GPA Standard 2286-95 Tentative Method of Extended Analysis for Natural Gas and Similar Gaseous Mixtures by Temperature

Programmed Gas Chromatography Adopted as a Tentative Standard 1986 Reprinted 1989, 1991, 1995 Revised 1995 Reprinted 1997, 1998, 1999 Gas Processors Association 6526 East 60th Street Tulsa, Oklahoma 74145 DISCLAIMER GPA publications necessarily address problems of a general nature and may be used by anyone desiring to do so. Every effort has been made by GPA to assure accuracy and reliability of the information contained in its publications. With respect to particular circumstances, local, state, and federal laws and regulations should be reviewed. It is not the intent of GPA to assume the duties of employers, manufacturers, or suppliers to warn and properly train employees, or others exposed, conceming health and safety risks or precautions. GPA makes no representation, warranty, or guarantee in connection with this publication and hereby expressly disclaims any liability or responsibility for loss or damage resulting from its use or for the violation of any federal, state, or municipal regulation with which this publication may conflict, or for any infringement of letters of patent regarding apparatus, equipment, or method so covered. Tentative Method of Extended Analysis for Natural Gas and Similar Gaseous Mixtures by Temperature Programmed Gas Chromatography 1. SCOPE 1.1 This method covers the determination of the chemical composition of natural gas and similar gaseous mixtures within the ranges listed in Table I. In cases where peaks are known to contain one or more components, groupings are shown in Table I and also again in Figure 4. Improved results for Btu content over those obtained using GPA 2261 will not necessarily be achieved. This method is intended for use with rich gas systems and in situations where the heptanes plus compositional breakdown is desired. 1.2 Components sometimes associated with natural gases, ie., helium, carbon monoxide and hydrogen are excluded from the main body of the method. These components are determined and made a

part of the complete compositional data by following special techniques outlined in Appendix B. NOTE 1--Hydrogen sulfide is eluted in a well defined peak between ethane and propane on the suggested partition column described in 3.1.4. For further discussion of the hydrogen sulfide content in natural gases see Appendix B. 2. SUMMARY OF METHOD 2.1 Components to be determined in a gaseous sample are physically separated by Gas Chromatography and compared to calibration data obtained under identical operating conditions. Set volumes of sample in the gaseous phase are charged by gas sample valves at designated times to three different packed column systems, effectively splitting the analysis into th ree sections. The first section separating oxygen, nitrogen and methane is tied mathematically to the second section which separates methane through normal pentane. The third section which separates the components eluting from iso-pentane through tetradecane (listed in Table I) are in turn tied to the second section by the common components iso and normal pentanes. Components in section one are separated under isothermal conditions on an adsorption type column and detected by thermal conductivity. The second section of the analysis is taken from a new sample charged to a partition-type column held isothermally for six minutes and then finished by a temperature program. This column effluent passes through a splitter which permits carbon dioxide and hydrogen s ulfide to be detected by thermal conductivity and the methane through pentane by hydrogen flame ionization methods. At the same time as section two components are passing through the partition column a third column system is charged with a fresh sample using the same temperature program to yield a breakdown of the components from iso-pentane to the tetradecanes with detection on a second flame ionization unit. (See suggested flow system in Figure 1.) Twelve programmable open collector transistor switch closures are required to perform the necessary valve operations in this method. NOTE 2--The TCD and FID may be run in series if desired instead of using an effluent splitter. NOTE 3--The times listed in this method are for informational purposes only and may vary with changes in operating parameters. r I ~ Tc II I 1-'i/2 in Chmmosorb,~ I [ lo~ (e

I Effluent Splitter I I Side A I -] Side B I Col. 2 ~-- ---.. ~ ~. Cot. 1 [ f Si[Icome ~ lr 6P V3 ~" Mol Sievo~ I ~Composite Col ~ ur ,= 13'/* COL ) Gas Sample Loop ~ i ~ ~ J Gas Sample Loop I CL Helium In. ~1 ~ I ' l J Manometer Vacuum Source u ~ ; Gas Sample Out ; Gas Sample In Figure 1 - Suggested Flow System Using an Effluent Splitter. Table I Natural Gas Components and Range of Components Covered Peak Conc. Range Peak Conc. Range Number Component Mol % Number Component Mol % Oxygen 0.005 - 20 16 lc,2t,4-Trimethylcyclopentane 0.001 - 2 Nitrogen 0.005- 100 lc,2t,3-Trimethylcyclopentane Carbon Dioxide 0.005 - 100 17 2,3,4-Trimethylpentane 0.001 - 2 Methane 0.001 - 100 Ethane 0.001 - 100 18 Toluene 0.001 - 2 Hydrogen Sulfide 0.10 - 100 2,3-Dimethylhexane Propane 0.001 - 100 19 2-Methylheptane 0.001 - 2 Iso-Butane 0.001 - 10 4-Methylheptane n-Butane 0.001 - 10 3-Methylheptane 1 iso-Pentane 0.001 - 5 20 3,4-Dimethylhexane 0.001 - 2 2 n-Pentane 0.001 - 5 lc,2c,4-Trimethylcyclopentane 3 2,2-Dimethylbutane 0.001 - 5 lc,3-Dimethylcyclohexane 4 2-Methylpentane 0.001 - 5 lt,4-Dimethylcyclohexane 2,3-Dimethylbutane 21 1,1-Dimethylcyclohexane 0.001 - 2 5 3-Methylpentane 0.001 - 5 1-Methyl-cis-3-ethylcyclopentane Cyclopentane 22 1-Methyl-trans-2-ethylcyclopentane 0.001 - 2 6 n-Hexane 0.001 - 5 1-Methyl-l-ethylcyclopentane Methylcyclopentane 23 n-Octane 0.001 - 2 2,2-Dimethylpentane 1 t,2-Dimethylcyclohexane 7 2,4-Dimethylpentane 0.001 - 2 24 lc,2c,3-Trimethylcyclopentane 0.001 - 2 2,2,3-Trimethylbutane 25 lc,2-Dimethylcyclohexane 0.001 - 2

8 Benzene 0.001 - 2 2,5-Dimethylheptane 3,3-Dimethylpentane 26 3,5-Dimethylheptane 0.001 - 2 9 Cyclohexane 0.001 - 2 Ethylbenzene 10 2-Methylhexane 0.001 - 2 1,3-Dimethylbenzene 2,3-Dimethylpentane 27 1,4-Dimethylbenzene 0.001 - 2 3-Methylhexane 2,3-Dimethylheptane 11 1,1-Dimethylcyclopentane 0.001 - 2 3,4-Dimethylheptane lt,3-Dimethylcyclopentane 28 2-Methyloctane 0.001 - 2 1 c,3-Dimethylcyclopentane 0.001 - 2 3-Methyloctane 12 1 t, 2-Dimethylcyclopentane 29 1,2-Dimethylbenzene 0.001 - 2 3-Ethylpentane 30 n-Nonane 0.001 - 2 13 n-Heptane 0.001 - 2 31 Decanes 0.001 - 1 Methylcyclohexane 32 Undecanes 0.001 - 1 14 2,2-Dimethylhexane 0.001 - 2 1,1,3-Trimethylcyclopentane 33 Dodecanes 0.001 - 1 Ethylcyclopentane 34 Tridecanes 0.001 - 1 15 2,4-Dimethylhexane 0.001 - 2 35 Tetradecanes 0.001 - 1 2,5-Dimethylhexane CAUTION: Peak identification and component groupings are based on the specific column arrangement and operating conditions used in the development of this method. 2.2 An equally acceptable method using a packed column/ capillary system is described in Appendix A. Use of a capillary column provides a more detailed characterization of the hexanes plus fraction identifying more individual components than packed columns. 3. APPARATUS 3.1 Chromatograph--Any gas chromatograph may be used which has the following specifications: 3.1.1 Detectors--The instrument should be equipped with thermal conductivity detection and dual flame ionization with dual electrometers. 3.1.2 Sample Valves--Valves capable of introducing gas volumes up to 0.5 ml will normally be required. The sample volume should be reproducible such that successive runs agree to +0.5% of the counts on each component peak. NOTE 4---The sample size limitation of O.5 ml or smaller is selected with the linearity of detector response and efficiency of the column separation in mind. Larger samples may occasionally be used to improve measurement accuracy in low concentration components.

