+04 2730E+00 1445E+01 1620E-03 1135E+04 5900E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 20331E-02 12711E-03 12573E-01 11653E-05 -14638E-06 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 10548E-02 12722E-03 31762E-02 28898E-06 -91698E-08 Remaining SSD is 74346 Weighted distances x-value x-dist y-dist 100E+00 130E+01 490E-01 -755E-01 200E+00 137E+01 -103E+00 228E+00 300E+00 144E+01 539E-01 -250E-01 Goodness-of-fit measure 22837 Parameter set 1 1054788657490729E-2 1272208026684145E-3 3176237146276368E-2 2889798108124711E-6 -
9169821653851327E-8 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_21c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13577E+01 25542E-03 10664E+04 15200E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 547E-06 328E-06 316E-06 784E-06 286E-06 652E-06 Linear model Parameters for the fit were (b0 b1) 10548E-02 12722E-03
59
СО2 - measurement 2
Data setCO2_20 The calibration data set is 1302E+01 1512E-03 1021E+04 4723E+00 1370E+01 1563E-03 1075E+04 1600E+00 1445E+01 1620E-03 1133E+04 7300E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -38760E-02 12784E-03 26817E-02 24890E-06 -66689E-08 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -62452E-02 12805E-03 47930E-02 43243E-06 -20716E-07 Remaining SSD is 03231 Weighted distances x-value x-dist y-dist 100E+00 130E+01 107E-01 -415E-01 200E+00 137E+01 -212E-01 283E-01 300E+00 144E+01 104E-01 -584E-02 Goodness-of-fit measure 04155 Parameter set 1 -6245240430658412E-2 1280492624666799E-3 4792952200361109E-2 4324266278840409E-6 -
2071623966851869E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_20c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13594E+01 10290E-02 10665E+04 78300E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 121E-05 683E-06 651E-06 315E-05 560E-06 106E-04 Linear model Parameters for the fit were (b0 b1) -62452E-02 12805E-03
60
С3Н8 - measurement 1
Data setC3H8 The calibration data set is 1900E-01 7800E-05 9057E+03 1098E+01 2002E-01 7900E-05 9552E+03 8569E+00 2101E-01 7960E-05 1007E+04 4049E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10529E-02 19831E-05 34552E-03 36109E-07 -12465E-09 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11642E-02 19714E-05 23073E-03 23522E-07 -54231E-10 Remaining SSD is 19453 Weighted distances x-value x-dist y-dist 100E+00 190E-01 -239E-01 666E-01 200E+00 200E-01 487E-01 -104E+00 300E+00 210E-01 -247E-01 248E-01 Goodness-of-fit measure 10414 Parameter set 1 1164239985182795E-2 1971441115316992E-5 2307269625077337E-3 2352198415608386E-7 -
5423119774765299E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19837E-01 14840E-04 94718E+03 45610E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
38
Appendix 3 SPECIFICATION OF POTENTIAL UNCERTAINTY SOURCES
a Uncertainty related to the balance and the weights Resolution of balance Accuracy of balance including linearity Incorrect zero point Drift (thermal and time effects) Instability due to draught Location of cylinder on the balance pan Uncertainties in the weights used Buoyancy effects on the weights used
b Uncertainties related to the gas cylinder Mechanical handling of cylinder
Loss of metal paints or labels from surface of cylinder Loss of metal from threads of valvefitting Dirt on cylinder valves or associated fitting
Absorptiondesorption effects on the external cylinder surface Buoyancy effects on the cylinder itself
Cylinder temperature differs from surrounding air due to eg filling with gas Change of cylinder volume during filling Change of density of surrounding air due to changes in temperature air pressure humidity and carbon dioxide content
Uncertainty in determination of external cylinder volume c Uncertainties related to the component gases Residual gas in cylinder Leakage Leakage of air into the cylinder after evacuation
Leakage of gas from the cylinder valve during filling Escape of gas from cylinder into transport lines
Gas remaining in transfer system when weight loss method is used Absorptionreaction of components on internal cylinder surface Reaction between components Impurities in all the initial gases Insufficient homogenization Uncertainty of molecular mass d Uncertainties related to the analysis
Repeatability and selectivity of the analyzer Appropriateness of the calibration curve
39
MEASUREMENT REPORT - All Ukrainian State Research-Industrial Center of Standardization Metrology Certification and Protection of Consumers Ukraine
gas ndash helium flow rate 15 cm3min detector TCD tdetector = 250 ordmС toven = 70 ordmС It was automatic data collection
Measurement and Calibration Methods Laboratory Measurement method Type of calibration curve
GCFID (С3Н8) 3 points linear Ukrmetrteststandard GCTCD (СО СО2) 3 points linear
GCFID ndash gas-chromatographic with flame-ionization detector GCTCD - gas-chromatographic with thermal-conductivity detector
42
Calibration Standards
Calibration standards ndash primary standard gas mixtures (PSGM) used for measurements by comparison method
PSGM-1 Cylinder 0116
PSGM-2 Cylinder 0107
PSGM-3 Cylinder 0093 Composition
x u(x) x u(x) x u(x) СО 27874 00015 29899 00015 31891 00015 СО2 130187 00015 144456 00016 137016 00016 С3Н8 019003 000008 020017 000008 021013 000008 N2 balance balance balance
Note x ndash mole fraction u(x) ndash absolute standard uncertainty
It was used gravimetric method of preparation of PSGM Electronic balance КА-20-3 of Mettler Toledo max limit of weighing is 20 kg least
limit of weighing is 01 g standard deviation is 0006 g Analysis of purity of parent gases was carried out with usage of chromatographs
НР6890N with helium ndash ionization detector flame ndash ionization detector thermal ndash conductivity detector and mass ndash spectrometric detector as well аs gas analyzers GIAM-15M and Onix condensate-thermometer hygrometer TOROS-3-2B
Calculation of uncertainties was carried out according to ISO 6142-2003 Corrections of temperature pressure and humidity of environment were considered
in calculations according to ISO 6142-2003 (program of ISO-6142 2000-03-17 designer is NMi) Protocols and explanations are in Annex A
Instrument (Comparator) Calibration Calibration of comparator ndash gas chromatograph HP 6890 was carried out with usage
of PSGM Measurement sequence PSGM -1 х 3 PSGM -2 х 3 COOMET gas mixture х 3 PSGM -2 х 3 PSGM -3 х 3 It is necessary to use PSGM-2 repeatedly for estimation of reproducibility of results
Program B_LEAST recommended by ISO 6143-2003 was used for constructing the curve Mathematical model of calibration curve is linear one
Sample Handling The cylinder was kept for 24 hrs at a room where comparators were disposed This room is a thermostatic room with t = (20plusmn2) ordmС
43
A method of sample input to a comparator is a method with flow stabilization Uncertainty The following uncertainties were included to the budget of uncertainty - uncertainty of the balance - uncertainties of impurities in parent gases Contribution from other uncertainty sources was insignificant A cabin of the balance is thermostatically The balance is the one-pan balance
Air transfer is absent in the cabin of the balance Drift of the balance is absent for PSGM preparation
Contribution from other uncertainty sources was considered in software according to ISO 6142-2003
Uncertainties related to the analysis (comparison) were considered in software according to ISO 6143-2003 and enclosed in Annex B
Uncertainty table СО2
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas mixture
B 001 1 001
Analysis A B 008 1 008
Coverage factor 2 Expanded uncertainty 002sdot10-2 molmol Uncertainty table СО
Protocols of analysis (comparison) in accordance with ISO 6143-2003
57
Explanation of protocols of comparison
Chapter I ldquoThe calibration data set isrdquo contains columns 1 mole fraction of a component 2 absolute standard uncertainty of mole fraction of a component 3 a signal of a comparator 4 absolute standard uncertainty of a comparator signal
Chapter II ldquoResults of ISO 6143 methodrdquo contains parameters of a calibration curve including its
uncertainty
Chapter ІІІ ldquoPart II Processing of datardquo contains columns
1 calc x - the results of comparison mole fraction of a component 2 u(x) - absolute standard uncertainty of mole fraction of a component 3 response y - a signal of a comparator 4 u(y) - absolute standard uncertainty of a comparator signal
58
СО2 - measurement 1 Data setCO2_21 The calibration data set is 1302E+01 1510E-03 1022E+04 1820E+00 1370E+01 1560E-03 1077E+04 2730E+00 1445E+01 1620E-03 1135E+04 5900E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 20331E-02 12711E-03 12573E-01 11653E-05 -14638E-06 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 10548E-02 12722E-03 31762E-02 28898E-06 -91698E-08 Remaining SSD is 74346 Weighted distances x-value x-dist y-dist 100E+00 130E+01 490E-01 -755E-01 200E+00 137E+01 -103E+00 228E+00 300E+00 144E+01 539E-01 -250E-01 Goodness-of-fit measure 22837 Parameter set 1 1054788657490729E-2 1272208026684145E-3 3176237146276368E-2 2889798108124711E-6 -
9169821653851327E-8 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_21c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13577E+01 25542E-03 10664E+04 15200E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 547E-06 328E-06 316E-06 784E-06 286E-06 652E-06 Linear model Parameters for the fit were (b0 b1) 10548E-02 12722E-03
59
СО2 - measurement 2
Data setCO2_20 The calibration data set is 1302E+01 1512E-03 1021E+04 4723E+00 1370E+01 1563E-03 1075E+04 1600E+00 1445E+01 1620E-03 1133E+04 7300E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -38760E-02 12784E-03 26817E-02 24890E-06 -66689E-08 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -62452E-02 12805E-03 47930E-02 43243E-06 -20716E-07 Remaining SSD is 03231 Weighted distances x-value x-dist y-dist 100E+00 130E+01 107E-01 -415E-01 200E+00 137E+01 -212E-01 283E-01 300E+00 144E+01 104E-01 -584E-02 Goodness-of-fit measure 04155 Parameter set 1 -6245240430658412E-2 1280492624666799E-3 4792952200361109E-2 4324266278840409E-6 -
2071623966851869E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_20c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13594E+01 10290E-02 10665E+04 78300E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 121E-05 683E-06 651E-06 315E-05 560E-06 106E-04 Linear model Parameters for the fit were (b0 b1) -62452E-02 12805E-03
60
С3Н8 - measurement 1
Data setC3H8 The calibration data set is 1900E-01 7800E-05 9057E+03 1098E+01 2002E-01 7900E-05 9552E+03 8569E+00 2101E-01 7960E-05 1007E+04 4049E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10529E-02 19831E-05 34552E-03 36109E-07 -12465E-09 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11642E-02 19714E-05 23073E-03 23522E-07 -54231E-10 Remaining SSD is 19453 Weighted distances x-value x-dist y-dist 100E+00 190E-01 -239E-01 666E-01 200E+00 200E-01 487E-01 -104E+00 300E+00 210E-01 -247E-01 248E-01 Goodness-of-fit measure 10414 Parameter set 1 1164239985182795E-2 1971441115316992E-5 2307269625077337E-3 2352198415608386E-7 -
5423119774765299E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19837E-01 14840E-04 94718E+03 45610E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
39
MEASUREMENT REPORT - All Ukrainian State Research-Industrial Center of Standardization Metrology Certification and Protection of Consumers Ukraine
gas ndash helium flow rate 15 cm3min detector TCD tdetector = 250 ordmС toven = 70 ordmС It was automatic data collection
Measurement and Calibration Methods Laboratory Measurement method Type of calibration curve
GCFID (С3Н8) 3 points linear Ukrmetrteststandard GCTCD (СО СО2) 3 points linear
GCFID ndash gas-chromatographic with flame-ionization detector GCTCD - gas-chromatographic with thermal-conductivity detector
42
Calibration Standards
Calibration standards ndash primary standard gas mixtures (PSGM) used for measurements by comparison method
PSGM-1 Cylinder 0116
PSGM-2 Cylinder 0107
PSGM-3 Cylinder 0093 Composition
x u(x) x u(x) x u(x) СО 27874 00015 29899 00015 31891 00015 СО2 130187 00015 144456 00016 137016 00016 С3Н8 019003 000008 020017 000008 021013 000008 N2 balance balance balance
Note x ndash mole fraction u(x) ndash absolute standard uncertainty
It was used gravimetric method of preparation of PSGM Electronic balance КА-20-3 of Mettler Toledo max limit of weighing is 20 kg least
limit of weighing is 01 g standard deviation is 0006 g Analysis of purity of parent gases was carried out with usage of chromatographs
НР6890N with helium ndash ionization detector flame ndash ionization detector thermal ndash conductivity detector and mass ndash spectrometric detector as well аs gas analyzers GIAM-15M and Onix condensate-thermometer hygrometer TOROS-3-2B
Calculation of uncertainties was carried out according to ISO 6142-2003 Corrections of temperature pressure and humidity of environment were considered
