Development and consolidation of gas chromatography ... Results/MCLR-Program...Development and...

DOE/CE/23810-109

Development and Consolidation of Gas Chromatography Methodsfor Appendix C to ARI 700

Final ReportSupersedes All Previous Additions

May 12, 2000

John J. ByrneAndrew M. Gbur

Douglas G. Gehring

Integral Sciences Incorporated1717 Arlingate Lane

Columbus, OH 43228

National Refrigerants, Inc.661 Kenyon AvenueBridgeton, NJ 08302

Prepared forThe Air-Conditioning and Refrigeration Technology Institute

UnderARTI MCLR Project Number 670-55000

This project is supported, in part, by US Department of Energy (Office of Building Technology) grant number DE-FG02-91CE23810: MaterialCompatibility and Lubricants Research (MCLR) on CFC-Refrigerant Substitutes. Federal funding supporting this project constitutes 93.57% ofallowable costs. Funding from non-government sources supporting this project consists of direct cost sharing of 6.43% of allowable costs, and in-kindcontributions from the air-conditioning and refrigeration industry.

1

Abstract

New Gas Chromatography methods for determining the composition of zeotropic andazeotropic refrigerant blends are reported. The new procedures provide a single columnto determine the blend composition of R-401, R-402, R-403B, R-404A, R-406A, R-407,R-408A, R-409, R-410, R-411, R-412A, R-500, R-502, R-503, R-507, R-509.This project also revised and generalized the format of each previously developed GCpurity method. These methods originally appeared in Appendix C to ARI 700-95 as wellas those set forth in a previous MCLR-funded project; namely, Methods Development forOrganic Contaminant Determination in Fluorocarbon Refrigerant Azeotropes andBlends.

Background

It has been almost 12 years since the inception of ARI Standard 700, Specifications forFluorocarbon and Other Refrigerants. This standard, in conjunction with its Appendix,Analytical Procedures for ARI Standard 700, is widely recognized as the technicalspecification which must be met by new and reclaimed refrigerants throughout therefrigeration and air-conditioning industry.

The current Gas Chromatographic (GC) procedures for organic purity and blendcompositions given in Appendix C to ARI Standard 700-95 are summarized in Tables 1and 2. As evidenced, these GC methods contain significant procedural differences fromone refrigerant to the next. In 1988, these procedural differences were largely overcomebecause there were only nine refrigerants in the initial version of ARI Standard 700. Bycustomizing each chromatographic method to a specific refrigerant, near-ideal separationand quantitation of the broadest possible range of manufacturing impurities was achieved.At that time a laboratory could analyze all nine refrigerants with only three different GCcolumns, and no sub-ambient temperature instrumentation was required.

Justification

What served well in 1988 has become complicated in the year 2000. In the 1995Standard 700 revision, the number of refrigerants requiring analysis quadrupled and nowstands at 36. Eleven different GC columns are now required (See Table 2). Manycolumns have no technical specificity in laboratories that analyze more than onerefrigerant. For example, the 105 meter DB1301 column required in the analysis of R-113 is unnecessary as the 120 meter DB1301 column required in the analysis of R-22,R32, and R134a can also be adapted to the R-113 analysis. Similarly, the 8 and 16 footCarbopack B columns used in the analysis of R-32, R-408A, and R-409A may bereplaced by one 24 foot Carbopack column. As Table 1 shows, ARI Standard 700presently mandates 13 separate GC methods for the determination of organic purity.Table 1 also shows 11 separate GC methods for determining the major componentcompositions of zeotropic and azeotropic blends with six blend composition methods stillto be added.

2

Because of these complications, the industry has requested simplified, technicallyappropriate GC test methods and/or method revisions for determining the organic purityand blend compositions of these refrigerants. The demand is especially great in theinternational standards community, as many parties have been reluctant to supportrefrigerant testing standards that are perceived as unnecessarily complex. Also, theinvestigators of this project have been in direct contact with several members of the ARIStandard 700 Engineering Subcommittee and with ISO TC 86/SC 8/WG 3 for aconsensus as to what work is required. Therefore, in order to safeguard domesticacceptance of ARI 700 and to facilitate international trade, it was most important torevise, simplify, and to consolidate all of the current methods.

Table 1. Refrigerant Type-Dependent GC Test Methods for ARI Standard 700

RefrigerantPurityMethod (1)

CompositionMethod(blends only)(1)

Detector Column(s) (2)TemperatureProgram(s) (3)

11 Part 6 FID K W12 Part 7 FID K N13 Part 8 TCD K N22 Part 9 FID E & K K & N23 Part 10 TCD H Q32 Part 11 FID E & J A & S113 Part 12 FID D I114 Part 13 FID K R123 Part 14 FID F & K C & V124 Part 15 FID K O125 Part 16 FID K L134a Part 17 FID A & E B & P143a Part 18 FID A & K H & P401 ∅ Part 19 TCD G M402 ∅ Part 20 TCD G M404A ∅ Part 21 TCD G G405 ∅ ∅406 ∅ ∅407 ∅ Part 24 TCD K T408A ∅ Part 25 FID I E409A ∅ Part 26 TCD I D410 ∅ Part 27 TCD B J411 ∅ ∅412 ∅ ∅500 ∅ Part 30 TCD C T502 ∅ Part 31 TCD C F503 ∅ Part 32 FID K U507 ∅ Part 33 TCD B J508 ∅ ∅509 ∅ ∅1. ∅ = Appendix does not contain any test method.2. A through K = See Table 2 for column information.3. A through W = See Table 3 for temperature program.

As a result, this project introduces a general test method using just one GC column thatdetermines the blend compositions of refrigerants 401 through 412, and for refrigerants500, 502, 503, 507, 508, and 509. This project also revised and generalized the format of

3

each previously developed GC purity method. These methods originally appeared inAppendix C to ARI 700-95 as well as those set forth in a previous MCLR-funded project;namely, Methods Development for Organic Contaminant Determination in FluorocarbonRefrigerant Azeotropes and Blends.

The completion of this work has produced new and revised test methods in a formatsimilar to Appendix C to ARI Standard 700. These methods can be advanced forconsideration in the next edition of ARI 700, ISO 12810, and other refrigerant standardsafter the appropriate review and revision processes of the respective committees havetaken place.

Table 2. Columns for Organic Purity and Blend Composition Testing for ARI 700-95Column Description (details in ARI 700 Appendix)A Bentone / Krytox / SP1000 / Porapak-T, connected in seriesB Carbowax / Dibutyl Maleate / SP1000, connected in seriesC DC200D DB1301 (105 meter)E DB1301 (120 meter)F DB1701 / SPB5, connected in seriesG KrytoxH Porapak-TI SP1000 (8 foot) on Carbopack-BJ SP1000 (16 foot) on Carbopack-BK SP1000 (24 foot) on Carbopack-B

Table 3. Temperature Programs for Organic Purity and Blend Composition Testing for ARI 700-95Program Initial Temp., º C Initial Time, min. Ramp, º C / min. Final Temp., º CA –28* 10 5 40B –20* 10 8 150C 15* 10 7 60D 30 3.75 15 100E 30 3.75 70 110F 35 isothermalG 35 7 20 75H 35 7 10 150I 35 10 8 160J 40 isothermalK 40 10 8 50L 40 6 5 130M 40 6 30 150N 40 6 10 160O 40 10 10 160P 40 6 10 165Q 40 3 18 175R 40 6 10 175S 45 8 8 150T 50 isothermalU 60 isothermalV 125 isothermalW 125 4 10 180

*Subambient capability is necessary for temperature programs A–C.

4

Objective

This work has been sponsored to develop gas chromatographic methods for determiningthe composition of refrigerants 401 through 412, 500, 502, 503, 507, 508, and 509 usinga single column. A second task, involving the same refrigerants, entailed rewriting eachpreviously developed method in simplified form. This second task was expanded toinclude refrigerants 11, 12, 13, 22, 23, 32, 113, 114, 123, 124, 125, 134a, and 143a thatwere not part of the original proposal.

The following goals were sought during the development and consolidation of the GasChromatography methods included herein:

• The new gas chromatographic procedures for determining the composition ofrefrigerant blends and azeotropes should all employ the same column.

• The new methods should allow any laboratory skilled in the art to readily use themethods to determine the composition of refrigerant azeotropes and blends.

• The gas chromatographic methods currently appearing in Appendix C to ARI700-95 and in the previously funded MCLR project: Methods Development forOrganic Contaminant Determination in Fluorocarbon Refrigerant Azeotropesand Blends, should be replaced with generalized procedures and GC Method DataSheets to allow for a reduction of redundancy currently existing in the standard.

• The simplified methods should provide all of the detail included in the previousmethods for which they are intended to replace. To the greatest extent possible,all of the generalized methods should employ calibration standard preparation,sample analysis, calculations (statistical and otherwise) and techniques consistentwith those already appearing in Appendix C to ARI 700-95.

Principle Features of the Resulting Methods

The new methods appear at the end of this report. Each of the 50 resulting procedureshas no more than 5 pages of text and in many cases 2 pages. The following new featuresare added over those previously published in ARI 700-95:

1. The new gas chromatographic procedures for the analysis of the composition ofblends do in fact employ a single column (See Table 4). The column utilized foreach composition analysis is a Supelco 1% SP-1000 on Carbopack B. Themethod describing the new generalized procedure for blend compositiondetermination appears in Part 15 of this report with the gas chromatographicmethods appearing in Parts 16-32.

5

Table 4. Summary of Refrigerant Testing Procedures

Refrigerant Testing ProcedurePages inCurrentARI 700

Pages inConsolidatedProcedure

Comment on NewMethods

General procedure for organic purity ∅ 10 Universal methodGeneral procedure for blend composition ∅ 5 Universal methodGeneral procedure for blend purity ∅ 5 Universal methodR-11 7 3 ConsolidatedR-12 9 4 ConsolidatedR-13 8 3 ConsolidatedR-22 10 5 ConsolidatedR-23 8 3 ConsolidatedR-32 10 4 ConsolidatedR-113 7 3 ConsolidatedR-114 9 3 ConsolidatedR-123 10 5 ConsolidatedR-124 9 4 ConsolidatedR-125 8 4 ConsolidatedR-134a 11 4 ConsolidatedR-143a 10 5 ConsolidatedR-401 (Composition) 5 2 New Single ColumnR-402 (Composition) 5 2 New Single ColumnR-403 (Composition) ∅ 2 New Single ColumnR-404 (Composition) 6 2 New Single ColumnR-406 (Composition) ∅ 2 New Single ColumnR-407 (Composition) 7 2 New Single ColumnR-408 (Composition) 6 2 New Single ColumnR-409 (Composition) 6 2 New Single ColumnR-410 (Composition) 5 2 New Single ColumnR-411 (Composition) 5 2 New Single ColumnR-412 (Composition) 5 2 New Single ColumnR-500 (Composition) 5 2 New Single ColumnR-502 (Composition) 5 2 New Single ColumnR-503 (Composition) 5 2 New Single ColumnR-507 (Composition) 5 2 New Single ColumnR-508 (Composition) 5 2 New Single ColumnR-509 (Composition) 5 2 New Single ColumnR-401 (Purity) ∅ 3 Single ColumnR-402 (Purity) ∅ 3 Single ColumnR-404 (Purity) ∅ 3 Single ColumnR-405 (Purity) ∅ 3 Single ColumnR-406 (Purity) ∅ 3 Single ColumnR-407 (Purity) ∅ 3 Single ColumnR-408 (Purity) ∅ 3 Single ColumnR-409 (Purity) ∅ 3 Single ColumnR-410 (Purity) ∅ 3 Single ColumnR-412 (Purity) ∅ 3 Single ColumnR-500 (Purity) ∅ 3 Single ColumnR-502 (Purity) ∅ 3 Single ColumnR-503 (Purity) ∅ 3 Single ColumnR-507 (Purity) ∅ 3 Single ColumnR-508 (Purity) ∅ 3 Single ColumnR-509 (Purity) ∅ 3 Single Column

6

2. The composition methods presently appearing in Appendix C to ARI 700 weredeveloped at different laboratories and employ some variety in both materials andlaboratory practice. This has imposed a considerable financial, procedural andtraining burden on laboratories that must employ the procedures of the standard orestablish procedures of their own and demonstrate equivalence (as currentlyrequired by law).

The new methods developed in the course of this study standardize, to the greatestextent possible, analytical procedures, equipment, calibration standard preparationand sampling methods. The methods reported herein are considered readilyusable by any refrigerant-testing laboratory skilled in the art.

3. The GC Method Data Sheet, found in Parts 2-14, 16-32, and 34-50, can standalone if used in conjunction with its respective Generalized Procedure found inPart 1, Part 15 or in Part 33. This simplification has allowed for a neededreduction in verbiage in the current edition of ARI 700-95 while maintaining itstechnical integrity.

4. All of the generalized methods employ similar calibration standard preparationtechniques, sample analysis, gas chromatographic equations, refrigerant transferprocedures and sampling techniques that are consistent with those alreadyappearing in ARI 700. Statistical parameters, definitions and calculations arethose used in ARI 700 and while not detailed in this report, are readily known andavailable to all personnel who would employ the procedures.

5. All of the methods appearing in this report are ready for review from allappropriate domestic and international committees for which they were originallywritten.

References

1. Air-Conditioning and Refrigeration Institute, Appendix C to ARI Standard700-95: Analytical Procedures for ARI Standard 700-95, 4301 North FairfaxDrive, Arlington, Virginia 22203.

2. BIPM, IEC, IFCC, ISO, IUPAP, and OIML, Guide to the Expression ofUncertainty in Measurement, ISO/TAG/WG3 Technical Advisory Group onMetrology, 1993.

3. NAMAS NIS 3003, Edition 8, The Expression of Uncertainty and Confidence inMeasurement for Calibrations, May 1995, NAMAS Executive, National PhysicalLaboratory, Teddington, Middlesex, TW11 0LW, England.

4. International Organization for Standardization, ISO 10012-1:1992(E), Qualityassurance requirements for measuring equipment—Part 1: Metrologicalconfirmation system for measuring equipment, ISO, Case Postale 56, CH-1211Genève 20, Switzerland.

5. Integral Sciences Incorporated, Standard Analytical Procedures, Document Q101Revision 1.2, January 5, 1997.

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6. Byrne, J., Abel, M., Gbur, A. (Integral Sciences Incorporated), ARTI MCLRProject Number 665-54600, Methods Development for Organic ContaminantDetermination in Fluorocarbon Refrigerant Azeotropes and Blends, March 3,1998.

7. Huber, M., Gallagher, J., McLinden, M., and Morrison, G. (National Institute ofStandards and Technology Chemical Science and Technology Laboratory), NISTStandard Reference Database 23: NIST Thermodynamic Properties ofRefrigerants and Refrigerant Mixtures (REFPROP), Version 5.10, 1996.

8. BIPM, IEC, ISO, and OIML, International vocabulary of basic and general termsin metrology (VIM), 1994.

9. Bruno, T. J., Handbook for the Analysis and Identification of AlternativeRefrigerants, CRC Press, Boca Raton, Florida, 1995.

10. Bruno, T. J., Wertz, K. H., and Caciari, M., Kovats Retention Indices ofHalocarbons on a Hexafluoropropylene Epoxide-Modified Graphitized CarbonBlack, Analytical Chemistry, Vol. 68, No. 8, April 15, 1996, p. 1347 ff.

11. Gehring, D. G., Barsotti, D. J., and Gibbon, H. E., ChlorofluorocarbonsAlternatives Analysis, Part I: The determination of HFC-134a Purity by GasChromatography, Journal of Chromatographic Science, Vol. 30, pp. 280-284,July 1992.

12. Gehring, D. G., Barsotti, D. J., and Gibbon, H. E., ChlorofluorocarbonsAlternatives Analysis, Part I: The determination of HFC-143a Purity by GasChromatography, Journal of Chromatographic Science, Vol. 30, pp. 301-305,August 1992.

13. National Refrigerants Inc. Methods: NR200.0, NR202.1, NR204.0, NR212.0,NR214.0, NR216.1, NR226.1, NR228.1, NR236.0, NR254.0, and NR265.0.

14. DuPont Chemicals Dept. Methods F0050.165.01.CW, F0055.165.01.CW,F0080.165.01.LV, F0090.165.01CW, F0095.165.01, F0100.160.01.CW,F0100.165.01.CW, F3275.165.01CC (P), F3295.165.01.CW, F3297.165.01CC,F3327.165.01.CW, F3333.165.01.CW, F3337.165.01.CW (P), andRC110.000.03.CW.

15. AlliedSignal Inc. Methods: 538T, 539T, R-410-A-7, and R-507-7.

16. ICI Analytical Method: Determination of Composition of Refrigerant MixturesContaining KLEA 32, KLEA 125, and KLEA 134a, M. A. Cleaver, February1993.

17. Elf Atochem North America Methods: WK408A-1 and WK409A-1.

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18. Cotton, J., Duncan, C., Spence, J., and Underwood, B., Elementary Statistics,Prentice Hall, 3rd Edition, 1976.

METHODS

DEVELOPMENT AND CONSOLIDATION

OF GAS CHROMATOGRAPHY METHODS

FOR APPENDIX C TO ARI 700

i

TABLE OF CONTENTS

PAGE

Part 1. General Procedure for the Determination of Purity ofNew and Reclaimed Refrigerants by Gas Chromatography........................1

Part 2. R-11 GC Method Data Sheet .....................................................................11






Part 8. R-113 GC Method Data Sheet ...................................................................33





Part 13. R-134a GC Method Data Sheet .................................................................52

Part 14. R-143a GC Method Data Sheet .................................................................57

Part 15. Determination of Component Concentrations ofRefrigerant 400 and 500 Series Blends and AzeotropesBy Gas Chromatography............................................................................61

Part 16. R-401 Composition GC Method Data Sheet .............................................66


Part 18. R-403B Composition GC Method Data Sheet...........................................70

Part 19. R-404A Composition GC Method Data Sheet...........................................72


ii

TABLE OF CONTENTS (CONTINUED)

PAGE













Part 33. General Procedure for the Determination of Purity ofNew and Reclaimed Refrigerant Blends and AzeotropesBy Gas Chromatography..........................................................................100

Part 34. R-401 Purity GC Method Data Sheet ......................................................105







iii

TABLE OF CONTENTS (CONTINUED)

PAGE











iv

LIST OF FIGURES

PAGE

Part 1. Figure 1. Apparatus Used for Sampling CalibrationStandards and Samples ......................................................10

Part 2. Figure 1. Gas Chromatogram of R-11...............................................12

Part 3 Figure 1. Gas Chromatogram of R-12...............................................15

Part 4 Figure 1. Gas Chromatogram of R-13...............................................19

Part 5. Figure 1. Packed Column Gas Chromatogram of R-22 ....................22Figure 2. Capillary Column Gas Chromatogram of R-22

For Determination of R-31 Impurity..................................23

Part 6. Figure 1. Gas Chromatogram of R-23...............................................27

Part 7. Figure 1. Packed Column Gas Chromatogram of R-32 ....................30Figure 2. Capillary Column Gas Chromatogram of R-32 .................31

Part 8. Figure 1. Gas Chromatogram of R-113.............................................34


Part 10. Figure 1. Packed Column Gas Chromatogram of R-123 ..................40Figure 2. Capillary Column Gas Chromatogram of R-123 ...............41



Part 13. Figure 1. Packed Column Gas Chromatogram of R-134a.................53Figure 2. Capillary Column Gas Chromatogram of R-134a .............54

Part 14. Figure 1. Combination Packed Column Gas Chromatogram of R-143a ..........................................................................58

Figure 2. 1% SP-1000 Packed Column Gas Chromatogram of R-143a ..........................................................................59

Part 15. Figure 1. Apparatus Used for Sampling CalibrationStandards and Samples ......................................................65



v

LIST OF FIGURES (CONTINUED)

PAGE

Part 18. Figure 1. Gas Chromatogram of R-403B ..........................................71

Part 19. Figure 1. Gas Chromatogram of R-404A..........................................73














Part 33. Figure 1. Apparatus Used for Sampling CalibrationStandards and Samples ....................................................104

Part 34. Figure 1. Gas Chromatogram of R-401...........................................105





vi

LIST OF FIGURES (CONTINUED)

PAGE












vii

LIST OF TABLES

PAGE

Part 1. Table 1. Vapor Volume and Dilution Ration for LiquidImpurities Used for Primary Calibration Standard ..............4

Table 2. Information for Gaseous and Liquid ImpurityAddition for Secondary Calibration Standard......................5

Table 3. Approximate Amount of Primary Refrigerant to AddTo Secondary Calibration Standard .....................................5

Table 4. Liquid Densities of Refrigerants..........................................6Table 5. Approximate Amount of Liquid VHP Refrigerant

To Add to Calibration Standard...........................................7

Part 2. Table 1. Component Statistical Parameters .....................................13Table 2. Primary Calibration Standard Components .......................13Table 3. Retention Time Data for Identified Impurities

Not Normally Observed.....................................................13

Part 3. Table 1. Component Statistical Parameters .....................................16Table 2. Primary Calibration Standard Components .......................16Table 3 Liquid Impurities For Calibration Standard

Preparation .........................................................................17Table 4. Retention Time Data for Identified Impurities


Part 4. Table 1. Component Statistical Parameters .....................................20Table 2. Primary Calibration Standard Components .......................20


Preparation .........................................................................25Table 4. Additional Impurities Observed in R-22............................25

Part 6. Table 1. Component Statistical Parameters .....................................28Table 2. Calibration Standard Components .....................................28


Preparation .........................................................................32Table 4. Additional Impurities Observed in R-32............................32

Part 8. Table 1. Component Statistical Parameters .....................................35Table 2. Primary Calibration Standard Components .......................35

viii

LIST OF TABLES (CONTINUED)PAGE


Preparation .........................................................................38

Part 10. Table 1. Component Statistical Parameters .....................................42Table 2. Primary Calibration Standard Components .......................42Table 3. Additional Impurities Observed in R-123,

Quantitation by Effective Carbon NumberMethod ...............................................................................43

Part 11. Table 1. Component Statistical Parameters .....................................46Table 2. Primary Calibration Standard Components .......................46Table 3 Primary Calibration Standard Liquid

Impurities ...........................................................................47Table 4. Retention Time Data for Identified Impurities


Part 12. Table 1. Component Statistical Parameters .....................................50Table 2. Primary Calibration Standard Components .......................50Table 3 Primary Calibration Standard Liquid

Impurities ...........................................................................50Table 4. Retention Time Data for Identified Impurities


Part 13. Table 1. Component Statistical Parameters .....................................55Table 2. Primary Calibration Standard Components .......................55Table 3. Primary Calibration Standard Liquid Impurities ...............56Table 4. Additional Impurities Observed in R-134a,

Quantitation by Effective Carbon NumberMethod ...............................................................................56

Part 14 Table 1. Component Statistical Parameters .....................................60Table 2. Primary Calibration Standard Components .......................60

Part 15. Table 1. GC Method Data Sheets.....................................................64

Part 16. Table 1. Blend Component Wt.% ...................................................66Table 2. Component Statistical Parameters .....................................66Table 3. Blend Calibration Standard Preparation ............................66

ix






Part 21. Table 1A. Blend Component Wt.% 407A ..........................................76Table 1B. Blend Component Wt.% 407B ..........................................76Table 1C. Blend Component Wt.% 407C ..........................................76Table 2. Component Statistical Parameters .....................................76Table 3. Blend Calibration Standard Preparation ............................76






x

LIST OF TABLES (CONTINUED)

PAGE





Part 31. Table 1A. Blend Component Wt.% R-508A ......................................96Table 1B. Blend Component Wt.% R-508B ......................................96Table 2. Component Statistical Parameters .....................................96Table 3. Blend Calibration Standard Preparation ............................96


Part 33. Table 1. GC Method Data Sheet ....................................................103

Part 34. Table 1A. Contaminant Statistical Parameters .................................106Table 1B. Component Statistical Parameters ...................................106Table 1C. Blend Component Balance Preparation ...........................106Table 2. Primary Calibration Standard Impurities .........................107



xi










Part 45. Table 1A. Contaminant Statistical Parameters .................................139

xii

LIST OF TABLES (CONTINUED)

PAGE

Table 1B. Component Statistical Parameters ...................................139Table 1C. Blend Component Balance Preparation ...........................139Table 2. Primary Calibration Standard Impurities .........................140






1

PART 1

GENERAL PROCEDURE FOR THE DETERMINATIONOF PURITY OF NEW AND RECLAIMED

REFRIGERANTS BY GAS CHROMATOGRAPHY

Section 1. Purpose

The purpose of this test method is to determine the purity ofnew and reclaimed refrigerants by gas chromatography (GC).