3.1.3 Adsorption Column (Column 1)--This column must completely separate oxygen, nitrogen and methane by returning to the baseline after each peak. Figure 2 shows an example chromatogram obtained using an acceptable adsorption column. 2 =E Column - 12 ft. 13X Mol Sieve Temperature - 60C Inlet Pressure - 25 psig Sample Size - 0.25 cc Type Detector - Thermal Conductivity Carrier Gas - Helium 1! Figure 2 - Separation of Oxygen, Nitrogen and Methane. NOTE 5--The preparation of a suitable adsorption column to perform this separation is described in Appendix C.1. 3.1.4 Partition Column (Column 2)---This column must separate the hydrocarbons methane through pentanes, and nonhydrocarbons nitrogen and/or air, carbon dioxide and hydrogen sulfide. All peaks must be completely resolved with a return to baseline following each peak. Figure 3 shows an example chromatogram obtained using a suitable partition column to separate these components. NOTE 6--The preparation of a suitable partition column to perform this separation is described in Appendix C.2. 3.1.5 Extended Analysis Packed Column (Column 3)This column must separate hydrocarbons, pentane through tetradecane. Principal components separated are shown in Table I. The column packing must be capable of withstanding temperature programming to 170 C. Figure 4 shows an example chromatogram obtained using a suitable extended analysis column to separate these components. NOTE 7 The preparation of a suitable extended analysis packed column to perform this separation is described in Appendix C-3. 3.1.6 Attenuator--The chromatograph should be equipped with an attenuator to control the signal manually, if needed. However most modern computing integrators have the ability to program the attenuation of the signal automatically and this procedure is strongly recommended. 3.1.7 Temperature Control--During the iso-thermal part of the method the analyzer columns shall be maintained at a temperature within +0.2C of the required temperature. The temperature rise versus time must be checked periodically to

determine that the program is repeatable. Care should be taken that the upper limit of the program never exceeds the maximum recommended temperature limit of the materials used in the column packings. 3.2 Carrier Gas--Pressure reducing and flow control devices shall provide a flow of helium or other suitable carrier gas to pass through the chromatographic columns at rates not varying more than +0.5% during the sample and reference standard runs while in the isothermal mode. 3.3 Recording Instruments--Either strip-chart recorders or electronic integrators with printer-plotters should be used to display and measure the peaks as they pass through the detectors. A chromatogram provides an evaluation of instrument performalace during the course of the run. TCD Signal Plot FID Signal Plot Column - Silicone Composite Temperature - Programmed 60C - 170C Inlet Pressure - 50 psig Sample Size - 0.25 cc Type Detector - See Fig. 3 Carrier Gas - Helium Figure 3 3 Column - 15 ft. UCL-45 Temperature - Programmed 60C - 170C Inlet Pressure - 80 psig Sample Size - 0.25 cc Type Detector- Flame Ionization Carrier Gas - Helium llll/l I I j~ I ~g I Figure 4. 3.3.1 Recorders--Recorders shall be strip-chart types with a full range scale of 1 mv and a response time of 1 second. Minimum chart speed is recommended to be 1 cm/min and maximum speed 10 cm/min and minimum chart width 10 cm. 3.3.2 Integrator~Computers--Wide range, 0-1 volt/0-10 volt, with both printing and plotting capabilities, baseline tracking and tangent skim peak detection. Integrator/computers should have sufficient memory to handle the large number of

components and have a minimum of 12 programmable external event relays. 3.4 Manometer--May be either U-tube type or well type equipped with an accurately graduated and easily read scale covering the range 0 to 900 mm (36 in.) of mercury or larger. The U-tube type is useful with the GPA Gas Standard, since it permits filling the sample loop with up to two atmospheres of sample pressure, thus extending the range of all components. The well type inherently offers better precision and is preferred when calibrating with pure components. Samples can be entered up to one atmosphere of pressure. With either manometer, the mm scale can be read more accurately than the inch scale. Caution should be used in handling mercury because of its toxic nature. Avoid contact with the skin. Wash thoroughly after any contact. 4. LINEARITY CHECK PROCEDURE 4. 1 For any specific chromatograph, the linear range of the major components of interest must be determined on their respective detectors. The linear range should be established for any new chromatograph and re-established whenever the instrument has undergone a major change (i.e., replaced detectors, increased sample size, switched column size, or dramatically modified run parameters). In order to determine the range of linearity it is necessary to construct response curves. These may be obtained by charging varying amounts of sample of each pure component to the chromatograph and then plotting all the response counts versus the appropriate partial pressures. Tables II and III show the range of partial pressures used for the various components. NOTE 9--To generate pure component data necessary to construct linearity plots, it is suggested that mini -programs be written to run just long enough to charge the GC with the component of interest, eIute it from the TCD, and return the sample value to the load position. This will avoid waiting for the instrument to proceed through the complete cycle of 35 minutes before another data point can be determined. NOTE 8--A suggested manifold arrangement for entering samples to the chromatograph under vacuum is shown in Figure 5. 3.5 Vacuum Pump--Must have the capability of producing a vacuum of 1 mm of mercury absolute or less. NOTE lO--Dry air can be used for the calibration of oxygen and nitrogen, using composition values of 21.87 mol %

for oxygen (includes argon which is eluted with oxygen on a molecular sieve column at these conditions) and 78.08 mol % for nitrogen. 4 Table II Range of Partial Pressures Used to Determine Pure Component Linearity Response Data on Partition Column (Column 2) by Thermal Conductivity Detection Partial Pressure Range Component mm of Mercury Nitrogen 50 - Atmosphere Methane 50 - Atmosphere Carbon Dioxide 50 - Atmosphere Ethane 50 - Atmosphere Hydrogen Sulfide* 50 - Atmosphere *CAUTION: Exercise appropriate handling procedures when using pure hydrogen sulfide. See Appendix B-3. Table III Range of Partial Pressures Used to Determine Pure Component Linearity Response Data on Adsorption Column (Column 1) by Thermal Conductivity Detection Partial Pressure Range Component mm of Mercury Oxygen 50 - Atmoshpere Nitrogen 50 - Atmoshpere Methane 50 - Atmoshpere Carbon Monoxide 20 - 200 Helium 20- 100 NOTE 11--Procedures for the calibration and analysis of helium and carbon monoxide found by test to meet requirements of this method are described in Appendix B. 4.2 For each of the components nitrogen, methane, carbon dioxide, ethane and hydrogen sulfide proceed as follows: 4.2.1 Connect sample source to gas sampling part of chromatograph. Evacuate manifold system, including sample loop and check for leaks. (See Figure 5 for suggested manifold arrangement.) Total system must be vacuum tight. 4.2.2 Carefully open metering valve to admit pure component up to approximately 50 mm mercury absolute (2 in. Hg). 4.2.3 Record exact partial pressure, operate appropriate gas sample valve to place sample onto Column 2. 4.2.4 Repeat steps 4.2.2 and 4.2.3 above at partial

pressures of 100, 200, 300, 400, 500, 600, 700 and atmospheric pressure in mm of mercury (4.0, 8.0, 12.0, 15.5, 19.5, 23.5, 27.5 and atmospheric pressure in inches of Hg). 4.3 For each of the compounds oxygen, nitrogen and methane separated on the adsoption column (Column 1) proceed as follows: 4.3.1 Connect sample source to gas sampling valve of chromatograph. Evacuate manifold system, including sample loop and check for leaks. 4.3.2 Carefully open metering valve to admit pure component up to approximately 50 mm absolute (2 in. of Hg). TO VACUUM NEEDLE ~ PUMP \ CA R R i E R.-.,'--._J'-~-~TO I GAS t COLUMN GAS CHROMATOGRAPH SAMPLE VALVE f VENT I CYLINDER I I MANOMETER Figure 5 -Suggested Manifold Arrangement for Entering Vacuum Samples. 4.3.3 Record exact partial pressure, operate appropriate gas sample valve to place sample on Column 1. 4.3.4 Repeat steps 4.3.2 and 4.3.3 above at partial pressures of 100, 200, 300, 400, 500, 600, 700 and atmospheric pressure in mm of mercury absolute (4.0, 8.0, 12.0, 15.5, 19.5, 23.5, 27.5 and atmospheric pressure in inches of Hg). NOTE 12--Dry air can be used for the calibration of oxygen and nitrogen in lieu of the pure components due to the hazard of handling pure oxygen. The procedure for air is exactly the same as for pure components (4.3) except that the partial pressure recorded for air is allocated proportionately 21.87 mol % to oxygen and 78.08 mol % to nitrogen. Thus, air sampled at 100 mm mercury absolute yields a point for the oxygen curve at 21.9 mm of mercury absolute and a point on the nitrogen curve at 78.1 mm of mercury absolute. Thus, a complete calibration curve using air to atmospheric pressure results in a linearity curve for oxygen over the range 0 to 21.9 mol % and a linearity curve for nitrogen over the range 0 to