in calculations according to ISO 6142-2003 (program of ISO-6142 2000-03-17 designer is NMi) Protocols and explanations are in Annex A
Instrument (Comparator) Calibration Calibration of comparator ndash gas chromatograph HP 6890 was carried out with usage
of PSGM Measurement sequence PSGM -1 х 3 PSGM -2 х 3 COOMET gas mixture х 3 PSGM -2 х 3 PSGM -3 х 3 It is necessary to use PSGM-2 repeatedly for estimation of reproducibility of results
Program B_LEAST recommended by ISO 6143-2003 was used for constructing the curve Mathematical model of calibration curve is linear one
Sample Handling The cylinder was kept for 24 hrs at a room where comparators were disposed This room is a thermostatic room with t = (20plusmn2) ordmС
43
A method of sample input to a comparator is a method with flow stabilization Uncertainty The following uncertainties were included to the budget of uncertainty - uncertainty of the balance - uncertainties of impurities in parent gases Contribution from other uncertainty sources was insignificant A cabin of the balance is thermostatically The balance is the one-pan balance
Air transfer is absent in the cabin of the balance Drift of the balance is absent for PSGM preparation
Contribution from other uncertainty sources was considered in software according to ISO 6142-2003
Uncertainties related to the analysis (comparison) were considered in software according to ISO 6143-2003 and enclosed in Annex B
Uncertainty table СО2
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas mixture
B 001 1 001
Analysis A B 008 1 008
Coverage factor 2 Expanded uncertainty 002sdot10-2 molmol Uncertainty table СО
Protocols of analysis (comparison) in accordance with ISO 6143-2003
57
Explanation of protocols of comparison
Chapter I ldquoThe calibration data set isrdquo contains columns 1 mole fraction of a component 2 absolute standard uncertainty of mole fraction of a component 3 a signal of a comparator 4 absolute standard uncertainty of a comparator signal
Chapter II ldquoResults of ISO 6143 methodrdquo contains parameters of a calibration curve including its
uncertainty
Chapter ІІІ ldquoPart II Processing of datardquo contains columns
1 calc x - the results of comparison mole fraction of a component 2 u(x) - absolute standard uncertainty of mole fraction of a component 3 response y - a signal of a comparator 4 u(y) - absolute standard uncertainty of a comparator signal
58
СО2 - measurement 1 Data setCO2_21 The calibration data set is 1302E+01 1510E-03 1022E+04 1820E+00 1370E+01 1560E-03 1077E+04 2730E+00 1445E+01 1620E-03 1135E+04 5900E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 20331E-02 12711E-03 12573E-01 11653E-05 -14638E-06 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 10548E-02 12722E-03 31762E-02 28898E-06 -91698E-08 Remaining SSD is 74346 Weighted distances x-value x-dist y-dist 100E+00 130E+01 490E-01 -755E-01 200E+00 137E+01 -103E+00 228E+00 300E+00 144E+01 539E-01 -250E-01 Goodness-of-fit measure 22837 Parameter set 1 1054788657490729E-2 1272208026684145E-3 3176237146276368E-2 2889798108124711E-6 -
9169821653851327E-8 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_21c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13577E+01 25542E-03 10664E+04 15200E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 547E-06 328E-06 316E-06 784E-06 286E-06 652E-06 Linear model Parameters for the fit were (b0 b1) 10548E-02 12722E-03
59
СО2 - measurement 2
Data setCO2_20 The calibration data set is 1302E+01 1512E-03 1021E+04 4723E+00 1370E+01 1563E-03 1075E+04 1600E+00 1445E+01 1620E-03 1133E+04 7300E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -38760E-02 12784E-03 26817E-02 24890E-06 -66689E-08 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -62452E-02 12805E-03 47930E-02 43243E-06 -20716E-07 Remaining SSD is 03231 Weighted distances x-value x-dist y-dist 100E+00 130E+01 107E-01 -415E-01 200E+00 137E+01 -212E-01 283E-01 300E+00 144E+01 104E-01 -584E-02 Goodness-of-fit measure 04155 Parameter set 1 -6245240430658412E-2 1280492624666799E-3 4792952200361109E-2 4324266278840409E-6 -
2071623966851869E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_20c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13594E+01 10290E-02 10665E+04 78300E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 121E-05 683E-06 651E-06 315E-05 560E-06 106E-04 Linear model Parameters for the fit were (b0 b1) -62452E-02 12805E-03
60
С3Н8 - measurement 1
Data setC3H8 The calibration data set is 1900E-01 7800E-05 9057E+03 1098E+01 2002E-01 7900E-05 9552E+03 8569E+00 2101E-01 7960E-05 1007E+04 4049E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10529E-02 19831E-05 34552E-03 36109E-07 -12465E-09 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11642E-02 19714E-05 23073E-03 23522E-07 -54231E-10 Remaining SSD is 19453 Weighted distances x-value x-dist y-dist 100E+00 190E-01 -239E-01 666E-01 200E+00 200E-01 487E-01 -104E+00 300E+00 210E-01 -247E-01 248E-01 Goodness-of-fit measure 10414 Parameter set 1 1164239985182795E-2 1971441115316992E-5 2307269625077337E-3 2352198415608386E-7 -
5423119774765299E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19837E-01 14840E-04 94718E+03 45610E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
40
Measurement 1 Date Results
(molmol) stand deviation
( relative) number of sub measurements
Carbon dioxide 2005-08-28 13594sdot10-2 0076 3
Carbon monoxide 2005-08-30 29536sdot10-2 0152 3
Propane 2005-09-01 19967sdot10-4 0079 3
Measurement 2 Date Result
(molmol) stand deviation
( relative) number of sub measurements
Carbon dioxide 2005-09-05 13577sdot10-2 0019 3
Carbon monoxide 2005-08-30 29477sdot10-2 0155 3
Propane 2005-09-07 19837sdot10-4 0075 3
41
Results
Gas mixture Result
(assigned value) (molmol)
Coverage factor Assigned expanded
uncertainty (molmol)
Carbon dioxide 13586sdot10-2 2 0022sdot10-2
Carbon monoxide 2951sdot10-2 2 0012sdot10-2
Propane 1990sdot10-4 2 004sdot10-4
II Description of Study
Instrument(s)
GC НР 6890 - for С3Н8 - column 15FT 25 DC-200 HP19006-80105 carrier gas ndash helium
flow rate 15 cm3min detector FID tdetector = 300 ordmС toven = 90 ordmС - for СО - column 10FT HAYESEP Q 80100 MESH HP19006-80110 carrier gas
gas ndash helium flow rate 15 cm3min detector TCD tdetector = 250 ordmС toven = 70 ordmС It was automatic data collection
Measurement and Calibration Methods Laboratory Measurement method Type of calibration curve
GCFID (С3Н8) 3 points linear Ukrmetrteststandard GCTCD (СО СО2) 3 points linear
GCFID ndash gas-chromatographic with flame-ionization detector GCTCD - gas-chromatographic with thermal-conductivity detector
42
Calibration Standards
Calibration standards ndash primary standard gas mixtures (PSGM) used for measurements by comparison method
PSGM-1 Cylinder 0116
PSGM-2 Cylinder 0107
PSGM-3 Cylinder 0093 Composition
x u(x) x u(x) x u(x) СО 27874 00015 29899 00015 31891 00015 СО2 130187 00015 144456 00016 137016 00016 С3Н8 019003 000008 020017 000008 021013 000008 N2 balance balance balance
Note x ndash mole fraction u(x) ndash absolute standard uncertainty
It was used gravimetric method of preparation of PSGM Electronic balance КА-20-3 of Mettler Toledo max limit of weighing is 20 kg least
limit of weighing is 01 g standard deviation is 0006 g Analysis of purity of parent gases was carried out with usage of chromatographs
НР6890N with helium ndash ionization detector flame ndash ionization detector thermal ndash conductivity detector and mass ndash spectrometric detector as well аs gas analyzers GIAM-15M and Onix condensate-thermometer hygrometer TOROS-3-2B
Calculation of uncertainties was carried out according to ISO 6142-2003 Corrections of temperature pressure and humidity of environment were considered
in calculations according to ISO 6142-2003 (program of ISO-6142 2000-03-17 designer is NMi) Protocols and explanations are in Annex A
Instrument (Comparator) Calibration Calibration of comparator ndash gas chromatograph HP 6890 was carried out with usage
of PSGM Measurement sequence PSGM -1 х 3 PSGM -2 х 3 COOMET gas mixture х 3 PSGM -2 х 3 PSGM -3 х 3 It is necessary to use PSGM-2 repeatedly for estimation of reproducibility of results
Program B_LEAST recommended by ISO 6143-2003 was used for constructing the curve Mathematical model of calibration curve is linear one
Sample Handling The cylinder was kept for 24 hrs at a room where comparators were disposed This room is a thermostatic room with t = (20plusmn2) ordmС
43
A method of sample input to a comparator is a method with flow stabilization Uncertainty The following uncertainties were included to the budget of uncertainty - uncertainty of the balance - uncertainties of impurities in parent gases Contribution from other uncertainty sources was insignificant A cabin of the balance is thermostatically The balance is the one-pan balance
Air transfer is absent in the cabin of the balance Drift of the balance is absent for PSGM preparation
Contribution from other uncertainty sources was considered in software according to ISO 6142-2003
Uncertainties related to the analysis (comparison) were considered in software according to ISO 6143-2003 and enclosed in Annex B
Uncertainty table СО2
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas mixture
B 001 1 001
Analysis A B 008 1 008
Coverage factor 2 Expanded uncertainty 002sdot10-2 molmol Uncertainty table СО
Protocols of analysis (comparison) in accordance with ISO 6143-2003
57
Explanation of protocols of comparison
Chapter I ldquoThe calibration data set isrdquo contains columns 1 mole fraction of a component 2 absolute standard uncertainty of mole fraction of a component 3 a signal of a comparator 4 absolute standard uncertainty of a comparator signal
Chapter II ldquoResults of ISO 6143 methodrdquo contains parameters of a calibration curve including its
uncertainty
Chapter ІІІ ldquoPart II Processing of datardquo contains columns
1 calc x - the results of comparison mole fraction of a component 2 u(x) - absolute standard uncertainty of mole fraction of a component 3 response y - a signal of a comparator 4 u(y) - absolute standard uncertainty of a comparator signal
58
СО2 - measurement 1 Data setCO2_21 The calibration data set is 1302E+01 1510E-03 1022E+04 1820E+00 1370E+01 1560E-03 1077E+04 2730E+00 1445E+01 1620E-03 1135E+04 5900E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 20331E-02 12711E-03 12573E-01 11653E-05 -14638E-06 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 10548E-02 12722E-03 31762E-02 28898E-06 -91698E-08 Remaining SSD is 74346 Weighted distances x-value x-dist y-dist 100E+00 130E+01 490E-01 -755E-01 200E+00 137E+01 -103E+00 228E+00 300E+00 144E+01 539E-01 -250E-01 Goodness-of-fit measure 22837 Parameter set 1 1054788657490729E-2 1272208026684145E-3 3176237146276368E-2 2889798108124711E-6 -
9169821653851327E-8 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_21c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13577E+01 25542E-03 10664E+04 15200E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 547E-06 328E-06 316E-06 784E-06 286E-06 652E-06 Linear model Parameters for the fit were (b0 b1) 10548E-02 12722E-03
59
СО2 - measurement 2
Data setCO2_20 The calibration data set is 1302E+01 1512E-03 1021E+04 4723E+00 1370E+01 1563E-03 1075E+04 1600E+00 1445E+01 1620E-03 1133E+04 7300E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -38760E-02 12784E-03 26817E-02 24890E-06 -66689E-08 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -62452E-02 12805E-03 47930E-02 43243E-06 -20716E-07 Remaining SSD is 03231 Weighted distances x-value x-dist y-dist 100E+00 130E+01 107E-01 -415E-01 200E+00 137E+01 -212E-01 283E-01 300E+00 144E+01 104E-01 -584E-02 Goodness-of-fit measure 04155 Parameter set 1 -6245240430658412E-2 1280492624666799E-3 4792952200361109E-2 4324266278840409E-6 -
2071623966851869E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_20c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13594E+01 10290E-02 10665E+04 78300E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 121E-05 683E-06 651E-06 315E-05 560E-06 106E-04 Linear model Parameters for the fit were (b0 b1) -62452E-02 12805E-03
60
С3Н8 - measurement 1
Data setC3H8 The calibration data set is 1900E-01 7800E-05 9057E+03 1098E+01 2002E-01 7900E-05 9552E+03 8569E+00 2101E-01 7960E-05 1007E+04 4049E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10529E-02 19831E-05 34552E-03 36109E-07 -12465E-09 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11642E-02 19714E-05 23073E-03 23522E-07 -54231E-10 Remaining SSD is 19453 Weighted distances x-value x-dist y-dist 100E+00 190E-01 -239E-01 666E-01 200E+00 200E-01 487E-01 -104E+00 300E+00 210E-01 -247E-01 248E-01 Goodness-of-fit measure 10414 Parameter set 1 1164239985182795E-2 1971441115316992E-5 2307269625077337E-3 2352198415608386E-7 -
5423119774765299E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19837E-01 14840E-04 94718E+03 45610E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
41
Results
Gas mixture Result