Section 2. Scope

This test method is for use in conjunction with the GC MethodData Sheets for all refrigerants as listed in section 12 of thismethod.

Section 3. Definitions

Definitions for this part are identical to those of ARI Standard700 and ARI Standard 740.

Section 4. Principle

The organic purity of new and reclaimed refrigerants isdetermined by programmed temperature gas chromatographyusing either a packed or capillary GC column and either a flameionization detector (FID) or thermal conductivity detector(TCD). Component peak areas are integrated electronically andquantified by the area normalization-response factor method byreference to a suitable calibration standard.

Section 5. Applicability

This method is applicable for the determination of the organicimpurities typically present in new and reclaimed refrigerant.These impurities are listed in the GC Method Data Sheet foreach respective refrigerant.

Section 6. Limitations and Interferences

This method will not detect impurities that coelute within thelarge peak matrix of the refrigerant being analyzed. Additionallimitations and interferences (if any) appear in the GC MethodData Sheet for each refrigerant.

Section 7. Sensitivity, Precision, and Accuracy

Values for these statistical parameters are given in Table 1 ofthe respective GC Method Data Sheet for each refrigerant.

Section 8. Special Apparatus and Reagents

NOTE: Equivalents may be substituted.

1. Gas chromatograph: Model 5890, equipped with FID,TCD and with capillary column split injection,subambient temperature valve and packed columncapability as specified in each refrigerant’s GC MethodData Sheet, Hewlett Packard, Wilmington, DE.

2. Electronic integrator: Model# 3396, Hewlett Packard,Wilmington, DE.

3. Gas chromatography columns specific to eachrefrigerant are given in Section 3 of the appropriate GCMethod Data Sheet.

4. Glass collecting tubes: 500 mL, 250 mL and 125 mL,LG-8601, Lab Glass Inc., Vineland, NJ. (Enlarge sideoutlet opening to accommodate a crimp-on 2-cm septum.Apply fiberglass tape outside for protection frombreakage)

5. Steel cylinder: 1L, with a single #9 valve (#1014-C,Superior Valve), 3/8" pipe neck, E. F. Britten Co.,Cranford, NJ.

6. Deflected point needles: Cat# 7174, #22, Popper andSons, Inc., New Hyde Park, NY.

7. Swivel union: US44, United Refrig. Inc., Philadelphia,PA.

8. Serum bottle: 125 mL, (Note: Bottle holds 160 mL whenliquid full.) Cat# 223748, Wheaton Glass, Vineland, NJ.

9. Impurities for calibration standard preparation: Thefluorochemicals may be purchased from Lancaster,Windham, NH and Synquest, Inc., Alachua, FL. Thehydrocarbons may be purchased from Scott SpecialtyGases, Inc., Plumbsteadville, PA. All other impuritiesmay be purchased from Aldrich, Milwaukee, WI. SeeTable 2 of the GC Method Data sheet for the specificimpurities required for each refrigerant. The purity ofeach calibration component must be predetermined bygas chromatography and, if necessary, by GC/MassSpectroscopy (GC-MS).

10. Stainless steel cylinder: 1L, 304L-WDF4-1000, 1/4"pipe, Whitey Co., Highland Heights, OH.

2

Section 9. Procedure for Low Pressure Refrigerants

NOTE: The following procedure is generalized for thedetermination of purity for low-pressure refrigerants,R-11, R-113, and R-123. Each respective GC MethodData Sheet contains the detector type, the column(s),the chromatographic conditions, and the impurities tobe added for calibration standard preparation requiredto perform the procedure stated herein.

9.1 Calibration Standard Preparation for Low PressureRefrigerants

a. Obtain a stock of the highest purity refrigerant for thedesired calibration standard preparation.

b. Determine the tare weight (to the nearest 0.01g) of a 125ml serum bottle with septum and cap loosely attached,then fill with stock refrigerant within about 1.5 cm of thetop. Crimp on the septum.

c. Reweigh and subtract the tare weight in step b to obtainthe grams of stock refrigerant added.

d. Individually, and in turn, add the volumes of eachcalibration component indicated in Table 2 of thecorresponding GC Method Data Sheet through the septumand below the surface of the stock refrigerant already inthe bottle. Use an appropriately sized milliliter gas tightsyringe with deflected point needles for gases and a liquidmicroliter syringe for liquids (care should be taken toaccount for syringe needle volumes). Shake the bottle tomix after the addition of each component.

e. Total the µg added column and combine this weight withthat of step c to obtain the total weight (to the nearest0.01g) of the calibration standard in the bottle.

f. Calculate the ppm added (to the nearest 1 ppm) for eachcomponent by dividing the µg added by the total weight ofstandard in the serum bottle. (step e)

g. Calculate the ppm present for each component bycombining the ppm present in the stock refrigerant (if any)and the ppm component added (refer to Section 5, Note 1in the GC Method Data Sheet). The ppm componentpresent values are those used for determining the methodresponse factors.

h. Place the serum bottle standard in an ice bath and, after itis ice cold, remove and immediately replace with a newseptum.

i. On the label, write the ppm present values for eachcomponent, date of preparation, gross weight and totalgrams of calibration sample. Store in a refrigerator.

Discard and prepare a new standard when the sampleweight falls below 60% of the original weight.

NOTE: For long term storage, the standard is transferred to asteel cylinder of appropriate volume.

9.2 Determination of Component Response Factors for LowPressure Refrigerants (See Section 9.6, Note 3)

a. Set up the electronic integrator for an area normalizationresponse factor calibration.

b. Analyze the calibration standard solution in triplicateusing the chromatographic conditions described inSection 3 of the respective refrigerant’s GC Method DataSheet.

c. Using the matrix of the primary low pressure refrigerant(R-11, R-113, R-123) as the reference peak, perform thenecessary functions to have the integrator determine eachcomponent’s Relative Response Factor (RRFi) which isthen stored. Response Factors are calculated as follows:

ARFWt% i in Cal. Std.

Aii

= x

xA

S-100.0000ARF =

Ai = peak area of component i. (average of 3 runs).ARFi = Absolute Response Factor of contaminant i.Ax = peak area of primary refrigerant (average of 3 runs).ARFx = Absolute Response Factor of primary refrigerant.S = Weight % sum of all impurities present.

Then, using the primary refrigerant as the reference peak:

x

ii

ARF

ARFRRF = 0.1

ARF

ARFRRF

x

xx ==

RRFi values are computed to the nearest 0.0001 unit.

9.3 Sampling

Submitted samples should be in either metal cylinders or inglass or plastic bottles such that the containers are at least 80%liquid full.

9.4 Sample Analysis

Analyze the sample using the chromatographic conditionsdescribed in Section 3 of the GC Method Data Sheet for eachrefrigerant. The sample and syringe are pre-cooled (refrigeratoror ice bath) to 10°C before sampling. This is to simplifyloading the sample into the microliter syringe. Use componentspiking and/or GC-MS to identify questionable peaks.

9.5 Calculations

3

a. The weight percentage of each component is calculated asfollows:

W100 x RRF x A

(A x RRFii i

i i

=∑ )

Where:

Wi = weight percentage of component i.RRFi = relative response factor for component i.Ai = peak area of component i.Σ…= sum of all component peak areas times their

respective relative response factors.

9.6 Notes for Low Pressure Refrigerants

1. The purest refrigerant will contain some of the impurities listedin Table 1 of the GC Method Data Sheet. The ppmamounts of impurities already in the primary refrigerant aredetermined via the method of Standards Addition.Individual impurity peak areas in the stock are increased inthe calibration standard by the ppm amount of thecorresponding impurity added. The ppm already present iscombined with the ppm added to give the total ppmcomponent present in the calibration standard.

2. To preserve the stock of calibration component, it issuggested to load a small evacuated 125 mL gas collectingtube to 101.325 kPa from the liquid phase as illustrated inFigure 1. The appropriate volume is then withdrawn andinjected into the serum bottle containing the primaryrefrigerant. For impurities that are liquid at roomtemperature, inject the indicated µl volumes of eachrespective component into the serum bottle.

3. Depending upon the electronic integrator used, it isoften more desirable to convert the ppm values to wt % forresponse factor calculations and for reporting purposes.

4. Typically, commercially available R-123 contains from 1to 7% R-123a isomer and 300 to 600 ppm R-123b isomer.The concentration of R-123a in the stock is determinedseparately by the method of Standards Addition (addingpercent amounts of R-123a to the stock R-123 andchromatographing as in Section 9.1). The calculatedRRF123a value is also assigned to the R-123b isomer, as R-123b is not commercially available for separate calibration.The amounts present are added to Table 2 in the GCMethod Data Sheet; the R-123a isomer shown as percentpresent.

Section 10. Procedure for High Pressure Refrigerants

NOTE: The following procedure is generalized for thedetermination of purity for high-pressure refrigerants,R-12, R-22, R-32, R-114, R-124, R-125, R-134a, and

R-143a. Each respective GC Method Data Sheetcontains the detector type, the column, thechromatographic conditions, and the impuritiesnecessary for the following calibration standardpreparation.

10.1 Primary Calibration Standard Preparation and Analysisfor High Pressure Refrigerants

a. Crimp-on the septum, then determine the internal volumeof the 500 ml gas bulb by weighing the bulb empty, thenfilled to maximum capacity with water. Record thegrams of water as ml volume capacity on the outside ofthe bulb (to the nearest 0.1ml).

b. Thoroughly dry the gas bulb, then assemble the apparatusas illustrated in Figure 1.

c. Attach a cylinder of the refrigerant for which acalibration standard is desired (hereafter referred to as theprimary refrigerant). Make sure that the refrigerant usedis of high purity. (Refer to Note 1 in Section 10.7)

d. With valve “A” closed, open all other valves andevacuate to 0.133 kPa.

e. Close valve “D” and monitor the gauge for severalminutes to ensure that the system is not leaking.

f. Close metering valve “E”. Open valve “A”, then slowlyopen valve “E” and flash liquid phase refrigerant to bringthe system to 101.325 kPa. Close Valve “A”.

g. Repeat steps d through f.

h. Close valves “B” and “C” and remove the bulb from thevacuum/sampling apparatus.

i. Calculate the grams of primary refrigerant added to thebulb as follows:

grams added = MW Ref. x Internal Volume of Bulb (mL) 24,450

Where:

MW Ref. = Molecular weight of the primary refrigerant24,450 = Volume occupied by 1 mole of the primary refrigerant

at 25°C and 101.325 kPa.

NOTE: Alternatively, the grams added may be determined byweighing (0.0001g) the dried, evacuated bulb (step dabove) and then reweighing at step h.

j. Individually, and in turn, add the volumes of eachgaseous calibration component indicated in Table 2 ofthe corresponding GC Method Data Sheet to the

4

calibration bulb. Use an appropriately sized microliter ormilliliter gas tight syringe with deflected point needles.(See Note 2 in Section 10.7 of this method)

k. Into a 30 ml serum bottle that has been capped andcrimped with a septum, add the exact volumes of theliquid impurities in the order given in Table 3 (if any) ofeach GC Method Data Sheet. Add each impurity bysyringe injection through the septum using a #22 needle(or smaller) as a vent. After addition, shake vigorouslyto mix. Label, date and store in a refrigerator.

NOTE: For refrigerants which have no liquid impurities listed in Table 4 of the GC Method Data Sheet skip steps k-n and proceed to step o.

l. Evacuate a 125 ml gas sampling bulb (refer to Figure 1)with its internal volume pre-measured, and fill to 101.325kPa with the primary refrigerant for which a calibrationstandard is desired.

NOTE: For R-114, a 250-mL gas sampling bulb is used.

m. Accurately withdraw and inject exactly 10 microliters ofsolution from the 30-mL serum bottle into the 125-mLbulb. Allow to equilibrate for 30 minutes.

NOTE: For R-114, 20 µL is added instead of 10 µL and for R-134a, 5 µL is added instead of 10 µL.

n. Using a gas tight syringe, withdraw vapor from the 125-mL bulb and inject the exact volume as listed in Table 1below into the 500-mL calibration bulb. The µg of eachcomponent thus added is calculated as follows and isadded to the fourth column of Table 2 of the appropriateGC Method Data Sheet as follows:

µµµµg of component i added = gi x D 32 x A

Where:

gi = g from step k and found in Table 4 of the GC Method DataSheet.

A = internal mL of the gas sampling bulb.32 = total (approximate) mL of solution in step k/Table 3.D = dilution ratio as listed in Table 1 below.

o. Total the µg added column in Table 2 (refer to the GCMethod Data Sheet) and combine this weight with that ofstep i to obtain the total weight of the sample (to thenearest 0.0001 g) in the bulb.

p. Calculate the ppm added (to the nearest 1 ppm) for eachcomponent by dividing the µg added by the total weightof sample in the gas bulb (step o).

Table 1. Vapor Volume and Dilution Ratio (D) for LiquidImpurities Used for Primary Calibration Standard

Refrigerant Vapor Volume(used in step n)

Dilution Ratio (D)

R-12 5.0 mL 50,000R-22 5.0 mL 50,000R-32 None added None

R-114 10.0 mL 200,000R-124 5.0 mL 50,000R-125 2.0 mL 20,000R-134a 5.0 mL 25,000R-143a None added None

q. Calculate the ppm present for each component bycombining the ppm present in the primary refrigerant (ifany) and the ppm component added (See Note 1 inSection 10.7 of this method). The ppm componentpresent values are those used for determining the methodresponse factors.

r. Allow the gas calibration bulb to stand for 20-30 minutesto equilibrate. The standard will be stable for 3 days.

10.2 Determination of Component Response Factors (Refer toSection 10.7, Note 3)

a. Set up the electronic integrator for an area normalization-response factor calibration.

b. Analyze the calibration standard bulb in triplicate usingthe chromatographic conditions described in Section 3 ofthe GC Method Data Sheet.

c. Using the primary refrigerant as the reference peak,perform the necessary functions to have the integratordetermine each component’s Relative Response Factor(RRFi) which is then stored. Response factors arecalculated as follows:


Aii

= x

xA

S-100.0000ARF =

Where:

ARFi = Absolute Response Factor of component i.Ai = peak area of component i (average of 3 runs)Ax = peak area of primary refrigerant (average of 3 runs).ARFx = Absolute Response Factor of Primary Refrigerant.S = Weight % sum of all impurities present.

5


x

ii

ARF

ARFRRF = 0.1

ARF

ARFRRF

x

xx ==


Refer to Note 5 in Section 10.7 for R-32 and refer to Note 6 inSection 10.7 for R-134a.

10.3 Secondary Calibration Standard Preparation

NOTE: A secondary calibration standard is prepared in muchlarger quantity due to the comparatively short lifetimeof the primary bulb standard. The primary bulbstandard is necessary initially because of inherentphase distribution of added components if simplypreparing and calibrating a standard such as describedhere. The secondary standard is analyzed as a sampleagainst the primary standard and then usedsubsequently as the daily calibration standard.

a. Evacuate a 1L steel cylinder and determine the tareweight to the 0.1g.

b. Attach a Swagelok nut and septum to the valve and thenexternally cool the cylinder in ice water. Open thecylinder valve.

c. While keeping the cylinder in ice water, individually andin turn add the volume of each gaseous component givenin Table 2 of the GC Method Data Sheet multiplied bythe factor given in Table 2 below for each refrigerant tothe cylinder by syringe injection through the septum.Similarly, add the volume of liquid refrigerant impuritiesfrom Section 10.1 k (if any) in the quantity specified inTable 2 below. Close the cylinder valve and remove theSwagelok nut and septum.

Table 2. Secondary Calibration Standard Gaseous andLiquid Impurity Addition Information

RefrigerantGaseous Impurities

Factor1Liquid Refrigerant

Impurities (mL)R-12 400 0.15R-22 500 0.20R-32 700 None

R-114 400 0.30R-124 400 0.15R-125 400 0.15R-134a 500 0.10R-143a 350 None

1 Multiply each gaseous impurity in Table 2 of the GC Method Data Sheet by the factor given above to give the total volume of impurity to be added for the secondary calibration standard.

d. Evacuate a second clean, dry 1L steel cylinder anddetermine the tare weight to the nearest 0.1g.

e. Cool the cylinder in ice water and attach a short (up to 61cm) section of flex line from the primary refrigerant’ssupply cylinder. Purge a small amount of the primaryrefrigerant through the flex line before immediatelyattaching to the 1L cylinder.

f. Open the 1L cylinder valve, then open the refrigerantcylinder of the primary refrigerant for which it is desiredto constitute a secondary calibration standard. Whilekeeping the 1L cylinder in ice water, fill the 1L cylinderwith the amount of liquid phase of the primaryrefrigerant listed in Table 3 below. If significantly morethan the prescribed weight of the primary refrigerant isadded, vent the cylinder to give approximately the weightdesired in Table 3 (See Note 4 in Section 10.7 of thismethod). Remove the 1L cylinder from the ice bath andallow it to warm to ambient temperature.

g. Place the 1L secondary calibration standard cylinder (thecylinder mentioned in steps a, b, and c) in the ice bathand cool for 30 minutes.

h. Using a short double female swivel coupler, invert the 1Lcylinder containing the primary refrigerant in step f, andconnect to the secondary calibration standard cylinder.Open the valve slightly and purge some of the primaryrefrigerant vapor to sweep the coupler before connectingto the secondary calibration standard cylinder. Warm,but do not overheat, the cylinder containing the primaryrefrigerant with a heat gun.

Table 3. Approximate Amount of PrimaryRefrigerant to Add to Secondary Calibration

Standard

Refrigerant Weight of Primary Refrigerant (g)

R-12

R-22

R-32

R-114

R-124

R-125

R-134a

R-143a

1200

1100

900

1300

1200

1100

1100

820

i. Open the valves on both cylinders and allow all of theprimary refrigerant to transfer into the calibrationstandard cylinder. Close the cylinder valves.

j. Remove the calibration cylinder from the ice bath andallow the cylinder to reach ambient laboratory

6

temperature before the final weighing. Dry off thecylinder then reweigh it to the nearest 0.1g.

k. Subtract the tare weight (from step a) from the totalweight (step j) to obtain the total grams of standard in thecylinder. Record this weight together with the cylindertare weight and the date of preparation on the cylinderlabel.

l. Roll the cylinder for at least 4 hours to thoroughly mix.

m. Analyze the cylinder contents in triplicate as described inSection 3 of the GC Method Data Sheet, loading first intoan evacuated gas bulb as shown in Figure 1.

n. Average the results calculated electronically (see Section10.6, Calculations) and tabulate to the nearest 1ppm. Listeach component on the cylinder label with the ppmamount for each. This cylinder is used henceforth as thecalibration standard until the loss of standard weightindicates that the internal volume of liquid phase is lessthan 60% of the total internal volume of the cylinder.Liquid densities of the primary refrigerants are listed inTable 4 below.