78.1 mol %. 4.4 From experimental data developed in accordance with 4.2, 4.3, response curves shall be prepared in the following manner: 4.4.1 Determine area counts of all peaks of interest. 4.4.2 Tabulate peak area counts opposite the appropriate partial pressure used for each calibration run. 4.4.3 Plot the data in 4.4.2. Use rectangular coordinate paper, the y-axis being partial pressure, the x-axis being peak area counts. Draw smooth lines through the points plotted for peak area count and extend down to zero. The linear range will be that portion from zero to the point at which the plot departs from a straight line. 5. CALIBRATION PROCEDURE 5.1 The routine method of calibration is to use the response factor from a gas reference standard of known composition. This method may be used for those components in an unknown that lie within the proven linear range for a specific chromatographic instrument. 5.1.1 Connect reference standard gas to gas sampling part of chromatograph. Evacuate manifold system, including sample loop and check for leaks. 5.1.2 Carefully open metering valve to admit reference standard gas up to pressure decided upon for all runs. (See analytical procedure.) 5.1.3 Record atmospheric pressure and start program to actuate sample valve to place sample on Column 2. 5.1.4 Determine peak area counts from the TCD and FID for all components of interest. These data shall be used to calculate response factors in accordance with section 7. 6. ANALYTICAL PROCEDURE 6.1 General--The full range analysis of a gaseous sample first requires a run on an adsorption column (Column 1) at isothermal conditions to determine oxygen, nitrogen and methane. It is suggested that a temperature of 60C be used in conjunction with thermal conductivity detection for this section of the analysis. In about three minutes, methane will have eluted from side A of the TC cell and the program should rotate the eight port routing valve (V3) so causing Column 1 to be placed in the back flush mode. The remaining components will now exit from the system through side B. This now places Column 2 in series with side A of the TC cell. At the same time as valve (V3) is rotated, both V1 and V2 sampling valves should automatically

be moved to the sample "load" position. (A schematic flow diagram of this procedure is shown in Figure 6.) Evacuate VI and V2 and then fill with fresh sample using the manifold arrangement shown in Figure 5. This part of the procedure must be carried out in approximately four minutes which is the period of time needed to complete the back-flushing of Column 1. The program has now reached an elapsed time of seven minutes. At this point V1 is rotated and a sample now passes into Column 2. Meanwhile the oven temperature still Molecular Sieve Column TC-Isothermal TCD (Col. 1) Oxygen Nitrogen Methane ~- Briged in Mol % UCL-45 Column FID(Col. 3) Weight Percent -iso-Pentane n-Pentane 2,2-Dimethylbutane 2-Methylpentane 2,3-Dimethylbutane 3-Methylpentane Cyclopentane n-Hexane Methylcyclopentane 2,2-Dimethylpentane 2,4-Dimethylpentane 2,2,3-Trimethylbutane Benzene 3,3-Dimethylpentane Cyclohexane 2-Methylhexane 2,3-Dimethylpentane 3-Methyihexane 1,1 -Dimethylcyclopentane lt,3-Dimethylcyclopentane lc,3-Dimethylcyclopentane lt,2-Dimethylcyclopentane 3-Ethylpantane n-Heptane Methylcyclohexane

2,2-Dimethylhexane 1,1,3-Trimethylcyclopentane Ethylcyclopentane 2,4-Dimethylhexane 2,5-Dimethylhexane 1 c,2t,4-Tdmethylcyc[opentane I c,2t,3-Tdmethylcyclopentane 2,3,4-Trimethylpentane Toluene 2,3-Dimethylhexane Silicone Comeosite Column TC/FID Split Effluent Part isothermal - part temperature programmed TCD (Col. 2) Nitrogen (Air Free) Methane Carbon Dioxide Hydrogen Sulfide ~-- Briged in Mol % ~---) Bdged in Weight % UCL-45 Column FID (Col. 3) Weight Percent -FID (CoL 2) Methane Ethane Propane iso-Butane n-Butane iso-Pentane n-Pentane In Weight Percent -- Converted to Mol Relationship 2-Methylheptane 4-Methylheptane 3-Methylheptane 3,4-Dimethylhexane lc,2c,4-Trimethylcyclopentane lc,3-Dimethylcyclohexane lt,4-Dimethylcyclohexane 1,1 -Dimethylcyclohexane 1-Methyl-cis-3-ethylcyclopentane

1-Methyl-trans-2-ethylcyclopentane 1-Methyl-l-ethylcyclopentane n-Octane lt,2-Dimethylcyclohexane lc,2c,3-Tdmethylcyclopentane 1 c,2-Dimethylcyclohexane 2,5-Dimethylheptane 3,5-Dimethylheptane Ethylbenzene 1,3-Dimethylbenzene 1,4-Dimethylbenzene 2,3-Dimethylheptane 3,4-Dimethylheptane 2-Methyloctane 3-Methyloctane 1,2-Dimethylbenzene n-Nonane Decanes Undecanes Dodecanes Tridecanes Tetradecanes Figure 6 - Calculation Procedure. NOTE 13mBridge FID (Col. 3) in weight % to FID (Col. 2). Convert both data columns to moles and then bridge to TCD (Col. 2 &l). (See 7.2) 6 remains at 60C isothermal. Components leave Column 2 in the following order - inerts, methane, carbon dioxide, ethane and hydrogen sulfide, as shown in Figure 3, and pass through the effluent splitter. Suggested split ratio is one part to the hydrogen flame detector, three parts to the thermal conductivity detector. At an elapsed time of 11 minutes, or after four minutes in Column 2, V2 is automatically rotated and a sample is charged to Column 3 that separates the components iso-pentane through tetra-decanes. At 14 minutes elapsed time the hydrogen sulfide will have cleared the TC cell and been integrated, and the TC detection part of the analysis is completed. At this time the oven temperature heating program commences and adds heat at approximately 20C per minute, reaching the final temperature of 170C at approximately 20 minutes elapsed time. Meanwhile, Column 3 is analyzing the heavy ends of the sample and detecting components on the

second hydrogen flame detector (FID 2) and yielding a chromatogram as shown in Figure 4. At 23 minutes elapsed time the propane, iso- and normal butanes and iso- and normal pentanes have eluted from Column 2 and have been detected on FID 1 (Figure 3). At this point the program causes V3 to rotate so back-flushing the hexanes plus to the atmosphere via'the TC ceil, and also returns both V1 and V2 to the sample "load" position. After two more minutes (25 minutes elapsed time) tetradecane has cleared FID 2 and the oven is switched to the "cool down" mode. Ten more minutes (35 minutes of elapsed time) and the system is now equilibriated at 60C, all valves are back to the starting position of the cycle and a new sample may be charged to the system. Response factors from natural gas reference standards used in conjunction with response curves derived from pure components as discussed in Sections 4 and 5 of this method are essential to accurately determine the composition of an unknown gas sample. Care must be maintained to ensure that identical instrument operating conditions exist during the running of the gas standard and the unknown. As long as this stipulation is met numerous samples can be analyzed using a single gas reference standard run. If the sample volumes are measured at atmospheric pressure the operator is at the mercy of the day-to-day variations in barometric pressure resulting in poor, unnormalized totals (see Note 15-Calculations). It is suggested that the operator always charge a consistent partial pressure of 400 mm pressure to the sample loop using the manifold arrangement discussed earlier-Figure 5. This procedure will remove the effect of fluctuating barometric pressure and make sure that the GC receives a representative sample, particularly when the gas is rich in heavy ends and has been sampled from a high temperature source. If a component concentration falls outside the established linear range of that component, reduce the sample volume so that all components stay in the linear range. One response factor can then be used for all concentrations of that component. 6.2 Preparation and Introduction of Sample-If field data indicate the gas sample was taken at a temperature greater than that of the laboratory, the sample must be heated to at least 20F above the sampling temperature. It is recommended that all lines connecting the sample to the GC be made of stainless steel and that these lines should be permanently heated to a temperature higher than any expected sampling temperature. This includes

any gas filter that may be in use in the charging line to the GC and also any tubing and connections that may be inside the chromatograph but not inside the oven. The purpose of this is to ensure that the gas shall not be allowed to drop below its dew point and shall be representative of the gas that was sampled. NOTE 14--To be sure of representative samples in the field, select appropriate sampling method from GPA Publication 2166. Table IV Example of Response Factors Determined from Reference Standard and Pure Components by Thermal Conductivity Component Mol % Response Factor 2.73 = 0.0001534 Oxygen 17795 Nitrogen .29.282 = 0.0001158 252925 Methane (Mol Sieve) 69.97 = 0.0001405 498116 Methane (Silicone Composite) 52.42 = 0.00003919 1337500 Carbon Dioxide 7.37 = 0.00002630 280215 Hydrogen Sulfide 2.5 = 0.00002857 87500 6.2.1 Evacuate charging system, including sample loop, back to the valve on sample cylinder to 1 mm of mercury absolute or less. Close valve to vacuum source and carefully meter gas from sample cylinder into charging system until sample loop is filled at the selected pressure as indicated on the manometer. The chromatograph is now ready to start the analysis procedure outlined in Section 6.1. 7. CALCULATIONS 7.1 Response factors are calculated for each component from nitrogen through normal pentane using the peak area counts of the reference standard. The appropriate mol or weight percent of each component is used depending upon whether the peak is taken from the TC cell or the FID. (Examples are shown in Tables IV and V.) The response factors are calculated by the following formula: Table V Example of Response Factors Determined from Reference Standard by FID Component Weight % Response Factor