(assigned value) (molmol)
Coverage factor Assigned expanded
uncertainty (molmol)
Carbon dioxide 13586sdot10-2 2 0022sdot10-2
Carbon monoxide 2951sdot10-2 2 0012sdot10-2
Propane 1990sdot10-4 2 004sdot10-4
II Description of Study
Instrument(s)
GC НР 6890 - for С3Н8 - column 15FT 25 DC-200 HP19006-80105 carrier gas ndash helium
flow rate 15 cm3min detector FID tdetector = 300 ordmС toven = 90 ordmС - for СО - column 10FT HAYESEP Q 80100 MESH HP19006-80110 carrier gas
gas ndash helium flow rate 15 cm3min detector TCD tdetector = 250 ordmС toven = 70 ordmС It was automatic data collection
Measurement and Calibration Methods Laboratory Measurement method Type of calibration curve
GCFID (С3Н8) 3 points linear Ukrmetrteststandard GCTCD (СО СО2) 3 points linear
GCFID ndash gas-chromatographic with flame-ionization detector GCTCD - gas-chromatographic with thermal-conductivity detector
42
Calibration Standards
Calibration standards ndash primary standard gas mixtures (PSGM) used for measurements by comparison method
PSGM-1 Cylinder 0116
PSGM-2 Cylinder 0107
PSGM-3 Cylinder 0093 Composition
x u(x) x u(x) x u(x) СО 27874 00015 29899 00015 31891 00015 СО2 130187 00015 144456 00016 137016 00016 С3Н8 019003 000008 020017 000008 021013 000008 N2 balance balance balance
Note x ndash mole fraction u(x) ndash absolute standard uncertainty
It was used gravimetric method of preparation of PSGM Electronic balance КА-20-3 of Mettler Toledo max limit of weighing is 20 kg least
limit of weighing is 01 g standard deviation is 0006 g Analysis of purity of parent gases was carried out with usage of chromatographs
НР6890N with helium ndash ionization detector flame ndash ionization detector thermal ndash conductivity detector and mass ndash spectrometric detector as well аs gas analyzers GIAM-15M and Onix condensate-thermometer hygrometer TOROS-3-2B
Calculation of uncertainties was carried out according to ISO 6142-2003 Corrections of temperature pressure and humidity of environment were considered
in calculations according to ISO 6142-2003 (program of ISO-6142 2000-03-17 designer is NMi) Protocols and explanations are in Annex A
Instrument (Comparator) Calibration Calibration of comparator ndash gas chromatograph HP 6890 was carried out with usage
of PSGM Measurement sequence PSGM -1 х 3 PSGM -2 х 3 COOMET gas mixture х 3 PSGM -2 х 3 PSGM -3 х 3 It is necessary to use PSGM-2 repeatedly for estimation of reproducibility of results
Program B_LEAST recommended by ISO 6143-2003 was used for constructing the curve Mathematical model of calibration curve is linear one
Sample Handling The cylinder was kept for 24 hrs at a room where comparators were disposed This room is a thermostatic room with t = (20plusmn2) ordmС
43
A method of sample input to a comparator is a method with flow stabilization Uncertainty The following uncertainties were included to the budget of uncertainty - uncertainty of the balance - uncertainties of impurities in parent gases Contribution from other uncertainty sources was insignificant A cabin of the balance is thermostatically The balance is the one-pan balance
Air transfer is absent in the cabin of the balance Drift of the balance is absent for PSGM preparation
Contribution from other uncertainty sources was considered in software according to ISO 6142-2003
Uncertainties related to the analysis (comparison) were considered in software according to ISO 6143-2003 and enclosed in Annex B
Uncertainty table СО2
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas mixture
B 001 1 001
Analysis A B 008 1 008
Coverage factor 2 Expanded uncertainty 002sdot10-2 molmol Uncertainty table СО
Protocols of analysis (comparison) in accordance with ISO 6143-2003
57
Explanation of protocols of comparison
Chapter I ldquoThe calibration data set isrdquo contains columns 1 mole fraction of a component 2 absolute standard uncertainty of mole fraction of a component 3 a signal of a comparator 4 absolute standard uncertainty of a comparator signal
Chapter II ldquoResults of ISO 6143 methodrdquo contains parameters of a calibration curve including its
uncertainty
Chapter ІІІ ldquoPart II Processing of datardquo contains columns
1 calc x - the results of comparison mole fraction of a component 2 u(x) - absolute standard uncertainty of mole fraction of a component 3 response y - a signal of a comparator 4 u(y) - absolute standard uncertainty of a comparator signal
58
СО2 - measurement 1 Data setCO2_21 The calibration data set is 1302E+01 1510E-03 1022E+04 1820E+00 1370E+01 1560E-03 1077E+04 2730E+00 1445E+01 1620E-03 1135E+04 5900E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 20331E-02 12711E-03 12573E-01 11653E-05 -14638E-06 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 10548E-02 12722E-03 31762E-02 28898E-06 -91698E-08 Remaining SSD is 74346 Weighted distances x-value x-dist y-dist 100E+00 130E+01 490E-01 -755E-01 200E+00 137E+01 -103E+00 228E+00 300E+00 144E+01 539E-01 -250E-01 Goodness-of-fit measure 22837 Parameter set 1 1054788657490729E-2 1272208026684145E-3 3176237146276368E-2 2889798108124711E-6 -
9169821653851327E-8 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_21c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13577E+01 25542E-03 10664E+04 15200E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 547E-06 328E-06 316E-06 784E-06 286E-06 652E-06 Linear model Parameters for the fit were (b0 b1) 10548E-02 12722E-03
59
СО2 - measurement 2
Data setCO2_20 The calibration data set is 1302E+01 1512E-03 1021E+04 4723E+00 1370E+01 1563E-03 1075E+04 1600E+00 1445E+01 1620E-03 1133E+04 7300E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -38760E-02 12784E-03 26817E-02 24890E-06 -66689E-08 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -62452E-02 12805E-03 47930E-02 43243E-06 -20716E-07 Remaining SSD is 03231 Weighted distances x-value x-dist y-dist 100E+00 130E+01 107E-01 -415E-01 200E+00 137E+01 -212E-01 283E-01 300E+00 144E+01 104E-01 -584E-02 Goodness-of-fit measure 04155 Parameter set 1 -6245240430658412E-2 1280492624666799E-3 4792952200361109E-2 4324266278840409E-6 -
2071623966851869E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_20c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13594E+01 10290E-02 10665E+04 78300E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 121E-05 683E-06 651E-06 315E-05 560E-06 106E-04 Linear model Parameters for the fit were (b0 b1) -62452E-02 12805E-03
60
С3Н8 - measurement 1
Data setC3H8 The calibration data set is 1900E-01 7800E-05 9057E+03 1098E+01 2002E-01 7900E-05 9552E+03 8569E+00 2101E-01 7960E-05 1007E+04 4049E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10529E-02 19831E-05 34552E-03 36109E-07 -12465E-09 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11642E-02 19714E-05 23073E-03 23522E-07 -54231E-10 Remaining SSD is 19453 Weighted distances x-value x-dist y-dist 100E+00 190E-01 -239E-01 666E-01 200E+00 200E-01 487E-01 -104E+00 300E+00 210E-01 -247E-01 248E-01 Goodness-of-fit measure 10414 Parameter set 1 1164239985182795E-2 1971441115316992E-5 2307269625077337E-3 2352198415608386E-7 -
5423119774765299E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19837E-01 14840E-04 94718E+03 45610E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
42
Calibration Standards
Calibration standards ndash primary standard gas mixtures (PSGM) used for measurements by comparison method
PSGM-1 Cylinder 0116
PSGM-2 Cylinder 0107
PSGM-3 Cylinder 0093 Composition
x u(x) x u(x) x u(x) СО 27874 00015 29899 00015 31891 00015 СО2 130187 00015 144456 00016 137016 00016 С3Н8 019003 000008 020017 000008 021013 000008 N2 balance balance balance
Note x ndash mole fraction u(x) ndash absolute standard uncertainty
It was used gravimetric method of preparation of PSGM Electronic balance КА-20-3 of Mettler Toledo max limit of weighing is 20 kg least
limit of weighing is 01 g standard deviation is 0006 g Analysis of purity of parent gases was carried out with usage of chromatographs
НР6890N with helium ndash ionization detector flame ndash ionization detector thermal ndash conductivity detector and mass ndash spectrometric detector as well аs gas analyzers GIAM-15M and Onix condensate-thermometer hygrometer TOROS-3-2B
Calculation of uncertainties was carried out according to ISO 6142-2003 Corrections of temperature pressure and humidity of environment were considered
in calculations according to ISO 6142-2003 (program of ISO-6142 2000-03-17 designer is NMi) Protocols and explanations are in Annex A
Instrument (Comparator) Calibration Calibration of comparator ndash gas chromatograph HP 6890 was carried out with usage
of PSGM Measurement sequence PSGM -1 х 3 PSGM -2 х 3 COOMET gas mixture х 3 PSGM -2 х 3 PSGM -3 х 3 It is necessary to use PSGM-2 repeatedly for estimation of reproducibility of results
Program B_LEAST recommended by ISO 6143-2003 was used for constructing the curve Mathematical model of calibration curve is linear one
Sample Handling The cylinder was kept for 24 hrs at a room where comparators were disposed This room is a thermostatic room with t = (20plusmn2) ordmС
43
A method of sample input to a comparator is a method with flow stabilization Uncertainty The following uncertainties were included to the budget of uncertainty - uncertainty of the balance - uncertainties of impurities in parent gases Contribution from other uncertainty sources was insignificant A cabin of the balance is thermostatically The balance is the one-pan balance
Air transfer is absent in the cabin of the balance Drift of the balance is absent for PSGM preparation
Contribution from other uncertainty sources was considered in software according to ISO 6142-2003
Uncertainties related to the analysis (comparison) were considered in software according to ISO 6143-2003 and enclosed in Annex B
Uncertainty table СО2
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas mixture
B 001 1 001
Analysis A B 008 1 008
Coverage factor 2 Expanded uncertainty 002sdot10-2 molmol Uncertainty table СО
Protocols of analysis (comparison) in accordance with ISO 6143-2003
57
Explanation of protocols of comparison
Chapter I ldquoThe calibration data set isrdquo contains columns 1 mole fraction of a component 2 absolute standard uncertainty of mole fraction of a component 3 a signal of a comparator 4 absolute standard uncertainty of a comparator signal
Chapter II ldquoResults of ISO 6143 methodrdquo contains parameters of a calibration curve including its
uncertainty
Chapter ІІІ ldquoPart II Processing of datardquo contains columns
1 calc x - the results of comparison mole fraction of a component 2 u(x) - absolute standard uncertainty of mole fraction of a component 3 response y - a signal of a comparator 4 u(y) - absolute standard uncertainty of a comparator signal
58
СО2 - measurement 1 Data setCO2_21 The calibration data set is 1302E+01 1510E-03 1022E+04 1820E+00 1370E+01 1560E-03 1077E+04 2730E+00 1445E+01 1620E-03 1135E+04 5900E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 20331E-02 12711E-03 12573E-01 11653E-05 -14638E-06 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 10548E-02 12722E-03 31762E-02 28898E-06 -91698E-08 Remaining SSD is 74346 Weighted distances x-value x-dist y-dist 100E+00 130E+01 490E-01 -755E-01 200E+00 137E+01 -103E+00 228E+00 300E+00 144E+01 539E-01 -250E-01 Goodness-of-fit measure 22837 Parameter set 1 1054788657490729E-2 1272208026684145E-3 3176237146276368E-2 2889798108124711E-6 -
9169821653851327E-8 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_21c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13577E+01 25542E-03 10664E+04 15200E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 547E-06 328E-06 316E-06 784E-06 286E-06 652E-06 Linear model Parameters for the fit were (b0 b1) 10548E-02 12722E-03
59
СО2 - measurement 2
Data setCO2_20 The calibration data set is 1302E+01 1512E-03 1021E+04 4723E+00 1370E+01 1563E-03 1075E+04 1600E+00 1445E+01 1620E-03 1133E+04 7300E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -38760E-02 12784E-03 26817E-02 24890E-06 -66689E-08 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -62452E-02 12805E-03 47930E-02 43243E-06 -20716E-07 Remaining SSD is 03231 Weighted distances x-value x-dist y-dist 100E+00 130E+01 107E-01 -415E-01 200E+00 137E+01 -212E-01 283E-01 300E+00 144E+01 104E-01 -584E-02 Goodness-of-fit measure 04155 Parameter set 1 -6245240430658412E-2 1280492624666799E-3 4792952200361109E-2 4324266278840409E-6 -
2071623966851869E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_20c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13594E+01 10290E-02 10665E+04 78300E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 121E-05 683E-06 651E-06 315E-05 560E-06 106E-04 Linear model Parameters for the fit were (b0 b1) -62452E-02 12805E-03
60
С3Н8 - measurement 1