Table 4. Liquid Densities of Refrigerants

Refrigerant Density at 25°C (g/mL)

R-12

R-13

R-22

R-23

R-32

R-114

R-124

R-125

R-134a

R-143a

1.311

0.907

1.194

0.670

1.100

1.456

1.364

1.250

1.202

0.946

10.4 Sampling

Submitted sample cylinders must contain sufficient liquid phase(80% liquid full is recommended) for analysis.

10.5 Sample Analysis

Analyze the sample using the chromatographic conditionsspecified in Section 3 of the respective GC Method Data Sheet.Load the sample as illustrated in Figure 1 by flashing the liquidphase into an evacuated gas bulb and bringing to 101.325 kPapressure.

NOTE: Alternatively, the sample liquid phase may be flashedinto a Tedlar bag (1L recommended) and the sample

for GC analysis is withdrawn from the bag.

10.6 Calculations


W100 x RRF x A

(A x RRFii i

i i

=∑ )

Where:



b. Report sample component concentrations to the nearest0.0001% (or to the nearest 1 ppm). If the results are lessthan the individual detection limits (see Table 1), thenreport < the detection limit (DL) value given.

10.7 Notes for High Pressure Refrigerants

1. The purest refrigerant will contain some of the impurities listedin Table 1 of the GC Method Data Sheet. The ppmamounts of impurities already in the primary refrigerant aredetermined via the method of Standards Addition.Individual impurity peak areas in the stock are increased inthe calibration standard by the ppm amount of thecorresponding impurity added. The ppm already present iscombined with the ppm added to give the total ppmcomponent present in the calibration standard.

2. To preserve the stock of calibration component, it issuggested to load a small evacuated 125 mL gas collectingtube to 101.325 kPa from the liquid phase as illustrated inFigure 1. The appropriate volume is then withdrawn andinjected into the 500-mL calibration bulb.


4. During the primary refrigerant’s addition to the 1L cylinder(secondary standard preparation), it is unnecessary to bringthe cylinder to ambient temperature between weighings asonly an approximate weight is required.

5. To determine the R-125 packed column response in thepresence of HCC-40 while analyzing R-32, it is necessaryto first establish an RRF ratio for HCC-40 between the twocolumns. This is done by analyzing the standard on bothcolumns and determining the RRF40 on the packed column

7

(i.e., RRF40-P) by the method of Standards Addition.Having established this ratio R (i.e., R = RRF40-c/RRF40-P),the area in the 125/40 combination peak attributed to HCC-40 is:

A40-P = R x Weight % R-40 RRF40-C x ARF32 -P

Then: A125 = Comb. Peak Area – A40-P

And: ARF125 = Weight % R-125A125

The same equations are used to determine the weight % ofR-125 present when analyzing samples. The R-value shouldbe checked periodically in conformance to standard qualitycontrol practice.

6. While analyzing R-134a, in order to separate 31 and 1140(which coelutes on the capillary column), repeat thecapillary column analysis exactly as given in Section 3 ofthe GC Method Data Sheet except that the columntemperature is held at 50°C (isothermal) throughout. Thetwo components will be resolved at about 15 minutesretention time with the 31 peak eluting 0.8 minutes beforethe 1140 peak.

11. Procedure for Very High Pressure Refrigerants

NOTE: The following procedure is generalized for thedetermination of purity for very high-pressurerefrigerants, R-13 and R-23. Each respective GCMethod Data Sheet contains the detector type, thecolumn, the chromatographic conditions, and theimpurities necessary for the following calibrationstandard preparation.

11.1 Calibration Standard Preparation and Analysis

a. Attach a Swagelok nut and septum to one end of aclean dry stainless steel cylinder and a vacuum pump lineto the other. Evacuate the cylinder to full vacuum, or0.133 kPa.

b. Referring to Table 2, Calibration Standard Components,of the appropriate GC Method Data Sheet, and, using theappropriately sized milliliter gastight syringe, carefullyadd the specified volume of each calibration componentto the cylinder via the Swagelok nut/septum. Also,refer to Section 11.6, Note 2.

c. Remove the Swagelok nut/septum, and then tare weighthe 1L cylinder to the nearest 0.1g.

d. Position the cylinder inside a cold bath, either alcohol ordry ice, and allow to cool while performing subsequentsteps e through i.

e. Obtain a stock cylinder of the VHP refrigerant underpreparation whose purity has been previously establishedby either GC analysis or by the Method of StandardsAddition (See Section 11.6 Note 1). This cylinder mustbe precooled either in a refrigerator or external ice bathto at least 20°C below the critical temperature (tc) of therefrigerant.

f. Evacuate a second clean, dry 1L stainless steel cylinder(as in step a above). Tare weigh this cylinder to thenearest 0.1g.

g. Place this second 1L cylinder into a dry ice or cold(alcohol) bath and cool for 10-15 minutes.

h. Using a Swagelok steel mesh Teflon line (flexline),invert the VHP source cylinder and connect it to thesecond 1L cylinder. Initially purge the flexline withVHP gas (flashed liquid phase) so as to purge air fromthe line before the final connection is made.

i. Transfer the specified amount of VHP stock refrigerantliquid phase into the 2nd 1L cylinder as specified in Table5 below. If too much gas has been added, then slowlyvent until the weight is about that specified.

NOTE: It is not necessary here to weigh back at room(ambient) temperature as only an approximate gramsof VHP stock is necessary.

Table 5. Approximate Amount of Liquid VHPRefrigerant to Add to Calibration Standard

Refrigerant Weight of VHPRefrigerant (g)

CorrespondingPressure (kPa)

R-13

R-23

150

200

1140

2516

j. Remove the second 1L cylinder from the cold bath, and,using the Teflon flexline, connect it to the 1LCalibration Standard cylinder still in the cold bath (stepd).

k. Using a heat gun, warm the second 1L cylinder and,when warmed to ambient temperature, transfer the entirecontents into the 1L Calibration Standard cylinder. Closethe cylinder valve, remove the flexline, and remove thecylinder from the cold bath.

8

l. Position the cylinder on a roller mill, and roll to mixwhile allowing the cylinder to slowly warm to ambient(room) temperature. Note that the liquid phase willslowly vaporize as the VHP gas warms to roomtemperature.

m. When equilibrated at room temperature, weigh thecylinder (to the nearest 0.1g). Subtract the tare weight(step c) and record the difference as the grams of stockVHP refrigerant added.

n. Total the grams of all added impurities (step b) and addthis sum to the grams of stock from step m above. Thisamount represents the total weight of calibration samplepresent.

o. Divide the grams of each added impurity multiplied by106 by the total weight of calibration sample and recordthese results in Table 2 of the GC Method Data Sheet asppm component added. Correct any amount for thepurity of the added component as previously established(Section 8, 9)

p. Add the ppm amount of any impurity component alreadypresent in the VHP stock refrigerant to the ppm amountof impurity added, and complete Table 2 by recordingeach respective value in the Total ppm Present column(see Section 11.6, Note 1)

q. Record the individual impurities and ppm amountspresent on the Standard Cylinder, the gross weight, andthe date of preparation. Because the standard mixture isall vapor, the mixture is stable indefinitely, or until all isconsumed.

11.2 Determination of Component Response Factors (Refer toSection 11.6, Note 3)

a. Set up the electronic integrator for an area normalization-response factor calibration.

b. Analyze the calibration standard cylinder in triplicateusing the chromatographic conditions described inSection 3 of the GC Method Data Sheet. Refer to Figure1 for loading into the gas sampling bulb.

c. Using the primary refrigerant as the reference peak,perform the necessary functions to have the integratordetermine each component’s Relative Response Factor(RRFi) which is then stored. Response factors arecalculated as follows:


Aii

= x

xA

S-100.0000ARF =

Where:

ARFi = Absolute Response Factor of component i.Ai = Peak Area of component i (average of 3 runs).Ax = Peak Area of primary refrigerant (average of 3 runs).ARFx = Absolute Response Factor of Primary Refrigerant.S = Wt% sum of all impurities present.


x

ii

ARF

ARFRRF = 0.1

ARF

ARFRRF

x

xx ==



Aii

= x

xA

S-100.0000ARF =

Where:

ARFi = Absolute Response Factor of component i.Ai = Peak Area of component i (average of 3 runs).Ax = Peak Area of primary refrigerant (average of 3 runs).ARFx = Absolute Response Factor of Primary Refrigerant.S = Wt% sum of all impurities present.


x

ii

ARF

ARFRRF = 0.1

ARF

ARFRRF

x

xx ==


11.3 Sampling

Submitted sample cylinders must be stainless steel, either 500mL or 1L volume. Source cylinders or containers are sampledabove the critical temperature (Tc) of the VHP refrigerant so asto ensure the refrigerant is all vapor phase (refer to Note 4).

11.4 Sample Analysis

Analyze the sample using the chromatographic conditionsspecified in Section 3 of each GC Method Data Sheet. Load thevapor sample into the gas bulb as illustrated in Figure 1. Becertain that metering valve “E” is rated above the pressure ofthe VHP refrigerant gas in the sample cylinder. Alternatively,the sample may be slowly purged through Tygon tubing and,after purging air from the tubing, the GC sample is withdrawnthrough the tubing in proximity to the cylinder valve.

NOTE: Alternatively, the sample liquid phase may beflashed into a Tedlar bag (1L recommended) and thevapor then sampled for GC analysis.

9

11.5 Calculations


W100 x RRF x A

(A x RRFii i

i i

=∑ )

Where:



b. Report sample component concentrations to the nearest0.0001% (or to the nearest 1 ppm). If the results are lessthan the individual detection limits (see Table 1), thenreport < the detection limit (DL) value given.

11.6 Notes for Very High Pressure Refrigerants

1. The purest refrigerant will contain some of the impuritieslisted in Table 1 of the GC Method Data Sheet. The ppmamounts of impurities already in the primary refrigerantare determined via the method of Standards Addition.Individual impurity peak areas in the stock are increasedin the calibration standard by the ppm amount of thecorresponding impurity added. The ppm already presentis combined with the ppm added to give the total ppmcomponent present in the calibration standard. The ppmadded amounts for calibration should be greater than theusual amounts present in typical samples. This is becausethe peak response of the TCD becomes increasingly non-linear as impurity concentration levels increase.

2. To preserve the stock of calibration component, it issuggested to load an evacuated 250-mL gas collecting tubeto 110 kPa from the liquid phase as illustrated in Figure 1.The appropriate volume is then withdrawn and injectedinto the 1L stainless steel cylinder.


4. VHP refrigerants all have Tc values either near or somewhatbelow room temperature. Because ARI Standard 700specifies that the liquid phase of refrigerants is sampled forpurity, et. al., the only way to form sufficient liquid phasefor these analyses is to cool the VHP sample to at least20°C below Tc. In practice, consistent impurity phasedistributions are difficult to control because the relativeamounts of sample liquid and vapor phases are strongly

dependent upon the temperature of the refrigerant at thetime of analytical sampling and analysis. For this reason,the decision was made to ensure sample homogeneity byconverting all source refrigerants to vapor phase beforeanalytical GC sampling. In cold weather, the sampling ofvery large containers (outdoors) is accomplished bysampling the liquid phase and then warming the samplecylinder and contents to above Tc before GC analysis.

5. A 32-fold increase in peak sensitivity is possible byoperating the chromatographic TCD at the high sensitivityposition. However, at higher sensitivity, the usefullifetime of the detector (hot wires) is diminished, thebaseline noise and background is often intolerable andpeak area reproducibility is generally degraded. For thesereasons, the lower sensitivity position was chosen forroutine applications.

Section 12. GC Method Data Sheets

The GC Method Data Sheet for each respective refrigerant canbe found in the following Part:

Table 6. GC Method Data Sheets

RefrigerantProcedure forCalibrationStandardPreparation

GC Method DataSheet PartNumber

R-11 Part 1, Section 9 Part 2R-12 Part 1, Section 10 Part 3R-13 Part 1, Section 11 Part 4R-22 Part 1, Section 10 Part 5R-23 Part 1, Section 11 Part 6R-32 Part 1, Section 10 Part 7

R-113 Part 1, Section 9 Part 8R-114 Part 1, Section 10 Part 9R-123 Part 1, Section 9 Part 10R-124 Part 1, Section 10 Part 11R-125 Part 1, Section 10 Part 12R-134a Part 1, Section 10 Part 13R-143a Part 1, Section 10 Part 14

Section 13. References

1. Air-Conditioning and Refrigeration Institute, Appendix Cto ARI Standard 700-95: Analytical Procedures for ARIStandard 700-95, 4301 North Fairfax Drive, Arlington,Virginia 22203.

10

Figure 1. Apparatus Used for Sampling Calibration Standards and Samples

11

Part 2

R-11 GC Method Data Sheet

Section 1. Scope

This GC Method Data Sheet is for use in conjunction withSection 9 of the General Procedure for the Determination ofPurity of New and Reclaimed Refrigerants by GasChromatography (hereafter referred to as General Procedure).This GC Method Data Sheet is for use with R-11.


This method is applicable and calibrated for only thoseimpurities found in Table 2. Other impurities that have beendetected on occasion are listed (with retention times) in Table 3.This method will not detect any impurities that may elute withinthe comparatively large R-11 peak matrix.

Section 3. Gas Chromatographic AnalysisEquipment and Conditions

Packed column: 7.32 m x 3.17 mm OD stainless steel, 1% SP-1000 on Carbopack B, 60/80 mesh, Supelco, Bellefonte, PA.

Detector FIDCarrier Gas 30 mL He/Min.Initial Column Temp. 125°CInitial Hold 4 Min.Program 10 K/Min.Final Column Temp. 180°CPost Hold 14 Min.Sample 1 µL (liquid syringe)Detector Temp. 250°CInj. Port Temp. 200°CMax Safe Column Temp. 225°C (for conditioning purposes)


Statistical parameters for each impurity are listed in Table 1.The data was obtained by analyzing an R-11 calibration mixture7 times during one day by one operator.

Section 5. Tables

The following tables are to be used in conjunction with Section 9of the General Procedure for the Determination of Purity of Newand Reclaimed Refrigerants by Gas Chromatography.

12

Figure 1. Gas Chromatogram of R-11

13

Table 1. Component Statistical Parameters

ComponentDetection

Limit, ppmConcentration

Investigated, ppmPrecision at 95%

Confidence Limit, ppmRelative Mean

Error, %

2313

152a22

11512

133a2130

114123a12320

11310

1120

2312221222322222

15203050306025302540255025602525

0.370.530.470.980.801.100.330.670.331.912.701.330.732.311.701.77

-2.8-3.11.7-0.80.71.1-2.51.2-2.5-2.7-4.83.30.72.2-3.31.8

Table 2. Primary Calibration Standard Components

Component Mol. Wt.Vol.

Added, mLµg

Added (1)ppm

Added (2)Total ppmPresent (3)

23(4)13(4)

152a(4)22(4)115(4)12(4)

133a(4)21(4)

30114(4)123a12320

11310

1120

701056686

13612111810385

170153153120188154132

1.21.02.53.21.22.81.11.6

5.0µL1.3

5.0µL10.0µL5.0µL

10.0µL10.0µL5.0µL

343642746748

113216650

1384553326740668090617490

147507445

15650159507278

15193050296124302940336433687032

(1) If necessary, correct the µg added for the purity of the calibration component previously established.(2) Values shown are for illustration; exact values are determined in Section 9.1 step f of the General Procedure.(3) Column to be filled in (Section 9.1 step g of the General Procedure) after determining ppm present in stock R-11 (see Note 1 in

Section 9.6 of the General Procedure).(4) These impurities are gases at ambient room temperature; the others are liquids with low boiling points.

Table 3. Retention Time Data for Identified ImpuritiesNot Normally Observed

Impurity Retention Time (Min.)

32(1)1114C3H8

2.374.108.00

(1)Coelutes with R-23. To separate, attach 30.5 cm section of Porapak-T column to detector end of columnand chromatograph (R-23 elutes first).

14

Part 3


Section 1. Scope

This GC Method Data Sheet is for use in conjunction withSection 10 of the General Procedure for the Determination ofPurity of New and Reclaimed Refrigerants by GasChromatography. This GC Method Data Sheet is for use with R-12.


This method is applicable and calibrated for only thoseimpurities found in Table 2 and Table 3. Other impurities thathave been detected on occasion are listed (with retention times)in Table 4. This method will not detect any impurities that mayelute within the comparatively large R-12 peak matrix.



Detector FIDCarrier Gas 30 mL He/Min.Initial Column Temp. 40°CInitial Hold 6 Min.Program 10K/Min.Final Column Temp. 160°CPost Hold 18 Min.Sample 0.50 mL (gas syringe)Detector Temp. 250°CInj. Port Temp. 150°CMax Safe Column Temp. 225°C (for conditioning purposes)



Section 5. Tables

The following tables are to be used in conjunction with Section10 of the General Procedure for the Determination of Purity ofNew and Reclaimed Refrigerants by Gas Chromatography.

15


16


ComponentDetection


Investigated, ppmPrecision at 95% Confidence

Limit, ppmRelative Mean

Error, %

Methane23

C2H4

C2H6

13143a152a140134a22

C3H6

115142b124133a21

isobutane114

n-butane2-butene-T

11123

2-butanolMEK113

n-pentane

0.52

0.50.5311112

0.521112

0.52

0.50.542222

0.5

52555

3025302045655

115202535502050205

40352025305

0.070.540.130.100.470.300.630.370.271.750.101.670.230.370.230.830.230.830.180.060.871.050.330.470.870.25

4.00-2.30-5.60-4.10-3.803.301.672.30-3.302.733.371.80-1.331.831.831.80-2.772.03-3.33-3.801.05-4.731.60-2.33-4.00-3.73



Added, µLµg

Added (1)ppm

Added (2)Total ppmpresent (3)

Methane23

C2H4

C2H6

13143a152a40

134a22

C3H6

115142b124133a21

isobutane114

n-butane2-butene-T

11(4)123(4)

MEK(4)113(4)

2-butanol(4)n-pentane(4)

16702830

104846650

1028642

15410013611810358

1705856

13715372

1887472

202212112020302830508

50151220322520256

13.163.013.713.585.468.881.057.8125.1176.913.7315.961.767.097.0134.759.3139.859.313.7(5)(5)(5)(5)(5)(5)

523553125302146645

11522243549225122557381727215

17

Table 2 Notes

(1) If necessary, correct the µg added for the purity of the calibration component previously established.(2) Values shown are for illustration; exact values are determined in Section 10, step p of the General Procedure.(3) Column to be filled in (Section 10.1, step q of the General Procedure) after determining the ppm present in

stock R-12 (see Note 1 in Section 10.7).(4) These components are liquids at ambient laboratory temperature and are added to the 500 mL bulb as described

in Section 10.1 of the General Procedure, steps k through n.(5) From Section 10.1 step n.

Table 3. Liquid Impurities For Calibration Standard Preparation

Component Vol. Added, mL Density at 20°C g

2-butanolMEK113

n-pentane12311

6.05.04.02.06.09.0

0.8080.8051.5650.6261.4701.487

4.8484.0256.2601.2528.82013.383



32(1)1114C3H8

302, 2-Dimethylpropane

Isopentane

3.456.00

11.6016.9319.8024.30

(1) Coelutes with R-23. To separate, attach 1 ft. (30.5 cm) section of Porapak-T column todetector end of column and re-chromatograph (23 elutes first).

18

Part 4


Section 1. Scope

This GC Method Data Sheet is for use in conjunction withSection 11 of the General Procedure for the Determination ofPurity of New and Reclaimed Refrigerants by GasChromatography. This GC Method Data Sheet is for use with R-13.


This method is applicable and calibrated for only thoseimpurities found in Table 2. This method will not detect anyimpurities that may elute within the comparatively large R-13peak matrix.



Detector TCD, Low Sensitivity*Carrier Gas 30 mL He/Min.Initial Column Temp. 40°CInitial Hold 6 Min.Program 10K/Min.Final Column Temp. 160°CPost Hold 4 Min.Sample 2.0 mL (gas syringe)Detector Temp. 200°CInj. Port Temp. 150°CMax Safe Column Temp. 225°C (for conditioning purposes)

*See Note 5 in Section 11.6.



Section 5. Tables


19


20


ComponentDetection




Error, %

1423

1161252231

11512

11411

12101412101012101212

300200250150175100200200100100

7.22.73.16.65.32.64.73.66.33.1

1.7-1.01.3-2.02.32.0-2.02.54.0-2.0



Added, mLgrams

Added (1)ppm


1423

1161252231

11512

11411 (4)

8870

13812086.568

154.5121171

137.4

10.010.05.05.010.05.05.08.03.04.0

0.03400.02860.02820.02450.03540.01390.03160.03960.02100.0225

22719118816323693211264140150

(1) If necessary, correct the grams added for the purity of the calibration component previously established.(2) Values shown are for illustration; exact values are determined in Section 11.1 step o of the General Procedure.(3) Column to be filled in (Section 11.1, step p of the General Procedure) after determining ppm present in stock R-13 (see Note 1 in Section

11.6).(4) Added by warming an uncapped vial of the liquid component to enrich the headspace vapor, capping, cooling, then removing headspace vapor

via a gas syringe.

21

Part 5


Section 1. Scope





3.1 Chromatographic Equipment and Conditions, Packed Column



3.2 Chromatographic Equipment and Conditions, Capillary Column

Capillary Column: 120m (or 2 60m) DB-1301, .25mm,1µ, J&W Scientific Co.,Folsom, CA.