Methane 47.69 = 0.00000688 6926850 Ethane 11.89 = 0.00000712 1670658 Propane 151417.3523 6 = 0.00000732 Iso-Butana 7.46 = 0.00000810 919943 n-Butane 7.28 = 0.00000806 902966 iso-Pentane 3.04 = 0.00000893 340424 n-eentane 3.06 = 0.00000899 340528 Where K = M (or W) P K - Response factor on either tool or weight basis M - Mol percent of component in reference standard W - Weight percent of component in reference standard P - Integrator area counts of component in reference standard NOTE 15--Some integrators determine a response factor K- P M (or W) Be sure to use the approach that is consistent with your integration equipment. 7.2 Response factors for a flame ionization detector from C 5 to C n can be determined relative to the response of pentane by analyzing a liquid blend of aliphatic, aromatic, and naphthenic hydrocarbons from C 5 to C n. (Examples of relative sensitivity values for the FID are shown in Table VI.) Weight sensitivities relative to i-C 5 and n-C 5 for the above components are very close to 1.00 so making peak area percent almost equal to weight percent. 1 Each area count is divided by the relative sensitivity for that particular component to convert to the true weight distribution in counts. This distribution is then connected to the C 1 through C 5 unnormalized weight percent distribution by the bridge components iC 5 and nC 5 and an unnormalized weight percent for the components C 6 to C n may then be calculated. Both of these parts of the analysis may then be

converted to a mole relationship by dividing by the molecular weight. The non-hydrocarbons oxygen, nitrogen, carbon dioxide and hydrogen sulfide which have been analyzed on the TC side of the system are then added to the rest of the analysis using the bridge component methane. (See Figure 6.) The unnormalized total of all the components analyzed should be within +1.0% of 100.00%. Any air is now removed from the analysis based on the oxygen percent and the results may be normalized to an air free basis. (See Table VII.) 7.2.1 Response factors for the liquid blend C 5 to C n are calculated by the following formula: K- W P Where K - Weight response factor W -Weight percent of component in liquid blend P - Peak area counts of component in liquid blend 7.2.2 Calculate the weight concentration of all the components in unknown determined by FID in 7.1 and 7.2 by the following formula: W=PxK Where W - Weight percent of component in unknown P - Peak area counts of component in unknown K - Weight response factor as determined in 7.1 or 7.2. I 7.2.3 Calculate the tool % of oxygen, nitrogen, methane, carbon dioxide and hydrogen sulfide in unknown as determined 8 by TC from the following formula: M=PxK Where M -Mol percent of component in unknown P -Peak area counts of each component in unknown K - Molar response factor as determined in 7.1 Table VI Example of Relative Sensitivity Values Determined from Liquid Blend by Flame Ionization Detector (as Described in 7.2) Component Relative Sensitivity iso-Pentane 1.00

n-Pentane 1.00 2,2-Dimethyibutane 0.99 2-Methylpentane 0.99 2,3-Dimethylbutane 0.98 3-Methylpentane 0.98 Cyclopentane 0.98 n-Hexane 0.99 Methylcyclopentane 0.97 2,2-Dimethylpentane 0.98 2,4-Dimethylpentane 0.98 2,2,S-Trimet hylbutane 0.98 Benzene 1.07 S,3-Dimethylpentane 0.96 Cyclohexane 0.97 2-Methylhexane 0.96 2,3-Dimethylpentane 0.96 3-Methylhexane 0.96 1,1-Dimethylcyclopentane 0.97 lt,S-Dimethylcyctopentane 0.97 1 c,3-Dimethylcyclopentane 0.97 lt,2-Dimethylcyclopentane 0.97 3-Ethylpentane 0.96 n-Heptane 0.96 Methylcyclohexane 0.97 2,2-Dimethylhexane 0.93 1,1,3-Trimet hylcyclop ent ane 0.94 Ethylcyclopentane 0.97 2,4-Dimethylhexane 0.93 2,5-Dimethylhexane 0.93 1 c,2t,4-Trimethylcyclopentane 0.97 1 c,2t,3-Tdmethylcyclopentane 0.97 2,8,4-Trimethylpentane 0.93 Toluene 1.02 2,3-Dimethylhexane 0.93 2-Methylheptane 0.93 4-Methylheptane 0.93 3-Methylheptane 0.93 3,4-Dimethylhexane 0.93 I c,2c,4-Trimethylcyclopent ane 0.97 1 c,3-Dimethylcyclohexane 0.97 lt,4-Dimethylcyclohexane 0.97 1,1 -Dimethylcyclohexane 0.97 1 -Methyl-cis-3-ethylcyclopentane 0.97

1 -Methyl-trans-2-ethylcyclopentane 0.97 1 -Methyl-1 -ethylcyclopentane 0.97 n-Octane 0.93 lt,2-Dimethylcyclohexane 0.97 1 c,2c,3-Trimethylcyclopentane 0.97 1 c,2-Dimet hylcyclohexane 0.97 2,5-Dimethylheptane 0.93 3,5-Dimethylheptane 0.93 Ethylbenzene 0.99 1,3-Dimethylbenzene 0.98 1,4-Dimethylbenzene 0.98 2,3-Dimethylheptane 0.94 3,4-Dimethylheptane 0.94 2-Methyloctane 0.94 3-Methyloctane 0.94 1,2-Dimethylbenzene 0.98 n-Nonane 0.94 Decanes 0.95 Undecanes 0.94 Dodecanes 0.95 Tridecanes 0.95 Tetradecanes 0.95 NOTE 16--Each area count is divided by the relative sensitivity value to get the true area count. 1 Table VII Calculation of Unknown Sample using Response Factors Adsorption Column - Thermal Conductivity Detection Air Containing Response Unnormalized Component Counts Factor Mol % Oxygen 210 0.0001534 0.032 Nitrogen 237928 0.0001158 27.545 Methane 378759 0.0001405 53.215 3omposite Silicone Column - Thermal Conductivity Detection Response Unnormalized Component Counts Factor Mol % Methane 1351682 0.00003919 52.972 Carbon Dioxide 240863 0.00002630 6.335 Hydrogen Sulfide 98732 0.00002857 2.821 Composite Silicone Column - Flame Ionization Detection Response Unnormalized Component Counts Factor Weight % Mol Wt. Methane 5322628 0.00000688 36.620* 16.04

Ethane 849288 0.00000712 6.047" 30.07 Propane 596340 0.00000732 4.365* 44.09 iso-Butane 228233 0.00000810 1.849" 58.12 n-Butane 286869 0.00000806 2.312" 58.12 iso-Pentane 135164 0.00000893 1.207" 72.15 n-Pentane 104274 0.00000899 0.937* 7215 Silicone UCL-45 Column - Flame Ionization Detection Moles 2.28304 0.20110 0.09900 0.03181 0.03978 0.01673 0.01299 Relative Corrected Unnormalized Component Counts Sensitivity Counts Weight % Mol Wt. Moles iso-Pentane 332181 1.00 332181 1.207 n-Pentane 268065 1.00 268065 0.937 2,2-Dimethylbutane 18200 0.99 18384 0.066* 86.18 0.00077 2-Methylpentane 93830 0.99 94778 0.339* 86.18 0.00393 2,3-Dimethylbutane 3-Methylpentane 64900 0.98 66224 0.237* 78.16 0.00303 Cyclopentane N-Hexane 145200 0.99 146667 0.524* 86.18 0.00608 Methylcyclopentane 2,2-Dimethylpentane 33916 0.98 34608 0.124" 85.76 0.00145 2,4-Dimethylpentane 2,2,3-Trimethylbutane Benzene 20550 1.06 19387 0.069* 80.31 0.00086 3,3-Dimethylpentane Cyclohexane 11352 0.97 11703 0.042* 84.16 0.00050 2-Methylhexane 16190 0.96 16865 0.060* 100.20 0.00060 2,3-Dimethylpentane 3-Methylhexane 8250 0.96 8594 0.031 * 99.76 0.00031 1,1 -Dimethyicyclopentane lt,3-Dimethylcyclopentane lc,3-Dimethylcyclopentane 15110 0.97 15577 0.056* 98.19 0.00057 lt,2-Dimethylcyciopentane 3-Ethylpentane n-Heptane 101176 0.96 105392 0.376* 100.20 0.00375 Methylcyciohexane 2,2-Dimethylhexane 21448 0.96 22342 0.080* 99.78 0.00080