Data setC3H8 The calibration data set is 1900E-01 7800E-05 9057E+03 1098E+01 2002E-01 7900E-05 9552E+03 8569E+00 2101E-01 7960E-05 1007E+04 4049E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10529E-02 19831E-05 34552E-03 36109E-07 -12465E-09 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11642E-02 19714E-05 23073E-03 23522E-07 -54231E-10 Remaining SSD is 19453 Weighted distances x-value x-dist y-dist 100E+00 190E-01 -239E-01 666E-01 200E+00 200E-01 487E-01 -104E+00 300E+00 210E-01 -247E-01 248E-01 Goodness-of-fit measure 10414 Parameter set 1 1164239985182795E-2 1971441115316992E-5 2307269625077337E-3 2352198415608386E-7 -
5423119774765299E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19837E-01 14840E-04 94718E+03 45610E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
43
A method of sample input to a comparator is a method with flow stabilization Uncertainty The following uncertainties were included to the budget of uncertainty - uncertainty of the balance - uncertainties of impurities in parent gases Contribution from other uncertainty sources was insignificant A cabin of the balance is thermostatically The balance is the one-pan balance
Air transfer is absent in the cabin of the balance Drift of the balance is absent for PSGM preparation
Contribution from other uncertainty sources was considered in software according to ISO 6142-2003
Uncertainties related to the analysis (comparison) were considered in software according to ISO 6143-2003 and enclosed in Annex B
Uncertainty table СО2
Uncertainty source
Xi
Evaluation type
Standard uncertainty u(xi) rel
Sensitivity coefficient
ci
Contribution to standard uncertainty ui(y) rel
Calibration gas mixture
B 001 1 001
Analysis A B 008 1 008
Coverage factor 2 Expanded uncertainty 002sdot10-2 molmol Uncertainty table СО
Protocols of analysis (comparison) in accordance with ISO 6143-2003
57
Explanation of protocols of comparison
Chapter I ldquoThe calibration data set isrdquo contains columns 1 mole fraction of a component 2 absolute standard uncertainty of mole fraction of a component 3 a signal of a comparator 4 absolute standard uncertainty of a comparator signal
Chapter II ldquoResults of ISO 6143 methodrdquo contains parameters of a calibration curve including its
uncertainty
Chapter ІІІ ldquoPart II Processing of datardquo contains columns
1 calc x - the results of comparison mole fraction of a component 2 u(x) - absolute standard uncertainty of mole fraction of a component 3 response y - a signal of a comparator 4 u(y) - absolute standard uncertainty of a comparator signal
58
СО2 - measurement 1 Data setCO2_21 The calibration data set is 1302E+01 1510E-03 1022E+04 1820E+00 1370E+01 1560E-03 1077E+04 2730E+00 1445E+01 1620E-03 1135E+04 5900E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 20331E-02 12711E-03 12573E-01 11653E-05 -14638E-06 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 10548E-02 12722E-03 31762E-02 28898E-06 -91698E-08 Remaining SSD is 74346 Weighted distances x-value x-dist y-dist 100E+00 130E+01 490E-01 -755E-01 200E+00 137E+01 -103E+00 228E+00 300E+00 144E+01 539E-01 -250E-01 Goodness-of-fit measure 22837 Parameter set 1 1054788657490729E-2 1272208026684145E-3 3176237146276368E-2 2889798108124711E-6 -
9169821653851327E-8 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_21c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13577E+01 25542E-03 10664E+04 15200E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 547E-06 328E-06 316E-06 784E-06 286E-06 652E-06 Linear model Parameters for the fit were (b0 b1) 10548E-02 12722E-03
59
СО2 - measurement 2
Data setCO2_20 The calibration data set is 1302E+01 1512E-03 1021E+04 4723E+00 1370E+01 1563E-03 1075E+04 1600E+00 1445E+01 1620E-03 1133E+04 7300E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -38760E-02 12784E-03 26817E-02 24890E-06 -66689E-08 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -62452E-02 12805E-03 47930E-02 43243E-06 -20716E-07 Remaining SSD is 03231 Weighted distances x-value x-dist y-dist 100E+00 130E+01 107E-01 -415E-01 200E+00 137E+01 -212E-01 283E-01 300E+00 144E+01 104E-01 -584E-02 Goodness-of-fit measure 04155 Parameter set 1 -6245240430658412E-2 1280492624666799E-3 4792952200361109E-2 4324266278840409E-6 -
2071623966851869E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_20c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13594E+01 10290E-02 10665E+04 78300E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 121E-05 683E-06 651E-06 315E-05 560E-06 106E-04 Linear model Parameters for the fit were (b0 b1) -62452E-02 12805E-03
60
С3Н8 - measurement 1
Data setC3H8 The calibration data set is 1900E-01 7800E-05 9057E+03 1098E+01 2002E-01 7900E-05 9552E+03 8569E+00 2101E-01 7960E-05 1007E+04 4049E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10529E-02 19831E-05 34552E-03 36109E-07 -12465E-09 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11642E-02 19714E-05 23073E-03 23522E-07 -54231E-10 Remaining SSD is 19453 Weighted distances x-value x-dist y-dist 100E+00 190E-01 -239E-01 666E-01 200E+00 200E-01 487E-01 -104E+00 300E+00 210E-01 -247E-01 248E-01 Goodness-of-fit measure 10414 Parameter set 1 1164239985182795E-2 1971441115316992E-5 2307269625077337E-3 2352198415608386E-7 -
5423119774765299E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19837E-01 14840E-04 94718E+03 45610E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
Protocols of analysis (comparison) in accordance with ISO 6143-2003
57
Explanation of protocols of comparison
Chapter I ldquoThe calibration data set isrdquo contains columns 1 mole fraction of a component 2 absolute standard uncertainty of mole fraction of a component 3 a signal of a comparator 4 absolute standard uncertainty of a comparator signal
Chapter II ldquoResults of ISO 6143 methodrdquo contains parameters of a calibration curve including its
uncertainty
Chapter ІІІ ldquoPart II Processing of datardquo contains columns
1 calc x - the results of comparison mole fraction of a component 2 u(x) - absolute standard uncertainty of mole fraction of a component 3 response y - a signal of a comparator 4 u(y) - absolute standard uncertainty of a comparator signal
58
СО2 - measurement 1 Data setCO2_21 The calibration data set is 1302E+01 1510E-03 1022E+04 1820E+00 1370E+01 1560E-03 1077E+04 2730E+00 1445E+01 1620E-03 1135E+04 5900E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 20331E-02 12711E-03 12573E-01 11653E-05 -14638E-06 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 10548E-02 12722E-03 31762E-02 28898E-06 -91698E-08 Remaining SSD is 74346 Weighted distances x-value x-dist y-dist 100E+00 130E+01 490E-01 -755E-01 200E+00 137E+01 -103E+00 228E+00 300E+00 144E+01 539E-01 -250E-01 Goodness-of-fit measure 22837 Parameter set 1 1054788657490729E-2 1272208026684145E-3 3176237146276368E-2 2889798108124711E-6 -
9169821653851327E-8 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_21c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13577E+01 25542E-03 10664E+04 15200E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 547E-06 328E-06 316E-06 784E-06 286E-06 652E-06 Linear model Parameters for the fit were (b0 b1) 10548E-02 12722E-03
59
СО2 - measurement 2
Data setCO2_20 The calibration data set is 1302E+01 1512E-03 1021E+04 4723E+00 1370E+01 1563E-03 1075E+04 1600E+00 1445E+01 1620E-03 1133E+04 7300E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -38760E-02 12784E-03 26817E-02 24890E-06 -66689E-08 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -62452E-02 12805E-03 47930E-02 43243E-06 -20716E-07 Remaining SSD is 03231 Weighted distances x-value x-dist y-dist 100E+00 130E+01 107E-01 -415E-01 200E+00 137E+01 -212E-01 283E-01 300E+00 144E+01 104E-01 -584E-02 Goodness-of-fit measure 04155 Parameter set 1 -6245240430658412E-2 1280492624666799E-3 4792952200361109E-2 4324266278840409E-6 -
2071623966851869E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_20c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13594E+01 10290E-02 10665E+04 78300E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 121E-05 683E-06 651E-06 315E-05 560E-06 106E-04 Linear model Parameters for the fit were (b0 b1) -62452E-02 12805E-03
60
С3Н8 - measurement 1
Data setC3H8 The calibration data set is 1900E-01 7800E-05 9057E+03 1098E+01 2002E-01 7900E-05 9552E+03 8569E+00 2101E-01 7960E-05 1007E+04 4049E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10529E-02 19831E-05 34552E-03 36109E-07 -12465E-09 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11642E-02 19714E-05 23073E-03 23522E-07 -54231E-10 Remaining SSD is 19453 Weighted distances x-value x-dist y-dist 100E+00 190E-01 -239E-01 666E-01 200E+00 200E-01 487E-01 -104E+00 300E+00 210E-01 -247E-01 248E-01 Goodness-of-fit measure 10414 Parameter set 1 1164239985182795E-2 1971441115316992E-5 2307269625077337E-3 2352198415608386E-7 -
5423119774765299E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19837E-01 14840E-04 94718E+03 45610E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
45
Annex A
Protocols of PSGM preparation in accordance with ISO 6142-2003
Protocols of analysis (comparison) in accordance with ISO 6143-2003
57
Explanation of protocols of comparison
Chapter I ldquoThe calibration data set isrdquo contains columns 1 mole fraction of a component 2 absolute standard uncertainty of mole fraction of a component 3 a signal of a comparator 4 absolute standard uncertainty of a comparator signal
Chapter II ldquoResults of ISO 6143 methodrdquo contains parameters of a calibration curve including its
uncertainty
Chapter ІІІ ldquoPart II Processing of datardquo contains columns
1 calc x - the results of comparison mole fraction of a component 2 u(x) - absolute standard uncertainty of mole fraction of a component 3 response y - a signal of a comparator 4 u(y) - absolute standard uncertainty of a comparator signal
58
СО2 - measurement 1 Data setCO2_21 The calibration data set is 1302E+01 1510E-03 1022E+04 1820E+00 1370E+01 1560E-03 1077E+04 2730E+00 1445E+01 1620E-03 1135E+04 5900E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 20331E-02 12711E-03 12573E-01 11653E-05 -14638E-06 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 10548E-02 12722E-03 31762E-02 28898E-06 -91698E-08 Remaining SSD is 74346 Weighted distances x-value x-dist y-dist 100E+00 130E+01 490E-01 -755E-01 200E+00 137E+01 -103E+00 228E+00 300E+00 144E+01 539E-01 -250E-01 Goodness-of-fit measure 22837 Parameter set 1 1054788657490729E-2 1272208026684145E-3 3176237146276368E-2 2889798108124711E-6 -
9169821653851327E-8 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_21c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13577E+01 25542E-03 10664E+04 15200E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 547E-06 328E-06 316E-06 784E-06 286E-06 652E-06 Linear model Parameters for the fit were (b0 b1) 10548E-02 12722E-03
59
СО2 - measurement 2
Data setCO2_20 The calibration data set is 1302E+01 1512E-03 1021E+04 4723E+00 1370E+01 1563E-03 1075E+04 1600E+00 1445E+01 1620E-03 1133E+04 7300E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -38760E-02 12784E-03 26817E-02 24890E-06 -66689E-08 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -62452E-02 12805E-03 47930E-02 43243E-06 -20716E-07 Remaining SSD is 03231 Weighted distances x-value x-dist y-dist 100E+00 130E+01 107E-01 -415E-01 200E+00 137E+01 -212E-01 283E-01 300E+00 144E+01 104E-01 -584E-02 Goodness-of-fit measure 04155 Parameter set 1 -6245240430658412E-2 1280492624666799E-3 4792952200361109E-2 4324266278840409E-6 -
2071623966851869E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_20c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13594E+01 10290E-02 10665E+04 78300E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 121E-05 683E-06 651E-06 315E-05 560E-06 106E-04 Linear model Parameters for the fit were (b0 b1) -62452E-02 12805E-03
60
С3Н8 - measurement 1
Data setC3H8 The calibration data set is 1900E-01 7800E-05 9057E+03 1098E+01 2002E-01 7900E-05 9552E+03 8569E+00 2101E-01 7960E-05 1007E+04 4049E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10529E-02 19831E-05 34552E-03 36109E-07 -12465E-09 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11642E-02 19714E-05 23073E-03 23522E-07 -54231E-10 Remaining SSD is 19453 Weighted distances x-value x-dist y-dist 100E+00 190E-01 -239E-01 666E-01 200E+00 200E-01 487E-01 -104E+00 300E+00 210E-01 -247E-01 248E-01 Goodness-of-fit measure 10414 Parameter set 1 1164239985182795E-2 1971441115316992E-5 2307269625077337E-3 2352198415608386E-7 -
5423119774765299E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19837E-01 14840E-04 94718E+03 45610E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
Protocols of analysis (comparison) in accordance with ISO 6143-2003
57
Explanation of protocols of comparison
Chapter I ldquoThe calibration data set isrdquo contains columns 1 mole fraction of a component 2 absolute standard uncertainty of mole fraction of a component 3 a signal of a comparator 4 absolute standard uncertainty of a comparator signal