Detector FIDCarrier Gas approx. 1mL He/MinInjection Port Temp 150°CDetector Temp. 250°CSample 1.0 mLMax. Safe Column Temp. 280°CInitial Col. Temp 40°CInitial Hold 10 Min.Program 8K/Min.Final Column Temp. 50°CPost Hold 18 Min.Split Ratio 30:1

Pressure 240 kPa



Section 5. Tables

The following tables are to be used in conjunction with Section10 of the General Procedure.

22


23

Figure 2. Capillary Column Gas Chromatogram of R-22 for Determination of R-31 Impurity

24


ComponentDetection




Error, %

CH4

23C2H4

C2H6

13143a152a40

134a31(1)C3H6

11512

142b124133a21

isobutane114

n-butane2-butene-T

11123a123113

0.52

0.50.5311112

0.5221112

0.52

0.50.54222

52055

3025402550405

80100203035601035105

40153025

0.100.880.080.050.470.670.830.870.503.330.133.052.880.170.450.831.330.131.330.130.051.671.331.671.33

4.71.7-6.2-5.77-3.331.7

-0.67-2.45-1.07-4.675.7-0.82.41.072.071.87-3.8-4.31.8-4.3-5.32.87-3.67-2.331.87

(1) In absence of n-butane.



Added, µLµg

Added (1)ppm


Methane23

C2H4

C2H6

13143a152a40

134a31

C3H6

11512

142b124133a21

isobutane114

n-butane2-butene-T

11(4)123a(4)123(4)113(4)

16702830

104846650

1026842

15412110013611810358

1705856

137153153188

151510101515302525285

2540101015301010105

9.843.011.412.364.051.681.051.6

104.378.58.6

158.0197.841.155.872.8

126.323.769.923.711.4(5)(5)(5)(5)

52266332641265340480

100212837641236126

133367047

See Table 2 Notes below.

25

Table 2 Notes

(1) If necessary, correct the µg added for the purity of the calibration component previously established.(2) Values shown are for illustration; exact values are determined in Section 10, step p of the General Procedure.(3) Column to be filled in (Section 10, step q of the General Procedure) after determining the ppm present in stock

R-22 (see Note 1 in Section 10).(4) These components are liquids at ambient laboratory temperature and are added to the 500-mL bulb as described

in Section 10.1 of the General Procedure, steps k through n.(5) From Section 10.1 step n.

Table 3. Liquid Impurities for Calibration Standard Preparation

Component Volume Added, mL Density At 20°C g

113123123a11

58415

1.5651.4701.4921.487

7.82511.765.96822.305

Table 4. Additional Impurities Observed in R-22

ImpurityPacked Column

Retention Time (Min.)

32(1)1114

Propane124a30

CCl4pentane

2.76.011.714.817.026.827.0

(1) Coelutes with R-23 on packed column; to separate, attach 1 foot (30.5 cm)section of Porapak-T column to detector end of column and re-chromatograph (23 elutes first).

26

Part 6


Section 1. Scope





Packed column: 6.09 m x 3.17 mm OD stainless steel, Porapak-T, 80/100 mesh, Supelco, Bellefonte, PA.

Detector TCD, Low Sensitivity*Carrier Gas 15 mL He/Min.Initial Column Temp. 40°CInitial Hold 3 Min.Program 18 K/Min.Final Column Temp. 175°CPost Hold 10 Min.Sample 2.0 mL (gas syringe)Detector Temp. 200°CInj. Port Temp. 150°CMax Safe Column Temp. 190°C (for conditioning purposes)

* See Note 5 in Section 11.6 of the General Procedure.



Section 5. Tables


27


28


ComponentDetection




Error, %

141161332

13B1122231

101510510555

200350400150120160450175

1.775.805.101.935.873.673.901.60

-0.40-0.850.601.40-1.050.880.32-1.37

Table 2. Calibration Standard Components


Added, mLµg

Added (1)ppm


141161322323112

13B1

8813810486.55268

121149

10.010.020.020.010.010.06.05.0

0.03600.05640.08510.07090.02130.02780.02970.0305

180282426355107139149153

(1) If necessary, correct the grams added for the purity of the calibration component previously established.(2) Values shown are for illustration; exact values are determined at Section 11.1 step o of the General Procedure.(3) Column to be filled in (Section 11.1, step p of the General Procedure) after determining the ppm present in stock

R-23 (see Note 1 of Section 11.6 of the General Procedure).

29

Part 7


Section 1. Scope



This method is applicable and calibrated for only thoseimpurities found in Table 2. Other impurities that have beendetected on occasion are listed (with retention times) in Table 4.This method will not detect any impurities that may elute withinthe comparatively large R-32 peak matrix.




Detector FIDCarrier Gas 20 mL He/Min.Initial Column Temp. 45°CInitial Hold 8 Min.Program 8 K/Min.Final Column Temp. 150°CPost Hold 15 Min.Sample 1.0 mL (gas syringe)Detector Temp. 200°CInj. Port Temp. 200°CMax Safe Column Temp. 225°C (for conditioning purposes)


Capillary Column: 120m (or 2-60m) DB-1301, 0.25mm,1µ, J&W Scientific Co.,Folsom, CA.

Detector FIDCarrier Gas approx. 1mL He/MinInjection Port Temp 150°CDetector Temp. 250°CSample 1.5 mLMax. Safe Column Temp. 280°CInitial Col. Temp -28°CInitial Hold 10 Min.Program 5K/Min.Final Column Temp. 40°CPost Hold 5 Min.Split Ratio 30:1

Pressure 200 kPaMakeup Gas 30 mL He/Min.

See Note 5 of Section 10.7 of the General Procedure for theDetermination of Purity of New and Reclaimed Refrigerants byGas Chromatography.



Section 5. Tables


30

Figure 1. Packed Column Gas Chromatogram of R-32

31

Figure 2. Capillary Gas Chromatogram of R-32

32


ComponentDetection




Error, %

41143a12540311151212423

114a

3111122122

100100100100100100100100100100

4.330.804.102.671.451.882.331.011.733.53

-2.1-1.1-0.81.41.32.1-1.00.7-3.02.8



Added, µLµg

Added (1)ppm


41143a1254031

11512

12423

114a

3484120506815412113670171

75302550402025204015

104.3103.2122.9103.3112.1126.4123.6111.8114.6104.8

88.487.4

104.087.595.0

107.0104.794.897.188.8

(1) If necessary, correct the µg added for the purity of the calibration component previously established.(2) Values shown are for illustration; exact values are determined at step p.(3) Column to be filled in (step q) after determining ppm present in stock R-32 (see Note 1 in Section

10.7 in the GC Method Data Sheet).

Table 3. Liquid Impurities for Calibration Standard Preparation

Component Volume Added, mL Density At 20°C g

None Added

Table 4. Additional Impurities Observed in R-32

The following impurities have been observed occasionally in samples of R-32 on the packed column:

Impurity Packed Col. Retention Time (Min.)

1322

142b133a21

11(1)123(1)

15.024.230.034.835.340

42.3

(1) Need to extend final hold time if presence of these impurities is suspected.

33

Part 8


Section 1. Scope





Capillary column: 105m x 0.25 mm, 1.0µ, Rtx-1301, Restek Corp., 110 Benner Circle, Bellefonte, PA.

Detector FIDCarrier Gas approx. 1 mL He/Min.Initial Column Temp. 35°CInitial Hold 10 Min.Program 8 K/Min.Final Column Temp. 160°CPost Hold 8 Min.Sample 2 µL (liquid syringe)Detector Temp. 250°CInj. Port Temp. 200°CMax Safe Column Temp. 280°C (for conditioning purposes)Split Ratio 30:1Aux. Flow 30 mL/Min.Pressure 200 kPa



Section 5. Tables


34


35


ComponentDetection




Error, %

11511131222

114216ba133a1112a

11C-316bb

123a123

225da318mbb

12210

11211201110

52

1055212

152221225322

5060707040505020120305050303080100753030

1.22.30.80.80.72.50.70.34.16.81.31.50.90.82.34.72.51.41.7

1.3-0.7-1.21.00.8-1.9-2.3-3.30.8-1.1-2.5-1.1-2.1-0.70.42.6-1.10.30.8



Added, mLµg

Added (1)ppm


115(4)1113(4)12(4)22(4)114(4)216ba

133a(4)1112a(4)

11123a123

225da318mbb

122C-316bb

112TCEPCE10

15411612186171221118133137153153203271169233204131166154

2.03.03.55.01.5

8 µL2.50.8

20 µL8 µL8 µL5 µL5 µL5 µL5 µL

--5 µL5 µL

15 µL

1265314294173361769010502127221213743492900011984119847782840077237650200007278815623925

5360727444535018

121505032353232833034

100

(1) If necessary, correct the µg added for the purity of the calibration component previously established.(2) Values shown are for illustration; exact values are determined at Section 9.1 step f of the General

Procedure.(3) Column to be filled in (Section 9.1, step g of the General Procedure) after determining ppm present in

stock R-113 (see Note 1 in Section 9.6 of the General Procedure).(4) These impurities are gases at ambient room temperature, the others are liquids with low boiling points.

For 1112a, warm the vial or cylinder and sample the headspace vapor.

36

Part 9


Section 1. Scope



This method is applicable and calibrated for only thoseimpurities found in Table 2 and Table 3. This method will notdetect any impurities that may elute within the comparativelylarge R-114 peak matrix.






Section 5. Tables


37


38


ComponentDetection


Investigated, ppmPrecision at 95% Confidence

Limit, ppmRelative Mean

Error, %

2313

152a2211512

124a124133a217ca217ba

11123a123113113a122TCE

231222111224222222

1525256010060153050202045256550303030

0.280.440.400.671.670.910.750.500.500.671.330.670.500.771.11.230.670.33

-3.2-3.80.81.71.1-1.1-2.31.61.12.7-3.41.7-2.7-3.4-3.7-2.7-1.3-2.3



Added, µLµg

Added (1)ppm


2313

152a2211512

124a124133a217ca

217ba(5)11(4)

123a(4)123(4)113a(4)113(4)122(4)TCE(4)

701046686154121136136118204204137153153188188169131

2020356560501020401010

57.285.694.5

230.0379.2247.255.8

111.7193.883.683.6(6)(6)(6)(6)(6)(6)(6)

152226609864142950222275193740603937

(1) If necessary, correct the µg added for the purity of the calibration component previously established.(2) Values shown are for illustration; exact values are determined at step p.(3) Column to be filled in (step q) after determining ppm present in stock R-114 (see Note 1 in

Section 10.7 of the General Procedure).(4) These components are liquids at ambient laboratory temperature and are added to the 500 mL bulb as

described in Section 10.1 of the General Procedure (steps k through n).(5) Note that 217ba often contains 15 to 20% of the 217ca isomer.(6) From step n.

Table 3. Liquid Impurities For Calibration StandardPreparation

Component Vol. Added (mL)Density at20°C

g

TCE122113113a123a12311

4.04.06.04.02.04.08.0

1.4561.5441.5651.5791.4921.4701.487

5.8246.1769.3906.3162.9845.88011.896

39

Part 10


Section 1. Scope



This method is applicable and calibrated for only thoseimpurities found in Table 2. Other impurities that have beendetected on occasion are listed (with retention times) in Table 3.This method will not detect any impurities that may elute withinthe comparatively large R-123 peak matrix. The packed columnis necessary because 123a, 113 and 113a all nearly coelute on thecapillary column. The other impurities do not interfere withthese isomers on the packed column.




Detector FIDCarrier Gas 40 mL He/Min.Column Temp. 125°C (isothermal)Sample 2.0 µL (liquid syringe)Detector Temp. 250°CInj. Port Temp. 150°CMax Safe Column Temp. 225°C (for conditioning purposes)

Externally cool the syringe to 10°C before sampling.


Capillary Column: 120m (Connect the below two columns together with the DB-1701 column end

attached to the injection port):

1. 60m DB-1701, 0.25mm, 1µ, J&W Scientific Co., FolsomCA.

2. 60m SPB-5, 0.32 mm, 1µ, Supelco, Bellefonte, PA.

Detector FIDCarrier Gas approx. 1mL He/MinInjection Port Temp 150°CDetector Temp. 250°CSample 2µlMax. Safe Column Temp. 280°C

Initial Col. Temp 15°C ???Initial Hold 10 Min.Program 7K/Min.Final Column Temp. 60°CPost Hold 22 Min.Split Ratio 50:1Pressure 200 kPaMakeup Gas 20 mL He/Min.



Section 5. Tables

The following tables are to be used in conjunction with Section 9of the General Procedure.

40

Figure 1. Packed Column Gas Chromatogram of R-123

41

Figure 2. Capillary Column Gas Chromatogram of R-123

42


Component ECN (1)Detection



Confidence Limit, ppmRelation Mean

Error, %

11131222

1141317mx

31216ba

1326mxz133a

114B11112a1112123a123b1130

113113a1111

1.690.350.401.043.630.922.163.651.930.951.641.641.841.800.430.631.601.681.90

1322111112112232332

2525255030102015405025155%4006050

30025015

0.370.370.241.200.880.520.670.330.670.800.300.27

0.13%12.72.201.107.307.000.67

0.95-1.11.4-2.1

4.3(2)2.2-1.80.71.92.4-0.7-0.50.30

--1.80.3-0.2

-0.150.8

(1) Effective Carbon Numbers (ECN) determined experimentally or estimated (see J. Chromatog. Sci., 30, 280 and 301 (1992).)(2) Combining both isomers.



Added, mLµg

Added (1)ppm


11131222

1141317mx(4)

31216ba(5)1326mxz

133a114B1(4)

1112a1112123a

123b

11(4)30(4)113(4)113a(4)1111(4)

1161218617021668221198118215133133153

153

13785188188149

1.001.001.501.50

6.0 µL0.750.500.401.80

6.0 µL1.000.50

Refer to Note 4in Section 9.6


10.0 µL10.0 µL50 µL50 µL6.0 µL

476549465307

1045492892101451732708720

1110954502725



148691336078795789869279

22232448

41(6)10211540492513

1-7%

200-700

6559

36136241

(1) If necessary, correct the µg added for the purity of the calibration component previously established.(2) Values shown are for illustration; exact values are determined at step f.(3) Column to be completed (Section 9.1, step g of the General Procedure) after determining ppm present in stock R-

123 (see Notes 1 and 4 in Section 9.6 of the General Procedure).(4) Add by syringe injection of the liquid.(5) Although other 216 isomers comprise the usual 216 peak multiplet, the 216ba isomer (available) is used for

calibration purposes.(6) The 1317mx will resolve into the cis and trans isomer peaks with a ratio of one to two, respectively.

43

Table 3. Additional Impurities Observed in R-123,Quantitation by Effective Carbon Number Method

1. Additional impurities observed in samples of R-123 are as follows:

ImpurityCapillary Column

Retention Times (Min.)Effective Carbon

Numbers (1)

1132125134a114a124a1122124

328lcc ether (2)114aB1

141b1121132b

1130-T123B1122b122a122112a

9.189.469.8

11.2211.5611.5711.7714.5915.019.923.025.3525.6428.7236.2837.2438.043.55

2.00.791.671.171.271.761.333.90.82.01.751.92.251.701.751.751.761.48

(1) Refer to References (see J. Chromatog. Sci., 30, 280 and 301 , (1992).)(2) Structure tentatively identified as: CHClF-CF2-O-CF2-CF3.

2. Quantitation by ECN Method

Select a nearby peak in the chromatogram whose identification and response factor (RF) have been established (the Internal Standard).

Then:

RFI = ECNr x MWi

ECNI MWr

Where: RF = either absolute or Relative Response Factor.MWi = molecular weight of the component to be determined.MWr = molecular weight of the Internal Standard Reference.

44

Part 11


Section 1. Scope









Section 5. Tables


45


46


ComponentDetection



Confidence Level, ppmRelative Mean

Error, %

2313

1123143a152a125134a22

13B111512

263fb124a133a217ba217ca114114a11

1112a123113

C-316bb

55211223334225323362233

203015102540502030352525

0.2%50202020504015302530

0.700.330.220.220.330.880.700.730.951.130.700.88

0.009%3.332.661.232.333.660.870.370.830.962.33

6.67-1.33-2.67-4.052.501.332.50-1.70-2.673.74.673.334.67-5.073.331.673.674.33-1.082.33-2.67-3.33-5.33



Added, µLµg

Added(1)ppm

Added(2)Total ppmPresent(3)

2313

1123143a152a125134a22

13B111512

263fb124a(4)

133a217ba217ca114114a11(5)

1112a(5)123(5)113(5)

C-316bb(5)

701048284661201028614915412198136118204204171171137133153187233

222014102825381815171520--25881020

63.085.447.034.475.6

122.7158.563.791.4

107.474.180.2

--121.266.966.969.9

139.8(6)(6)(6)(6)(6)

20.028.015.011.024.039.051.020.029.034.524.026.0

--39.021.521.522.545.056.011.044.647.525.0

(1) If necessary, correct the µg added for the purity of the calibration component previously established.(2) Values shown are for illustration; exact values are determined at Section 10.1, step p of the General

Procedure.(3) Column to be filled in (Section 10.1, step q of the General Procedure) after determining ppm present

in stock R-124 (see Note 1 in Section 10.7 of the General Procedure).(4) Refer to Note 1 in Section 10.7 of the General Procedure.(5) These components are liquids at ambient laboratory temperature and are added to the 500 mL bulb

as described in Section 10.1 of the General Procedure, steps k through n.(6) From Section 10.1 of the General Procedure, step n.

47

Table 3. Primary Calibration StandardLiquid Impurities

Comp. Vol. Added, mL Density at 20°C g

C-316bb11312311

1112a

4.08.08.010.02.0

1.6441.5651.4701.487

1.439(10°C)

6.57612.52011.76014.8702.878



32(1)116111413414331

142b365mc1113

1225yeMet. Formate

1331318my-T1318my-C

1327123b

114B1123a216113a

123aB1122a1222341111

2.703.845.008.078.308.53

15.2215.3016.0616.1316.9219.0519.7021.0520.5022.9023.5023.6023.8027.1028.5032.7033.5035.3535.60

(1) 32 and 23 coelute. A one (1) ft. column section of Porapak-T attached to thedetector side of the column will resolve these two components—the 23 peakeluting first.

48

Part 12


Section 1. Scope









Section 5. Tables


49


50


ComponentDetection




Error, %

Methane2311613

143a13B111512

1113124a

115B1124133a114a123113

0.2547551104211411222

515200301030

0.20%251510152015253030

0.060.705.860.240.151.10

0.006%0.530.200.200.350.300.330.650.701.10

4.006.672.50-3.33-5.002.301.50-2.40-4.004.405.332.55-1.051.33-2.66-3.35



Added, µLµg

Added (1)ppm


Methane23

11613

143a13B1115(4)

121113124a

115B1124133a114a

123(5)113(5)

167013810484149154121116136199136118171153187

2115

0.10 mL20814(4)1485510810

14.042.556485.427.585.3

--69.238.127.940.755.838.869.9(6)(6)

515

207311031--251410152114265132

(1) If necessary, correct the µg added for the purity of the calibration component previously established.(2) Values shown are for illustration; exact values are determined at Section 10.1, step p.(3) Column to be filled in Section 10.1 step q of the General Procedure after determining ppm present in

stock R-125 (see Note 1 in Section 10.7).(4) Refer to Note 1 in Section 10.7.(5) These components are liquids at ambient laboratory temperature and are added to the 500 mL bulb as

described in 10.1, steps k through n.(6) From Section 10.1 step n.


Comp. Vol. Added, mL Density at 20°C g

R-113 12.0 1.565 18.78

R-123 20.0 1.470 29.40

51

Table 4. Retention Time Data for IdentifiedImpurities Not Normally Observed


114114

32(1)C2H4

C2H6

111422

134a218

C-318329

31-10114

1318my-T1318my-C

2271327

2.002.352.753.334.084.947.778.3210.614.415.019.121.520.7723.1024.024.85

(1) 32 and 23 coelute. A one (1) ft. column section of Porapak-T attached to the detector side of thecolumn will resolve these two components—the 23 peak eluting first.

52

Part 13

R-134a GC Method Data Sheet

Section 1. Scope

This GC Method Data Sheet is for use in conjunction withSection 10 of the General Procedure for the Determination ofPurity of New and Reclaimed Refrigerants by GasChromatography (hereafter referred to as General Procedure).This GC Method Data Sheet is for use with R-134a.


This method is applicable and calibrated for only thoseimpurities found in Table 2 and Table 3. Other impurities thathave been detected on occasion are listed (with retention times)in Table 4. This method will not detect any impurities that mayelute within the comparatively large R-134a peak matrix.



Packed column: Formed by joining in series the following 4columns in the following order given:

1. 1.83 m 5% Bentone 34/5%-SP-1200-on Supelcoport,100/200 mesh.

2. 6m 5% Krytox on Carbopack B, 60/80 mesh.

3. 4.88m x 3.17 mm OD stainless steel, 1% SP-1000 onCarbopack B, 60/80 mesh.

4. .35m Porapak T, 60/80 mesh.

NOTE: The Bentone column is attached to the injection port all columns are made from 3.17mm OD stainless steel tubing. The individual columns are conditioned separately before joining together. Columns are available from , Supelco, Bellefonte, PA.



Capillary Column: 120m (or 2-60m) DB-1301, 0.25mm,1µ, J&W Scientific Co.,Folsom, CA.

Detector FIDCarrier Gas approx. 1mL He/MinInjection Port Temp 150°CDetector Temp. 250°CSample 1.0 mLMax. Safe Column Temp. 280°CInitial Col. Temp -20°CInitial Hold 7 Min.Program 8 K/Min.Final Column Temp. 50°CPost Hold 5 Min.Split Ratio 30:1Pressure 240 kPaMakeup Gas 30 mL He/Min.Sub-ambient Cooling Liquid Nitrogen

See Note 6 of Section 10.7 of the General Procedure for theDetermination of Purity of New and Reclaimed Refrigerants byGas Chromatography.