1,1,3-Trimethylcyclopentane Ethylcyclopentane 2,4-Dimethylhexane 7982 0.94 8492 0.030" 110.22 0.00027 2,5-Dimethylhexane lc,2t,4-Trimethylcyclopentane 4940 0.97 5093 0.018" 112.22 0.00016 Air Containing Air Free Air Free Corrected Mol % Corrected Mol % Mol % (Unnormalized) (Unnormalized) (Normalized) 0.032 27.545 27.429 27.435 53.215 53.215 53.225 Air Containing Air Free Air Free Corrected Mol % Corrected Mol % Mol % (Unnormalized) (Unnormalized) (Normalized) 53.215 53.215 6.364 6.364 6.365 2.834 2.834 2.835 Air Containing Corrected Mol % (Unnormalized) Air Free Air Free Corrected Mol % Mol % (Unnormalized) (Normalized) 53.215 53.215 4.687 4.687 4.688 2.308 2.308 2.309 0.742 0.742 0.742 0.927 0.927 0.927 0.390 0.390 0.390 0.303 0.303 0.303 Air Containing Air Free Air Free Corrected Mol % Corrected Mol % Mol % (Unnormalized) (Unnormalized) (Normalized) 0.018 0.018 0.018 0.092 0.092 0.092 0.071 0.071 0.071 0.142 0.142 0.142 0.034 0.034 0.034 0.020 0.020 0.020 0.012 0.012 0.012 0.014 0.014 0.014 0.007 0.007 0.007

0.013 0.013 0.013 0.087 0.087 0.087 0.019 0.019 0.019 0.006 0.006 0.006 0.004 0.004 0.004 Table VII - Continued Silicone UCL-45 Column - Flame Ionization Detection Air Containing Air Free Air Free Relative Corrected Unnormalized Corrected Mol % Corrected Mol % Mol % Component Counts Sensitivity Counts Weight % Mol Wt. Moles (Unnormalized) (Unnormalized) (Normalized) lc,2t,3-Trimethylcyclopentane 5420 0.97 5588 0.020" 113.22 0.00018 0.004 0.004 0.004 2,3,4-Trimethylpentane Toluene 34318 1.02 33645 0.120" 92.13 0.00130 0.030 0.030 0.030 2,3-Dimethylhexane 2-Methylheptane 15722 0.93 16905 0.060* 114.23 0.00053 0.012 0.012 0.012 4-Methylheptane 3-Methylheptane 3,4-Dimethylhexane 5249 0.93 5644 0.020* 114.23 0.00018 0.004 0.004 0.004 1 c,2c,4-Trimethylcyclopentan e lc,3-Dimethylcyclohexane 10651 0.97 10980 0.039* 112.21 0.00035 0.008 0.008 0.008 lt,4--Dimethylcyclohexane 1-1-Dimethylcyclohexane 1-Methyl-cis-3-ethylcyclopentane 1-MethyI-Trans-2-ethylcyclopentane 2252 0.97 2322 0.008* 112.21 0.00007 0.002 0.002 0.002 1-Methyl-1 -ethylcyclopentane n-Octane lt,2-Dimethylcyclohexane 43566 0.93 46845 0.167* 114.23 0.00146 0.034 0.034 0.034 lc,2c,3-Trimethylcyclopentane 1453 0.97 1498 0.005* 112.21 0.00005 0.001 0.001 0.001 lc,2-Dimethylcyclohexane 2251 0.97 2321 0.008* 112.21 0.00007 0.002 0.002 0.002 2,5-Dimethylheptane 10519 0.93 11311 0.040* 128.25 0.00031 0.007 0.007 0.007 3,5-Dimethylheptane Ethylbenzene

1,3-Dimethylbenzene 1,4-Dimethylbenzene 35740 0.96 37229 0.133" 117.23 0.00114 0.027 0.027 0.027 2,3-Dimethylheptane 3,4-Dimethylheptane 2-Methyloctane 15482 0.94 16470 0.059* 128.25 0.00046 0.011 0.011 0.011 3-Methyioctane 1,2-Dimethylbenzene 10251 0.98 10460 0.037* 106.16 0.00035 0.008 0.008 0.008 n-Nonane 30120 0.94 32043 0.115" 128.25 0.00090 0.021 0.021 0.021 Decanes 63980 0.95 67347 0.241 * 142.28 0.00169 0.039 0.039 0.039 Undecanes plus 56871 0.94 60501 0.216" 156.30 0.00138 0.032 0.032 0.032 100.128* 99.980 100.000 *NOTE 17--1fall components are measured, the unnormalized total should not vary more than + 1.O0% from 100.00%. APPENDIX A Supplementary Procedures A. 1 Extended Analysis by Capillary Gas Chromatography A. 1.1 Scope-This method covers the determination of the chemical composition of natural gas by combining the analysis described in GPA Standard 2261 with an extended analysis of the hexanes and heavier components using capillary gas chromatography. Table A-I and Table A-II name the individual or grouping of components for GPA Standard 2261 and Extended Analysis respectively. A.1.2 Summary of Method-An analysis of a gaseous mixture is made according to GPA Standard 2261 except results are reported to three places to the right of the decimal for more accurate normalization of the combined data. On the same gaseous mixture, an analysis is made on the iso-pentane and heavier fraction by capillary gas chromatography. The latter analysis provides essentially an individual component characterization of this fraction as shown in Figure A-I. For convenience of calculation, some peak groupings are made according to hydrocarbon type to produce Table A-II for calculating the physical properties of gaseous mixtures. Table A-I GPA Standard 2261

1. Hexanes and heavier 2. Nitrogen 3. Methane 4. Carbon Dioxide 5. Ethane 6. Propane 7. Iso-butane 8. n-Butane 9. leo-pentane 10. n-Pentane The two analyses are combined into a simple report using the common peaks iso-pentane and normal pentane in each analysis as the bridge to correctly adjust the peak areas of the 10 components shown in Table A-II to the same sample size as the components of Table A-I. The peak areas of Table A-II are then converted to molar response using response factors (if needed) and molecular weight factors relative to pentane. These converted areas are calculated to mol percent relative to the total mol percent of pentanes determined by GPA Standard 2261. Peaks 2 through 10 in Table A-I are summed with peaks 11 through 33 in Table A-II and normalized to 100.000%. Table A-II Capillary Extended Analysis 9. Iso-pentane 10. n-Pentane 11. Neohexane 12. 2-Methylpentane 13. 3-Methytpentane 14. n-Hexane 15. Methylcyclopentane 16. Benzene 17. Cyclohexane 18. 2-Methyihexane 19. 3-Methylhexane 20. Dimethylcyclopentanes 21. n-Heptane 22. Methyicyclohexane 23. Trimethylcyclopentanes 24. Toluene 25. 2-Methylheptane 26. 3-Methylheptane 27. Dimethylcyclohexanes

28. n-Octane 29. C 8 Aromatics 30. C 9 Naphthenes 31. C 9 Paraffins 32. n-Nonane 33. Decanes and heavier A.2 Apparatus A.2.1 Apparatus description includes only that additional apparatus required for a capillary gas chromatography system. Reference should be made to GPA Standard 2261 for information on apparatus requirements. A.2.2 Chromatograph-The chromatograph must be equipped with flame ionization detector, temperature programming that includes settable initial and final constant temperature periods, and settable temperature programming rates over the range of 2 - 10C per minute; inlet splitter in heated zone; small volume capillary connectors at inlet splitter and detector inlet to allow proper location of capillary column ends in inlet splitter and detector inlet, and provision for makeup gas at detector inlet if detector manifold design requires such gas. A.2.3 Sample Inlet System-A gas sampling valve must be provided to introduce about 2 cc of sample gas into the inlet splitter. The gas sampling valve should be mounted in its own temperature controlled oven capable of being maintained at 2050F above the highest expected field sampling temperature. NOTE A-1--A vacuum sample entry system, such as described in GPA Standard 2261, can be used to avoid heating the sample valve. For example, a 5 cc sample loop filled to 300 mm partial pressure would provide the approximate 2 cc of gas for analysis. The 300 mm partial pressure would greatly reduce the possibility of condensation of heavier sample components. A.2.4 Capillary Column-A 60 meter x 0.26 mm ID fused silica capillary coated with a 1.0 micron film thickness of DB -1 has been found by experiment to be suitable for this analysis. A.2.5 Integrator/computer-Wide range, 0-1 V/0-10 V, with both printing and plotting capabilities, baseline tracking, and tangent skim peak detection. A.2.6 Carrier Gas-The sensitive flame ionization detector requires hydrocarbon free carrier gas. Chromatographic grade helium (99.998% pure) has proven satisfactory for this analysis. A.2.7 Pressure Reducing and Flow Control Devices-Upstream restrictions such as flow controllers are not permitted when using inlet sample splitters. Column inlet

