FINAL REPORT
HYDROCARBON SAMPLING METHODS
FOR
SOURCE SAMPLING
JANUARY 23, 1980
Contract Ne. A?-124-30
From: Thomas J. Kehoe* and Philio Deming**
Beckman Instruments, Inc. Process Instruments Division 2500 Harbor Boulevard ~i~ Fullerton, CA 92634 · -r-
*Principal Investigator, Manager Technical Services Department
**Principal Application Engineer, Technical Services Department
TD
K53 890
1.
(
(
TABLE OF CONTENTS
Table of Contents
List of Figures
Acknowledgements
Conclusions
Recommendations
Body of Report
a. Introduction b. Design
1. Dynamic dilution for calibration 2. Man:ifold system to analyze gas blends 3. Sample injection and dilution system4. Grab sample transfer and dilution
c. Evaluation 1. FID Model 402 Calibration 2 cc/minute 2. FID Model 402 Calibration at 0.32 cc/min.3. The catalytic combustion co2 infrared analyzer system4. Continuous sampling and dilution system5. Cyclic sampling and dilution system 6. Grab sample transfer and dilution
d. Discussion 1. Accuracy of Measurement 2. Simplicity of Measurement-Continuous
Vs. Cyclic3. Dependability of Measurement System4. 6rab Sample Techniques5. Proposed Field Sampling/Analysis System
Glossary of Terms
Appendix
1
2
4
5
6
7 8 8 8 8
12
12 13 17 17
17 17 23
23 23 25
27 27 28
30
31
2.
( LIST OF FIGURES
Title Figure Page
Dynamic Dilution System 1 9
Simple Manifold System 2 10
Syringe Injection System 3 11
Grab Sample Dilution/Transfer System 4 14
Model 402 Calibration - 2.0 cc/minute 5 15
Model 402 Calibration - 0.32 cc/minute 6 16
Model 402 Diluted Calibration - 1.0 cc/minute 7 18
FID vs. co2 IR, Calibration with Methane 8 19 FID vs. CO2 IR, Comparisons with 3 Hydrocarbons 9 20
Continuous Dynamic Dilution System 10 21 ( CO2 IR Syringe Injection Calibration 11 22
Gas Flow vs. Varying Propane 12 26
Recorrmended Field Monitoring Systems 13 29
(
3.
(
DISCLAIMER
The statements and conclusions in this report are those of the contractor and not necessarily those of the California Air Resources Board. The mention of commercial products, their source or their use in connection with material reported herein is not to be construed as either an actual or implied endorsement of such products.
(
4.
(
ACKNOWLEDGEMENTS
Throughout the evolution of this study, the guidance and patience of Messrs. Jack Paskind and Dean Simeroth of the State Air Resources Board was greatly appreciated.
The word 'patience' was chosen since the project suffered from illnesses and losses of key personnel causing sizeable delays.
Within Beckman Instruments, we wish to thank the followingfor their cooperation and assistance: Roy Awalt, Jack Christiansen, Jim Crabtree, Bob Belcher, Glen Heyman, and Rick Villalobos. .
This report was submitted in fulfillment of California State ARB No. A?-124-30 - "Hydrocarbon Sampling Methods for Source Sampling" by Beckman Instruments,. Inc. under the sponsorship of the California Air Resources B'Jard. Work was completed as of August, 1979.
(
5.
( CONCLUSIONS
1. The use of the ARB version of the Beckman Total Hydrocarbon Analyzer as a source monitor must be done around the calibration curve shown in Figure 5. This figure illustrates saturaticn of the flame ionization detector when fed concentrations greater than about five percentequivalent propane. The curve also shows that precision of measurement is better by a factor of eight in the range of zero to five percent propane than it is in the range of ten to seventy percent.
2. Two methods of sample dilution are available to give usable samples to the measuring instrument:
a. Dynamic dilution - a continuous system with an estimated precision of the order of ten percent.
b. Volumetric dilution - a cyclic system operating at one dilution per minute with a precision one percent.
3. An alternative system of oxidizing hydrocarbon to carbon dioxide and then measuring this with a non-dispersive infrared analyzeris practical. It, too, requires a diluted sample.
4. A system of taking 11 grab 11 samples in a small bomb has been developed.These samples may be taken from the source itself, or from a sampleline. Samples are subsequently diluted and may be given to either measuring system used in this investigation.
(
6.
(
RECOMMENDATIONS
As with many investigations that depart from established methods and techniques, the results often generate more questions than anticipated.In this project we believe that the practicality of a dilution systemfor field measurements as well as a means for the procuring and analyzing of "grab" samples has been established.
These conclusions must still be compatible to the requirements of the California ARB source monitoring program. If our conclusions offer the ARB practical methods for them to achieve their requirements, it is recommended that the dynamic and/or cyclic dilution systems, as described, be assembled for field evaluation. This (these) in conjunction with the existing ARB Model 402, or preferably, a CO IR systemcould provide a 'real world' evaluation of the proposed t~chniques.
In conjunction with the above, the described "grab" sample techniqueshould be incorporated into the evaluation. This would also provide means to establish the quantitative analysis, periodically, of emissions during a continuous field sampling and analysis run.
Since the oven and related components employed in this study as de( fined during contract negotiations become the property of ARB, these could form the nucleus of the proposed field evaluation system together with the ARB 1s existing test equipment.
(
7. INTRODUCTION
( The scope of work was diVided into three dis ti net segments : 1. The basic calibration of the heated Flame Ionization Detector
(FID) Hydrocarbon Analyzer (Beckman Model 402).
2. The response of the FID to an array of hydrocarbon blends consisting of saturates, unsaturates, and aromatics;
3. And attempt to establish the best sampling and detection techniques to assure accurate analysis regardless of hydrocarbon type and regardless of varying composition, viscosity and specificgravity.
One of the primary objectives of this study was to include, wherever possible, a parallel measurement of the test hydrocarbons by catalytically combusting the hydrocarbons to CO? with the subsequent analysis of the CO2 by means of a non-dispersive infrared analyzer (Beckman Model 865).
To assure that comparable results could be achieved, both the FID and CO2IR were first subjected to the following hydrocarbon gas blends (in air).
1. CH4 through c7H16 2. C2H4, C3H6
( 3. C6H6
These gases were at +60% of their respective L.E.L.s (from 3.75% to about 0.75%). -
Since it was established that very good correlation was achieved comparing the two detection techniques, the program was focused toward similar analyses but starting with pure hydrocarbons followed by appropriate dilution. Such diluted gas streams were then routed to the two different emthods of analysis.It was at this point that the extreme importance of proper sample handlingand adequate dilution became overwhelmingly evident. Although the sample injection (via a multi-port GC sample valve) and subsequent dilution was performed within a heated constant-temperature enclosu:--e, results were typically erratic and consistently low, particularly with the FID. By the insertion of a 50 milliliter dilution syringe to initially receive the hydrocarbonsample from the slider valve, results were better but continued to be lower than predicted.
Attempts to calibrate the FID 402 with propane clearly illustrated the problem of dropoff of conversion efficiency as propane concentration increased. At sample flow of 2 cc/minute lessening response started at about 5% propane.Only by lowering the sample flow to 0.3 cc/minute were we able to obtain linear response in the 0-20% propane range. Above 20% response againdropped off.