Statistical parameters for each impurity are listed in Table 1.The data was obtained by analyzing an R-134a calibrationmixture 7 times during one day by one operator.

Section 5. Tables


53

Figure 1. Packed Column Gas Chromatogram of R-134a

54

Figure 2. Capillary Gas Chromatogram of R-134a

55


ComponentEffective Carbon

Number (1)Detection




Error, %

2332

1123143a125115

1243zf12

112212431

133a1336mzz

114114a11

1112a1121-C

1231121-T

113134152a

1234yf

0.160.621.932.120.790.762.840.351.761.330.921.932.901.041.100.431.641.751.761.751.601.611.082.65

421125121111122411212211

151520203060104015401525--30505015102030203030--

0.700.300.200.200.250.650.200.300.200.450.800.50

0.5(2)1.101.202.600.300.300.901.001.30.200.20

0.5(2)

1.81.2-0.81.53.2-1.3-3.61.82.22.01.71.7--

-3.34.32.6-0.2-6.7-3.34.31.71.40.8--

(1) Effective Carbon Numbers (ECN) were determined experimentally (see J. Chromatog. Sci., 30, 280, (1992).)(2) Precision estimated at 10 ppm based upon sample reproducibility.



Added, µLµg

Added (1)ppm


2332

1123143a125115134152a12

112212431

133a114114a11(4)

1112a(4)1121-C(4)

123(4)1121-T(4)

113(4)

70528284120154102661219813668118170170137133115153115188

12161414142228252081612121020

34.7334.0346.9848.1068.72139.05116.8167.4998.8932.2389.3233.6158.1769.46138.92

(6)(6)

(5,6)(6)

(5,6)(6)

1515202030605030431539

14.52530603018519

23.524

(1) If necessary, correct the µg added for the purity of the calibration component previously established.(2) Values shown are for illustration; exact values are determined at 10.1, step p of Part 1. Column to be

filled in (Section 10.1, step q) after determining ppm present in stock R-134a.(3) These components are liquids at ambient temperature and are added to the 500 mL bulb as described

in Section 10.1, steps k through n of the General Procedure.(5) 1121 typically contains about 17.5% cis isomer. µg 1121 added x 0.175 is assigned to the cis isomer,

the balance to the trans isomer.(6) From Section 10.1 of the General Procedure, step n.

56


Comp. Vol. Added, mLDensityat 20°C g

1131121C&T

12311

1112a

6.08.05.08.05.0

1.5651.4031.4701.487

1.439(10°C)

9.39011.2247.35011.8967.195

Table 4. Additional Impurities Observed in R-134a,Quantitation by Effective Carbon Number Method

1. Additional impurities occasionally observed in sample of R-134a are tabulated below.

ImpurityColumn Retention

Time (Min.) PackedColumn Retention

Time (Min.) CapillaryEffective CarbonNumber ECN (1)

1243zf1336mzz1234yf

22123a124a245cb1225ye1113263fb1140132b13

1318my-T1318my-C

18.2331.1218.20

29.5019.7518.5019.2119.2019.2118.5031.1212.1623.1824.60

14.98

13.7516.40

21.50

2.842.902.650.401.841.272.602.421.692.952.081.900.232.952.95

(1) Refer to J. Chromatog. Sci., 30, 280, (1992).

2. Quantitation by ECN Method

Select a nearby peak in the chromatogram whose identification and response factor (RF) have been established (theInternal Standard).

Then:

RFI = ECNr x MWi

ECNI MWr

Where: RF = either Absolute or Relative Response Factor.MWi = molecular weight of the component to be determined.MWr = molecular weight of the Internal Standard Reference.

57

Part 14

R-143a GC Method Data Sheet

Section 1. Scope

This GC Method Data Sheet is for use in conjunction withSection 10 of the General Procedure for the Determination ofPurity of New and Reclaimed Refrigerants by GasChromatography (hereafter referred to as General Procedure).This GC Method Data Sheet is for use with R-143a.


This method is applicable and calibrated for only thoseimpurities found in Table 2. This method will not detect anyimpurities that may elute within the comparatively large R-143apeak matrix.


3.1 Chromatographic Equipment and Conditions, Combination Packed Column.

Packed column: Formed by joining in series the following 4columns in the following order given:

1. 1.83 m 5% Bentone 34/5%-SP-1200-on Supelcoport,100/200 mesh.

2. 6m 5% Krytox on Carbopack B, 60/80 mesh.

3. 4.88m x 3.17 mm OD stainless steel, 1% SP-1000 onCarbopack B, 60/80 mesh.

4. 0.35m Porapak T, 60/80 mesh.

NOTE: The Bentone column is attached to the injection port all columns are made from 3.17mm OD stainless steel tubing. The individual columns are conditioned separately before joining together. Columns are available from, Supelco, Bellefonte, PA.


3.2 Chromatographic Equipment and Conditions, 1% SP-1000 Packed Column

Packed Column: 7.32m x 3.17 m OD stainless steel, 1% SP-1000 on Carbopack B, 60/80 mesh,

Supelco, Bellefonte, PA.

Detector FIDInjection Port Temp 200°CDetector Temp. 250°CSample 0.50 mL (gas syringe)Max. Safe Column Temp. 225°C (for conditioning purposes)Initial Col. Temp 35°CInitial Hold 7 Min.Program 10 K/Min.Final Column Temp. 150°C


Statistical parameters for each impurity are listed in Table 1.The data was obtained by analyzing an R-143a calibrationmixture 7 times during one day by one operator.

Section 5. Tables


58

Figure 1. 1% SP-1000 Packed Column Gas Chromatogram of R-143a

59

Figure 2. Combination Packed Column Gas Chromatogram of R-143a

60


ComponentDetection




Error, %

412332

C2H4

C2H6

152a40

125134a22

142b1113124

isobutane114a

n-butaneC3H8

115121612

14111238561231511325

30252055

50404025406515255

3555

752540

0.531.190.730.530.371.811.532.131.871.191.430.870.730.330.870.330.472.131.010.88

-1.00.82.1-3.7-4.22.61.32.7-1.21.81.2-0.92.18.2-0.85.1-3.70.9-1.73.1



Added, µLµg

Added (1)ppm


412332

C2H4

C2H6

152a40125134a22

142b1113124

isobutane114a

n-butaneC3H8

115121612

34705228306650

12010286

10011613658

1705844

154150121

40161888

353515102030686

1065

228

15

55.745.838.39.99.894.572.373.641.770.8

123.328.644.714.269.714.29.0

139.049.174.2

29242055503838223765152383785732639

(1) If necessary, correct the µg added for the purity of the calibration component previously established.(2) Values shown are for illustration; exact values are determined in Section 10.1, step p of the General

Procedure.(3) Column to be filled in (Section 10.1, step q of the General Procedure) after determining ppm present in

stock R-143a (see Note 1 in Section 10.7 of the General Procedure).

61

PART 15

DETERMINATION OF COMPONENT CONCENTRATIONS OFREFRIGERANT 400 AND 500 SERIES BLENDS AND AZEOTROPES BY

GAS CHROMATOGRAPHY

Section 1. Purpose

The purpose of this test method is to determine the componentcompositions of new and reclaimed Refrigerants 400 (R-400)and 500 (R-500) blends and azeotropes by Gas Chromatography(GC). This method utilizes one (1) GC packed column toseparate and quantify the individual components for all of therefrigerant blends and azeotropes.

Section 2. Scope

This test method is for use with all R-400 and R-500 blends andazeotropes as outlined in Section 11.


Definitions for this part are identical to those of ARI Standards700-95 and 740-95.


The compositions of new and reclaimed blends and azeotropesare determined by either isothermal or programmed temperaturegas chromatography using a packed column and a thermalconductivity detector (TCD). Component peak areas areintegrated electronically and quantified by the areanormalization-response factor method by reference to a suitablecalibration standard prepared to closely match the expectedcomposition of the particular blend.


This method is applicable to the determination of thecomposition of new and reclaimed R-400 and R-500 blends andazeotropes.


This method is calibrated for each of the respective R-400 andR-500 blends. If components other than those comprising thegiven mixture are present in significant amounts, results can beerroneous and/or misleading. Any impurity that coelutes withone of the blend components will interfere if present insignificant concentration. This method is limited to thecomposition of the blends and does not address the organicpurity of the blend sample.


Values for these statistical parameters are given in theappropriate GC Method Data Sheet.



1. Programmable temperature gas chromatograph, singleor dual packed column, TCD detector, low sensitivityposition: Model 6890, Hewlett Packard, Wilmington,DE.

2. Electronic integrator: Model# 3396 or suitable dataacquisition system and GC software, Hewlett Packard,Wilmington, DE.

3. Packed column: 7.32 m x 3.17 mm OD stainless steel,1% SP-1000 on Carbopack B, 60/80 mesh. Thiscolumn may be assembled by attaching two or threeshorter columns together in series. Condition O/N at225°C. Supelco, Bellefonte, PA.

4. Gas collecting tube: 250 mL, LG-8601, Lab Glass Inc.,Vineland, NJ. (Enlarge side outlet opening toaccommodate a crimp-on 2-cm septum. Applyfiberglass tape outside for protection from breakage).


6. Syringe, Gastight, 1.0 mL, Hamilton 1001TLL; Supelco,P/N 2-0997M.

7. HP Steel Cylinder, EFB-56, 400 psig, single #9 valve(#1014-C Superior Valve), 3/8” pipe neck,approximately 925 mL internal volume, E.F. Britten Co.,Cranford, NJ.

8. VHP Stainless Steel Cylinder, 1L, 1800 psig, 304L-HDF4-100. Valve SS-IRS4-A, Whitey, WilmingtonValve and Fitting, Co., New Castle, DE.

62

9. The fluorochemicals may be purchased from Lancaster,Windham, NH and Synquest, Inc., Alachua, FL. Thehydrocarbons may be purchased from Scott SpecialtyGases, Inc., Plumbsteadville, PA.

NOTE: The purity of each calibration component must bepredetermined by gas chromatography and, ifnecessary, by GC/Mass Spectroscopy (GC-MS).

Section 9. Procedure

9.1 Calibration Standard Preparation

NOTE: The following procedure is generalized and is followedfor the preparation of each blend calibration standard.The weights of each blend component to be added andthe order of addition are given in the appended GCMethod Data Sheets for each respective refrigerantblend. Normally, the least volatile components areadded first. Refer to Note 1 for additional information.

a. Pressure test the clean, dry calibration standard cylinder toabout 2000 kPa (using N2) to insure there are no leaks.

b. Evacuate the cylinder to below 0-10 kPa (i.e. fullvacuum). Close the valve and record the cylinder weightto the nearest 0.1 g (i.e. tare weight)

c. Using the Teflon transfer line, loosely connect thecylinder containing the first component to be added to thecalibration standard cylinder. Briefly purge the transferline, then connect tightly to the standard cylinder valve.

d. Transfer the calculated weight (approximately) of thecomponent to the standard cylinder.

NOTE: If the amount added is less than desired, the cylinder ispurged until the desired weight is obtained. Purgingthe cylinder is permitted only during addition of thefirst component.

e. Reweigh and record the cylinder weight. This weight lessthe tare weight (step b) gives the weight of the first addedcomponent.

f. Externally cool the calibration cylinder in an ice waterbath for at least 20 minutes (Refer to Note 4).

g. Connect the Teflon transfer line from the secondcomponent cylinder and transfer the desired weight of thesecond component as was done above.

NOTE: Generally, it is simpler to prepare a second cylindercontaining the exact weight of the second componentto be added, then transferring the entire contents (ornearly so) into the calibration standard cylinder.

h. Close the cylinder valves, remove the transfer line,remove the calibration standard cylinder from the icewater bath, and allow the cylinder and contents to warmto ambient laboratory temperature.

i. After drying the cylinder externally, weigh the calibrationstandard cylinder and then subtract the gross weightrecorded in step e. The net difference is the weight of thesecond added component.

j. Repeat above steps f through i for a third and (ifnecessary) for a fourth component.

k. Add the weights of all the added components and thendetermine the weight percentage (to the nearest 0.01%) ofeach component in the calibration mixture. If necessary,correct the individual component percentages for thepurities determined in Section 8.

l. Attach a label to the calibration standard cylindercontaining the name of the refrigerant standard, weightpercentage of each component present, date ofpreparation, total gross weight (i.e. cylinder pluscontents), and gross weight for renewal (See Note 2).Store the standard in a cool, secure location.

9.2 Determination of Component Response Factors

a. Set-up the cylinder sampling apparatus as shown inFigure 1. The plastic line connecting metering valve “E”to the gas bulb valve “B” must be kept as short as possibleas to minimize component fractionation during thetransfer.

b. With valves “E”, “B”, and “C” open, slowly open valve“D” and evacuate the apparatus up to cylinder valve “A”.Close valve “D” and insure the system is holding vacuum.

c. Close valve “E” and then open cylinder valve “A”.

d. Slowly open valve “E” and introduce sample into the gasbulb until the vacuum gauge reads 102 kPa pressure.Close valve “A”.

e. Repeat steps b through d.

f. Set the GC integrator (or work station) for an areanormalization response factor calibration run.

g. Set the GC to the operating conditions given in the GCMethod Data Sheet for the refrigerant blend to becalibrated. The TCD is always set in the least sensitiveposition for all blend component analyses.

h. Using the 1.0 mL syringe, withdraw vapor sample fromthe gas bulb and inject into the GC. Withdraw slowly,

63

allowing sufficient time (5 seconds) for the calibrationstandard to fill the syringe.

i. Repeat the GC analysis twice more.

j. Store the average of the three determined RelativeResponse Factors for each blend component in theMethod Table as follows:

ii

A

Std. Cal.in i Comp. Wt% ARF =

n

ii ARF

ARFRRF =

Where:

ARFi = absolute response factor for component i.ARFn= absolute response factor for the component with the

highest weight percentage in the mixture. RRFi = relative response factor for component i.Ai = peak area of component i.

NOTE: RRFn will always equal 1.0. The largest component(peak area) is normally selected as the reference peak.RRF values are computed to the nearest 0.0001 unit.

9.3 Sampling

High Pressure (HP) sample cylinders should be filled at least80% but no more than 90% liquid full. This will both minimizecomponent fractionation within the sample container and willavoid overfilling for safety considerations. Very high-pressure(VHP) sample cylinders (vapor phase) may be filled to less thansaturation pressure, if desired.

9.4 Sample Analysis

Analyze the sample using the chromatographic conditionsdescribed in the GC Method Data Sheet. Load the sample asillustrated in Figure 1 in the same manner as described for theGC method calibration standard. Questionable sample resultsare most often resolved by re-analysis of the calibrationstandard. The temperature of the sample must equal(essentially) that of the calibration standard at the time of GCcalibration. In the case of VHP refrigerants, the sample must beat or above the critical temperature before analysis.

9.5 Calculations


∑=

)RRF x (A

A x RRF x 100W

ii

iii

Where:



Report weight percentage results to the nearest 0.01%. (Note 3)

Section 10. Notes

1. The weights of each HP Standard component to be addedhave been calculated such that, after final loading, the HPstandard cylinder will be about 90% filled with liquidphase. This is not the case for the very high-pressure(VHP) standards whose critical temperatures are either ator below ambient laboratory temperatures. For VHPstandards (R-508, for example), the refrigerant vaporphase is used for calibration and sample analysis.Because of pressure considerations, two calibrationstandard cylinders are used, one for HP and the other forVHP refrigerants. In cases where one refrigerant blendhas more than one composition (for example, R-401A andR-401B), where possible, just one calibration standard isprepared with composition approximately the average ofthe A and B compositions.

2. Experimental data has shown that vapor/liquid phaseequilibrium for several R-400 series blends is essentiallyconstant within a container following removal (and afterre-equilibration) of about one third of the original liquidphase from the cylinder (see Reference 1). Hence, afreshly prepared calibration standard with 90% liquidphase will retain its original component ratio until theliquid phase has been depleted to below 60% of thecylinder volume—at which point the standard should berenewed. This renewal point is conveniently determinedby subtracting the cylinder tare weight from the finalcylinder gross weight, taking 66% of this difference, andthen adding the tare weight to this 66% value. This value(recorded on the calibration standard label) is the cylindergross weight at which the HP standard should be renewed.This equilibrium consideration does not apply to the VHPstandards that are all vapor at ambient laboratorytemperature.

3. The sum of the individual component weight percentageswill not necessarily equal 100.00%. This proceduredetermines the blend component amounts present anddoes not address other volatile organic impurities that aremore or less present in the mixture.

4. In preparing the VHP refrigerant calibration standards, itis usually necessary to externally cool the 1L cylinder in

64

dry ice in order to add the remaining refrigerantcomponents.


Table 1. GC Method Data SheetsRefrigerant GC Method Data

Sheet PartNumber

R-401 Part 16R-402 Part 17

R-403B Part 18R-404A Part 19R-406A Part 20R-407 Part 21

R-408A Part 22R-409 Part 23R-410 Part 24R-411 Part 25R-412 Part 26R-500 Part 27R-502 Part 28R-503 Part 29R-507 Part 30R-508 Part 31R-509 Part 32


1. Vapor-liquid equilibrium studies regarding liquid phasedepletion have been examined for R-407C, R-408A, R-409A, and R-416A, unpublished work, NationalRefrigerants, Inc., Rosenhayn, NJ.

2. Air-Conditioning and Refrigeration Institute, Appendix Cto ARI Standard 700-95: Analytical Procedures for ARIStandard 700-95, 4301 North Fairfax Drive, Arlington,Virginia 22203.

3. Methods Development for Organic ContaminantDetermination in Fluorocarbon Refrigerant Azeotropesand Blends, Final Report, Nov. 30, 1997, ARTI MCLRProject Number 665-54600, Integral Sciences Inc.,Columbus, OH.

65


66

Part 16

R-401 Composition GC Method Data Sheet

Section 1. Gas Chromatographic Conditions

Detector TCD, Low SensitivityCarrier Gas 30 mL He/Min.Initial Column Temp. 75°CInitial Hold 5 Min.Program 20 K/Min.Final Column Temp. 175°CPost Hold 5 Min.Sample 1.0 mL (gas syringe)Detector Temp. 250°CInj. Port Temp. 200°CMax Safe Column Temp. 225°C (for conditioning purposes)

Table 1. Blend Component Weight %

R-401 Blend Wt%

Component R-401A R-401B Tolerance GCRetention

Time

R-152a

R-22

R-124

13.0

53.0

34.0

11.0

61.0

28.0

+.50,-1.50

±2.0

±1.0

6.20

6.60

10.55

Section 2. Precision, and Accuracy

Statistical parameters for each impurity are listed below. Thedata was obtained by analyzing an R-401 calibration mixture 7times during one day by one operator.


R-401Component

95% CL

Relative MeanError, wt%

R-22R-152aR-124

±0.03%±0.03%±0.06%

0.060.220.17

Section 3. Calibration Standard Preparation

The following table is to be used in conjunction with Part 15,The Determination of the Component Concentrations ofRefrigerant 400 and 500 Series Blends and Azeotropes by GasChromatography.

Table 3. Blend Calibration Standard Preparation

R-401Component

Amount to Weigh(g)

ApproximateWeight %

R-124

R-152a

R-22

307

119

564

31

12

57


67

68

Part 17




Table 1. Blend Component Wt %

R-402 Blend Wt%

Component R-402A R-402B Tolerance GCRetention

Time(Min)

R-125

R-22

HC-290

60.0

38.0

2.0

38.0

60.0

2.0

±2.0

±2.0

±1.0

6.00

6.95

9.40




R-402Component

95% CL


R-125R-22

HC-290

±0.010%±0.009%±0.001%

0.080.070.07




Amount to Weigh(g) Approximate Weight

% R-402Component

R-402A R-402B R-402A R-402B

HC-290

R-22

R-125

19

364

575

19

578

366

2

38

60

2

60

38


69

70

Part 18

R-403B Composition GC Method Data Sheet


Detector TCD, Low SensitivityCarrier Gas 30 mL He/Min.Initial Column Temp. 100°C (isothermal)Initial Hold -- Min.Program -- K/Min.Final Column Temp. 100°CPost Hold 10 Min.Sample 0.25 mL (gas syringe)Detector Temp. 250°CInj. Port Temp. 200°CMax Safe Column Temp. 225°C (for conditioning purposes)

Table 1. Blend Component Wt. %

R-403 Blend Wt%

Component R-403B

(%)

Tolerance

(%)

GC RetentionTime (Min.)

R-22

FC-218

HC-290

56.0

39.0

5.0

±2.0

±2.0

±0.2

5.20

6.20

7.20


Statistical parameters for each impurity are listed below. Thedata was obtained by analyzing an R-403B calibration mixture 7times during one day by one operator.


R-403BComponent

95% CL


R-22FC-218HC-290

±0.018%±0.019%±0.024%

0.090.101.62




R-403BComponent

Amount to Weigh(g)

ApproximateWeight %

FC-218

HC-290

R-22

374

48

537

39

5

56

Figure 1. Gas Chromatogram of R-403B

71

72

Part 19

R-404A Composition GC Method Data Sheet




R-404 Blend Wt%

Component R-404A

(%)

Tolerance

(%)


R-125

R-143a

R-134a

44.0

52.0

4.0

±1.0

±1.0

±1.0

10.90

9.55

11.60


Statistical parameters for each impurity are listed below. Thedata was obtained by analyzing an R-404A calibration mixture 7times during one day by one operator.