pressures should remain constant during splitting and the period of analysis. A.3 Preliminary Preparations A.3.1 Hydrocarbon Test Blend-Prepare a gravimetric standard of n-hexane, n-octane, n-decane and n-dodecane using >98% purity of the pure hydrocarbons. Weigh accurately approximately 1 gram of each hydrocarbon into a narrow mouth 4 ounce bottle followed by approximately 96 grams of hexanefree n-pentane. Cap the bottle tight and keep refrigerated except during use. From the recorded weights calculate the exact concentration of the hydrocarbons in the blend. A.3.2 Instrument Conditions-The capillary instrument should be installed according to the manufacturer's instructions, including installation of the capillary column and inlet splitter system. Parameters to be recorded for the operation file include: Hydrogen Press., psig Air Press., psig Carrier Gas Press., psig Initial Temperature Temperature Program Final Hold Inlet Splitter Temp. Detector Temperature Split Ratio (15-30) (Nominal Range) (40-60) (Nominal Range) (40-60) (Nominal Range) 30C for 3.0 rain. 6C/rain. for 20.0 min. 150C for 1 min. 175C 175C 1:400 (nominal) NOTE A-2--Before the capillary column is inserted into the detector inlet, the carrier gas flow through this column should be measured at 30C, using a soap bubble meter or similar technique to measure flow as a function of time. At 30C, establish a flow of 1.8-2.0 cc/minute by adjusting the column inlet pressure up or down until the desired flow rate is achieved. A.3.3 Setting Split Ratio-Connect a reference gas to the sample inlet system and with splitter set near 1:200, inject a 2 cc sample of gas and record the iso- and normal pentane peaks on scale. Repeat the above step at a ratio of 1:300, record the

pentane peaks and observe whether the resolution has improved. Repeat this step and increase the split ratios until no visual resolution differences are observed for these two peaks. Select the smallest split ratio that exhibits the best resolution for this operating parameter. 11 A.3.4 Sample Discrimination Check-Using a microliter syringe, inject 1.0 microliter of the blend prepared in A.3.1, using the split ratio parameter determined in A.3.3 and the temperature program parameters detailed in A.3.2. Record the peak retention times and peak areas. For the blend components used, the flame ionization detector responds relative to mass (weight), therefore since the same mass of each of the four components was injected, the area under the individual peaks should be very close to the same value. If not, adjust inlet splitter temperature upward and repeat test until the four peak areas agree to within +1% relative. NOTE A-3--This blend can be used for guidance in adjusting instrument parameters for optimum analysis time since n-decane is usually the last significant component in natural gas. A.4 Analysis Procedure A.4.1 Make an analysis on the unknown gas according to GPA Standard 2261. If this analysis is made at 120C or above, record the unnormalized mol percent values for nitrogen through n-butane, the peak areas and unnormalized tool percent for isoand normal pentane, and the peak area for hexanes and heavier. For an analysis made below 120C, do not record the peak area for hexanes and heavier. NOTE A-4--At temperatures above 120C, the GPA Standard 2261 is expected to measure all of the hexanes and heavier components. This may not be the case for lower column temperatures. A.4.2 Connect the unknown gas to the sample inlet system of the capillary gas chromatograph and inject about 2 cc of gas. Record the peak areas, beginning with iso- and normal pentane, of the heavier peaks in the sample. A typical chromatogram of a capillary column separation is shown in Figure A-I. A.5 Calculations A.5.1 Assemble Peak Areas for Table A-II by appropriately grouping like hydrocarbon types of the same molecular weight into a single area for inclusion in Table A-II. Figure A-I has every peak labeled with its corresponding location in Table A-II.

A.5.2 GPA Standard 2261 above 120 C-Areas in Table AII heavier than n-pentane are normalized to 100%. The normalized area percent of each Table A-II component is multiplied by the total area of hexanes and heavier from GPA Standard 2261 (Table A-I). This correctly distributes the total hexanes and heavier area of GPA Standard 2261 (Table A-I) according to the components named in Table A-II. Next the areas in Table A-II are calculated to tool percent as follows: Cn = (Ac x Ms x Rn) (As x Mc) x Cs Where Cn = Mol percent of component n Ac = Peak area of component n As = Peak area of iso- and normal pentane Cs = Mol percent of iso- and normal pentane Mc = Molecular weight of component n Ms = Molecular weight of iso- and normal pentane Rn = Flame ionization response factor for component n (if needed) NOTE A-5--Flame ionization response factors are significant for benzene and toluene. These are also significant components in natural gas residues. For this method the response factor (multiplying factor)for benzene is assumed to be 0.928 and for toluene 0.972. All remaining components in Table A-I have assumed response factors relative to iso-and normal pentane having response factors of 1.000. (Refer to Table V1, main text.) Wi \\ \\ Time - Minutes Figure A-I - Natural Gas Residue by Capillary Gas Chromatography. 42 Table A-III Example Calculations (above 120C) TABLE A-I Area Unnorm. Norm. Mol % Mol % 1. 4400 4.031 4.012 2. 71.456 71.129 3. 1.062 1.057 4. 9.843 9.797 5. 5.462 5.437 6. 2.998 2.984

7. 3.014 3.000 8. 1.012 1.007 9. 5500 .921 .917 10. 5000 TABLE A-II Area Norm. x Area (1) Apportioned C n Area % Area (1) 9. 10. 11. 600 .397 4400 17.468 .003 .003 12. 18500 12.229 538.076 .083 .083 13. 14250 9.419 414.436 .064 .064 14. 21350 14.113 620.972 .096 .096 15. 15600 10.312 453.728 .072 .072 16. 9500 6.280 276.320 .042 .042 17. 17890 11.826 520.344 .082 .082 18. 6500 4.297 189.068 .025 .025 19. 6450 4.263 187.572 .025 .025 20. 7540 4.984 219.296 .029 .029 21. 11840 7.826 344.344 .045 .045 22. 10560 6.980 307.120 .041 .041 23. 1200 .793 34.892 .004 .004 24. 4560 3.014 132.616 .018 .018 25. 1100 .727 31.988 .004 .004 26. 905 .598 26.3t6 .003 .003 27. 1360 .899 39.556 .005 .005 28. 826 .546 24.024 .003 .003 29. 425 .281 12.364 .001 .001 30. 100 .066 2.904 <.001 <.001 31. 100 .066 2.904 <.001 <.001 32. 75 .049 2.156 <.001 <.001 33. 50 .033 1.452 <.001 <.001 151281 100.000 4400.000 100.450 100.000 TABLE A-I Area 1. 2. 3. 4. 5. 6. 7. 8.

9. 5500 10. 5000 TABLE A-II Area Table A-IV Example Calculations (below 120C) Unnorm. Mol % 4.031 71.456 1.062 9.843 5.462 2.998 3.014 1.012 .921 Norm. Mol % 4.012 71.129 1.057 9.797 5.437 2.984 3.000 1.007 .917 x A-I (9)(10) Adjusted for A-II (9)(10) Sample Size On 9. 186700 10. 167900 11. 600 .02961 17.766 .003 .003 12. 18500 547786 .084 .084 13. 14250 421.942 .065 .065 14. 21350 632.174 .097 .097 15. 15600 461.816 .073 .073 16. 9500 281.295 .043 .043 17. 17890 529.723 .084 .084 18. 6500 192.465 .025 .025 19. 6450 190.984 .025 .025 20. 7540 223.259 .030 .030