(
8.
Since it was established that a typical field sampling condition would involve a mixed hydrocarbon concen&ration of up to 75%, balance air, and
( a head-space temperature up to 100 C, the remaining efforts were focused on a test program to provide systems for both continuous sampling and dilution plus a grab sample technique for obtaining such concentration levels.
The following sections describe in detail the systems used for the above efforts and the subsequent tests employed for the high concentration studies.
DESIGN
Four basic designs were used to meet the three principal objectives of this investigation:
1. A dynamic dilution system to generate concentrations of propane in air from zero to one hundred percent (See Figure 1). This system was used to develop response curves for the two -measurement systems involved.
Industrial grade propane and 11 Zero Air" (contining less than one part p.er mi llJon bydroca,rbon) .were mixed to gene.rate s.tandards from ten to ninety percent propane in ten percent increments. Each gas was pressure regulated and the flow controlled with a throttling valve before going to its flcwmeter. Each flowmeter wa.s ca.librated with the gas to be metered using .a bubble flowmeter. Pressure, temperature, and water vapor corrections were applied.
2. A simple manifold system (Figure 2) which allowed sampling of standard cylinder gases at ambient pressure. .This system was used to sample hydrocarbons at a level of less than four percentin air to determine detector response to various hydrocarbons.
Two sources of cylinder gases were used. The initial effort was with blends prepared by a nationally known and respected manufacturer. Of the eight blends used, four fit the curve expected,while four were random. Additional blends were prepared in the Beckman facilities, all of which fit the expected curve. Beckman blends were used as the basis of this report.
3. A sample inject system which allowed a one microliter sample of liquid, or a one milliliter sample of vapur (Figure 3) to be diluted with air. This diluted pure hydrocarbons to the linear range of measurement for the ARB instrument, again to determine how the detector responded to different compounds.
The first effort injected a one milliliter aliquot of propane vapor into a flowing stream of zero air. Giving this to a mixing chamber resulted in an exponential dilution which made peakheight measurements difficult to reproduce.
- ---,...___
Hydrocarbon
200 Ifcc/min. ,Dl(]-----1--,-C>
- ---,-....
Vent
_f to AnalyzerMix
FIGURE 2
SIMPLE MANIFOLD SYSTEM
..... 0
11.
r----------- -7 Oven
( Air
1 100 cc/min.
Samo1e In
200 cc/r.iin.
( ,-- - - - - - - - - - -7
Vent ._______
Converter ~
(
Oven Air
100 cc/min.
50 cc
+- Air /'~-- Samole InSample LoopConverter (for Vaoor Samples)
~ Bypass I'--------- - - - - - rorFro- - -: - - - - - -
200 cc/min.
FIGURE 3 - SYRINGE INJECTION SYSTEM
12.
A variation of this system was to inject into a syringe, follow with zero air to dilute to fifty milliliters, and then withdraw this dilution to the measuring systems. Reproducibility was excellent for any one concentration, but linearity was marginal.
4. A system to allow taking of a grab-sample. This allowed~ highconcentration of hydrocarbons, such as from the head space of a tank, to be sampled, diluted and then measured by a standard instrument.
This system employed a 100 cc sampling cylinder fitted with valves at each end. The cylinder was evacuated and taken to the sampling point. Any lines connecting the cylinder to the samplingpoint were purged with sample, the cylinder va·ive opened, and the pressure of cylinder and sample allowed to come to equilibrium. When this was done, the cylinder valve was closed.
If .the temperature. of the. vapors betn.g sampled. was higher than the temperature of the cylinder, condensate formed in the cylinder. To get a reproducible volume of sample the 100 cc cylinder was putinto an oven maintained at 150 C (see Figure 4). This cylinder was connecte
13.
( In source monitoring of crude oil storage tanks, the ARB must measure up to 75% hydrocarbons typically. The composition of these tank overheads is generally unknown. It must be expected that the rangeof carbon numbers will vary widely, depending on how long the mixture has been held and the temperature of the tank. A test was devised to determine flame ionization detector response to mixtures of en, c7, c8, c9, and c10 in propane in approximation of the mixtures expected. A mixture of air and propane is sparged through a liquid hydrocarbonkept at a constant temperature in a bath. The effluent is maintained at a ratio of 75% hydrocarbon/25% air by adjusting propane flow to keep oxygen content at 5%. When the system has reached equilibrium, the mixture is analyzed with the Model 402. (See Appendix for calcu-1ations).
The table following lists test conditions and results. The scale readings of the test are in relation to calibrating the Model 402 with a 75% propane/25% air mixture and spanning to 15% of scale. To show a fit on the calibration curve of Figure 5, th~se scale readings were recalculated for a cur:ve develop~d with a mixture of 50% propane/SO%air and spanning for 50% of scale.
Test Mixture Span@ 75% Span@ 50%( HC t 0 c Air C3H8 HC Scale Replotc3H8
25 75 75 75 61.5C3H8 17 .4 25 61.7 13.35 88.5 83 68. lC6Hl4
43.0 25 60.3 14. 7 94.6 85 69.7C7H16
i-c8H18 46. l 25 57.8 17.2 103. 7 87 71.3
40.2 25 73.6 1.4 77.8 77 63. lC9H20
38.5 25 74.5 0.52 76.2 77 63. lClOH22
Replacing the long capillary with a shorter one of smaller diameter allowed a feed of 0.32 cc per minute to the flame at a head pressureof 0.25 psig. The response curve for the same instrument with this lower feed is now linear to twenty percent propane (Figure§_).
-- ...-..~
T
CylinderDilution Air
400
cc
100 cc
Samp~es of Hydrocarbons to be prepared per system descriibed in previous report whereby25% air plus 75% mixtures of propane plusheavier hydrocarbons are blended and admitted into evacuated sample cylinder
Contra 11 ed Constant Temperature Oven~
FID ("102)
.. 1cA.T CD"-.IV. ~ c.02. t R.,.., , y
Tedlar Bag __, .i::,.
FIGURE 4. GRAB SAMPLE DILUTiml[l'.RANSFER SYSTEM
15.
, t::: :l1 ~':: i !
'. t
- ~'.!' ·~ i ◄ I it
..! t
' ~ i Jr .
Ii ']I', j·t! •! I , !
t t ·ii! tj/i t '
-r ttrt 1±11-H:·
0.,,
2
•-•' ' I (
,-.._ ,.,,-..,. .,-..,
80
70
60
59 % fZ.E.sPONSC:.
40
30
."/4 PROPANE IN AJK.. 20 BE.C..K.MAN MDDE:.L 402.. FJD
'F"LOW TO FLAJ-AE.. O. '3 "2.. c_c../1vt1N.Y'I P61C- -10; ~o H2.//-4. e... To t=='LA.>-..AE:, @ 100 C.c/Ml._1, .
10 350 c.
17.
It is obvious that the flame ionization detector becomes saturated when the level of propane fed to the flame reaches 0.1 mol percent.( Inasmuch as it is not practical to restrict the feed of sample to the flame to less than l cc per minute, the only alternative is to make a source dilution of the sample to prevent concentrations greaterthan an equivalent of ten percent propane from being sampled. Figure.I shows linearity of the detector feeding l cc per minute to the flame while sampling from zero to ten percent propane.