Chapter II ldquoResults of ISO 6143 methodrdquo contains parameters of a calibration curve including its
uncertainty
Chapter ІІІ ldquoPart II Processing of datardquo contains columns
1 calc x - the results of comparison mole fraction of a component 2 u(x) - absolute standard uncertainty of mole fraction of a component 3 response y - a signal of a comparator 4 u(y) - absolute standard uncertainty of a comparator signal
58
СО2 - measurement 1 Data setCO2_21 The calibration data set is 1302E+01 1510E-03 1022E+04 1820E+00 1370E+01 1560E-03 1077E+04 2730E+00 1445E+01 1620E-03 1135E+04 5900E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 20331E-02 12711E-03 12573E-01 11653E-05 -14638E-06 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 10548E-02 12722E-03 31762E-02 28898E-06 -91698E-08 Remaining SSD is 74346 Weighted distances x-value x-dist y-dist 100E+00 130E+01 490E-01 -755E-01 200E+00 137E+01 -103E+00 228E+00 300E+00 144E+01 539E-01 -250E-01 Goodness-of-fit measure 22837 Parameter set 1 1054788657490729E-2 1272208026684145E-3 3176237146276368E-2 2889798108124711E-6 -
9169821653851327E-8 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_21c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13577E+01 25542E-03 10664E+04 15200E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 547E-06 328E-06 316E-06 784E-06 286E-06 652E-06 Linear model Parameters for the fit were (b0 b1) 10548E-02 12722E-03
59
СО2 - measurement 2
Data setCO2_20 The calibration data set is 1302E+01 1512E-03 1021E+04 4723E+00 1370E+01 1563E-03 1075E+04 1600E+00 1445E+01 1620E-03 1133E+04 7300E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -38760E-02 12784E-03 26817E-02 24890E-06 -66689E-08 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -62452E-02 12805E-03 47930E-02 43243E-06 -20716E-07 Remaining SSD is 03231 Weighted distances x-value x-dist y-dist 100E+00 130E+01 107E-01 -415E-01 200E+00 137E+01 -212E-01 283E-01 300E+00 144E+01 104E-01 -584E-02 Goodness-of-fit measure 04155 Parameter set 1 -6245240430658412E-2 1280492624666799E-3 4792952200361109E-2 4324266278840409E-6 -
2071623966851869E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_20c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13594E+01 10290E-02 10665E+04 78300E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 121E-05 683E-06 651E-06 315E-05 560E-06 106E-04 Linear model Parameters for the fit were (b0 b1) -62452E-02 12805E-03
60
С3Н8 - measurement 1
Data setC3H8 The calibration data set is 1900E-01 7800E-05 9057E+03 1098E+01 2002E-01 7900E-05 9552E+03 8569E+00 2101E-01 7960E-05 1007E+04 4049E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10529E-02 19831E-05 34552E-03 36109E-07 -12465E-09 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11642E-02 19714E-05 23073E-03 23522E-07 -54231E-10 Remaining SSD is 19453 Weighted distances x-value x-dist y-dist 100E+00 190E-01 -239E-01 666E-01 200E+00 200E-01 487E-01 -104E+00 300E+00 210E-01 -247E-01 248E-01 Goodness-of-fit measure 10414 Parameter set 1 1164239985182795E-2 1971441115316992E-5 2307269625077337E-3 2352198415608386E-7 -
5423119774765299E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19837E-01 14840E-04 94718E+03 45610E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
Protocols of analysis (comparison) in accordance with ISO 6143-2003
57
Explanation of protocols of comparison
Chapter I ldquoThe calibration data set isrdquo contains columns 1 mole fraction of a component 2 absolute standard uncertainty of mole fraction of a component 3 a signal of a comparator 4 absolute standard uncertainty of a comparator signal
Chapter II ldquoResults of ISO 6143 methodrdquo contains parameters of a calibration curve including its
uncertainty
Chapter ІІІ ldquoPart II Processing of datardquo contains columns
1 calc x - the results of comparison mole fraction of a component 2 u(x) - absolute standard uncertainty of mole fraction of a component 3 response y - a signal of a comparator 4 u(y) - absolute standard uncertainty of a comparator signal
58
СО2 - measurement 1 Data setCO2_21 The calibration data set is 1302E+01 1510E-03 1022E+04 1820E+00 1370E+01 1560E-03 1077E+04 2730E+00 1445E+01 1620E-03 1135E+04 5900E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 20331E-02 12711E-03 12573E-01 11653E-05 -14638E-06 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 10548E-02 12722E-03 31762E-02 28898E-06 -91698E-08 Remaining SSD is 74346 Weighted distances x-value x-dist y-dist 100E+00 130E+01 490E-01 -755E-01 200E+00 137E+01 -103E+00 228E+00 300E+00 144E+01 539E-01 -250E-01 Goodness-of-fit measure 22837 Parameter set 1 1054788657490729E-2 1272208026684145E-3 3176237146276368E-2 2889798108124711E-6 -
9169821653851327E-8 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_21c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13577E+01 25542E-03 10664E+04 15200E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 547E-06 328E-06 316E-06 784E-06 286E-06 652E-06 Linear model Parameters for the fit were (b0 b1) 10548E-02 12722E-03
59
СО2 - measurement 2
Data setCO2_20 The calibration data set is 1302E+01 1512E-03 1021E+04 4723E+00 1370E+01 1563E-03 1075E+04 1600E+00 1445E+01 1620E-03 1133E+04 7300E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -38760E-02 12784E-03 26817E-02 24890E-06 -66689E-08 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -62452E-02 12805E-03 47930E-02 43243E-06 -20716E-07 Remaining SSD is 03231 Weighted distances x-value x-dist y-dist 100E+00 130E+01 107E-01 -415E-01 200E+00 137E+01 -212E-01 283E-01 300E+00 144E+01 104E-01 -584E-02 Goodness-of-fit measure 04155 Parameter set 1 -6245240430658412E-2 1280492624666799E-3 4792952200361109E-2 4324266278840409E-6 -
2071623966851869E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_20c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13594E+01 10290E-02 10665E+04 78300E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 121E-05 683E-06 651E-06 315E-05 560E-06 106E-04 Linear model Parameters for the fit were (b0 b1) -62452E-02 12805E-03
60
С3Н8 - measurement 1
Data setC3H8 The calibration data set is 1900E-01 7800E-05 9057E+03 1098E+01 2002E-01 7900E-05 9552E+03 8569E+00 2101E-01 7960E-05 1007E+04 4049E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10529E-02 19831E-05 34552E-03 36109E-07 -12465E-09 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11642E-02 19714E-05 23073E-03 23522E-07 -54231E-10 Remaining SSD is 19453 Weighted distances x-value x-dist y-dist 100E+00 190E-01 -239E-01 666E-01 200E+00 200E-01 487E-01 -104E+00 300E+00 210E-01 -247E-01 248E-01 Goodness-of-fit measure 10414 Parameter set 1 1164239985182795E-2 1971441115316992E-5 2307269625077337E-3 2352198415608386E-7 -
5423119774765299E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19837E-01 14840E-04 94718E+03 45610E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
Protocols of analysis (comparison) in accordance with ISO 6143-2003
57
Explanation of protocols of comparison
Chapter I ldquoThe calibration data set isrdquo contains columns 1 mole fraction of a component 2 absolute standard uncertainty of mole fraction of a component 3 a signal of a comparator 4 absolute standard uncertainty of a comparator signal
Chapter II ldquoResults of ISO 6143 methodrdquo contains parameters of a calibration curve including its
uncertainty
Chapter ІІІ ldquoPart II Processing of datardquo contains columns
1 calc x - the results of comparison mole fraction of a component 2 u(x) - absolute standard uncertainty of mole fraction of a component 3 response y - a signal of a comparator 4 u(y) - absolute standard uncertainty of a comparator signal
58
СО2 - measurement 1 Data setCO2_21 The calibration data set is 1302E+01 1510E-03 1022E+04 1820E+00 1370E+01 1560E-03 1077E+04 2730E+00 1445E+01 1620E-03 1135E+04 5900E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 20331E-02 12711E-03 12573E-01 11653E-05 -14638E-06 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 10548E-02 12722E-03 31762E-02 28898E-06 -91698E-08 Remaining SSD is 74346 Weighted distances x-value x-dist y-dist 100E+00 130E+01 490E-01 -755E-01 200E+00 137E+01 -103E+00 228E+00 300E+00 144E+01 539E-01 -250E-01 Goodness-of-fit measure 22837 Parameter set 1 1054788657490729E-2 1272208026684145E-3 3176237146276368E-2 2889798108124711E-6 -
9169821653851327E-8 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_21c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13577E+01 25542E-03 10664E+04 15200E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 547E-06 328E-06 316E-06 784E-06 286E-06 652E-06 Linear model Parameters for the fit were (b0 b1) 10548E-02 12722E-03
59
СО2 - measurement 2
Data setCO2_20 The calibration data set is 1302E+01 1512E-03 1021E+04 4723E+00 1370E+01 1563E-03 1075E+04 1600E+00 1445E+01 1620E-03 1133E+04 7300E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -38760E-02 12784E-03 26817E-02 24890E-06 -66689E-08 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -62452E-02 12805E-03 47930E-02 43243E-06 -20716E-07 Remaining SSD is 03231 Weighted distances x-value x-dist y-dist 100E+00 130E+01 107E-01 -415E-01 200E+00 137E+01 -212E-01 283E-01 300E+00 144E+01 104E-01 -584E-02 Goodness-of-fit measure 04155 Parameter set 1 -6245240430658412E-2 1280492624666799E-3 4792952200361109E-2 4324266278840409E-6 -
2071623966851869E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_20c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13594E+01 10290E-02 10665E+04 78300E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 121E-05 683E-06 651E-06 315E-05 560E-06 106E-04 Linear model Parameters for the fit were (b0 b1) -62452E-02 12805E-03
60
С3Н8 - measurement 1
Data setC3H8 The calibration data set is 1900E-01 7800E-05 9057E+03 1098E+01 2002E-01 7900E-05 9552E+03 8569E+00 2101E-01 7960E-05 1007E+04 4049E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10529E-02 19831E-05 34552E-03 36109E-07 -12465E-09 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11642E-02 19714E-05 23073E-03 23522E-07 -54231E-10 Remaining SSD is 19453 Weighted distances x-value x-dist y-dist 100E+00 190E-01 -239E-01 666E-01 200E+00 200E-01 487E-01 -104E+00 300E+00 210E-01 -247E-01 248E-01 Goodness-of-fit measure 10414 Parameter set 1 1164239985182795E-2 1971441115316992E-5 2307269625077337E-3 2352198415608386E-7 -
5423119774765299E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19837E-01 14840E-04 94718E+03 45610E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
49
Mixture data Cylinder code 0086 Preparation date 130905 Producer ukr Maincomponent Propane Cylinder code
Protocols of analysis (comparison) in accordance with ISO 6143-2003
57
Explanation of protocols of comparison
Chapter I ldquoThe calibration data set isrdquo contains columns 1 mole fraction of a component 2 absolute standard uncertainty of mole fraction of a component 3 a signal of a comparator 4 absolute standard uncertainty of a comparator signal
Chapter II ldquoResults of ISO 6143 methodrdquo contains parameters of a calibration curve including its
uncertainty
Chapter ІІІ ldquoPart II Processing of datardquo contains columns
1 calc x - the results of comparison mole fraction of a component 2 u(x) - absolute standard uncertainty of mole fraction of a component 3 response y - a signal of a comparator 4 u(y) - absolute standard uncertainty of a comparator signal
58
СО2 - measurement 1 Data setCO2_21 The calibration data set is 1302E+01 1510E-03 1022E+04 1820E+00 1370E+01 1560E-03 1077E+04 2730E+00 1445E+01 1620E-03 1135E+04 5900E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 20331E-02 12711E-03 12573E-01 11653E-05 -14638E-06 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 10548E-02 12722E-03 31762E-02 28898E-06 -91698E-08 Remaining SSD is 74346 Weighted distances x-value x-dist y-dist 100E+00 130E+01 490E-01 -755E-01 200E+00 137E+01 -103E+00 228E+00 300E+00 144E+01 539E-01 -250E-01 Goodness-of-fit measure 22837 Parameter set 1 1054788657490729E-2 1272208026684145E-3 3176237146276368E-2 2889798108124711E-6 -
9169821653851327E-8 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_21c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13577E+01 25542E-03 10664E+04 15200E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 547E-06 328E-06 316E-06 784E-06 286E-06 652E-06 Linear model Parameters for the fit were (b0 b1) 10548E-02 12722E-03
59
СО2 - measurement 2
Data setCO2_20 The calibration data set is 1302E+01 1512E-03 1021E+04 4723E+00 1370E+01 1563E-03 1075E+04 1600E+00 1445E+01 1620E-03 1133E+04 7300E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -38760E-02 12784E-03 26817E-02 24890E-06 -66689E-08 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -62452E-02 12805E-03 47930E-02 43243E-06 -20716E-07 Remaining SSD is 03231 Weighted distances x-value x-dist y-dist 100E+00 130E+01 107E-01 -415E-01 200E+00 137E+01 -212E-01 283E-01 300E+00 144E+01 104E-01 -584E-02 Goodness-of-fit measure 04155 Parameter set 1 -6245240430658412E-2 1280492624666799E-3 4792952200361109E-2 4324266278840409E-6 -