21. 11840 350.582 .047 .047 22. 10560 312.682 .042 .042 23. 1200 35.532 .004 .004 24. 4560 135.022 .018 .018 25. 1100 32.571 .004 .004 26. 905 26.970 .003 .003 27. 1360 40.269 .005 .005 28. 826 24.458 .003 .003 29. 425 12.584 .001 .001 30. 100 2.961 <.001 <.001 31. 100 2.961 <.001 <.001 32. 75 2.221 <.001 <.001 33. 50 1.480 <.001 <.001 151281 4479.502 100.456 100.000 A.5.3 The mol percent from the individual components from A.5.2 are summed with the n-pentane and lighter components from GPA Standard 2261 (Table A-I) and normalized to 100.000%. An example calculation is shown in Table A-III. A.5.4 GPA Standard 2261 below 120C - The summed areas of iso and normal pentane in Table A-II are divided into the summed areas of iso and normal pentane of Table A-I to produce a multiplying factor to convert the component areas of Table A-II to the same sample size as used in GPA Standard 2261 (Table A-I). These adjusted areas are calcula-ted to mol % in exactly the same manner as described in A.5.2. These tool % data are summed into the n-pentane and lighter data from GPA Standard 2261 and the combined data is normalized to 100.000%. An example calculation is shown in Table A-IV. APPENDIX B B.1 Determination of Carbon Monoxide-This component is encountered in association with oxygen, nitrogen, carbon dioxide and the conventional hydrocarbons in the effluent streams from combustion processes such as insitu combustion, manufactured gas, and many varied types of stack gas. A 10 ft. molecular sieve 5A column, 100/120 mesh substituted for the adsorption column shown in 3.1.3 of the main text, will determine carbon monoxide since it elutes shortly after methane. If a calibration gas is available containing carbon monoxide, obtain a response factor as for methane on the molecular sieve column. However, should a gas blend not be available, a calibration curve should be developed using pure carbon

monoxide to determine the extent of the nonlinearity, if present. B.2 Determination of Hydrogen and Helium-If hydrogen is to be separated from helium, a 40 ft. molecular sieve 13X column 13 30# nitrogen carrier 40C even 1/2 cc. loop 250 m.a. 40-foot tool sieve 13X (1/8- inch col.) Thermal conductivity detection E -r,o ,-rIIII 01234 Time, minutes Figure B-1-Separation of Helium and Hydrogen. using nitrogen or argon as a carrier gas may be used (Figure B-1). Low temperature, 40C or less, is necessary to effect this separation. When helium is used as a carrier gas and hydrogen is present, hydrogen will elute on the standard molecular sieve column just before oxygen. It will also be noted that a low percentage recovery is obtained in the case where helium is present in the unknown gas indicating the nee.d for a separate helium determination on the long 40 ft. (12 meters) molecular sieve 13X column. If a calibration gas blend is available containing hydrogen and helium, it should be used to obtain response factors. However, this not being the case, the pure components, hydrogen and helium, may be used to develop response curves in the manner set forth in section 4.3, main text. B.3 Determination of Hydrogen Sulfide As indicated earlier in this text, to determine the hydrogen sulfide content of a gas accurately, analyses should be made at the sample source. However, in the case where a field analysis has not been made and although corrosion of the sample bottle may have resulted in some loss of hydrogen sulfide, an analysis of the in-place component may be made by gas chromatography. It is necessary to charge a sample of pure hydrogen sulfide to the column prior to charging the unknown gas. As soon as the pure hydrogen sulfide has cleared the column, the unknown gas

should be charged. (All calibrations should be done the same way, that is, each partial pressure charge of pure hydrogen sulfide must be preceded by a full sample loop of pure hydrogen sulfide.) The Maximum Allowable Concentration to which a person may be exposed without approved respiratory protection equipment is 10 ppm for an eight hour working period. Concentrations as low as 15.0 ppm may cause severe irritation to the eyes and respiratory tract if the exposure lasts through the working day. Exposure of 800 to 1,000 ppm may be fatal in a few minutes. The nose cannot be depended upon to detect the pressure of hydrogen sulfide, as 2- 15 minutes of exposure will cause the loss of sense of smell. APPENDIX C Preparation of Equipment C.1 Linde Molecular Sieve Column--Clean a 12 ft. (3.6 meter) length of 1/8 in. (3.18 mm) stainless steel tubing with acetone and dry with a stream of clean, dry air or inert gas. Plug one end of the tubing with about 1/2 in. of glass wool. Attach a small funnel to the other end and fill the tubing with Type 13X, 100/120 mesh, dry Linde Molecular Sieve. Continuously vibrate the tubing while filling by moving an electric vibrator up and down the length of the tubing. When completely full, remove about 1/2 in. (10-15 mm) of the packing and replace with glass wool. Shape the finished column to mount conveniently in the chromatograph. Condition new column at 300C overnight with carrier flow and disconnected from TC cell. This column will separate hydrogen, oxygen, nitrogen and methane. About 25 psig of carrier gas pressure at the inlet will give a suitable flow rate. A column that has proved satisfactory for this type of analysis is the Silicone 200-500 column. It is most convenient since this is the recommended column for analyzing the hydrocarbons in natural gas. Hydrogen sulfide elutes between ethane and propane with good resolution. Extreme care must be taken when working with hydrogen sulfide due to the very toxic nature of the gas. The best ventilation possible must be maintained in the laboratory. C.2 Silicone 200-500 Composite Column-A suitable partition column to resolve the components nitrogen and/or air, methane and all hydrocarbons and non-hydrocarbons through normal pentane (as discussed in 3.1.4 and shown in Figure 3 main text)

can be made as follows: Clean a 20 ft., 2 ft., and 1 1/2 ft. (6, 0.6, and 0.4 meter) length of 1/8 in. (3.2 ram) stainless steel column tubing with 14 chloroethane followed by acetone, and then dry with a stream of clean, dry air or inert gas. Bend into a U-shape for filling. Dilute 30 grams of Silicone 200-500 with about 300 grams of ethyl ether in a filter flask and add 80 grams of 100/120 mesh Chromosorb P or equivalent support material. Shake the flask gently to disperse the solvent. Connect a vacuum line to the flask and evaporate the solvent. Swirl the flask gently several times while removing the solvent, to avoid concentration of the silicone in the upper layer. Pour the dry packing into both ends of the 20 ft. length of tubing using a small funnel and electric vibrator to completely fill the column. Plug each end with 1/2 in. (10-15 mm) of glass wool. Shape the finished column to mount conveniently in the chromatograph. Pour some 80/100 mesh Chromosorb 102 into the 2 ft. length of tubing using a funnel and electric vibrator to completely fill the column. Plug each end with 1/2 in. (10-15 mm) of glass wool. Repeat above procedure with Porapak T and the 1 1/2 ft. length of tubing. Using two 1/8 in. (3.2 mm) stainless steel unions join the 2 ft. length of Chromosorb 102 and the 1 1/2 ft. length of Porapak T to the 20 ft. length of Silicone 200-500 in that order. Condition column at 200C (maximum) overnight before using. Caution: temperatures in excess of 200C will harm this column. This column will separate air, methane, carbon dioxide ethane, hydrogen sulfide, propane, iso-butane, n-butane, isopentane, n-pentane and other natural gas hydrocarbons as described in the method procedure. C.3 UCL-45 Column-A suitable packed column to resolve the components iso-pentane through tetradecane (as discussed in 3.1.5 and shown in Figure 4 main text) can be made as follows: Clean a 15 ft. (4.5 m) length of 1/8 in. (3.2mm) stainless steel tubing (0.021 in. wall) with chloroethane followed by acetone, and then dry with a stream of clean, dry air or inert gas. Bend into a U-shape for filling. Weigh approximately 1.4 grams Silicone UCL-45 (methyl)

in a clean beaker and add 60 cc of chloroform. Allow several hours for mixture to become completely homogeneous, stirring during this time at regular intervals. Weigh 10.6 grams Gas Chrom QII or Supelcoport (100/120 mesh) in a side-arm flask and add dissolved liquid phase. With the flask gently rotating pull a vacuum on the side-arm of flask and apply mild heat. Continue until material is dry and can be poured satisfactorily into a bottle. Place open bottle and material in oven at 120F for one hour. Pack column in U-shape using a vibrator. Do not use a vacuum pump on the column during the packing process. Plug each end with 1/2 in. (10-15 ram) glass wool, and bend finished column to required shape for installation in the chromatograph. Condition column at 200C overnight with carrier gas flow before using. C.4 Preparation of a Reference Standard by Weight-Materials required: a. Five gallon cylinder. b. 2,000 gram balance, sensitivity 10 mg. c. 100 ml pressure cylinder. d. Pure components, methane through n-pentane, and carbon dioxide. All materials except methane, carbon dioxide and possibly ethane, will be added as a liquid. The pure components should be 99+% pure. Run chromatogram on each component to check on given composition. Evacuate the five gallon cylinder for several hours. Evacuate the 100 ml cylinder and obtain its true weight. Connect the 100 ml cylinder to a source of pure n-pentane with a metal connection of calculated length to contain approximately the amount of n-pentane to be added. Flush the connection with the n-pentane by loosening the fitting at the 100 ml cylinder valve. Tighten the fitting. Close the n-pentane valve and open the 100 ml cylinder valve to admit the n-pentane from the connection and then close. Disconnect and weigh the 100 ml cylinder to obtain the weight of n-pentane added. Similarly, using connections of suitable length for each component, add iso-pentane, n-butane, iso-butane, propane, ethane and carbon dioxide as desired to include in the reference standard. Weigh the 100 ml cylinder after each addition to obtain weight of component added. Connect the 100 ml cylinder to the five gallon cylinder using as short a connection as possible. Open valves on both cylinders to transfer the sample. Disconnect and weigh the 100 ml cylinder to obtain weight of sample not transferred. Analyze the