2. An alternative approach to measure hydrocarbons in air is oxidation to carbon dioxide and measuring with a non-dispersive infrared analyzer. The systememployed in this investigation was a catalyst oed of palladium on alumina held at 500°c for oxidation and a Beckman Model 865 Non-Dispersive Infrared Analyzer to measure carbon dioxide.
This system also requires sample dilution. For one volume of propane to be oxidized, twenty-five volumes of air are required; for one volume of octane, 62.5 volumes of air. The combustion approach, however, does have the advan-tage of always measuring the same component (carbon dioxide) and thus eliminates the problem associated with the flame ionization detector of relative response to different compounds. Figure 8 shows a comparison of these two measu~~men~ systems ana,lyzir19 the source samples of methane.. Fi.gu.re 2_ compares the response of these two systems to one mol percent samples of three different hydrocarbons.
Two methods of source dilution were considered:
( 3. A continuous dilution at the sample probe. This would involve metering a zero air to the probe as a diluent. To meter sample flow directly presents the problem of contending with varying temperaturesand viscosities from point to point. These effects can be minimized by measuring total flow through the sample tubP.. That is, if 2000 cc per minute of zero air is given to the probe and 2100 cc per minute is metered through the sample line, 100 cc per minute of sample is being diluted by a factor of twenty to one. Th~ sketch of such a system(Figure 10) illustrates the two-stage dilution system in further detail.
4. Cyclic dilutions, described above, which involve taking a discrete sample at timed intervals, diluting it in a heated chamber and givingthis dilution to the measuring instrument. The principal disadvantage to this method is that the volumes prepared are too low to be used by the Model 402 Total Hydrocarbon Analyzer, so the investigation was restricted to catalytic oxidation of the sample and then measuring CO2by infrared.
This method makes dilutions with great precision (see Figure 11). The curve superimposed on the chart of Figure 11 s:1ows an exagerated Beer Lambert curve believed to be the result of inaccuracies in the blends given to the system. It does appear to hold the most promise for a reliable system for source monitoring.
The cyclic rate is a function of flow rates. Using a 50 cc dilution, a ( carrier flow of 100 cc per minute and an exhaust flow of 200 cc per
minute, a forty-five second cycle is used. This appears to be a goodcompromise between speed of.response and precision of dilution ..
https://Fi.gu.re
18.
( 100
90
80
70
60
50
40
30
20
10
0
%PR,OPANC. IN AJR. BE..GK.MAJ..J f',,A.D D C:.L- -4 0 z.. F ID D/LL/"rE..D -=,AMPLE.. l='"LOw To FLAME:.. © I, 0 cc./MIJ..J.1 \ '?~I
19.
80 (
70
60
% -~l 1LL
"SC.ALE: 50
40
(
30
20
10
(
0
I
CAUB. e COMPAR.lSOt.l OF
~OTE... ~ s L.. C.UK.VA.TUR£.. GUIZVE.... TYPlc:.AL LAW SFFEL..T
4
FIGURE 8. FID VS. CO IR, CALIBRATION WITH2
FID vs C.0 z.l F(.
OF C.OZIR.. BE..E.J
20.
(
0 00 r-... 0 t.O 1
\,0
lo
,.
' -I----r -1--
I I
---! l
I j___ ----+I·------ -t---~ +--:------11
. i . ' . I .
: t~ . l
I . i . l
~~~-+-~ ' +----- t--'
21.
FROM
,-----=-~----,I5: 1 MIX
ZONE I IMIX ANALYZER4 1
: ZONE t---1~-S_Y_ST_EM_____,J
't' r 'f
I I I I I
( I I
DILUTION AIR I ________ _J TEMPERATURE CONTROLLED OVEN
FIGURE 10.
CONTINUOUS 2-STAGE DILUTION SYSTEM
(
(
(
23.
5. The "grab sampling" system was used to evaluate both the flame ionization detector and the catalytic combustion infrared measuring techniques. Inasmuch as linearity of both of these systems with respect
( to concentration had already been demonstrated, this part of the demonstration was restricted to system response to constant volumes of pure hydrocarbon vapor. Each test was done in duplicate, using propane, hexane, and iso-octane.
The procedure followed was to evacuate both bombs with a high-vacuum pump, introduce sample, bring up to temperature, equilibrate the sample bomb with ambient pressure, release sample bomb to the largerbomb, equilibrate, and purge both bombs with forty liters of air into a Tedlar bag. After kneading the bag to insure an homogeneoussample, it was sampled with the Model 402 Total Hydrocarbon Analyzer.The bypass of the Model 402 was used to feed the infrared system. The comparison of these two systems is shown on the previously referenced Figure 4.
DISCUSSION
The following discussion will first consider the dynamic sampling and analysis.The subject of grab sampling techniques will be treated separately in the second segment of this section.
Since the ultimate objective of this study is to provide a more accurate means of accessing the hydrocarbon emissions at point sources, such as at crude oil storage tant
24.
(
(
(
B. When the air/oxygen background of the sample varies, the 11 oxygen synergism 11 effect will impact upon the accuracy of the analysis.
C. Use of capillaries to restrict flow, which in turn is aimed at permitting higher% level hydrocarbon measurements, causes unknowr. variability of flow rate to changing viscosities of the unknown hydrocarbon mixture. This also impacts upon the accuracyof the measurement.
D. At least two cylinder gases are required.The CO2 IR Analyzer - This analyzer actually i~ an analytical system consisting of a standard non-dispersive infrared analyzer sensitized to measure CO preceded by a catalytic combustion zone. This zone typically con~ists of a quartz tube filled with a catalyst, such as palladium, on a ceramic or asbestos substrate. The tube is surrounded by a hegting mantle and the temperature is typically maintained at 500-600 C. No evidence of catalytic conversion deficiency has been found to date. It was 8riginally planned to use a cobalt oxide catalyst and operate at 950 C since this has been widely tested and employed to. convert hydrocarbons to CO2 in organics in wastewater applications. For this, "p.urpase no organic compound .has bee.n found to date that ooes not convert with 100% efficiency. However, the former approach (palladium at 500°C) was selected since the temperature requirements are much less demanding looking ahead to some semi-portable system for use in the field. Regardless, the higher temperature cob:?.lt catalyst approach is available should future shortcomings be found using the palladium.
Attributes: A. Rugged, widely employed for many years for ambient, source, and automotive pollution monitoring networks. Measurement parameters include CO, so2, NOx and total hydrocarbons (as hexane).
B. Probably has the best on-line performance record of any stream analyzer.
C. Lends itself readily to auto zero/auto cal. calibration systems often supp~ied with the IR analyzers.
D. In measuring CO? essentially no interferences variable responses are encountered.
or
Limitations: A. Cannot reach the PPB levels. Typical minimum range is 0-50 ppm, +1%/24 hours reproducibility.