2071623966851869E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_20c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13594E+01 10290E-02 10665E+04 78300E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 121E-05 683E-06 651E-06 315E-05 560E-06 106E-04 Linear model Parameters for the fit were (b0 b1) -62452E-02 12805E-03
60
С3Н8 - measurement 1
Data setC3H8 The calibration data set is 1900E-01 7800E-05 9057E+03 1098E+01 2002E-01 7900E-05 9552E+03 8569E+00 2101E-01 7960E-05 1007E+04 4049E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10529E-02 19831E-05 34552E-03 36109E-07 -12465E-09 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11642E-02 19714E-05 23073E-03 23522E-07 -54231E-10 Remaining SSD is 19453 Weighted distances x-value x-dist y-dist 100E+00 190E-01 -239E-01 666E-01 200E+00 200E-01 487E-01 -104E+00 300E+00 210E-01 -247E-01 248E-01 Goodness-of-fit measure 10414 Parameter set 1 1164239985182795E-2 1971441115316992E-5 2307269625077337E-3 2352198415608386E-7 -
5423119774765299E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19837E-01 14840E-04 94718E+03 45610E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
Protocols of analysis (comparison) in accordance with ISO 6143-2003
57
Explanation of protocols of comparison
Chapter I ldquoThe calibration data set isrdquo contains columns 1 mole fraction of a component 2 absolute standard uncertainty of mole fraction of a component 3 a signal of a comparator 4 absolute standard uncertainty of a comparator signal
Chapter II ldquoResults of ISO 6143 methodrdquo contains parameters of a calibration curve including its
uncertainty
Chapter ІІІ ldquoPart II Processing of datardquo contains columns
1 calc x - the results of comparison mole fraction of a component 2 u(x) - absolute standard uncertainty of mole fraction of a component 3 response y - a signal of a comparator 4 u(y) - absolute standard uncertainty of a comparator signal
58
СО2 - measurement 1 Data setCO2_21 The calibration data set is 1302E+01 1510E-03 1022E+04 1820E+00 1370E+01 1560E-03 1077E+04 2730E+00 1445E+01 1620E-03 1135E+04 5900E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 20331E-02 12711E-03 12573E-01 11653E-05 -14638E-06 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 10548E-02 12722E-03 31762E-02 28898E-06 -91698E-08 Remaining SSD is 74346 Weighted distances x-value x-dist y-dist 100E+00 130E+01 490E-01 -755E-01 200E+00 137E+01 -103E+00 228E+00 300E+00 144E+01 539E-01 -250E-01 Goodness-of-fit measure 22837 Parameter set 1 1054788657490729E-2 1272208026684145E-3 3176237146276368E-2 2889798108124711E-6 -
9169821653851327E-8 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_21c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13577E+01 25542E-03 10664E+04 15200E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 547E-06 328E-06 316E-06 784E-06 286E-06 652E-06 Linear model Parameters for the fit were (b0 b1) 10548E-02 12722E-03
59
СО2 - measurement 2
Data setCO2_20 The calibration data set is 1302E+01 1512E-03 1021E+04 4723E+00 1370E+01 1563E-03 1075E+04 1600E+00 1445E+01 1620E-03 1133E+04 7300E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -38760E-02 12784E-03 26817E-02 24890E-06 -66689E-08 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -62452E-02 12805E-03 47930E-02 43243E-06 -20716E-07 Remaining SSD is 03231 Weighted distances x-value x-dist y-dist 100E+00 130E+01 107E-01 -415E-01 200E+00 137E+01 -212E-01 283E-01 300E+00 144E+01 104E-01 -584E-02 Goodness-of-fit measure 04155 Parameter set 1 -6245240430658412E-2 1280492624666799E-3 4792952200361109E-2 4324266278840409E-6 -
2071623966851869E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_20c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13594E+01 10290E-02 10665E+04 78300E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 121E-05 683E-06 651E-06 315E-05 560E-06 106E-04 Linear model Parameters for the fit were (b0 b1) -62452E-02 12805E-03
60
С3Н8 - measurement 1
Data setC3H8 The calibration data set is 1900E-01 7800E-05 9057E+03 1098E+01 2002E-01 7900E-05 9552E+03 8569E+00 2101E-01 7960E-05 1007E+04 4049E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10529E-02 19831E-05 34552E-03 36109E-07 -12465E-09 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11642E-02 19714E-05 23073E-03 23522E-07 -54231E-10 Remaining SSD is 19453 Weighted distances x-value x-dist y-dist 100E+00 190E-01 -239E-01 666E-01 200E+00 200E-01 487E-01 -104E+00 300E+00 210E-01 -247E-01 248E-01 Goodness-of-fit measure 10414 Parameter set 1 1164239985182795E-2 1971441115316992E-5 2307269625077337E-3 2352198415608386E-7 -
5423119774765299E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19837E-01 14840E-04 94718E+03 45610E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
Protocols of analysis (comparison) in accordance with ISO 6143-2003
57
Explanation of protocols of comparison
Chapter I ldquoThe calibration data set isrdquo contains columns 1 mole fraction of a component 2 absolute standard uncertainty of mole fraction of a component 3 a signal of a comparator 4 absolute standard uncertainty of a comparator signal
Chapter II ldquoResults of ISO 6143 methodrdquo contains parameters of a calibration curve including its
uncertainty
Chapter ІІІ ldquoPart II Processing of datardquo contains columns
1 calc x - the results of comparison mole fraction of a component 2 u(x) - absolute standard uncertainty of mole fraction of a component 3 response y - a signal of a comparator 4 u(y) - absolute standard uncertainty of a comparator signal
58
СО2 - measurement 1 Data setCO2_21 The calibration data set is 1302E+01 1510E-03 1022E+04 1820E+00 1370E+01 1560E-03 1077E+04 2730E+00 1445E+01 1620E-03 1135E+04 5900E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 20331E-02 12711E-03 12573E-01 11653E-05 -14638E-06 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 10548E-02 12722E-03 31762E-02 28898E-06 -91698E-08 Remaining SSD is 74346 Weighted distances x-value x-dist y-dist 100E+00 130E+01 490E-01 -755E-01 200E+00 137E+01 -103E+00 228E+00 300E+00 144E+01 539E-01 -250E-01 Goodness-of-fit measure 22837 Parameter set 1 1054788657490729E-2 1272208026684145E-3 3176237146276368E-2 2889798108124711E-6 -
9169821653851327E-8 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_21c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13577E+01 25542E-03 10664E+04 15200E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 547E-06 328E-06 316E-06 784E-06 286E-06 652E-06 Linear model Parameters for the fit were (b0 b1) 10548E-02 12722E-03
59
СО2 - measurement 2
Data setCO2_20 The calibration data set is 1302E+01 1512E-03 1021E+04 4723E+00 1370E+01 1563E-03 1075E+04 1600E+00 1445E+01 1620E-03 1133E+04 7300E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -38760E-02 12784E-03 26817E-02 24890E-06 -66689E-08 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -62452E-02 12805E-03 47930E-02 43243E-06 -20716E-07 Remaining SSD is 03231 Weighted distances x-value x-dist y-dist 100E+00 130E+01 107E-01 -415E-01 200E+00 137E+01 -212E-01 283E-01 300E+00 144E+01 104E-01 -584E-02 Goodness-of-fit measure 04155 Parameter set 1 -6245240430658412E-2 1280492624666799E-3 4792952200361109E-2 4324266278840409E-6 -
2071623966851869E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_20c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13594E+01 10290E-02 10665E+04 78300E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 121E-05 683E-06 651E-06 315E-05 560E-06 106E-04 Linear model Parameters for the fit were (b0 b1) -62452E-02 12805E-03
60
С3Н8 - measurement 1
Data setC3H8 The calibration data set is 1900E-01 7800E-05 9057E+03 1098E+01 2002E-01 7900E-05 9552E+03 8569E+00 2101E-01 7960E-05 1007E+04 4049E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10529E-02 19831E-05 34552E-03 36109E-07 -12465E-09 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11642E-02 19714E-05 23073E-03 23522E-07 -54231E-10 Remaining SSD is 19453 Weighted distances x-value x-dist y-dist 100E+00 190E-01 -239E-01 666E-01 200E+00 200E-01 487E-01 -104E+00 300E+00 210E-01 -247E-01 248E-01 Goodness-of-fit measure 10414 Parameter set 1 1164239985182795E-2 1971441115316992E-5 2307269625077337E-3 2352198415608386E-7 -
5423119774765299E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19837E-01 14840E-04 94718E+03 45610E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
Protocols of analysis (comparison) in accordance with ISO 6143-2003
57
Explanation of protocols of comparison
Chapter I ldquoThe calibration data set isrdquo contains columns 1 mole fraction of a component 2 absolute standard uncertainty of mole fraction of a component 3 a signal of a comparator 4 absolute standard uncertainty of a comparator signal
Chapter II ldquoResults of ISO 6143 methodrdquo contains parameters of a calibration curve including its
uncertainty
Chapter ІІІ ldquoPart II Processing of datardquo contains columns
1 calc x - the results of comparison mole fraction of a component 2 u(x) - absolute standard uncertainty of mole fraction of a component 3 response y - a signal of a comparator 4 u(y) - absolute standard uncertainty of a comparator signal
58
СО2 - measurement 1 Data setCO2_21 The calibration data set is 1302E+01 1510E-03 1022E+04 1820E+00 1370E+01 1560E-03 1077E+04 2730E+00 1445E+01 1620E-03 1135E+04 5900E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 20331E-02 12711E-03 12573E-01 11653E-05 -14638E-06 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 10548E-02 12722E-03 31762E-02 28898E-06 -91698E-08 Remaining SSD is 74346 Weighted distances x-value x-dist y-dist 100E+00 130E+01 490E-01 -755E-01 200E+00 137E+01 -103E+00 228E+00 300E+00 144E+01 539E-01 -250E-01 Goodness-of-fit measure 22837 Parameter set 1 1054788657490729E-2 1272208026684145E-3 3176237146276368E-2 2889798108124711E-6 -
9169821653851327E-8 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_21c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13577E+01 25542E-03 10664E+04 15200E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 547E-06 328E-06 316E-06 784E-06 286E-06 652E-06 Linear model Parameters for the fit were (b0 b1) 10548E-02 12722E-03
59
СО2 - measurement 2
Data setCO2_20 The calibration data set is 1302E+01 1512E-03 1021E+04 4723E+00 1370E+01 1563E-03 1075E+04 1600E+00 1445E+01 1620E-03 1133E+04 7300E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -38760E-02 12784E-03 26817E-02 24890E-06 -66689E-08 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -62452E-02 12805E-03 47930E-02 43243E-06 -20716E-07 Remaining SSD is 03231 Weighted distances x-value x-dist y-dist 100E+00 130E+01 107E-01 -415E-01 200E+00 137E+01 -212E-01 283E-01 300E+00 144E+01 104E-01 -584E-02 Goodness-of-fit measure 04155 Parameter set 1 -6245240430658412E-2 1280492624666799E-3 4792952200361109E-2 4324266278840409E-6 -
2071623966851869E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_20c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13594E+01 10290E-02 10665E+04 78300E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 121E-05 683E-06 651E-06 315E-05 560E-06 106E-04 Linear model Parameters for the fit were (b0 b1) -62452E-02 12805E-03
60
С3Н8 - measurement 1
Data setC3H8 The calibration data set is 1900E-01 7800E-05 9057E+03 1098E+01 2002E-01 7900E-05 9552E+03 8569E+00 2101E-01 7960E-05 1007E+04 4049E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10529E-02 19831E-05 34552E-03 36109E-07 -12465E-09 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11642E-02 19714E-05 23073E-03 23522E-07 -54231E-10 Remaining SSD is 19453 Weighted distances x-value x-dist y-dist 100E+00 190E-01 -239E-01 666E-01 200E+00 200E-01 487E-01 -104E+00 300E+00 210E-01 -247E-01 248E-01 Goodness-of-fit measure 10414 Parameter set 1 1164239985182795E-2 1971441115316992E-5 2307269625077337E-3 2352198415608386E-7 -
5423119774765299E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19837E-01 14840E-04 94718E+03 45610E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
53
Mixture data Cylinder code 0093 Preparation date 130605 Producer ukr Maincomponent Nitrogen Cylinder code
Protocols of analysis (comparison) in accordance with ISO 6143-2003
57
Explanation of protocols of comparison
Chapter I ldquoThe calibration data set isrdquo contains columns 1 mole fraction of a component 2 absolute standard uncertainty of mole fraction of a component 3 a signal of a comparator 4 absolute standard uncertainty of a comparator signal
Chapter II ldquoResults of ISO 6143 methodrdquo contains parameters of a calibration curve including its
uncertainty
Chapter ІІІ ldquoPart II Processing of datardquo contains columns
1 calc x - the results of comparison mole fraction of a component 2 u(x) - absolute standard uncertainty of mole fraction of a component 3 response y - a signal of a comparator 4 u(y) - absolute standard uncertainty of a comparator signal
58