R-404AComponent

95% CL


R-125R-143aR-134a

±0.017%±0.024%±0.038%

0.0230.0970.740




R-404AComponent

Amount to Weigh(g)

ApproximateWeight %

R-134a

R-143a

R-125

35

454

384

4

52

44

Figure 1. Gas Chromatogram of R-404A

73

74

Part 20



Detector TCD, Low SensitivityCarrier Gas 30 mL He/Min.Initial Column Temp. 150°C (Isothermal)Initial Hold -- Min.Program -- K/Min.Final Column Temp. 150°CPost Hold 9 Min.Sample 1.0 mL (gas syringe)Detector Temp. 250°CInj. Port Temp. 200°CMax Safe Column Temp. 225°C (for conditioning purposes)


R-406 Blend Wt%

Component R-406A

(%)

Tolerance

(%)


R-142b

HC-600a

R-22

41.0

4.0

55.0

±1.0

±1.0

±2.0

3.90

5.30

2.85




R-406AComponent

95% CL


R-142bHC-600a

R-22

±0.060%±0.009%±0.023%

-0.120.250.07




R-406AComponent

Amount to Weigh(g)

ApproximateWeight %

HC-600a

R-142b

R-22

37

380

509

4

41

55


75

76

Part 21




Table 1A. Blend Component Wt. % for R-407A

R-407ABlend

Wt%

Component R-407A

(%)

Tolerance

(%)

GC Retention Time(Min.)

R-32

R-125

R-134a

20.0

40.0

40.0

±1.0

±2.0

±2.0

4.05

9.30

9.90


Statistical parameters for each impurity are listed below. Thedata was obtained by analyzing an R-407C calibration mixture 7times during one day by one operator.


R-407CComponent

95% CL


R-32R-125

R-134a

±0.020%±0.052%±0.059%

0.130.060.03




R-407AComponent

Amount to Weigh(g)

ApproximateWeight %

R-134a

R-32

R-125

380

190

380

40

20

40

Table 1B. Blend Component Wt. % for R-407B

R-407BBlend

Wt%

Component R-407B

(%)

Tolerance

(%)


R-32

R-125

R-134a

10.0

70.0

20.0

±1.0

±2.0

±2.0

4.05

9.30

9.90

Table 1C. Blend Component Wt. % for R-407C

R-407CBlend

Wt%

Component R-407C

(%)

Tolerance

(%)


R-32

R-125

R-134a

23.0

25.0

52.0

±1.0

±2.0

±2.0

4.05

9.30

9.90

R-407BComponent

Amount to Weigh(g)

ApproximateWeight %

R-134a

R-32

R-125

194

97

680

20

10

70

R-407CComponent

Amount to Weigh(g)

ApproximateWeight %

R-134a

R-32

R-125

502

222

241

52

23

25


77

78

Part 22



Detector TCD, Low SensitivityCarrier Gas 30 mL He/Min.Initial Column Temp. 40°C (isothermal)Initial Hold 6 Min.Program 10 K/Min.Final Column Temp. 130°CPost Hold 0 Min.Sample 1.0 mL (gas syringe)Detector Temp. 250°CInj. Port Temp. 200°CMax Safe Column Temp. 225°C (for conditioning purposes)

Table 1. Blend Component Wt %

R-408ABlend

Wt%

Component R-408A

(%)

Tolerance

(%)


R-143a

R-125

R-22

46.0

7.0

47.0

±1.0

±2.0

±2.0

8.45

9.85

10.55




R-408AComponent

95% CL


R-125

R-143a

R-22

±0.015%±0.034%±0.023%

0.0010.0440.044




R-408AComponent

Amount to Weigh(g)

ApproximateWeight %

R-143a

R-22

R-125

407

416

62

46

47

7


79

80

Part 23





R-409 Blend Wt%

Component R-409A

(%)

R-409B

(%)

Tolerance

(%)

GCRetention

Time(Min)

R-22

R-142b

R-124

60.0

15.0

25.0

65.0

10.0

25.0

±2.0

±1.0

±2.0

5.20

9.50

11.00




R-409Component

95% CL


R-22R-142bR-124

±0.027%±0.039%±0.027%

-0.03-0.130.17




R-409Component

Amount to Weigh(g)

ApproximateWeight %

R-124

R-142b

R-22

255

153

611

25

15

60


81

82

Part 24





R-410Blend

Wt%

Component R-410A

(%)

R-410B

(%)

Tolerance

(%)

GCRetention

Time(Min)

R-32

R-125

50.0

50.0

45.0

55.0

-1.50, +.50,±1.0

_________

-.50, +1.50,±1.0

3.00

4.60


Statistical parameters for each impurity are listed below. Thedata was obtained by analyzing an R-410B calibration mixture 7times during one day by one operator.


R-410Component

95% CL


R-32

R-125±0.030%±0.025%

0.0470.13




R-410Component

Amount to Weigh(g)

ApproximateWeight %

R-32

R-125

430

465

48

52


83

84

Part 25




Table 1A. Blend Component Wt. % for R-411A

R-411ABlend

Wt%

Component R-411A

(%)

Tolerance

(%)

GCRetention

Time (Min.)

R-152

HC-1270

R-22

11.0

1.5

87.5

+0, -1.0

+0, -1.0

+2.0, -0

6.15

6.60

9.55


Statistical parameters for each impurity are listed below. Thedata was obtained by analyzing an R-406A calibration mixture7 times during one day by one operator.


R-411Component

95% CL


R-152aHC-1270

R-22

±0.004%±0.002%±0.002%

00.09

0




R-411AComponent

Amount to Weigh(g)

ApproximateWeight %

HC-1270

R-152a

R-22

28

46

855

3.0

5.0

92.0

Table 1B. Blend Component Wt. % for R-411B

R-411BBlend

Wt%

Component R-411A

(%)

Tolerance

(%)


R-152

HC-1270

R-22

3.0

3.0

94.0

+0, -1.0

+0, -1.0

+2.0, -0

6.15

6.60

9.55

Table 1C. Blend Component Wt. % for R-411C

R-411CBlend

Wt%

Component R-411A

(%)

Tolerance

(%)


R-152

HC-1270

R-22

1.5

3.0

95.5

+0, -1.0

+0, -1.0

+2.0, -0

6.15

6.60

9.55


85

86

Part 26





R-412ABlend

Wt%

Component R-412A

(%)

Tolerance

(%)


R-22

FC-218

R-142b

70.0

5.0

25.0

±2.0

±2.0

±1.0

3.9

4.5

6.9




R-412AComponent

95% CL


R-22FC-218R-142b

±0.034%±0.014%±0.037%

00.230.4




R-412AComponent

Amount to Weigh(g)

ApproximateWeight %

R-142b

FC-218

R-22

244

49

682

25

5

70


87

88

Part 27





R-500 Wt%

Component R-500

(%)

Tolerance

(%)


R-152a

R-12

26.2

73.8

±1.0

±1.0

2.60

3.15




R-500Component

95% CL


R-12

R-152a

±0.011%

±0.011%

0.05

0.16




R-500Component

Amount to Weigh(g)

ApproximateWeight %

R-12

R-152a

718

255

73.8

26.2


89

90

Part 28





R-502 Wt%

Component R-502

(%)

Tolerance

(%)


R-22

R-115

48.8

51.2

±4.0

±4.0

2.85

3.30




R-502Component

95% CL

Relative MeanError, Wt%

R-22

R-115

±0.062%

±0.062%

0.06

0.06




R-502Component

Amount to Weigh(g)

ApproximateWeight %

R-22

R-115

495

519

48.8

51.2


91

92

Part 29





R-503 Wt%

Component R-503

(%)

Tolerance

(%)


R-23

R-13

40.0

60.0

±1.0

±1.0

2.85

3.95




R-503Component

95% CL


R-23

R-13

±0.02%

±0.02%

0.03

0.03




R-503Component

Amount to Weigh(g)

ApproximateWeight %

R-23

R-13

200

300

40

60


93

94

Part 30





R-507 Wt%

Component R-507

(%)

Tolerance

(%)


R-143a

R-125

50.0

50.0

±1.0

±1.0

7.00

8.15




R-507Component

95% CL


R-143a

R-125

±0.049%

±0.047%

0.11

-0.15




R-507Component

Amount to Weigh(g)

ApproximateWeight %

R-143a

R-125

488

488

50

50

95


96

Part 31




Table 1A. Blend Component Wt. % R-508A

R-508 Wt%

Component R-508A

(%)

Tolerance

(%)


R-23

R-116

39.0

61.0

±2.0

±2.0

2.80

3.35

Table 1B. Blend Component Wt. % R-508B

R-508 Wt%

Component R-508B

(%)

Tolerance

(%)


R-23

R-116

46.0

54.0

±2.0

±2.0

2.80

3.35




R-508BComponent

95% CL


R-23

R-116

±0.020%

±0.020%

0.043

0.028




R-508Component

Amount to Weigh(g)

ApproximateWeight %

R-23

R-116

342

258

57

43


97

98

Part 32





R-509 Wt%

Component R-509

(%)

Tolerance

(%)


R-22

FC-218

44.0

56.0

±2.0

-0, +4.0

5.20

5.90




R-509Component

95% CL


R-22

FC-218

±0.044%

±0.041%

0.10

0.08




R-509Component

Amount to Weigh(g)

ApproximateWeight %

FC-218

R-22

597

469

56

44


99

100

PART 33

GENERAL PROCEDURE FOR THE DETERMINATION OF PURITY OF NEW AND RECLAIMED REFRIGERANT BLENDS AND

AZEOTROPES BY GAS CHROMATOGRAPHY

Section 1. Purpose

The purpose of this test method is to determine the purity ofnew and reclaimed Refrigerants 400 (R-400) and 500 (R-500)series blends and azeotropes by Gas Chromatography (GC).

Section 2. Scope

This test method is for use in conjunction with the GC MethodData Sheets for the refrigerants listed in Section 11 of thismethod.


Definitions for this part are identical to those of ARI Standards700-95 and 740-95.


The organic purity of new and reclaimed refrigerant blends andazeotropes is determined by programmed temperature gaschromatography using a packed column and a flame ionizationdetector (FID). Component peak areas are integratedelectronically and quantified by the area normalization-responsefactor method.


This method is applicable to the determination of the impuritiestypically present in new and reclaimed refrigerants.


For new refrigerant blends and azeotropes, it is imperative thatthe constituent components of the blend be separately analyzedprior to blending; this will permit greater scrutiny than analysisafter blending. This method will not detect any impurity thatmay elute with one of the blend components.

If blend composition determination is desired, refer to Part 15,Determination of the Component Concentrations of Refrigerant400 and 500 Series Blends and Azeotropes by GasChromatography.


7.1 Sensitivity

Values for these statistical parameters are given in Table 1Aand 1B of each respective refrigerant’s GC Method Data Sheet.



1. Gas chromatograph: Model 5890, equipped with FID,Hewlett Packard, Wilmington, DE.

2. Electronic integrator: Model# 3396, Hewlett Packard,Wilmington, DE.

3. Packed column: formed by joining together two 7.32 mx 3.17 mm OD stainless steel, 1% SP-1000 onCarbopack B, 60/80 mesh, Supelco, Bellefonte, PA.

4. Glass collecting tubes: 500 mL, 250 mL and 125 mL,LG-8601, Lab Glass Inc., Vineland, NJ. (Enlarge sideoutlet opening to accommodate a crimp-on 2-cm septum.Apply fiberglass tape outside for protection frombreakage)


6. Deflected point needles: Cat# 7174, #22, Popper andSons, Inc., New Hyde Park, NY.

7. Swivel union: US44, United Refrig. Inc., Philadelphia,PA.

8. Serum bottle: 125 mL, (Note: Bottle holds 160 mL whenliquid full.) Cat# 223748, Wheaton Glass, Vineland, NJ.

9. Impurities for calibration standard preparation: Thefluorochemicals may be purchased from Lancaster,Windham, NH and Synquest, Inc., Alachua, FL. Thehydrocarbons may be purchased from Scott SpecialtyGases, Inc., Plumbsteadville, PA. All other impuritiesmay be purchased from Aldrich, Milwaukee, WI. SeeTable 2 of the GC Method Data sheet for the specificimpurities required for each refrigerant.

NOTE: The purity of each calibration component must bepredetermined by gas chromatography and, ifnecessary, by GC/Mass Spectroscopy (GC-MS).

10. Stainless steel cylinder: 1L, 304L-WDF4-1000, and300mL cylinder, 304L-WDF4-300, 1/4" pipe, WhiteyCo., Highland Heights, OH.

Section 9. Procedure

NOTE: The following procedure is generalized for thedetermination of purity for blends and azeotropes.Each respective GC Method Data Sheet contains thechromatogram, statistical parameters and impurities tobe added for calibration standard preparation.

101

9.1 Chromatographic Operating Conditions

Detector FIDCarrier Gas Helium; 28 ml min-1

Initial Column Temp. 35º CInitial Hold 14 minProgram 10 K min-1

Final Column Temp. 160º CPost Hold 34 minSample 500 µl loopDetector Temp. 200º CInjection Port Temp. 150º C

9.2 Calibration Standard Preparation: Major Components

NOTE: The procedure here is generalized and is followed forthe preparation of each blend calibration standard. Theweights of each blend component to be added and theorder of addition are given in the appended GCMethod Data Sheets for each respective refrigerantblend. Normally, the least volatile components areadded first. To determine the composition of theprepared blends and azeotropes, refer to Part 15,Determination of the Component Concentrations ofRefrigerants 400 and 500 Series Blends andAzeotropes by Gas Chromatography.

a. Evacuate a clean, dry 1L stainless steel CalibrationStandard cylinder to 25 Pa. Break the vacuum and allowthe cylinder to fill with air. Re-evacuate the cylinder to25 Pa.

b. Weigh the Calibration Standard cylinder to the nearest0.01 gram.

c. Using a Teflon flex transfer line, attach the CalibrationStandard cylinder to the first component supply cylinder(liquid phase valve) via a vacuum manifold and absolutepressure gauge (refer to Table 1C of the appropriate GCMethod Data Sheet).

d. Gradually open the metering valve and add the firstcomponent as a vapor (vaporized liquid phase) until thegauge reaches the pressure indicated in Table 1C of theGC Method Data Sheet.

NOTE: If too much refrigerant component is added, thecylinder must be vented. Venting is permitted onlyduring addition of the first component and notthereafter.

e. Close the Calibration Standard cylinder valve, remove itfrom the vacuum manifold, and reweigh the cylinder tothe nearest .01g.

f. Subtract the cylinder tare weight (step b) from the weightin step e and record the as the weight of the firstcomponent.

g. Repeat steps c through f for the second component.

NOTE: It is often simpler to prepare a second cylindercontaining the exact weight of the second and also

subsequent components to be added—then transferringthe entire contents (or nearly so) into the CalibrationStandard cylinder using dry ice or liquid nitrogen toexternally cool the Calibration Standard cylinder.Allow the cylinder to warm to ambient temperaturebefore weighing.

h. Repeat steps c through f for a third and (if necessary) afourth component.

i. Add the weights of all the added components and thendetermine the weight percentage (to the nearest 0.01%) ofeach component in the component mixture. If necessary,correct the individual component percentages for thepurities determined in the Note of Section 8.9. (Also, seeNote 1 of Section 10)

9.3 Calibration Standard Preparation: Addition ofContaminants

a. Attach a Swagelok nut and septum to the CalibrationStandard cylinder and then chill the base of the cylinder inliquid nitrogen for 15 minutes. Do not purge the cylinderwhen attaching the septum, as this would alter therelationship between the blend components and thecontaminants. Instead, the small amount of air behind theseptum is permitted to enter the standard when the valveis opened.

b. Verify that the septum is still attached securely, then openthe cylinder valve while keeping the cylinder immersed inthe liquid nitrogen.

c. Using appropriately sized vapor syringes, individually andin turn add the gaseous contaminants listed in Table 2 ofeach respective GC Method Data Sheet in the amountsindicated. This is done by flashing liquid phase into thegas bulb shown in Figure 1 and then withdrawing thespecified amount of vapor into the gas tight syringe andinjecting through the septum attached to the cylinder. Theindicated vapor densities are based on a laboratorytemperature of 20.0º C and a barometric pressure of 100.0kPa. This data must be adjusted to reflect actuallaboratory conditions.

d. Using appropriately sized liquid syringes, individuallyand in turn add the liquid contaminants listed in Table 2 inthe amounts indicated (Special care must be taken toaccount for the syringe needle volume). For bestaccuracy, these contaminants and syringes should bepre-chilled in a freezer (approximately -20º C) andpromptly transferred. The indicated liquid densities arebased on a liquid temperature of 0º C and a barometricpressure of 100.0 kPa. This data must be adjusted toreflect the actual conditions surrounding the transfer.

e. Close the Standard Cylinder valve and allow theCalibration Standard cylinder to return to ambienttemperature. Set the cylinder aside for a minimum of 12hours to allow the cylinder’s contents to equilibrate. Rollthe cylinder while still cold for at least 4 hours to ensurethorough mixing.

102

f. Using a gas tight syringe, withdraw the vapor samplefrom the Calibration Standard cylinder andchromatograph the exact volume listed in Section 9.1. Ifa gas sampling loop is attached to the GC, purge the loopwith the calibration standard, allow the loop to return toatmospheric pressure and then inject the sample into theGC. Chromatograph the standard as indicated in Section9.1, and adjust the standard’s recorded component andcontaminant levels, in milligrams, to account for anysignificant impurities present in the starting materialsusing the method of Standards Addition (see Note 1 inSection 10).

g. Determine the weight percentage of each majorcomponent and each contaminant in the calibrationstandard using the formula:

Std. Cal. of Mass Total

Std.) Cal.in x of Mass)(100( xWt% =

Weight percentages are calculated to the nearest 0.01%for each major component and to the nearest 0.0001% foreach contaminant.

9.4 Determination of Major Component Response Factors

a. Analyze the standard in triplicate using thechromatographic conditions given in Section 9.1.Because the standard is vapor phase, it can be transferreddirectly to the gas chromatograph (via the gas samplingloop or gas sampling bulb/syringe) without furtherpreparation or sampling.

b. Average the peak areas obtained for each majorcomponent of either the blend or azeotrope.

c. Calculate relative response factors (RRF’s) for each majorcomponent as follows:

ii

A

Std. Cal.in i Comp. Wt% ARF =

Where:

RRFi = relative response factor for component i.Ai = peak area of component i.

Then, using the component with the highest area count inthe mixture as the reference peak the RRF Factors aredetermined as follows:

x

ii ARF

ARFRRF = and

1ARF

ARFRRF

x

x ==x

ARFi = absolute response factor for component i.ARFx = absolute response factor for the component withthe highest area count in the mixture.RRFi = relative response factor for component i.

RRFx = relative response factor for the component withthe highest area count in the mixture.

RRF values are computed to the nearest 0.0001 unit.

9.5 Determination of Contaminant Response Factors

Using the highest area count major component as thereference peak, determine and record each contaminant’srelative response factor (RRF) as follows:


Aii

=

Where:

ARFi = Absolute Response Factor of contaminant i.Ai = peak area of component i (average of 3

determinations).

Then using the highest area count component in theblend as the reference peak:

RRFi =

Again, RRFi values are computed to the nearest 0.0001unit.

9.6 Sampling

High Pressure (HP) sample cylinders should be filled at least80% but no more than 90% liquid full. This will both minimizecomponent fractionation within the sample container and willavoid overfilling for safety considerations. Very high pressure(VHP) sample cylinders (vapor phase) may be filled to less thansaturation pressure, if desired.

9.7 Sample Analysis

Analyze the sample using the chromatographic conditionsdescribed in Section 9.1. Load the sample as illustrated inFigure 1 except that the gas sampling bulb is replaced by a 300mL stainless steel cylinder. Flash the sample liquid phase so asto bring the pressure to just below saturation. Questionablesample results are most often resolved by re-analysis of thecalibration standard. The temperature of the sample must equal(essentially) that of the calibration standard at the time of GCcalibration. In the case of VHP refrigerants, the sample must beat or above the critical temperature before analysis.

9.8 Calculations


W100 x RRF x A

(A x RRFii i

i i

=∑ )

Where:

Wi = weight percentage of component i.RRFi = relative response factor for component i.

ARFi–––––ARFx

103

Ai = peak area of component i.Σ…= sum of all component peak areas times their


Section 10. Notes

1. The purest refrigerant blend will contain some of thecontaminants listed in Table 1 of the GC Method DataSheet in low concentrations. Individual impurity peakareas are increased in the calibration standard by the peakareas that correspond to the mass of the impurity added.The amounts of each contaminant in the stockcomponents are thereby determined by the method ofStandards Addition. The mass of each contaminantpresent is combined with the mass added to give the totalmass of each contaminant in the calibration standard.


Table 1. GC Method Data Sheets

RefrigerantGC Method Data

Sheet PartNumber

R-401 Part 34R-402 Part 35R-404 Part 36R-405 Part 37R-406 Part 38R-407 Part 39R-408 Part 40R-409 Part 41R-410 Part 42R-411 Part 43R-412 Part 44R-500 Part 45R-502 Part 46R-503 Part 47R-507 Part 48R-508 Part 49R-509 Part 50


1. Air-Conditioning and Refrigeration Institute, Appendix C toARI Standard 700-95: Analytical Procedures for ARIStandard 700-95, 4301 North Fairfax Drive, Arlington,Virginia 22203.

2. Integral Sciences, Inc., Methods Development for OrganicContaminant Determination in Fluorocarbon RefrigerantAzeotropes and Blends, ARTI MCLR Project Number 665-54600.