B. Depending upon concentrations being measured, the output is not strictly linear but follows Beer's law.
Both analytical techniques suffer a common lim·itation - neither can measure hydrocarbon concentrations much in excess of +5% total carbon concentration*. With this seemingly unalterable conclusion, it becomes
*This is not a maximum limitation for the IR in normal applications not involving preliminary catalytic conversion to co2.
https://cob:?.lt
25.
obvious that a pre-dilution step must be integrated into any field analysis procedure when it is anticipated that a double-digit hydrocarbonatmosphere is to be measured. With that fact in mind, the decision must be made as to the selection of the best analytical technique - FID versus CO IR. Once it is recognized that an approximate 20:1 dilution must be i~corporated into the measurement system, the di lemma of unknowr: viscosity influences are drastically reduced - also oxygen synergism.However, the FID response factor variations remain despite the dilution effect. Contrarily, the CO IR remains free of such problems. This aspect, coupled with the si~plicity and freedom from peripheral gases and maintenance requirements, tends to make the CO2 IR the most attractive option.
2. Simplicity of the Measurement - If it is accepted that the CO2 IR analysisis the optimum measurement technique,.the key to successful future field measurements of source hydrocarbons will be the simplicity and dependabilityof the total system.
At present, the California State Air Resources Board employs a 100-foot heated sample probe that is capable of withdrawing a headspace, or ventingsample of a hydrocarbon mixture from the top of a tank, such as crude oil stora~e tank, to ground level. Such a sample is pulled from its source by means of a pump downstream of the FID 402 analyzer. In order to interject a precise dilution which, for the sake of discussion, will be assumed to be a 20:l dilution, at least two options are available.
( A. D~namic continuous dilution - Since the flow of the saijple gas from t e source may require maintaining temperatures to 100 C and the hydrocarbon concentration may range from low level to 100%, the use of flow measuring and controlling devices becomes tedious, of questionable accuracy, and certainly not simple. Again, the problems of viscosityand density must also be recognized.
Thus it is our recommendation that, if a truly continuous sampling system is required (contrary to the following Part B in this section), a dynamic flow measurement and control of the dilution gas and the combined diluted sample gas flow be accomplished. Again, assuming a 20:1 dilution of the gas to be analyzed, the dilution required should be done in cascade. It will be noted from Figure 12 that metered flow of propane and air mixtures changes by a factor oftwo over the actual flow in going from pure air to pure propane. To suppress this effect, a preliminary dilution of five to one is done. This ratio is selected as a compromise between the viscosity effect demanding a large ratio and the dilution error demanding a small ratio. A final dilution of four to one will bring total dilution error of about eleven percentwith a dilution of 20:l.
B. Intennittent sample dilution - As describ~d earlier under Methods of Source Dilution, highly accurate dilutions can be achieved by employingvolumetric sample and dilution technique. By the use of a slider valve, a precise volume of sample can be measured and dispensed. This sample
-
6Ao FLOW_ y~ ¼ PRDPAt-JE:.r: 1)..J A\R
C~AMt::.T"E...R. © Co/.J6TAfl....rl 100 c..cj J....J....1J..J .)
,---.._ ---..,
200
180
160 :i
t8 140 )
~ 120
J
~ b -
(
(
(
27.
can be contained within the valve itself or, for larger samples, be contained in a sample loop into and out of the slider valve. Since this sample must be contained and diluted, at least initially, within an elevated temperature zone to avoid any condensation, a heated chamber must also be included in this scheme. Also, a programmable timer must be inluded to actuate the cycle. This cycle can be repeated on a once per minute timing. This may still not be acceptable to the Air Resources Board since we have been advised verbally that a continuous measurement is desired. The concentration levels should appear as a series of peaks whose heights should correspond to prevailing concentrations.
From a simplicity standpoint in comparing the two above options, the continuous technique must be the simplest but at the sacrifice of the accuracy we know can be achieved in the intermittent method. To bolster the accuracy of the continuous method to the level of the intermittent method, we suspect that the desired simplicity would be lost. We believe that the combination of precise, calibrated rotameters coupled with highsensitivity pressure differential flow controllers on both the dilution gas and combined diluted hydrocarbon gas will result in a known sample gas stream whose volume will be known to about 10% accuracy. Presumably, this would provide an acceptable total system accuracy. If not acceptable, the volumetric intermittent technique is recommended.
3. Dependability of the Measurement - Dependability of the measurement system encompasses a number of critical segments; the primary sample probe and transmission, the dilution control system and the analytical system.Inputs from the ARB staff im.l:ica:te that time spans for on-site me,asurements are about 24-48 continuous hours. If this is correct, it is believed that all segments used in this investigation survive this period with minimal attention following initial calibration. Stability could be further improvedby incorporating an off-the-shelf auto zero/auto span module to account for any short term span or zero drift.
Grab Sample Analysis of Source Hydrocarbons
The technique described previously wherein an evacuated cylinder receives a headspace or venting source hydrocarbon sample for subsequent analysis is an obvious and attractive method of sampling. However, the technique to reliably transfer and dilute the sample prior to analysis has a number of potential pitfalls and opportunitites for error.
The results obtained during this project, although not refined to the extent desired, were very promising. Once a large, heated, evacuated cylinder was employed downstream from the heated sample cylinder, the problems of condensation and subsequent revolatizing were eliminated. The evacuated sample cylinder (100 ml) must be filled with the desired sample with a minimum dead space between sample source and cylinder inlet. Thus, the sample should flow directly to the cylinder inlet valve prior to admitting sample into the cylinder. Since the cylinder probablywill be at a lower temperature than the flowing sample, the sample flow into the cylinder should be stopped when pressure equilibrium is reached. This should prevent the partitioning of heavies within the cylinder due to condensation.
Once the sample cylinder is heated to a temperature above the original sample and the excess pressure vented as described earlier, a known volume sample is available for subsequent dilution into the larger evacuated and heated cylinder fol-
(
(
(
28.
lowed ~Y dil~ti~n gas to fill a Tedlar bag to an ultimate volume of 40 liters. Once mixed w1th1n the bag, a 400:l diluted sample is available for analysis byGC, FID, or CO2 IR.
We believe that this sampling procedure represents a practical means to sample source hydrocarbons. To calibrate the instrument the same technique can be employed as we did during our tests. A slight excess of hexane or octane can be injected into the same type ·of evacuated cylinder. Once the cylinder is heated to a temperature higher than the boiling point, the cylinder can be vented back to atmospheric pressure and diluted as described.
Recortmended Hydrocarbon Monitoring System for Future Field Measurements by the ARB
As suggested in the above discussion, Figure No. 13 attempts to summarize the features of an optimum field monitoring system forsource hydrocarbons. The system is based on the assumption that a heated flexible sample probe is available and of such length that the dilution and analysis can be performed at a convenient ground level. The sample will be withdrawn by means of a pump similar to the heated stainless steel bellows pump employed in the Model 402 HydrocarbonAnalyzer. A portion of the discharge is directed to a gas mixing chamber which al so r~9~iv.es .an clc:c:yrc1t.ely ~c1sur-ed .and. cont.rolle.d. flow of dilution air. To e 1 imi -nate ambient temperature variations, both flow measuring and consrol systems should be mounted within the common temperature controlled oven lat 100 or greater) together with the pump and mix zone. The analyser system should be close coupled to the oven but external to it.
As mentioned earlier, this system will suffer from the unalterable problem of multiplying by two any flow measurement inaccuracies. Thus, if at least a 20:1 dilution is required, the flow difference which represents the true flow rate of raw sample, will suffer from these cumulative inaccuracies. Thus, it is urgedthat the intermittent dilution by controlled temperature slider/dilution syringebe given serious consideration as an alternate. Regardless of choice, the accuracyof either analytical system will be a vast improvement compared to the use of the FID 402 directly whenever dealing with high hydrocarbon concentrations.
https://r~9~iv.es
29.