СО2 - measurement 1 Data setCO2_21 The calibration data set is 1302E+01 1510E-03 1022E+04 1820E+00 1370E+01 1560E-03 1077E+04 2730E+00 1445E+01 1620E-03 1135E+04 5900E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 20331E-02 12711E-03 12573E-01 11653E-05 -14638E-06 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 10548E-02 12722E-03 31762E-02 28898E-06 -91698E-08 Remaining SSD is 74346 Weighted distances x-value x-dist y-dist 100E+00 130E+01 490E-01 -755E-01 200E+00 137E+01 -103E+00 228E+00 300E+00 144E+01 539E-01 -250E-01 Goodness-of-fit measure 22837 Parameter set 1 1054788657490729E-2 1272208026684145E-3 3176237146276368E-2 2889798108124711E-6 -
9169821653851327E-8 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_21c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13577E+01 25542E-03 10664E+04 15200E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 547E-06 328E-06 316E-06 784E-06 286E-06 652E-06 Linear model Parameters for the fit were (b0 b1) 10548E-02 12722E-03
59
СО2 - measurement 2
Data setCO2_20 The calibration data set is 1302E+01 1512E-03 1021E+04 4723E+00 1370E+01 1563E-03 1075E+04 1600E+00 1445E+01 1620E-03 1133E+04 7300E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -38760E-02 12784E-03 26817E-02 24890E-06 -66689E-08 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -62452E-02 12805E-03 47930E-02 43243E-06 -20716E-07 Remaining SSD is 03231 Weighted distances x-value x-dist y-dist 100E+00 130E+01 107E-01 -415E-01 200E+00 137E+01 -212E-01 283E-01 300E+00 144E+01 104E-01 -584E-02 Goodness-of-fit measure 04155 Parameter set 1 -6245240430658412E-2 1280492624666799E-3 4792952200361109E-2 4324266278840409E-6 -
2071623966851869E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_20c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13594E+01 10290E-02 10665E+04 78300E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 121E-05 683E-06 651E-06 315E-05 560E-06 106E-04 Linear model Parameters for the fit were (b0 b1) -62452E-02 12805E-03
60
С3Н8 - measurement 1
Data setC3H8 The calibration data set is 1900E-01 7800E-05 9057E+03 1098E+01 2002E-01 7900E-05 9552E+03 8569E+00 2101E-01 7960E-05 1007E+04 4049E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10529E-02 19831E-05 34552E-03 36109E-07 -12465E-09 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11642E-02 19714E-05 23073E-03 23522E-07 -54231E-10 Remaining SSD is 19453 Weighted distances x-value x-dist y-dist 100E+00 190E-01 -239E-01 666E-01 200E+00 200E-01 487E-01 -104E+00 300E+00 210E-01 -247E-01 248E-01 Goodness-of-fit measure 10414 Parameter set 1 1164239985182795E-2 1971441115316992E-5 2307269625077337E-3 2352198415608386E-7 -
5423119774765299E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19837E-01 14840E-04 94718E+03 45610E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
54
Mixture data Cylinder code 0107 Preparation date 130905 Producer ukr Maincomponent Nitrogen Cylinder code Producer Component Transferred
Protocols of analysis (comparison) in accordance with ISO 6143-2003
57
Explanation of protocols of comparison
Chapter I ldquoThe calibration data set isrdquo contains columns 1 mole fraction of a component 2 absolute standard uncertainty of mole fraction of a component 3 a signal of a comparator 4 absolute standard uncertainty of a comparator signal
Chapter II ldquoResults of ISO 6143 methodrdquo contains parameters of a calibration curve including its
uncertainty
Chapter ІІІ ldquoPart II Processing of datardquo contains columns
1 calc x - the results of comparison mole fraction of a component 2 u(x) - absolute standard uncertainty of mole fraction of a component 3 response y - a signal of a comparator 4 u(y) - absolute standard uncertainty of a comparator signal
58
СО2 - measurement 1 Data setCO2_21 The calibration data set is 1302E+01 1510E-03 1022E+04 1820E+00 1370E+01 1560E-03 1077E+04 2730E+00 1445E+01 1620E-03 1135E+04 5900E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 20331E-02 12711E-03 12573E-01 11653E-05 -14638E-06 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 10548E-02 12722E-03 31762E-02 28898E-06 -91698E-08 Remaining SSD is 74346 Weighted distances x-value x-dist y-dist 100E+00 130E+01 490E-01 -755E-01 200E+00 137E+01 -103E+00 228E+00 300E+00 144E+01 539E-01 -250E-01 Goodness-of-fit measure 22837 Parameter set 1 1054788657490729E-2 1272208026684145E-3 3176237146276368E-2 2889798108124711E-6 -
9169821653851327E-8 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_21c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13577E+01 25542E-03 10664E+04 15200E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 547E-06 328E-06 316E-06 784E-06 286E-06 652E-06 Linear model Parameters for the fit were (b0 b1) 10548E-02 12722E-03
59
СО2 - measurement 2
Data setCO2_20 The calibration data set is 1302E+01 1512E-03 1021E+04 4723E+00 1370E+01 1563E-03 1075E+04 1600E+00 1445E+01 1620E-03 1133E+04 7300E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -38760E-02 12784E-03 26817E-02 24890E-06 -66689E-08 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -62452E-02 12805E-03 47930E-02 43243E-06 -20716E-07 Remaining SSD is 03231 Weighted distances x-value x-dist y-dist 100E+00 130E+01 107E-01 -415E-01 200E+00 137E+01 -212E-01 283E-01 300E+00 144E+01 104E-01 -584E-02 Goodness-of-fit measure 04155 Parameter set 1 -6245240430658412E-2 1280492624666799E-3 4792952200361109E-2 4324266278840409E-6 -
2071623966851869E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_20c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13594E+01 10290E-02 10665E+04 78300E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 121E-05 683E-06 651E-06 315E-05 560E-06 106E-04 Linear model Parameters for the fit were (b0 b1) -62452E-02 12805E-03
60
С3Н8 - measurement 1
Data setC3H8 The calibration data set is 1900E-01 7800E-05 9057E+03 1098E+01 2002E-01 7900E-05 9552E+03 8569E+00 2101E-01 7960E-05 1007E+04 4049E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10529E-02 19831E-05 34552E-03 36109E-07 -12465E-09 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11642E-02 19714E-05 23073E-03 23522E-07 -54231E-10 Remaining SSD is 19453 Weighted distances x-value x-dist y-dist 100E+00 190E-01 -239E-01 666E-01 200E+00 200E-01 487E-01 -104E+00 300E+00 210E-01 -247E-01 248E-01 Goodness-of-fit measure 10414 Parameter set 1 1164239985182795E-2 1971441115316992E-5 2307269625077337E-3 2352198415608386E-7 -
5423119774765299E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19837E-01 14840E-04 94718E+03 45610E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
55
Mixture data Cylinder code 0116 Preparation date 130905 Producer ukr Maincomponent Nitrogen Cylinder code Producer Component Transferred
Protocols of analysis (comparison) in accordance with ISO 6143-2003
57
Explanation of protocols of comparison
Chapter I ldquoThe calibration data set isrdquo contains columns 1 mole fraction of a component 2 absolute standard uncertainty of mole fraction of a component 3 a signal of a comparator 4 absolute standard uncertainty of a comparator signal
Chapter II ldquoResults of ISO 6143 methodrdquo contains parameters of a calibration curve including its
uncertainty
Chapter ІІІ ldquoPart II Processing of datardquo contains columns
1 calc x - the results of comparison mole fraction of a component 2 u(x) - absolute standard uncertainty of mole fraction of a component 3 response y - a signal of a comparator 4 u(y) - absolute standard uncertainty of a comparator signal
58
СО2 - measurement 1 Data setCO2_21 The calibration data set is 1302E+01 1510E-03 1022E+04 1820E+00 1370E+01 1560E-03 1077E+04 2730E+00 1445E+01 1620E-03 1135E+04 5900E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 20331E-02 12711E-03 12573E-01 11653E-05 -14638E-06 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 10548E-02 12722E-03 31762E-02 28898E-06 -91698E-08 Remaining SSD is 74346 Weighted distances x-value x-dist y-dist 100E+00 130E+01 490E-01 -755E-01 200E+00 137E+01 -103E+00 228E+00 300E+00 144E+01 539E-01 -250E-01 Goodness-of-fit measure 22837 Parameter set 1 1054788657490729E-2 1272208026684145E-3 3176237146276368E-2 2889798108124711E-6 -
9169821653851327E-8 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_21c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13577E+01 25542E-03 10664E+04 15200E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 547E-06 328E-06 316E-06 784E-06 286E-06 652E-06 Linear model Parameters for the fit were (b0 b1) 10548E-02 12722E-03
59
СО2 - measurement 2
Data setCO2_20 The calibration data set is 1302E+01 1512E-03 1021E+04 4723E+00 1370E+01 1563E-03 1075E+04 1600E+00 1445E+01 1620E-03 1133E+04 7300E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -38760E-02 12784E-03 26817E-02 24890E-06 -66689E-08 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -62452E-02 12805E-03 47930E-02 43243E-06 -20716E-07 Remaining SSD is 03231 Weighted distances x-value x-dist y-dist 100E+00 130E+01 107E-01 -415E-01 200E+00 137E+01 -212E-01 283E-01 300E+00 144E+01 104E-01 -584E-02 Goodness-of-fit measure 04155 Parameter set 1 -6245240430658412E-2 1280492624666799E-3 4792952200361109E-2 4324266278840409E-6 -
2071623966851869E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_20c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13594E+01 10290E-02 10665E+04 78300E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 121E-05 683E-06 651E-06 315E-05 560E-06 106E-04 Linear model Parameters for the fit were (b0 b1) -62452E-02 12805E-03
60
С3Н8 - measurement 1
Data setC3H8 The calibration data set is 1900E-01 7800E-05 9057E+03 1098E+01 2002E-01 7900E-05 9552E+03 8569E+00 2101E-01 7960E-05 1007E+04 4049E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10529E-02 19831E-05 34552E-03 36109E-07 -12465E-09 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11642E-02 19714E-05 23073E-03 23522E-07 -54231E-10 Remaining SSD is 19453 Weighted distances x-value x-dist y-dist 100E+00 190E-01 -239E-01 666E-01 200E+00 200E-01 487E-01 -104E+00 300E+00 210E-01 -247E-01 248E-01 Goodness-of-fit measure 10414 Parameter set 1 1164239985182795E-2 1971441115316992E-5 2307269625077337E-3 2352198415608386E-7 -
5423119774765299E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19837E-01 14840E-04 94718E+03 45610E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
56
Annex B
Protocols of analysis (comparison) in accordance with ISO 6143-2003
57
Explanation of protocols of comparison
Chapter I ldquoThe calibration data set isrdquo contains columns 1 mole fraction of a component 2 absolute standard uncertainty of mole fraction of a component 3 a signal of a comparator 4 absolute standard uncertainty of a comparator signal
Chapter II ldquoResults of ISO 6143 methodrdquo contains parameters of a calibration curve including its
uncertainty
Chapter ІІІ ldquoPart II Processing of datardquo contains columns
1 calc x - the results of comparison mole fraction of a component 2 u(x) - absolute standard uncertainty of mole fraction of a component 3 response y - a signal of a comparator 4 u(y) - absolute standard uncertainty of a comparator signal
58
СО2 - measurement 1 Data setCO2_21 The calibration data set is 1302E+01 1510E-03 1022E+04 1820E+00 1370E+01 1560E-03 1077E+04 2730E+00 1445E+01 1620E-03 1135E+04 5900E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 20331E-02 12711E-03 12573E-01 11653E-05 -14638E-06 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 10548E-02 12722E-03 31762E-02 28898E-06 -91698E-08 Remaining SSD is 74346 Weighted distances x-value x-dist y-dist 100E+00 130E+01 490E-01 -755E-01 200E+00 137E+01 -103E+00 228E+00 300E+00 144E+01 539E-01 -250E-01 Goodness-of-fit measure 22837 Parameter set 1 1054788657490729E-2 1272208026684145E-3 3176237146276368E-2 2889798108124711E-6 -
9169821653851327E-8 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_21c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13577E+01 25542E-03 10664E+04 15200E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 547E-06 328E-06 316E-06 784E-06 286E-06 652E-06 Linear model Parameters for the fit were (b0 b1) 10548E-02 12722E-03
59
СО2 - measurement 2
Data setCO2_20 The calibration data set is 1302E+01 1512E-03 1021E+04 4723E+00 1370E+01 1563E-03 1075E+04 1600E+00 1445E+01 1620E-03 1133E+04 7300E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -38760E-02 12784E-03 26817E-02 24890E-06 -66689E-08 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -62452E-02 12805E-03 47930E-02 43243E-06 -20716E-07 Remaining SSD is 03231 Weighted distances x-value x-dist y-dist 100E+00 130E+01 107E-01 -415E-01 200E+00 137E+01 -212E-01 283E-01 300E+00 144E+01 104E-01 -584E-02 Goodness-of-fit measure 04155 Parameter set 1 -6245240430658412E-2 1280492624666799E-3 4792952200361109E-2 4324266278840409E-6 -
2071623966851869E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_20c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13594E+01 10290E-02 10665E+04 78300E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 121E-05 683E-06 651E-06 315E-05 560E-06 106E-04 Linear model Parameters for the fit were (b0 b1) -62452E-02 12805E-03