104


105

Part 34

R-401 Purity GC Method Data Sheet

Section 1. Scope

This GC Method Data Sheet is for use in conjunction with Part33, General Procedure for the Determination of Purity of Newand Reclaimed Refrigerant Blends and Azeotropes by GasChromatography (hereafter referred to as General Procedure).This GC Method Data Sheet is for use with R-401 blends.


This method is applicable and calibrated for only thoseimpurities commonly present in R-401 blends (See Table 2).This method will not detect any impurity that may elute withinthe comparatively large HCFC-22, HCFC-124, and HFC-152apeak matrices. For example, HFC-125 elutes on the far shoulderof the large HFC-152a peak and is therefore difficult to detect atlow concentrations. Linearity of the HFC-125 response is

marginal and limits the precision in the determination of thisimpurity. The contaminants HFC-23 and HFC-32 also elutetogether, but these may be separated if needed by adding a0.30 m column section of Porapak-T to the end of the primarycolumn.


Statistical parameters for each impurity are listed in Table 1Aand B. The data was obtained by analyzing an R-401 calibrationmixture 7 times during one day by one operator.

Section 4. Tables



106

Table 1A. Contaminant Statistical Parameters

Component DetectionLimit, ppm

RangeInvestigated,

ppm

Precision at 95%Confidence Limit, ppm

methane 1 100 2.823 10 450 10.32 5 450 7.8

ethene 1 450 7.1ethane 1 200 2.6

13 12 450 9.5143a 2 450 12134a 3 450 5.11301 9 450 4.1218 6 450 7.0

propene 1 100 1.4115 7 450 3212 8 450 13

142b 2 450 29133a 2 450 1821 5 450 31

isobutane 1 100 2.3114 5 450 8.011 6 450 41

123 2 450 44113 2 450 60.

Table 1B. Component Statistical Parameters


RangeInvestigated,

Wt. %

Precision at 95%Confidence Limit

152a 2 13 % 0.10 %22 5 53 % 0.51 %

124 5 34 % 0.26 %

Table 1C. Blend Component Balance Preparation

ComponentFinal Pressure

AfterComponent

Addition (kPa)

Weight of RefrigerantAdded (g)

HCFC-124 118 6.80

HFC-152a 206 2.60

HCFC-22 466 10.60

107

Table 2. Primary Calibration Standard Impurities

ComponentVapor

Density,mg/ml

VolumeAdded,

ml

mgAdded

(1)

ppmAdded

(2)

Total ppm Present

(3)methane 0.656 4.0 2.62 130

23 2.895 3.5 10.13 50032 2.162 4.7 10.16 502

ethene 1.147 4.0 4.58 226ethane 1.230 4.0 4.92 243

13 4.331 2.4 10.39 513143a 3.511 2.9 10.18 503125 5.004 2.1 10.50 519134a 4.279 2.4 10.26 5071301 6.205 1.7 10.54 521218 7.923 1.3 10.29 508

propene 1.756 5.8 10.18 503115 6.486 1.6 10.37 51212 5.077 2.0 10.15 501

142b 4.248 2.4 10.19 503133a 4.846 2.1 10.17 50221 4.367 2.4 10.48 517

isobutane 2.452 4.2 10.29 508114 7.319 1.4 10.24 506

ComponentLiquid

Density,mg/µl

VolumeAdded,

µl

mgAdded

(1)

ppmAdded

(2)

Total ppmPresent

(3)11 1.537 6.6 10.14 501

123 1.526 6.7 10.22 505113 1.619 6.3 10.19 503

(1) If necessary, correct the mg added for the purity of the calibration componentpreviously established.

(2) Values shown are for illustration; exact values are determined at Part 33,Section 9.3, steps c and d.

(3) Column to be filled in (Part 33, Section 9.3, step g) after determining ppmpresent in the stock components (see Note 1 in Section 10).

108

Part 35


Section 1. Scope



This method is calibrated only for those impurities commonlypresent in R-402 blends. This method will not detect anyimpurity that may elute within the comparatively largeHCFC-22, HFC-125, and propane peak matrices. For example,HFC-134a elutes on the far shoulder of the large HFC-125 peakand is therefore difficult to detect at low concentrations.Linearity of the HFC-134a response is marginal and limits theprecision in the determination of this impurity. Detection of

CFC-115 is not resolved as it would coelute with the propane.The contaminants HFC-23 and HFC-32 also elute together, butthese may be separated if needed by adding a 0.30 m columnsection of Porapak-T to the end of the primary column.



Section 4. Tables

The following tables are to be used in conjunction with Part 33of the General Procedure for the Determination of Purity ofReclaimed Refrigerant Blends and Azeotropes by GasChromatography.


109



RangeInvestigated,

ppm


methane 1 100 0.823 9 500 8.532 4 500 38

ethene 1 200 1.5ethane 1 280 2.5

13 11 500 14143a 1 500 6.7134a 100 500 821301 8 500 4.5218 5 500 3.6

propene 1 100 0.712 8 500 2.9

142b 2 500 49124 3 500 9.0133a 2 500 4.421 5 500 11

isobutane 1 150 1.4114 5 500 2.8

n-butane 1 100 1.411 7 500 15

123 2 500 13113 2 500 18



RangeInvestigated,

%


125 5 60 % 0.17 %22 5 38 % 0.20 %

propane 1 2 % 0.01 %


Component Final PressureAfter

ComponentAddition (kPa)


Propane 22 0.40

HCFC-22 340 12.00

HFC-125 472 7.60

110


ComponentVapor

Density,mg/ml

VolumeAdded,

ml

mgAdded

(1)

ppmAdded

(2)

Total ppmPresent

(3)methane 0.656 4.0 2.62 130

23 2.895 3.5 10.13 50032 2.162 4.7 10.16 502

ethene 1.147 4.0 4.58 226ethane 1.230 4.0 4.92 243

13 4.331 2.4 10.39 513143a 3.511 2.9 10.18 503152a 2.772 3.7 10.25 506134a 4.279 2.4 10.26 5071301 6.205 1.7 10.54 521218 7.923 1.3 10.29 508

propene 1.756 5.8 10.18 50312 5.077 2.0 10.15 501

142b 4.248 2.4 10.19 503124 5.758 1.8 10.36 512133a 4.846 2.1 10.17 50221 4.367 2.4 10.48 517

isobutane 2.452 4.2 10.29 508114 7.319 1.4 10.24 506

n-butane 2.463 4.2 10.34 511

ComponentLiquid

Density,mg/µl

VolumeAdded,

µl

mgAdded

(1)

ppmAdded

(2)

Total ppm Present

(3)11 1.537 6.6 10.14 501123 1.526 6.7 10.22 505113 1.619 6.3 10.19 503


(2) Values shown are for illustration; exact values are determined in Part 33,Section 9.3, steps c and d.

(3) Column to be filled in (Part 33, Section 9.3 step g) after determining ppmpresent in the stock components (see Note 1 in Section 10).

111

Part 36


Section 1. Scope



This method is calibrated only for those impurities commonlypresent in R-404A. This method will not detect any impuritythat may elute within the comparatively large HFC-125,HFC-134a, and HFC-143a peak matrices. The contaminantsHFC-23 and HFC-32 also elute together, but these may be

separated if needed by adding a 0.30 m column section ofPorapak-T to the end of the primary column.



Section 4. Tables



112



RangeInvestigated,

ppm


methane 1 120 3.123 10 520 6.732 4 520 7.9

ethene 1 520 5.1ethane 1 230 2.5

13 10 520 9.422 7 520 12

1301 7 520 21218 5 520 16

propene 1 130 2.1115 6 4400 9712 7 520 19

142b 2 520 89124 3 520 82133a 2 520 1221 5 520 39

isobutane 1 130 3.0114 4 350 4.6114a 4 170 2.911 7 520 73

123 2 520 50



RangeInvestigated,

%


143a 4 52 % 0.62 %125 4 44 % 0.61 %134a 3 4 % 0.15 %



AfterComponent

Addition (kPa)


R-134a 19 0.80

R-143a 304 10.4

R-125 458 8.80

113


ComponentVapor

Density,mg/ml

VolumeAdded,

ml

mgAdded

(1)

ppmAdded

(2)

Total ppmPresent

(3)methane 0.656 4.0 2.62 130

23 2.895 3.5 10.13 50032 2.162 4.7 10.16 502

ethene 1.147 4.0 4.58 226ethane 1.230 4.0 4.92 243

13 4.331 2.4 10.39 513152a 2.772 3.7 10.25 50622 3.606 2.9 10.45 516

1301 6.205 1.7 10.54 521218 7.923 1.3 10.29 508

propene 1.756 5.8 10.18 503115 6.486 1.6 10.37 51212 5.077 2.0 10.15 501

142b 4.248 2.4 10.19 503124 5.758 1.8 10.36 512133a 4.846 2.1 10.17 50221 4.367 2.4 10.48 517

isobutane 2.452 4.2 10.29 508114 7.319 1.4 10.24 506

ComponentLiquid

Density,mg/µl

VolumeAdded,

µl

mgAdded

(1)

ppmAdded

(2)

Total ppmPresent

(3)11 1.537 6.6 10.14 501123 1.526 6.7 10.22 505113 1.619 6.3 10.19 503




114

Part 37


Section 1. Scope



This method is calibrated only for those impurities commonlypresent in R-405A. This method will not detect any impuritythat may elute within the comparatively large HCFC-22,HCFC-142b, HFC-152a, and FC-C318 peak matrices. Forexample, HFC-125 elutes on the far shoulder of the largeHFC-152a peak and is therefore difficult to detect at lowconcentrations. Linearity of the HFC-125 response is marginal

and limits the precision in the determination of this impurity.The contaminants HFC-23 and HFC-32 also elute together, butthese may be separated if needed by adding a 0.30 m columnsection of Porapak-T to the end of the primary column.



Section 4. Tables



115



RangeInvestigated,

ppm


methane 1 100 0.923 13 500 15032 7 500 3.9

ethene 1 200 1.4ethane 1 200 1.6

13 20 500 7.6143a 2 500 3.9134a 4 500 8.01301 16 500 3.0218 9 500 2.8

propene 1 100 0.6115 16 500 2112 9 500 2.8

124 6 500 5.1133a 3 500 5.821 10 500 10.

isobutane 1 100 1.1114 8 500 5.9

n-butane 1 100 1.711 13 500 10.

123 4 500 13113 4 500 21



RangeInvestigated,

%


152a 1 7 % 0.05 %22 5 45 % 0.32 %

C318/142b 4 48 % 0.42 %



AfterComponent

Addition (kPa)


FC-C318 105 9.00

R-142b 136 1.40

R-152a 173 1.10

R-22 394 8.5

116


ComponentVapor

Density,mg/ml

VolumeAdded,

ml

mgAdded

(1)

ppmAdded

(2)

Total ppm Present

(3)methane 0.656 4.0 2.62 130

23 2.895 3.5 10.13 50032 2.162 4.7 10.16 502

ethene 1.147 4.0 4.58 226ethane 1.230 4.0 4.92 243

13 4.331 2.4 10.39 513143a 3.511 2.9 10.18 503125 5.004 2.1 10.50 519134a 4.279 2.4 10.26 5071301 6.205 1.7 10.54 521218 7.923 1.3 10.29 508

propene 1.756 5.8 10.18 503115 6.486 1.6 10.37 51212 5.077 2.0 10.15 501124 5.758 1.8 10.36 512133a 4.846 2.1 10.17 50221 4.367 2.4 10.48 517

isobutane 2.452 4.2 10.29 508114 7.319 1.4 10.24 506

n-butane 2.463 4.2 10.34 511

ComponentLiquid

Density,mg/µl

VolumeAdded,

µl

mgAdded

(1)

ppmAdded

(2)

Total ppmPresent

(3)11 1.537 6.6 10.14 501123 1.526 6.7 10.22 505113 1.619 6.3 10.19 503




117

Part 38


Section 1. Scope



This method is calibrated only for those impurities commonlypresent in R-406A. This method will not detect any impuritythat may elute within the comparatively large HCFC-22,HCFC-142b, and isobutane peak matrices. The contaminantsHFC-23 and HFC-32 also elute together, but these may be




Section 4. Tables



118



RangeInvestigated,

ppm


methane 1 100 3.323 11 450 2432 4 450 9.0

ethene 1 450 15ethane 1 200 6.5

13 13 450 18143a 2 650 17152a 1 450 30.125 11 450 15134a 2 450 20.1301 11 450 6.4218 6 450 18

propene 1 100 3.2115 7 450 6.212 8 450 5.3

124 4 450 23133a 2 450 1421 5 450 4

114 6 450 10.n-butane 3 100 2.9

11 7 450 6.2123 2 450 5.0113 2 450 7.1



RangeInvestigated,

%


22 6 55 % 0.21 %142b 4 41 % 0.35 %

isobutane 1 4 % 0.09 %



AfterComponent

Addition (kPa)


Isobutane 25 0.60

R-142b 166 6.15

R-22 371 8.25

119


ComponentVapor

Density,mg/ml

VolumeAdded,

ml

mgAdded

(1)

ppmAdded

(2)

Total ppm Present

(3)methane 0.656 4.0 2.62 130

23 2.895 3.5 10.13 50032 2.162 4.7 10.16 502

ethene 1.147 4.0 4.58 226ethane 1.230 4.0 4.92 243

13 4.331 2.4 10.39 513143a 3.511 2.9 10.18 503152a 2.772 3.7 10.25 506125 5.004 2.1 10.50 519134a 4.279 2.4 10.26 5071301 6.205 1.7 10.54 521218 7.923 1.3 10.29 508

propene 1.756 5.8 10.18 503115 6.486 1.6 10.37 51212 5.077 2.0 10.15 501124 5.758 1.8 10.36 512133a 4.846 2.1 10.17 50221 4.367 2.4 10.48 517114 7.319 1.4 10.24 506

n-butane 2.463 4.2 10.34 511

ComponentLiquid

Density,mg/µl

VolumeAdded,

µl

mgAdded

(1)

ppmAdded

(2)

Total ppm Present

(3)11 1.537 6.6 10.14 501123 1.526 6.7 10.22 505113 1.619 6.3 10.19 503




120

Part 39


Section 1. Scope

This GC Method Data Sheet is for use in conjunction with Part33, General Procedure for the Determination of Purity of Newand Reclaimed Refrigerant Blends and Azeotropes by GasChromatography. This GC Method Data Sheet is for use withR-407, blends of R-32, R-125, and R-134a.


This method is calibrated only for those impurities commonlypresent in R-407 blends. This method will not detect anyimpurity that may elute within the comparatively largeHFC-32, HFC-125, and HFC-134a peak matrices. Althoughthis method only partially separates HFC-152a from HFC-125,

the HFC-152a peak can be resolved by reducing the loop sizeto 100 µl.



Section 4. Tables



121



RangeInvestigated,

ppm


methane 1 100 0.323 3 440 3.6

ethene 1 440 0.7ethane 1 200 0.3

13 19 440 2.7143a 2 440 30.22 15 440 8.5

1301 14 440 11218 10 440 5.5

propene 1 100 5.1115 11 20,000 14012 43 440 3.7

142b 3 440 3.3124 5 440 1.5133a 3 440 1.221 10 440 15

isobutane 1 100 0.4114 8 440 3.211 11 440 13

123 3 440 5.3113 4 440 11



RangeInvestigated,

%


32 3 20 % 0.05 %125 4 40 % 0.14 %134a 100 40 % 0.08 %



AfterComponent

Addition (kPa)


R-134a 94 4.00

R-125 355 14.00

R-32 438 2.00

122


ComponentVapor

Density,mg/ml

VolumeAdded,

ml

mgAdded

(1)

ppmAdded

(2)

Total ppm Present

(3)methane 0.656 4.0 2.62 130

23 2.895 3.5 10.13 500ethene 1.147 4.0 4.58 226ethane 1.230 4.0 4.92 243

13 4.331 2.4 10.39 513143a 3.511 2.9 10.18 503152a 2.772 3.7 10.25 50622 3.606 2.9 10.45 516

1301 6.205 1.7 10.54 521218 7.923 1.3 10.29 508

propene 1.756 5.8 10.18 503115 6.486 1.6 10.37 51212 5.077 2.0 10.15 501

142b 4.248 2.4 10.19 503124 5.758 1.8 10.36 512133a 4.846 2.1 10.17 50221 4.367 2.4 10.48 517

isobutane 2.452 4.2 10.29 508114 7.319 1.4 10.24 506

ComponentLiquid

Density,mg/µl

VolumeAdded,

µl

mgAdded

(1)

ppmAdded

(2)

Total ppm Present

(3)11 1.537 6.6 10.14 501123 1.526 6.7 10.22 505113 1.619 6.3 10.19 503




123

Part 40


Section 1. Scope



This method is calibrated only for those impurities commonlypresent in R-408A. This method will not detect any impuritythat may elute within the comparatively large HCFC-22,HFC-125, and HFC-143a peak matrices. For example,HFC-134a elutes on the far shoulder of the large HFC-125 peakand is therefore difficult to detect at low concentrations.Linearity of the HFC-134a response is marginal and limits the

precision in the determination of this impurity. Thecontaminants HFC-23 and HFC-32 also elute together, but thesemay be separated if needed by adding a 0.30 m column sectionof Porapak-T to the end of the primary column.



Section 4. Tables


Table 1. Gas Chromatogram of R-408A

124



RangeInvestigated,

ppm


methane 1 100 0.623 10 430 2.132 4 430 1.8

ethene 1 430 2.6ethane 1 200 1.6

13 11 430 7.5152a 1 430 37134a 100 430 3.41301 9 430 7.5218 6 430 1.5

propene 1 100 6.8115 7 1400 1112 6 430 51

142b 1 430 4.3124 4 430 2.3133a 2 430 0.921 5 430 11

isobutane 1 100 0.9114 5 430 0.811 7 430 12

123 2 430 4.6113 2 430 7.9



RangeInvestigated,

%


143a 3 46 % 0.06 %125 5 7 % 0.10 %22 6 47 % 0.17 %



AfterComponent

Addition (kPa)


R-22 254 9.40

R-143a 487 9.20

R-125 510 1.40

125


ComponentVapor

Density,mg/ml

VolumeAdded,

ml

mgAdded

(1)

ppmAdded

(2)

Total ppm Present

(3)methane 0.656 4.0 2.62 130

23 2.895 3.5 10.13 50032 2.162 4.7 10.16 502

ethene 1.147 4.0 4.58 226ethane 1.230 4.0 4.92 243

13 4.331 2.4 10.39 513152a 2.772 3.7 10.25 506134a 4.279 2.4 10.26 5071301 6.205 1.7 10.54 521218 7.923 1.3 10.29 508

propene 1.756 5.8 10.18 503115 6.486 1.6 10.37 51212 5.077 2.0 10.15 501

142b 4.248 2.4 10.19 503124 5.758 1.8 10.36 512133a 4.846 2.1 10.17 50221 4.367 2.4 10.48 517

isobutane 2.452 4.2 10.29 508114 7.319 1.4 10.24 506

ComponentLiquid

Density,mg/µl

VolumeAdded,

µl

mgAdded

(1)

ppmAdded

(2)

Total ppmPresent (3)

11 1.537 6.6 10.14 501123 1.526 6.7 10.22 505113 1.619 6.3 10.19 503




126

Part 41


Section 1. Scope



This method is calibrated only for those impurities commonlypresent in R-409 blends. This method will not detect anyimpurity that may elute within the comparatively largeHCFC-22, HCFC-124, and HCFC-142b peak matrices. Thecontaminants HFC-23 and HFC-32 also elute together, but

these may be separated if needed by adding a 0.30 m columnsection of Porapak-T to the end of the primary column.



Section 4. Tables



127



RangeInvestigated,

ppm


methane 1 100 2.823 16 440 1232 9 440 9.3

ethene 1 440 9.2ethane 1 200 4.2

13 25 440 8.0143a 3 440 9.2152a 2 440 3.2125 13 440 13134a 5 440 7.01301 24 440 9.6218 12 440 9.5

propene 1 100 0.5115 14 440 2712 14 440 2.7

133a 4 440 1321 12 440 31

isobutane 1 100 1.6114 10 440 1.711 12 440 42

123 3 440 41113 3 440 66



RangeInvestigated,

%


22 6 60 % 0.34 %142b 3 15 % 0.17 %124 5 25 % 0.03 %



AfterComponent

Addition (kPa)


R-142b 71 3.00

R-124 155 5.00

R-22 450 12.00

128


ComponentVapor

Density,mg/ml

VolumeAdded,

ml

mgAdded

(1)

ppmAdded

(2)


methane 0.656 4.0 2.62 13023 2.895 3.5 10.13 50032 2.162 4.7 10.16 502

ethene 1.147 4.0 4.58 226ethane 1.230 4.0 4.92 243

13 4.331 2.4 10.39 513143a 3.511 2.9 10.18 503152a 2.772 3.7 10.25 506125 5.004 2.1 10.50 519134a 4.279 2.4 10.26 5071301 6.205 1.7 10.54 521218 7.923 1.3 10.29 508

propene 1.756 5.8 10.18 503115 6.486 1.6 10.37 51212 5.077 2.0 10.15 501

133a 4.846 2.1 10.17 50221 4.367 2.4 10.48 517

isobutane 2.452 4.2 10.29 508114 7.319 1.4 10.24 506

ComponentLiquid

Density,mg/µl

VolumeAdded,

µl

mgAdded

(1)

ppmAdded

(2)

Total ppmPresent

(3)11 1.537 6.6 10.14 501123 1.526 6.7 10.22 505113 1.619 6.3 10.19 503




129

Part 42


Section 1. Scope



This method is calibrated only for those impurities commonlypresent in R-410 blends. This method will not detect anyimpurity that may elute within the comparatively large HFC-32and HFC-125 peak matrices. HFC-134a elutes on the far

shoulder of the large HFC-125 peak, is poorly resolved and isdifficult to detect at low concentrations.