(
I1.....-z-- HEATED SAMPLE PROBE II II ~ CONTINUOUS
DYNAMIC t--___. CO2 IRCAT. COMBN.DILUTION SYSTEM HEATED OVEN
:./ ALTERNATE
c::_ See Figure 10. ~ FID
( 11 ~HEATED SAMPLE PROBE
11
11
11I~ CYCLIC
SYRINGE INJECTION DILUTION SYSTEM CAT. COMBN. CO IR
HEATED OVEN I
-------~ (!_ See Figure 3
I ,...,!J
ALTERNATE
DILUTION AIR 7 FID
FIGURE 13.
( RECOMMENDED FIELD MONITORING SYSTEH(S)
30.
(
GLOSSARY OF TERMS
CO2 Carbon Dioxide
CO2IR Carbon Dioxide Infrared (analyzer)
FID Flame Ionization Detector
GC Gas Chromatograph
IR Infrared (analyzer)
L. E. L. Lower Explosive Limit
NDIR Non-Dispersive Infrared (analyzer)
PPB Parts per Billion
PPM Parts per Million
( PSIG Pounds per Square Inch
(
31.
APPENDIX
This contains a series of calibration curves spanning with 3.58% methane and using an array of +60% L.E.L. hydrocarbon blends to establish equivalent response using the Beckman Model 400 FID.
These calibration curves have been presented in previous contract progress reports and are included here for further information for those who may not have such earlier reports.
LI ST OF FI GU RES
Figure Page
Calibration of the FID vs. Various Hydrocarbons
:(
FID Vs.
FID Vs.
FID Vs.
FID Vs.
FID Vs.
FID Vs.
FID Vs.
FID Vs.
FID Vs.
FID Vs.
CO2 IR, 1.8% Ethane Calibration Data
CO2 IR, 1.35% Propane Calibration Data
CO2 IR, 1.2% Butane Calibration Data
CO2 IR, 0.84% Pentane CAlibration Data
CO2 IR, 0.71% Hexane Calibration Data
CO2 IR, 0.44% Heptane Calibration Data
CO2 IR, 2.4% Ethylene Calibration Data
CO2 IR, 1.2% Propylene Calibration Data
CO2 IR, 0.96 Butylene Calibration Data
CO2 IR, 0.84 Benzene Calibration Data
Calculations for Dilutions of Various Hydrocarbonsin 25% Air
14 32
15 33
16 34
17 35
18 36
19 37
20 38
21 39
22 40
23 41
24 42
43
(
100
80
60
40
C..q 1410 -----------I►
C-OMPAR,1-SQIJ 01=" ~'../DJWC.A,R..8Qt,J'6
ey i=ID
32.
( A.-PPE>JDI)
I I !
l
1---_.....-------+----1-~-L I :--------1-------
-- - j- ----- ------ -1· ·- -
....... •-·...--+-
i ./ ..
';
·:--,_J__ _,_.__;__ ---!--" :
__ : _, .l-,- : ; .1. ,_
---4-l--l.-...L- -+-~- _: i '
;
j
t ----i-- -- . - --- - - --•--·- '----- ---- ! ~ : ·---,--,-.. .-·--·--
,i_
, I j t + :
I
; ' i
! \. l l
-l fiI I I
I
t ; i
I., i., I
i
f I
! ! i ! ! 1 \ ! I
i
' il l
l l ; I
I '
,,.
; I
I I ' iI . !
i '
' ' i ,i
I
j 1
l l
-··f -+-t---1 - ,
I
I .. ~-
(
I i
: i
i I ! I j
; .. ; j(
I
I I
I
I i I I I
I 33.
0 U") - ,-LJ.Ja:
~ :::> t.!) ..... I.J..
CiO \)
.....,x
" .J CD?
\i. q"
~
('I)
-0 c,, co N --
8
34.
(
: I I
.+.L-----.. ~.- -~ .;-L- -__.___ J..~_:.__
. t .. '--~-..:. - ~__: -~+-i -·
l !
: r I
; ' 'l I I
!
1-'·_-•;.._...._i_;_4...;.....1_-..:._,_..l."--j...__,'---'-~--+--'-\..--:.-...-;..+-+---~'----"---+--'---'-'-!--;-...........,....-+----'·~..--t-----+----+-----1------+-;'-----~ +- ~ I __ ; .: !
.. i- ). I •
. "'
.~ f-.. l"'l
rc ' I I
I I,_.
--- .---- ---+----·-··
l I
--• --- -- --- _;__. : , - __)__ , N __ ; __~
~ -· ----- --- - ~ --~ ' --- '- ' _j-flll +--- ➔-
__ _:_:~=t~~ ~-=-tt.:r= ~t=·tti-_ j
-t I. • j
'
JI. : t:i:
Ii , ..
I
I :
l --H ' j
:
.j
l
j
I i
I !
l t
! I
,-
l
I
I
I ,a,
I
j :0
I i
1.0-Lu( 0::: :::, (!:!
LL -
I ,co
' ' t l I !
-r--~~~-
:,....i 0 'X
c.o ti w . I ' I ~
~-+- --~·----t-+· ill) ti !
i i
I G :.- i.L
. ' ~
( T ,! +i t ' ,!! :t:1, Ii I ·___i:___ 1_ i..-,__ _;_.....j__-i-__;_~.j.__.__;_----+_...1..._-'-l->----'-'---+--+---,-+--1f---'----+--'--- --~ ----------+------- .--I : - -
i .:I · 0 a, co (") 0 --
35.
(
(
(
I •
0 a,-
i i
I •
l l t j I
-j t :!·
00
OIX
,....
l I
r :
t> . ..-·
l -
• K{)~' r--- .
!1; ()
, I
j I
In
0
: I ·-I a,
I
~'00
" 0 X
U)
rd. lJ
U'-) C) ~ C.. \) w \!-
- O·
........... 1.1.J 0:::
-~ (.!3 LL
36.
I '' .. +--
' '
i' i
( 1--,""'.--................_
( .: I
l
: I '
I I 1 .......+-'-------'---.-,~+----4i-----'-i--+--..----1----'-~-+------1--..,: ------,----+-·------· i
; !
\ i ti ... ~ i I ~·
I
"" e! ! ! I I I
I ~ i I :
! i t
' i -·-•---·-t--•· .. ·_ 'J_,_,.·
I I I
--- ,....._._ -- . _____ ... _......_! I
37.
! ! ' I :I :
~-~--,..-.....·--l------l---+--,....,...-...-------i---'--+--:-..---.-+--t---:-------1·.----
1 I t
I '
I I
'I I
-I
N -
0-,..... °' LLl
3 (.!' ..... LL
----
· · -
-- -------
_.......,__,-..__,-...