60
С3Н8 - measurement 1
Data setC3H8 The calibration data set is 1900E-01 7800E-05 9057E+03 1098E+01 2002E-01 7900E-05 9552E+03 8569E+00 2101E-01 7960E-05 1007E+04 4049E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10529E-02 19831E-05 34552E-03 36109E-07 -12465E-09 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11642E-02 19714E-05 23073E-03 23522E-07 -54231E-10 Remaining SSD is 19453 Weighted distances x-value x-dist y-dist 100E+00 190E-01 -239E-01 666E-01 200E+00 200E-01 487E-01 -104E+00 300E+00 210E-01 -247E-01 248E-01 Goodness-of-fit measure 10414 Parameter set 1 1164239985182795E-2 1971441115316992E-5 2307269625077337E-3 2352198415608386E-7 -
5423119774765299E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19837E-01 14840E-04 94718E+03 45610E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
57
Explanation of protocols of comparison
Chapter I ldquoThe calibration data set isrdquo contains columns 1 mole fraction of a component 2 absolute standard uncertainty of mole fraction of a component 3 a signal of a comparator 4 absolute standard uncertainty of a comparator signal
Chapter II ldquoResults of ISO 6143 methodrdquo contains parameters of a calibration curve including its
uncertainty
Chapter ІІІ ldquoPart II Processing of datardquo contains columns
1 calc x - the results of comparison mole fraction of a component 2 u(x) - absolute standard uncertainty of mole fraction of a component 3 response y - a signal of a comparator 4 u(y) - absolute standard uncertainty of a comparator signal
58
СО2 - measurement 1 Data setCO2_21 The calibration data set is 1302E+01 1510E-03 1022E+04 1820E+00 1370E+01 1560E-03 1077E+04 2730E+00 1445E+01 1620E-03 1135E+04 5900E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 20331E-02 12711E-03 12573E-01 11653E-05 -14638E-06 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 10548E-02 12722E-03 31762E-02 28898E-06 -91698E-08 Remaining SSD is 74346 Weighted distances x-value x-dist y-dist 100E+00 130E+01 490E-01 -755E-01 200E+00 137E+01 -103E+00 228E+00 300E+00 144E+01 539E-01 -250E-01 Goodness-of-fit measure 22837 Parameter set 1 1054788657490729E-2 1272208026684145E-3 3176237146276368E-2 2889798108124711E-6 -
9169821653851327E-8 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_21c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13577E+01 25542E-03 10664E+04 15200E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 547E-06 328E-06 316E-06 784E-06 286E-06 652E-06 Linear model Parameters for the fit were (b0 b1) 10548E-02 12722E-03
59
СО2 - measurement 2
Data setCO2_20 The calibration data set is 1302E+01 1512E-03 1021E+04 4723E+00 1370E+01 1563E-03 1075E+04 1600E+00 1445E+01 1620E-03 1133E+04 7300E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -38760E-02 12784E-03 26817E-02 24890E-06 -66689E-08 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -62452E-02 12805E-03 47930E-02 43243E-06 -20716E-07 Remaining SSD is 03231 Weighted distances x-value x-dist y-dist 100E+00 130E+01 107E-01 -415E-01 200E+00 137E+01 -212E-01 283E-01 300E+00 144E+01 104E-01 -584E-02 Goodness-of-fit measure 04155 Parameter set 1 -6245240430658412E-2 1280492624666799E-3 4792952200361109E-2 4324266278840409E-6 -
2071623966851869E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_20c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13594E+01 10290E-02 10665E+04 78300E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 121E-05 683E-06 651E-06 315E-05 560E-06 106E-04 Linear model Parameters for the fit were (b0 b1) -62452E-02 12805E-03
60
С3Н8 - measurement 1
Data setC3H8 The calibration data set is 1900E-01 7800E-05 9057E+03 1098E+01 2002E-01 7900E-05 9552E+03 8569E+00 2101E-01 7960E-05 1007E+04 4049E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10529E-02 19831E-05 34552E-03 36109E-07 -12465E-09 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11642E-02 19714E-05 23073E-03 23522E-07 -54231E-10 Remaining SSD is 19453 Weighted distances x-value x-dist y-dist 100E+00 190E-01 -239E-01 666E-01 200E+00 200E-01 487E-01 -104E+00 300E+00 210E-01 -247E-01 248E-01 Goodness-of-fit measure 10414 Parameter set 1 1164239985182795E-2 1971441115316992E-5 2307269625077337E-3 2352198415608386E-7 -
5423119774765299E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19837E-01 14840E-04 94718E+03 45610E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
58
СО2 - measurement 1 Data setCO2_21 The calibration data set is 1302E+01 1510E-03 1022E+04 1820E+00 1370E+01 1560E-03 1077E+04 2730E+00 1445E+01 1620E-03 1135E+04 5900E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 20331E-02 12711E-03 12573E-01 11653E-05 -14638E-06 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 10548E-02 12722E-03 31762E-02 28898E-06 -91698E-08 Remaining SSD is 74346 Weighted distances x-value x-dist y-dist 100E+00 130E+01 490E-01 -755E-01 200E+00 137E+01 -103E+00 228E+00 300E+00 144E+01 539E-01 -250E-01 Goodness-of-fit measure 22837 Parameter set 1 1054788657490729E-2 1272208026684145E-3 3176237146276368E-2 2889798108124711E-6 -
9169821653851327E-8 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_21c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13577E+01 25542E-03 10664E+04 15200E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 547E-06 328E-06 316E-06 784E-06 286E-06 652E-06 Linear model Parameters for the fit were (b0 b1) 10548E-02 12722E-03
59
СО2 - measurement 2
Data setCO2_20 The calibration data set is 1302E+01 1512E-03 1021E+04 4723E+00 1370E+01 1563E-03 1075E+04 1600E+00 1445E+01 1620E-03 1133E+04 7300E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -38760E-02 12784E-03 26817E-02 24890E-06 -66689E-08 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -62452E-02 12805E-03 47930E-02 43243E-06 -20716E-07 Remaining SSD is 03231 Weighted distances x-value x-dist y-dist 100E+00 130E+01 107E-01 -415E-01 200E+00 137E+01 -212E-01 283E-01 300E+00 144E+01 104E-01 -584E-02 Goodness-of-fit measure 04155 Parameter set 1 -6245240430658412E-2 1280492624666799E-3 4792952200361109E-2 4324266278840409E-6 -
2071623966851869E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_20c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13594E+01 10290E-02 10665E+04 78300E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 121E-05 683E-06 651E-06 315E-05 560E-06 106E-04 Linear model Parameters for the fit were (b0 b1) -62452E-02 12805E-03
60
С3Н8 - measurement 1
Data setC3H8 The calibration data set is 1900E-01 7800E-05 9057E+03 1098E+01 2002E-01 7900E-05 9552E+03 8569E+00 2101E-01 7960E-05 1007E+04 4049E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10529E-02 19831E-05 34552E-03 36109E-07 -12465E-09 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11642E-02 19714E-05 23073E-03 23522E-07 -54231E-10 Remaining SSD is 19453 Weighted distances x-value x-dist y-dist 100E+00 190E-01 -239E-01 666E-01 200E+00 200E-01 487E-01 -104E+00 300E+00 210E-01 -247E-01 248E-01 Goodness-of-fit measure 10414 Parameter set 1 1164239985182795E-2 1971441115316992E-5 2307269625077337E-3 2352198415608386E-7 -
5423119774765299E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19837E-01 14840E-04 94718E+03 45610E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
59
СО2 - measurement 2
Data setCO2_20 The calibration data set is 1302E+01 1512E-03 1021E+04 4723E+00 1370E+01 1563E-03 1075E+04 1600E+00 1445E+01 1620E-03 1133E+04 7300E-01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -38760E-02 12784E-03 26817E-02 24890E-06 -66689E-08 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -62452E-02 12805E-03 47930E-02 43243E-06 -20716E-07 Remaining SSD is 03231 Weighted distances x-value x-dist y-dist 100E+00 130E+01 107E-01 -415E-01 200E+00 137E+01 -212E-01 283E-01 300E+00 144E+01 104E-01 -584E-02 Goodness-of-fit measure 04155 Parameter set 1 -6245240430658412E-2 1280492624666799E-3 4792952200361109E-2 4324266278840409E-6 -
2071623966851869E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO2_20c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 13594E+01 10290E-02 10665E+04 78300E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 121E-05 683E-06 651E-06 315E-05 560E-06 106E-04 Linear model Parameters for the fit were (b0 b1) -62452E-02 12805E-03
60
С3Н8 - measurement 1
Data setC3H8 The calibration data set is 1900E-01 7800E-05 9057E+03 1098E+01 2002E-01 7900E-05 9552E+03 8569E+00 2101E-01 7960E-05 1007E+04 4049E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10529E-02 19831E-05 34552E-03 36109E-07 -12465E-09 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11642E-02 19714E-05 23073E-03 23522E-07 -54231E-10 Remaining SSD is 19453 Weighted distances x-value x-dist y-dist 100E+00 190E-01 -239E-01 666E-01 200E+00 200E-01 487E-01 -104E+00 300E+00 210E-01 -247E-01 248E-01 Goodness-of-fit measure 10414 Parameter set 1 1164239985182795E-2 1971441115316992E-5 2307269625077337E-3 2352198415608386E-7 -
5423119774765299E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19837E-01 14840E-04 94718E+03 45610E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
60
С3Н8 - measurement 1
Data setC3H8 The calibration data set is 1900E-01 7800E-05 9057E+03 1098E+01 2002E-01 7900E-05 9552E+03 8569E+00 2101E-01 7960E-05 1007E+04 4049E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10529E-02 19831E-05 34552E-03 36109E-07 -12465E-09 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11642E-02 19714E-05 23073E-03 23522E-07 -54231E-10 Remaining SSD is 19453 Weighted distances x-value x-dist y-dist 100E+00 190E-01 -239E-01 666E-01 200E+00 200E-01 487E-01 -104E+00 300E+00 210E-01 -247E-01 248E-01 Goodness-of-fit measure 10414 Parameter set 1 1164239985182795E-2 1971441115316992E-5 2307269625077337E-3 2352198415608386E-7 -
5423119774765299E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19837E-01 14840E-04 94718E+03 45610E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
61
С3Н8 - measurement 2
Data setC3H8_14 The calibration data set is 1900E-01 7800E-05 1066E+04 4425E+00 2002E-01 7900E-05 1129E+04 4063E+00 2101E-01 7960E-05 1189E+04 1261E+01 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 14872E-02 16419E-05 20927E-03 18531E-07 -38743E-10 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 16125E-02 16303E-05 19143E-03 17264E-07 -33027E-10 Remaining SSD is 14769 Weighted distances x-value x-dist y-dist 100E+00 190E-01 288E-01 -266E-01 200E+00 200E-01 -596E-01 500E-01 300E+00 210E-01 306E-01 -790E-01 Goodness-of-fit measure 07901 Parameter set 1 1612516316404608E-2 1630344048324982E-5 1914349241689507E-3 1726393754008018E-7 -
3302701233478155E-10 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file C3H8_14c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 19967E-01 15845E-04 11258E+04 85110E+00 More than 1 prediction Calculated values have covariances VC matrix of predictions 168E-08 570E-09 542E-09 181E-08 637E-09 251E-08 Linear model Parameters for the fit were (b0 b1) 16125E-02 16303E-05
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
62
СО - measurement 1
Data setCO The calibration data set is 2787E+00 1496E-03 1901E+03 3045E+00 2990E+00 1500E-03 2032E+03 2102E+00 3189E+00 1500E-03 2157E+03 1545E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov -18937E-01 15655E-03 27792E-02 13671E-05 -37945E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov -19949E-01 15704E-03 44525E-02 21438E-05 -95352E-07 Remaining SSD is 04343 Weighted distances x-value x-dist y-dist 100E+00 279E+00 107E-01 -341E-01 200E+00 299E+00 -213E-01 469E-01 300E+00 319E+00 107E-01 -172E-01 Goodness-of-fit measure 04694 Parameter set 1 -1994919907095992 1570356532205788E-3 4452516736737186E-2 2143794414858978E-5 -
9535194343176842E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO_c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29536E+00 44841E-03 20079E+03 23713E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
63
СО - measurement 2
Data setCO_ The calibration data set is 2787E+00 1496E-03 1889E+03 1416E+00 2990E+00 1505E-03 2034E+03 6445E-01 3189E+00 1502E-03 2172E+03 1956E+00 Fit type x vs y Calibration Linear case Ordinary-least-squares results b0 b1 u (b0) u (b1) cov 10834E-01 14178E-03 21704E-02 10666E-05 -23112E-07 Results of ISO 6143 method b0 b1 u (b0) u (b1) cov 11251E-01 14155E-03 28122E-02 13917E-05 -39096E-07 Remaining SSD is 09539 Weighted distances x-value x-dist y-dist 100E+00 279E+00 270E-01 -362E-01 200E+00 299E+00 -549E-01 333E-01 300E+00 319E+00 277E-01 -511E-01 Goodness-of-fit measure 05490 Parameter set 1 112511530253064 1415485104605818E-3 2812193018795215E-2 1391730320259904E-5 -
3909572230036017E-7 0 0 0 0 0 0 0 0 0 End set Part II Processing of data Parameters from file CO__c Data set Input from keyboard (max 30 points) MF type l calc x u(x) response y u(y) 29477E+00 45573E-03 20030E+03 30802E+00