Section 4. Tables



130



RangeInvestigated,

ppm


methane 1 120 2.123 5 510 5.4

ethene 1 510 8.7ethane 1 230 4.1

13 13 510 11143a 3 550 7.3152a 2 510 11134a 100 510 1722 7 510 14

1301 8 510 17218 6 510 15

propene 1 130 1.6115 6 1900 2312 9 510 12

142b 1 510 5.8124 4 510 6.7133a 2 510 7.021 7 510 10.

isobutane 1 130 2.1114 6 510 10.11 8 510 23

123 2 510 5.2113 3 510 6.4



RangeInvestigated,

%


32 7 50 % 0.38 %125 5 50 % 0.25 %



AfterComponent

Addition (kPa)


R-125 197 10.00

R-32 616 10.00

131


ComponentVapor

Density,mg/ml

VolumeAdded,

ml

mgAdded

(1)

ppmAdded

(2)

Total ppmPresent

(3)methane 0.656 4.0 2.62 130

23 2.895 3.5 10.13 500ethene 1.147 4.0 4.58 226ethane 1.230 4.0 4.92 243

13 4.331 2.4 10.39 513143a 3.511 2.9 10.18 503152a 2.772 3.7 10.25 506134a 4.279 2.4 10.26 50722 3.606 2.9 10.45 516

1301 6.205 1.7 10.54 521218 7.923 1.3 10.29 508

propene 1.756 5.8 10.18 503115 6.486 1.6 10.37 51212 5.077 2.0 10.15 501

142b 4.248 2.4 10.19 503124 5.758 1.8 10.36 512133a 4.846 2.1 10.17 50221 4.367 2.4 10.48 517

isobutane 2.452 4.2 10.29 508114 7.319 1.4 10.24 506

ComponentLiquid

Density,mg/µl

VolumeAdded,

µl

mgAdded

(1)

ppmAdded

(2)

Total ppmPresent

(3)11 1.537 6.6 10.14 501123 1.526 6.7 10.22 505113 1.619 6.3 10.19 503




132

Part 43


Section 1. Scope



This method is calibrated only for those impurities commonlypresent in R-411 blends. This method will not detect anyimpurity that may elute within the comparatively largeHCFC-22, HFC-152a, and propene peak matrices. For example,HFC-125 elutes on the far shoulder of the large HFC-152a peak,is poorly resolved and is difficult to detect at low concentrations.The same difficulty is encountered measuring the CFC-115contaminant because of its proximity to the large propene peakmatrix. The contaminants HFC-23 and HFC-32 also elutetogether, but these may be separated if needed by adding a 0.30m column section of Porapak-T to the end of the primarycolumn.



Section 4. Tables



133



RangeInvestigated,

ppm


methane 1 100 1223 7 420 3632 5 420 17

ethene 1 420 12ethane 1 200 6.5

13 1 420 30.143a 2 420 19134a 3 420 571301 14 420 14218 6 420 14115 10 420 2512 9 420 5.3

142b 2 420 12124 5 420 22133a 2 420 2521 7 420 22

isobutane 1 100 4.2114 6 420 2211 9 420 12

123 2 420 34113 3 420 36



RangeInvestigated,

%


152a 1 3 % 0.16 %22 9 94 % 2.6 %

propene 1 3 % 0.06 %



AfterComponent

Addition (kPa)


Propene 35 0.60

R-152a 56 0.60

R-22 533 18.80

134


ComponentVapor

Density,mg/ml

VolumeAdded,

ml

mgAdded

(1)

ppmAdded

(2)


methane 0.656 4.0 2.62 13023 2.895 3.5 10.13 50032 2.162 4.7 10.16 502

ethene 1.147 4.0 4.58 226ethane 1.230 4.0 4.92 243

13 4.331 2.4 10.39 513143a 3.511 2.9 10.18 503125 5.004 2.1 10.50 519134a 4.279 2.4 10.26 5071301 6.205 1.7 10.54 521218 7.923 1.3 10.29 508115 6.486 1.6 10.37 51212 5.077 2.0 10.15 501

142b 4.248 2.4 10.19 503124 5.758 1.8 10.36 512133a 4.846 2.1 10.17 50221 4.367 2.4 10.48 517

isobutane 2.452 4.2 10.29 508114 7.319 1.4 10.24 506

ComponentLiquid

Density,mg/µl

VolumeAdded,

µl

mgAdded

(1)

ppmAdded

(2)

Total ppmPresent

(3)11 1.537 6.6 10.14 501123 1.526 6.7 10.22 505113 1.619 6.3 10.19 503


(2) Values shown are for illustration; exact values are determined in Part 33,Section 9.3, steps c and d.


135

Part 44


Section 1. Scope



This method is calibrated only for those impurities commonlypresent in R-412A. This method will not detect any impuritythat may elute within the comparatively large HCFC-22,HCFC-142b, and FC-218 peak matrices. The contaminantsHFC-23 and HFC-32 also elute together, but these may be




Section 4. Tables



136



RangeInvestigated,

ppm


methane 1 100 1.023 10 520 7.132 4 520 4.3

ethene 1 200 2.2ethane 1 200 2.3

13 12 520 6.2143a 1 700 9.2152a 1 520 48125 6 520 11134a 2 520 6.91301 10 520 13

propene 1 150 7.4115 6 520 1612 7 520 19

124 4 520 5.2133a 2 520 1.021 5 520 14

isobutane 1 150 0.3114 5 520 3.9

n-butane 1 150 0.211 5 520 21

123 2 520 8.2113 3 520 14



RangeInvestigated,

%


22 7 70 % 0.21 %218 5 5 % 0.06 %

142b 2 25 % 0.08%



AfterComponent

Addition (kPa)


FC-218 13 1.00

R-142b 129 5.00

R-22 475 14.00

137


ComponentVapor

Density,mg/ml

VolumeAdded,

ml

mgAdded

(1)

ppmAdded

(2)


methane 0.656 4.0 2.62 13023 2.895 3.5 10.13 50032 2.162 4.7 10.16 502

ethene 1.147 4.0 4.58 226ethane 1.230 4.0 4.92 243

13 4.331 2.4 10.39 513143a 3.511 2.9 10.18 503152a 2.772 3.7 10.25 506125 5.004 2.1 10.50 519134a 4.279 2.4 10.26 5071301 6.205 1.7 10.54 521

propene 1.756 5.8 10.18 503115 6.486 1.6 10.37 51212 5.077 2.0 10.15 501124 5.758 1.8 10.36 512133a 4.846 2.1 10.17 50221 4.367 2.4 10.48 517

isobutane 2.452 4.2 10.29 508114 7.319 1.4 10.24 506

n-butane 2.463 4.2 10.34 511

ComponentLiquid

Density,mg/µl

VolumeAdded,

µl

mgAdded

(1)

ppmAdded

(2)


11 1.537 6.6 10.14 501123 1.526 6.7 10.22 505113 1.619 6.3 10.19 503




138

Part 45


Section 1. Scope

This GC Method Data Sheet is for use in conjunction with Part33, General Procedure for the Determination of Purity of Newand Reclaimed Refrigerant Blends and Azeotropes by GasChromatography (hereafter referred to as General Procedure).This GC Method Data Sheet is for use with R-500.


This method is calibrated only for those impurities commonlypresent in R-500. This method will not detect any impurity thatmay elute within the comparatively large CFC-12 andHFC-152a peak matrices. For example, HFC-134a elutes onthe far shoulder of the large HFC-152a peak and is thereforedifficult to detect at low concentrations. Linearity of theHFC-134a response is marginal and limits the precision in the

determination of this impurity. The contaminants HFC-23 andHFC-32 also elute together, but these may be separated ifneeded by adding a 0.30 m column section of Porapak-T to theend of the primary column.



Section 4. Tables



139



RangeInvestigated,

ppm


methane 2 100 1.123 7 440 8.532 4 440 3.3

ethene 1 440 2.3ethane 1 200 0.9

13 9 440 5.0143a 1 440 1.7134a 3 440 1.722 5 440 3.1

1301 7 440 3.7218 5 440 1.4

propene 1 100 4.5115 6 440 8.5

142b 2 440 4.6124 3 440 4.2133a 2 440 5.421 5 440 12

isobutane 1 100 6.6114 4 440 4.211 6 440 14

123 2 440 16113 2 440 23



RangeInvestigated,

%


152a 2 26.2 % 0.02 %12 7 73.8 % 0.07 %



AfterComponent

Addition (kPa)


R-152a 185 5.24

R-12 441 14.76

140


ComponentVapor

Density,mg/ml

VolumeAdded,

ml

mgAdded

(1)

ppmAdded

(2)

Total ppmPresent

(3)methane 0.656 4.0 2.62 130

23 2.895 3.5 10.13 50032 2.162 4.7 10.16 502

ethene 1.147 4.0 4.58 226ethane 1.230 4.0 4.92 243

13 4.331 2.4 10.39 513143a 3.511 2.9 10.18 503134a 4.279 2.4 10.26 50722 3.606 2.9 10.45 516

1301 6.205 1.7 10.54 521218 7.923 1.3 10.29 508

propene 1.756 5.8 10.18 503115 6.486 1.6 10.37 512142b 4.248 2.4 10.19 503124 5.758 1.8 10.36 512133a 4.846 2.1 10.17 50221 4.367 2.4 10.48 517

isobutane 2.452 4.2 10.29 508114 7.319 1.4 10.24 506

ComponentLiquid

Density,mg/µl

VolumeAdded,

µl

mgAdded

(1)

ppmAdded

(2)

Total ppmPresent

(3)11 1.537 6.6 10.14 501123 1.526 6.7 10.22 505113 1.619 6.3 10.19 503




141

Part 46


Section 1. Scope



This method is calibrated only for those impurities commonlypresent in R-502. This method will not detect any impurity thatmay elute within the comparatively large HCFC-22 andCFC-115 peak matrices. Propene and CFC-115 are poorlyresolved which complicates the quantification of the propene.The contaminants HFC-23 and HFC-32 elute together, but

these may be separated if needed by adding a 0.30 m columnsection of Porapak-T to the end of the primary column.



Section 4. Tables



142



RangeInvestigated,

ppm


methane 1 100 8.423 5 440 1332 3 440 15

ethene 1 440 8.7ethane 1 200 3.5

13 8 440 11143a 1 440 11152a 1 440 11125 5 440 14134a 2 440 161301 21 440 31218 5 440 14

propene 1 100 8.712 5 440 16

142b 1 440 11124 2 440 11133a 2 440 9.321 4 440 32

isobutane 1 100 0.9114 4 440 9.511 9 440 74

123 2 440 11113 3 440 21



RangeInvestigated,

%


22 5 48.8 % 0.11 %115 5 51.2 % 0.10 %



AfterComponent

Addition (kPa)


R-115 156 10.24

R-22 405 9.76

143


ComponentVapor

Density,mg/ml

VolumeAdded,

ml

mgAdded

(1)

ppmAdded

(2)

Total ppmPresent

(3)methane 0.656 4.0 2.62 130

23 2.895 3.5 10.13 50032 2.162 4.7 10.16 502

ethene 1.147 4.0 4.58 226ethane 1.230 4.0 4.92 243

13 4.331 2.4 10.39 513143a 3.511 2.9 10.18 503152a 2.772 3.7 10.25 506125 5.004 2.1 10.50 519134a 4.279 2.4 10.26 5071301 6.205 1.7 10.54 521218 7.923 1.3 10.29 508

propene 1.756 5.8 10.18 50312 5.077 2.0 10.15 501

142b 4.248 2.4 10.19 503124 5.758 1.8 10.36 512133a 4.846 2.1 10.17 50221 4.367 2.4 10.48 517

isobutane 2.452 4.2 10.29 508114 7.319 1.4 10.24 506

ComponentLiquid

Density,mg/µl

VolumeAdded,

µl

mgAdded

(1)

ppmAdded

(2)

Total ppmPresent

(3)11 1.537 6.6 10.14 501123 1.526 6.7 10.22 505113 1.619 6.3 10.19 503




144

Part 47


Section 1. Scope



This method is calibrated only for those impurities commonlypresent in R-503. This method will not detect any impurity thatmay elute within the comparatively large CFC-13 and HFC-23peak matrices. For example, HFC-32 cannot be detected using

this method as it elutes within the large HFC-23 componentpeak matrix.



Section 4. Tables



145



RangeInvestigated,

ppm


methane 1 100 0.9ethene 1 440 3.9ethane 1 200 1.6143a 2 440 15152a 1 440 4.2125 7 440 14134a 2 440 5.622 5 440 20.

1301 7 440 2.5218 5 440 3.9

propene 1 100 3.1115 7 440 20.12 8 440 1.0

142b 2 440 10.124 3 440 19133a 2 440 1621 5 440 7.9

isobutane 1 100 1.7114 5 440 9.111 7 440 20

123 2 440 14113 3 440 15



RangeInvestigated,

%


23 11 40.1 % 0.07 %13 10 59.9 % 0.09 %



AfterComponent

Addition (kPa)


R-13 272 11.98

R-23 533 8.02

146


ComponentVapor

Density,mg/ml

VolumeAdded,

ml

mgAdded

(1)

ppmAdded

(2)

Total ppmPresent

(3)methane 0.656 4.0 2.62 130ethene 1.147 4.0 4.58 226ethane 1.230 4.0 4.92 243143a 3.511 2.9 10.18 503152a 2.772 3.7 10.25 506125 5.004 2.1 10.50 519134a 4.279 2.4 10.26 50722 3.606 2.9 10.45 516

1301 6.205 1.7 10.54 521218 7.923 1.3 10.29 508

propene 1.756 5.8 10.18 503115 6.486 1.6 10.37 51212 5.077 2.0 10.15 501

142b 4.248 2.4 10.19 503124 5.758 1.8 10.36 512133a 4.846 2.1 10.17 50221 4.367 2.4 10.48 517

isobutane 2.452 4.2 10.29 508114 7.319 1.4 10.24 506

ComponentLiquid

Density,mg/µl

VolumeAdded,

µl

mgAdded

(1)

ppmAdded

(2)

Total ppmPresent

(3)11 1.537 6.6 10.14 501123 1.526 6.7 10.22 505113 1.619 6.3 10.19 503




147

Part 48


Section 1. Scope



This method is calibrated only for those impurities commonlypresent in R-507A. This method will not detect any impuritythat may elute within the comparatively large HFC-125 andHFC-143a peak matrices. For example, HFC-134a elutes onthe far shoulder of the large HFC-125 peak and is thereforedifficult to detect at low concentrations. Because of this poorresolution, the precision of the HFC-134a impurity is

comparitively large. The contaminants HFC-23 and HFC-32also elute together, but these may be separated if needed byadding a 0.30 m column section of Porapak-T to the end of theprimary column.



Section 4. Tables



148



RangeInvestigated,

ppm


methane 1 100 0.523 17 450 1232 8 450 3.3

ethene 1 450 1.8ethane 1 200 0.8

13 23 450 5.4134a 100 450 5.322 15 450 29

1301 16 450 4.3218 11 450 0.9

propene 1 100 0.5115 17 3400 11012 17 450 4.3

142b 3 450 6.6124 7 450 1.9133a 4 450 3.321 11 450 13

isobutane 1 100 1.1114 10 450 3.911 12 450 9.6

123 4 450 11113 5 450 14



RangeInvestigated,

%


143a 4 50 % 0.05 %125 5 50 % 0.07 %



AfterComponent

Addition (kPa)


R-143a 276 10.00

R-125 453 10.00

149


ComponentVapor

Density,mg/ml

VolumeAdded,

ml

mgAdded

(1)

ppmAdded

(2)

Total ppm Present

(3)methane 0.656 4.0 2.62 130

23 2.895 3.5 10.13 50032 2.162 4.7 10.16 502

ethene 1.147 4.0 4.58 226ethane 1.230 4.0 4.92 243

13 4.331 2.4 10.39 513152a 2.772 3.7 10.25 506134a 4.279 2.4 10.26 50722 3.606 2.9 10.45 516

1301 6.205 1.7 10.54 521218 7.923 1.3 10.29 508

propene 1.756 5.8 10.18 503115 6.486 1.6 10.37 51212 5.077 2.0 10.15 501

142b 4.248 2.4 10.19 503124 5.758 1.8 10.36 512133a 4.846 2.1 10.17 50221 4.367 2.4 10.48 517

isobutane 2.452 4.2 10.29 508114 7.319 1.4 10.24 506

ComponentLiquid

Density,mg/µl

VolumeAdded,

µl

mgAdded

(1)

ppmAdded

(2)

Total ppm Present

(3)11 1.537 6.6 10.14 501123 1.526 6.7 10.22 505113 1.619 6.3 10.19 503




150

Part 49


Section 1. Scope



This method is calibrated only for those impurities commonlypresent in R-508 blends. This method will not detect anyimpurity that may elute within the comparatively large HFC-23and FC-116 peak matrices. For example, HFC-32 cannot bedetected using this method as it elutes within the large HFC-23

component peak matrix. In addition, ethane cannot be detectedas it elutes within the FC-116 component peak.



Section 4. Tables



151



RangeInvestigated,

ppm


methane 1 100 0.4ethene 1 200 1.0

13 14 450 2.0143a 2 450 3.0152a 2 450 5.3125 8 450 41134a 4 450 2.022 12 450 31

1301 14 450 3.6218 11 450 1.5

propene 1 100 6.0115 13 450 2112 16 450 2.4

142b 3 450 4.9124 7 450 3.9133a 3 450 5.221 8 450 5.4

isobutane 1 100 2.6114 9 450 4.8

n-butane 1 100 2.411 15 450 12

123 4 450 11113 5 450 7.8



RangeInvestigated,

%


23 8 39 % 0.12 %116 98 61 % 1.7 %



AfterComponent

Addition (kPa)


R-23 266 7.80

R-116 465 12.20

152


ComponentVapor

Density,mg/ml

VolumeAdded,

ml

mgAdded

(1)

ppmAdded

(2)


methane 0.656 4.0 2.62 130ethene 1.147 4.0 4.58 226

13 4.331 2.4 10.39 513143a 3.511 2.9 10.18 503152a 2.772 3.7 10.25 506125 5.004 2.1 10.50 519134a 4.279 2.4 10.26 50722 3.606 2.9 10.45 516

1301 6.205 1.7 10.54 521218 7.923 1.3 10.29 508

propene 1.756 5.8 10.18 503115 6.486 1.6 10.37 51212 5.077 2.0 10.15 501

142b 4.248 2.4 10.19 503124 5.758 1.8 10.36 512133a 4.846 2.1 10.17 50221 4.367 2.4 10.48 517

isobutane 2.452 4.2 10.29 508114 7.319 1.4 10.24 506

n-butane 2.463 4.2 10.34 511

ComponentLiquid

Density,mg/µl

VolumeAdded,

µl

mgAdded

(1)

ppmAdded

(2)

Total ppmPresent

(3)11 1.537 6.6 10.14 501123 1.526 6.7 10.22 505113 1.619 6.3 10.19 503




153

Part 50


Section 1. Scope

This GC Method Data Sheet is for use in conjunction with Part33, General Procedure for the Determination of Purity of Newand Reclaimed Refrigerant Blends and Azeotropes by GasChromatography. This GC Method Data Sheet is for use withR-509.


This method is calibrated only for those impurities commonlypresent in R-509A. This method will not detect any impuritythat may elute within the comparatively large HCFC-22 andFC-218 peak matrices. The contaminants HFC-23 and HFC-32also elute together, but these may be separated if needed by

adding a 0.30 m column section of Porapak-T to the end of theprimary column.



Section 4. Tables



154



RangeInvestigated,

ppm


methane 1 100 0.923 8 450 8.332 3 450 4.8

ethene 1 200 1.4ethane 1 200 1.9

13 9 450 2.7143a 1 450 4.8152a 1 450 5.4125 4 450 5.2134a 2 450 3.61301 7 450 4.5

propene 1 100 0.5115 6 450 1212 8 450 1.3

142b 1 450 83124 3 450 7.3133a 2 450 7.621 4 450 6.0

isobutane 1 100 1.2114 4 450 4.9

n-butane 1 100 1.211 6 450 17

123 2 450 5.2113 2 450 13



RangeInvestigated,

%


22 5 44 % 0.01 %218 5 56 % 0.12 %



AfterComponent

Addition (kPa)


FC-218 140 11.20

R-22 363 8.80

155


ComponentVapor

Density,mg/ml

VolumeAdded,

ml

mgAdded

(1)

ppmAdded

(2)

Total ppmPresent

(3)methane 0.656 4.0 2.62 130

23 2.895 3.5 10.13 50032 2.162 4.7 10.16 502

ethene 1.147 4.0 4.58 226ethane 1.230 4.0 4.92 243

13 4.331 2.4 10.39 513143a 3.511 2.9 10.18 503152a 2.772 3.7 10.25 506125 5.004 2.1 10.50 519134a 4.279 2.4 10.26 5071301 6.205 1.7 10.54 521

propene 1.756 5.8 10.18 503115 6.486 1.6 10.37 51212 5.077 2.0 10.15 501

142b 4.248 2.4 10.19 503124 5.758 1.8 10.36 512133a 4.846 2.1 10.17 50221 4.367 2.4 10.48 517

isobutane 2.452 4.2 10.29 508114 7.319 1.4 10.24 506

n-butane 2.463 4.2 10.34 511

ComponentLiquid

Density,mg/µl

VolumeAdded,

µl

mgAdded

(1)

ppmAdded

(2)

Total ppmPresent

(3)11 1.537 6.6 10.14 501123 1.526 6.7 10.22 505113 1.619 6.3 10.19 503




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