I- I . I . . I ,j . . . - l . - . I . ~ ... j------ ·-- ---··--·------+----- ·-- -·----- I--·--------
. I ' --·I·-·[... .• i , l :1 II, --.-I l I___ I -·-·+----·-I ' -- -- --·· --+--L___ f II '-------
. Ii
_ 1 - - ! . r _ 1 - i . . .... C) ...-1 ~ ~/ ,,,,- . w L A: l ' 0 . G'A.6 l I A I r:7 .- ... r 1·.. . J.. .~· ...... ·1 en /~-~-~--L4t ~~L: . -;~ ~- '-" -~~~T.--
10------~- : .. : .: .. : ·~ . : : : . !:.. : '. :: .. . . -rt·:. ·--···. :(: _:__ ----·---•-1·±.I · - i·- · · ·· · ···· - · ·· · · · · · ..::I·C - •• : : .: : ; : •. • •. • - ·- .•.•.• - • . : • - ! .: •. : .. . -. i : :· : : : : :. . :1·-···-r ·l·· ···r ··- ·-· ···· ···· · :....::-: ··· · ······ ·· ·· · :.c. -. .. ..:.... · · · · ···· ·- ··
.. i ·+---··-2 .----:.- - :- .:.: :. ~ :: :-:: :::: .: ~-: ~ j :-:_ :.. )( 8~- . . . . . ' . . . . . - .. - i ... -· - -- --· .. ---- j ·····- . ~ t l ~+- -.- .. :r. ~ ·_: :• ::·: ::-:.• :: J:-~-:~-: \J :- : : : : . : : : : : ·: : L .-- -- . -----· - - . . ·- -- --·-- ----
'
. r. .. . . . . . . . . -I : ·. ~ : . l.JAL ~00 1r---+-r,I-~~~~:~-~~~~~::::::::::_ ..4~(') :1< ~ .J~:,~,j;..~~: . :··-i--···
CA~l5R.. JO~ :D_lfr>.. -•~pAJQ· · 3-;;S----Bfil·CH:{r-
-400 -r1 y-z... 'Prv:
~ 71A,~t-f
. . . • t •
i I-----+------- .. - .31------------- .. -· . '! . I . . .
. •J· :: :· t• :: :J: ·::: --·----·-
2 ... ;':: .... ~: ·-·-\:·:~ .....J··· ··-1··::······1·· ·\.· ! ; ~ :~O. [: ::·: ::: _: :: :_ :: >___ :::___J_ -•-········ ·•
--1----- ----~------. I
1t- _#t--··· ·· I .. - • ··+------•fl !
' ... ' ~I 0 2 3 4 5 6 7 8 9 10 w
co A O '.'J ~· F' ,,.. ,,-.., K 1 ') t=" K-1 (,.. ....l.. .• -·._, .. ._,. l-- • ,i( l 0
FIGURE 20.
,,,........_ .,,..-,.,·----~ I t l l ·11· : : · ·I·· '· ·1•. ·: I I I I; : : :· ·.: : . . . . . . ..... : ·: : '. : : : . : : : .
...... - ·- • . - -·. -- -· -t -. -- - •.
: ; 1 :-·
i
t
lli ·T- f I t . I: : : . . . : : : LL : : :.. : : ·= ~ =:.:L~ ·: I : : _: :·.-:-:: : : :.:.:: : : : =·: : ~ . : . . . ~ C : c,' >L . . . --1 ... l f ..... ..........., : - :· :~~~r~·;~:. ;.. ·~===-=fi-?-~r=·~~-~=1,-~~ '._'j: 1 :·=~••:~: _. dt .~· ·+----+-------+--------
·t '
I :--t.--------. . •·•-I ... t· ~. r·
•·r •- i ..
·-- ..J ....... L ... . -- -"· -· -- ---I--·- 1- ... -·•--·-1---+-----~----+--~--,..--.. ·---t----···--·-----
4
40.
(
I f I
0
O\X
&I')
. 4--·• ------
I i!en' '-. -. ----~-..-.-r----+--i---i ICl0
I i" \..'~,
I II i ! ! CD
II
I &I')
I
q'
M I
M 0
N N
0 LLJ c:::·- =>(1' ...... LL
C _:
-~ I:..;
... __
\\.
C (\
·:r
,........,__.,-.... ~
10 ()
)( 9
~ .A
--1--· ~-
_____ ,___,. -•--+-·--• . . ·--, f -· •.• I ' • ' I . ' - I ' I - - - I - - I I - I I I
-- 4-~T-
+: . · -f--·-·-,·--·--1-----r---;-y-,..---•·r--c·- I l I . "-·-· ---1----·· 1-- · . -I ·-·-· -re--~-~;Lj_/ri~ >: L:~:_::_1_: ::: : ,_:: ~: · ·· - · · · ,· · · · · · -- 1 - · · · · · · · .. • • .. .i~ L
: r f 1- ·-+-··!""'····· -- t···--· ---• --- t •-·- -· • ,- i
_________,,._:~~1:~~---, ----,- --r~~--,·--_:· -----,·~ i:: j· ··•·• J;.;i"'.•~ G"l H~ S~P.4 ••·.. ___ ___ .... ------P - 11" -:- 1 . - - - - ;
•· -· ... - ---+------t
I ----- -------+---- -_____J_ -- -- --- ·----··
·- --1- -·• - ~ - l!
-~ . ..;_ __
1------·--+------·----- -i----- I l - l --- f - L. ·. -+- -+----- !
L .. ,
W 8 L-i--t~7--:-·[\ CORR
-- - 1-- . - -.- ~t~1#uC:;-'. ·1· __ ;-•·- - : ... - r---j~ ('\ 7
8 --,
. -· . ·l. - .. !
~ 6 /--------·--! ·--•--t-------+----'t-,l~----1----------t------,-----+----+-----+-----t-----t 1
t..-.. ; ..S) 5 , ___ ·- ➔- ·-·· 0
I • • • • - _J,_,_,.. L..lf'--""'-1 .i -- .. """-I-.-._.. - -·----
-•- :: :_: : - :::: .:-➔· 58 o/e C..K1 "5PA1'1 - --- •• : : •- : ·-- -: · : - ~ -~oo 7/. 'f D 11v. ·
!
l L\ - -· 4 1--·----·--.f------•·-- ------1·-----,.-
I - - - ·- -1--:- : -- - -_ . -1-. -. - · 1- -_ - - --1 · - . ,,...Au ,i::t; r7 A -r-- o·N ·o· A,..._-' J . - .
--JR - 78 D l,V ----------j ! . · l2.E.ko AJ~
3,_ __ ,__ -
2 j 1
1
V!.y
I : I -·. i 20 3
i
4 5
I ---- .-------- j------
l I i
•+__J __________,______
6 7 8
------- -r··-- ________ ,._ --- ----- -----------!1--·---------t---- ·•·· ---l -
1 ' -I .
' ------t- -·-
---
9. ----··10 ·--~.l---·-··
. !
--- ----- --;------,- -! I -! ij I .
- 1I ---- •. -l I
_,A Ol"" t< r·· .-- ~, r::· D c o ~ \ . V ...... l ~ ff-"''-· X!C......, .,/ f'\.,,...,.
FIGURE 23.
""" ---·--·-----.,---.--------,-----,-----,-- ,,-... l ' .-·-• ..
-----,,-------i------1----+--·-----j ----t--,---,----+---;-......;--t-- -----------i------t ---- -- .•.. -·-t--- ! __ '~~~~-:-·r; ;--: t-- -c-r;r ,_;:-
-- - -- .. -•---1 ·-+-·- t I '
.. t . ... ··-·· I ....... .
- - - - I -- ........ T .... .
i I
11 ~_:___:__ __ J_ .--- __ . f . l
,--------!
l t I 10 I ' - -----1-- · -t
-l ~-: : , t-: :·-: -~-:L~:::·~-,T-. ---• --
- 1--• .....
-- ~- ,_ -- .· -· I . i .
! --- ...
.. l
. , !
i . I • '
9 A:TfiAL. -~-~f-r ~--~~C-QK..~£.~TEJ2 __400 ~E...A.l2 HJ!G:-$__ :__ -~-- -1-~------1------1 81 L. I . . l .. i .. !....-#.I ... 1.... 1..... J. I l 7 ,_ _____ _
I .
6•-·-- .....
. . ; p/7-/2 --: : : : : : I ~AL1B~t-1au PA(A 5 r :-:· ~-- :--- --· - -------- t-· •---- ---·
' ' ' . ' '
41------· ,- -----"1--- ----·-· !
3 •·-----· ...
: l . ----- -~~ 5"8 ~ a:r~- EVAN:-~ ""100 7 ( 1/i.. DIV. . : .
[
I I I I I ] .LR '78 .DJV, ..>J • · · · : . \z.e:rto AIP. • i ' i 1
2 -·-----.. ---- ------➔ ------~--r---------1-- ---'-- ··--· ··------ - . __________._ ------
1 1·- 1 .:~- -i- -- ·-t--· . : - -!
0 1 2 3 4 5 6 ---~ --·-·'--···-·- --·-·-10
7 8 9
"'1 c'',-l f
43.
( APPENDIX
An air-propane mixture is sparged through a liquid hydrocarbon at a controlled temperature. The output gas is controlled at five percent oxygen by adjusting propane flow.
What is the distribution of the test hydrocarbon in propane? System pressure is 760 torr.
ASSUMPTION l. Air is totally insoluble. in hydrocarbons.
ASSUMPTION 2. The dynamic mixing of gas and liquid is complete. This allows the use of Raoult's Law, which states:
"Molar weights of non-volatile non-electrolytes when dissolved in a definite weight of a given solvent under the same conditions lower the solvent's 'freezing point, elevate its boiling point,and redtrce its vapo·r pressure equally for all such solutes."
Where the subscript 3 represents propane and the subscript n representsthe test hydrocarbon, Raoult's Law may be written:
( (1) (2)
given (3)
and P3 + Pn = Pt (4)
where Pt= total pressure= (75%)(1 atmosphere)= 570 torr
To solve for Pn:
= p - pP3 t n
P3 = pt - (XnP~)
but X = 1 - X3n p -P3 = pO (1-X3)t n
but X3 = P3/P30
-P3 = p pO (1-P3/P~)t n ( P3P30 p pO _ pOpO + p pO= t 3 n 3 3 n
44.
(
given Pn = Pt - P3 then Pn = P~ (Pt - P~)
p~ - p~
VAPOR PRESSURE vs. 1000 (After Stull, 1947) T°K
(
torr C3 c6 C7 Iso-Ca Cg ClO
1 6.93 4.56 4. 18 4.22 3.63 3.45
5 6.34 4. 19 3.83 3.87 3.34 3. 17
10 6.07 4.03 3.69 3. 72 3.21 3.04
20 5. 81 3.86 3.54 3.56 3.08 2.92
40 5.53 3.69 3.38 3.40 2.95 2.80
60 5.37 3.59 3.29 3.31 2.88 2. 72
100 5.17 3.46 3. 18 3. 19 2.78 2.62
200 4.88 3.28 3.01 3.02 2.65 2.49
400 4.60 3. 10 2.85 2.84 2.50 2.36
760 4.33 2.93 2.69 2.69 2.37 2.24
(
- -
45.
(
Pressure, in torr1000 p- p- P3 PnT°Kt 0cn 3 n
6 46917.4 3.44 7,400 101108
4587 43.0 3. 16 15.,000 108 112
439i-8 46. l 3. 13 16,000 135 131
9 40.2 3. 19 14,000 559 10.611
38.5 56610 3.21 13,000 4. 1 3.9
( for n = 6
Pn
p6
=
=
P~ (P~ - Pt)
p~ - p~
108 {7,400 - 570}7,400 - 108
= 101 torr
pt = 570 torr
P3 = 469 torr
for n = 7 P7 = 108 (15,000 - 570)15,000 - 108
= 112 torr
P3 = 458 torr
for n = 8 Pa = 135 {16,000 - 570) 16,000 - 135
= 131 terr
P3 = 4.39 torr
for n = 9 Pg = 11 {14,000 14,000
- 570} - 11
= 10.6 torr
P3 = 559 torr
( for n = 10 plO = 4.1~13,000 - 570)3,000 - 4. 1 = 3.9 torr
p3 = 566 torr
4o.
(
n %Air %Propane %Test HC
6 25 469 X l 00 = 61. 7 101 X 100 = 13.3 760 760
7 25 458 X 100 = 60.3 112 x l 00 = 14. 7 i6lr 760
8 25 439 X 100 - 57. 8 135 X 100 = 17.2 760 i6o
9 25 559 X 100 - 73.6 11 X 100 = l. 4 760 760
10 25 566 X 100 = 74.5 4.1 X 100 = 0.5 i6lr 760
(
47.
(
..:Fi ---1~ F,_,_·:_---r+.;.---+;I~----+-+---'-:.:~--+--t--+-t-+-+--+-+-+-H-1--+-+--+-+++-+-+-~--+--+--+---+------'-+---~~--+ ' +-: - l::TFT=-t= ---,r ----+---+--+-+----1--+--+--+--+---+-+-'-+-~'--"'-'_,___.---+___,__---1--+--+--+--11--'-+ ,.._,___,___,____,__.,.....J.--,--+---'----,'-----'__,_---+----'--......-- ··· · -- ~ - - - : -- l , · · ----i--··"'"··-- .......... t-
_..,::..".:...,. -~-- :~
(
4--
l "" 9""
RA
51\ -+
1 I ·-r---
L-i--c:-·T
t· ;":"T
-.-- ~ -+
-l
l
l"" 9
,_:T::.ic:-.Jc:_;'_--·r.=--:i:8
7 ·:·l'f:f~ : j~-. ~--~----
~- ··---
===I---' I
I
6
5
4
3 j .. ttJ- ~,__ ,_,_ -+--+
,-tr~ J=J-----t- -=•----tJ_~-r----~,-~-i= --t=~=- ~ ~-r--,- ---~--
2-+·-tl+:i+-H1-1·__:+t--·+-t-f-t-+-+-,i-+H-.......-+:--,-f-+--H-+-+-++!-++-l-+--l-+-!-4-1-i--l-.L..!--!-4+-l-+-J-\.-i-4..;,...c_;___-+-I--_-_-_-_--~-----------T+--_-_-----~ I-rtt~t ~•-e-- c--i--t-t--t-+-++-+-+-+--t----++---t-+--+-+--c--+--t-++-+-+-+---1---+-+--+-+-+--l-+-+-+---'-l--+--~~.+--+-;........~----l-------------l-------iI \i
II i I( ~lr- :::;.. --t-H---++-+--t-+--t-+-t-+--+---il--+-+++-f-l-+--++-+~c-+-+-++-1--+--e---+-+--+--l-----l--t-l----+--t---l--+---l___;___.;......;......L...j.__;_!.......L~------4------l II i I'I+-.L..:.....1-\---,----j.....l.....l-+....;.-+-+--'---+----4 - -----+ j-- -- - - ~+--'--+--+--e---l--- ++-!'-+--+--+-+-+-J_ f--i--~- ' ,\ Il __(_..L~ i- -i-- - - ... --- -~ ____,__,-+--+-
10--1 ··:~:..t:J:.·:r:tt+=:-=:f:::j:::1:::L=L -~ 9- i 1A:- ·r ,I' -c~I: :i
48.
f i , · l·: ! 1 I : ·_- t-ff: .,c::'\:---i--,. .__,.,. ·. . • •· C •· ·!8•¥11...-+---'--_;,c..+-·~+.
l ..... ~·----+-:
(
4""'
3--
2'"'
1""' 9"'
8ft
711.
(
I . , . ..;. ·, : •· ' '
.. . ,•
(
9
8
7
- ;~-,-: . ·-- ,_:..:_'._ i~ - . --1---
1--- :--:_ - -+ L_ ±.j
6
5
4
3
' I I '
I :
---l
I
I I i i
I I
:~:........;_•
'---, - . --+ r -:·-.
' ---+-+-+---
• •w.....i -... .,.,, --■--
. ; ::·:.
+ ---- --t··---_ ~ -
-.-•
I I I I ' I i : I ,1 I I I ! i i \I i I I
' ! \ I I ! ! I I\!
i i l. i
(
,,.f--t'-:,i~f" r - t;',~ ';:~,~.L.-,
5"' ,_ ,,. 411
~ .. a, 3"( ►-J.,..
- "' QJ"di U)
)- 2n C'l "' z p.0 ,..
"' :;: 0 u . a ..... -oo ~ 0,.. d J: Q'. X ~ I-"' -
,...-..,_ ·"'"',SEMI-LOGARITHMIC S59-~1! - K,>;E KEUFFEL & ESSER CO. MACr lN ll,S,A. 3 CYCLES X 70 DIVISIONS
Vo.~Ol" ~t!.SSU."r~. To~\"' .... w ... 0,--: Cll
51. --:-~~: 1= ··--=;=_ -~---~-~~=;"~ -~~--=t-~ -· +__ ,~~::·:__ ~:J=~-~~-::t~-1u
,-1--1 __ ~ i-~ ·= =t'.:~=r -~=:F·:-~~f-1-=t~:.0f;:: ~=~-~:~:~~ -~ ~::r-=::::::::~ :-J-;0:gl ~ _J'f-Jt _lt ;_ ;'"~:ffL:f-;="f~ci
(
EJ=_-i=:;::_t q= Ek+.:-t:: ?:'. ~-+-·t-· -,
---+--q=:-:_;3~-'-
7
6 ::::q=;_
.~~q_-+--' ,_;--l-· --~-t-4-+-5
-tr~--F+~~-=1== ~-::_-: ~ f
4
•·1 'l-1· -
3
LJ-- ·- -+ --_j::::-J- -- r -- ~1-~ -
1 1-ff=t·...-=-~=-!::j-::.::-::.t-::.tj'.:=::t-::..i+_-:1-1-_-;_'-_t_----1+_-++_--1-1--_-j__~---1-+._-_,+_+1-_-i-1---i------1+_-++_-+1---i-'----14--_,+_-++-_-;_'---___--j_----1+'crct~;jc.tct~;_::tc.tc.:;:-ct:._-c~c.tctc;-t-ccct~c;c;:---_---\:__,,._-__-_--_-:-:_-__-'-'---------__, 2--;--!--+-+--rl-+-t-+-H-+-+-_+;-_f_-ft"":J_-l_;_+;-_f_-f~J--l_;-'+f---_t-_-+~j-_--l_;j_::_t-_+;-_f_-++-J_--i_t-_+;-_t-_-+_;:_j-_--l_;jf---_t-_+_;:_f_-+_;:J_°'."'_;_+_::_r_++--J_-_;_:i_::_::_-,::-_f_::_::_::_-_::_-_::J'__,-..';_-:__-:__-:__-:__-:__4+:_-:__-:__-:__-:__-:__~---l
( J:l ~-=·=~===--- ----~~l-~-~H~-+_-_+l_-+_j;::j=1=tjtj=1=11=t=!;::j=:t_-__t'1:::t:!=t=t=t=1=t=t=t,j!=1=t=::::=='.=:1 =t===·==,==-=t="="~\~=-==-=t===:_-_---j ':::_ -1· +-1-1--+-+-+-I- - -·----1--+----1-1--+--+-+-·---+---+-L-+-----~ -----'-1-+-++-i-+-,-t--+-+-l--'-:-t-+-1-+-+-1--+++-'-+-+--'--+-+---'~_.,.,-+---_.;_~
- I i ilt-H-+-'--'-+-'--~H1---c----''"rl~--,----~-f- . I i- i I I : ! l I : i
10 ,..,. S?. 9 A.As.liiUSL-Hj-+-l-li·_
-4 ! ___'- .1--=;..:.._-i.:-.::t::-.:f---i-"1- - - -
;:.:,:t:=J :,=r:~~ - ~~-J?ah.n
7--
5---
5a.a.
!Aft.
9A
8"-
S" ~ ~
4A
,. ti 36, ~.,. Ill
"J,, 2" ~
l" 9
8
7
6
5
4
3
i 1 --+-+--
- :__J____L - +-f--t---+--t-t--t--lr-,t- J f- ++-L__l Ir-i ·- :, -·1-· __µ __ 1'-+'-+-+--+- +---t--l---t--f----t\.___,__,_--_,1-+!--+--t---+--+--'f--f----+--+-+--+---+---+---+-+---+--+-~+--+---+---t--,r-l----tl__ L+-+- -~·_i-'--· -~-------- +t i--i-r -r+-1 -~ --l--+--·c--+--+--t----i·-+"'---+--t--- -- I -l--+-+-i-+-+-+--l-i--+-+-1--+-+-+--1--+-+--+--l--+-+-+--l--+--+-+--+-+1__+-+l--1-+l--1-'+I--!--'--'---:'\--l,-~'----1--~-,-.-._- ---- ,=:--~a- _ _ -t-+-~~ ! _ i : : I I I I '{ +--7f--+--,-+-t-f--+-+--+---+---+--t--+--+-4---+. I ! T i i I '+-i' -t-+-+-;-'-'--;--'\-+--'--~--+--,----'--,--!
l~~'._.__._._._....·_---1,_---=·-...c----'----.1..-.--..J.-...,:__J....j_..J.~...J--.L..--~-...- ----.L..=.l..-_,_·t==:================
1
-:
1
=,======-J=l·-=-~t-_!.J..:~..1.t+...1·....1...2..1.l~.J.r_1._:.J..:-..J..~...1:_....·-,-'-:...11....1...\..1.:~}W_,~-.,.,..1.l...1•_.:_:+-+..1.:...1:_1....J,:
(
{ - ..".:d, 0 lO:?. Ul-z (") ~ Q
~ Iii
> u ,ii -oo::Eu ... J: It XI- .. -o,