material remaining in the 100 ml cylinder and calculate the weight of all components transferred into the five gallon cylinder. Weigh a one quart cylinder containing pure methane at about 1500 pounds pressure. Transfer the methane to the five gallon cylinder until the pressure equalizes. Weigh the quart cylinder to determine the weight of methane transferred. Thoroughly mix the contents of the five gallon cylinder by heating at the bottom by convenient means such as hot water or heat lamp and leaving in vertical position for six hours or longer. From the weights and purities of all components added, calculate the composition and convert the weight percent to mol percent. NOTE C-I--Maintain the GPA Reference Standard at 21C or above, which is safely above the hydrocarbon dew point. If it should be exposed to lower temperature, heat the bottom of the cylinder for several hours before using. REFERENCE 1Dietz. W. A., J of GC, February, 1967, Pages 68-71. 2 NIOSH No. MX1225000. 15 Appendix D Calculations Performed in Association with Gas Analyses PREF ACE All physical constants used in these calculations should come from the most recent edition of GPA 2145. The constants used in the examples that follow are from GPA 2145-95. The following physical constants not listed in GPA 2145 have been used in some of the calculations: 0.25636 = vapor pressure of H20 (psia) @ 60 F (reference: U.S. Bureau of Standards) 1230 = vapor pressure of CO 2 (psia) @ 100F 5000 = vapor pressure of N 2 (psia) @ 100F = Gas Constant = 1545.3504 ft. - Ibf0b - mol R Cu.ft./lb - mol of any gas at 14.696 psia and 60F - V _ RT nP (1545.3504)(459.67 + 60) (144)(14.696) = 379.48357 Constant values for hexanes plus (C6+) or heptanes plus (C7+) if not actually determined by extended analysis should be mutually agreed upon by all concerned parties.

For ease of hand calculations in the examples shown the number of significant figures does not match those shown in GPA2145. Precision of numbers in computer generated calculations should match that of GPA-2145. Rounding of numbers can cause some differences in final results. Computer generated calculatio ns should only round those final numbers displayed on analyses, not numbers generated in intermediate calculations. For those calculations that are pressure dependent, the mathematics should be carried out using the constants at a pressure base of 14.696 and the final result converted to the desired pressure base after all other mathematical functions are completed. Conversion of the physical constants to equivalent values at other pressure bases or the use of generated secondary factors prior to performing calculations is not recommended. It is further recommended that computer software be written to follow these methods and recommendations and that hardbound documentation of the software programs be maintained and available at all times. For use in these calculations, mol fraction shall be equal to: mo1%/100. 16 Calculation of Physical Properties from Mol Fraction .D.1 D.2 Calculation of Heating Value (Btu), Relative Density (Specific Gravity) and Compressibility Factor (Z). The reader is referred to GPA 2172 for the proper method of calculation for these properties. Calculation of GPM (Liquid Volume Equivalent Expressed as Gallons per 1000 cu. ft. of Gas) of Natural Gas. Component Column 1 Column 2 Column 3 Column 4 Mol Fraction Cu. Ft./Gallon GPM @ 14.696 psia GPM @ 14.650 psia @ 14.696 psia (Col. 1 x 1000)/Co1.2 Col. 3 x 14.650 GPA-2145 14.696 Nitrogen 0.0068 91.413 Methane 0.7987 59.135 Carbon Dioxide 0.0056 58.807 Ethane 0.1034 37.476 2.759 2.7504 Propane 0.0523 36.375 1.438 1.4335 Iso-Butane 0.0074 30.639 0.242 0.2412

N-Butane 0.0138 31.791 0.434 0.4326 Iso-Pentane 0.0040 27.380 0.146 0.1455 N-Pentane 0.0035 27.673 0.126 0.1256 Hexanes Plus 0.0045 23.235* 0.194 0.1934 Totals 1.0000 C2 + GPM = 5.339 5.3222 C3 + GPM = 2.580 2.5718 IC5 + GPM = 0.466 0.4645 * Arbitrarily assumed value (used if average value not determined). Note: It is recommended that this calculation be carried out using cu.ft./gallon constants at a pressure base of 14.696 psia until the final calculation at which time GPM can be converted to any desired pressure base as shown. Conversion of or manipulation of constants prior to performing the calculation is not recommended. D.3 Calculation of 26-70 Gasoline Content of Natural Gas. Column 1 Column 2 Column 3 Mol Fraction Vapor Pressure Partial Pressure Component GPA-2145 Col. 1 x Col. 2 Iso-Pentane 0.0040 20.450 0.0818 N-Pentane 0.0035 15.580 0.0545 Hexanes Plus 0.0045 3.683* 0.0166 Total A = 0.0120 B = 0.1529 Note: * Arbitrarily assumed value (used if average value not determined). The reader is directed tO the GPSA Engineering Data Book, Vol. I, Section 6 (Storage), Figure 6-4for conversion of Reid Vapor Pressure to True Vapor Pressure. 17 Mol Fraction of NC 4 Required to Produce 26 PSI Gasoline: [(27.5 x A) - B ] - 24.22 = mol fraction of NC 4 required [(27.5 x 0.012) - 0.1529 ] - 24.22 = 0.0073 Where: 27.5 24.22 A B = True Vapor Pressure (psia) required to obtain an ASTM Reid Vapor Pressure of 26 psi. = NC 4 Vapor Pressure (51.72) - required pressure (27.5) = Sum of mol fractions of C5 + components. = Sum of Partial Pressures of C5 + components. Component Column 1 Column 2 Column 3 Mol Fraction Cu. Ft./Gallon GPM @ 14.696 psia

Col. 1 x 1000 GPA-2145 Col. 2 N-Butane 0.0073 31.791 0.2296 Iso-Pentane 0.0040 27.380 0.1461 N-Penatane 0.0035 27.673 0.1265 Hexanes Plus 0.0045 23.235* 0.1937 Total 26 psi Reid V.P. Gasoline GPM = 0.6959 * Arbitrarily assumed value (used if average value not determined). D.4 Calculation of 14 psi Reid Vapor Pressure Gasoline Content of Natural Gas. 14 psi Reid Vapor Pressure Gasoline content is calculated in exactly the same manner as 26 psi Gasoline with the following two changes: (1) 15.25 is used in place of 27.5 as the required True Vapor Pressure to obtain a correct reading of 14 psi Reid. (2) 36.47 is used in place of 24.22 as the difference between NC 4 True Vapor Pressure and required pressure. D.5 Calculation of Actual Btu (Based on Field Determined H20 Content) of Natural Gas. Actual Btu/cu. ft. = Dry Btu @ PB x rl _ Pound_______~s (21.0649 ca. ft./lb x 14.696/PB)] I_ 1000000 _1 Where: PB = Pressure Base (psia) of Dry Btu Pounds = Field determined H20 Content in pounds per MMcf 21.0649 = 379.48357 (cu. ft. per mol t-I20 ) 18.015 (mol wt. H20 ) 18 D.6. Calculation of Btu per pound of Natural Gas. D.6a Calculation of Weight Fraction. Component Column 1 Column 2 Column 3 Column 4 Mol Fraction Molecular Wt. Comp. Pounds Weight Fraction GPA-2145 Col. 1 x Col. 2 Col. 3 Sample Mol. Wt. Nitrogen 0.0068 28.013 0.1905 0.0091 Methane 0.7987 16.043 12.8135 0.6144 Carbon Dioxide 0.0056 44.010 0.2465 0.0118 Ethane 0.1034 30.070 3.1092 0.1491 Propane 0.0523 44.097 2.3063 0.1106 Iso-Butane 0.0074 58.123 0.4301 0.0206 N-Butane 0.0138 58.123 0.8021 0.0385 Iso-Pentane 0.0040 72.150 0.2886 0.0138 N-Pentane 0.0035 72.150 0.2525 0.0121

Hexanes Plus 0.0045 92.489* 0.4162 0.0200 Totals 1.0000 Sample mol wt. = 20.8555 1.0000 * Arbitrarily assumed value (used if average value not determined). D.6b Calculation of Btu/Ib. Component Column 1 Column 2 Column 3 Weight Fraction Btu/Ib. Mass Comp. Btu/lb. GPA-2145 Col. 1 x Col. 2 Nitrogen Methane Carbon Dioxide Ethane Propane Iso-Butane N-Butane Iso-Pentane N-Pentane Hexanes Plus Total 0.0091 m 0 0.6144 23891 14679 0.0118 m 0 0.1491 22333 3330 0.1106 21653 2395 0.0206 21232 437 0.0385 21300 820 0.0138 21043 290 0.0121 21085 255 0.0200 20899* 418 1.0000 Btu/Ib. mass = 22624 Notes: 1. 2. * Arbitrarily assumed value (used if average value not determined). Btu/lb. mass constants from GPA-2145 are fuel as ideal gas. Since mass is not pressure dependent the final sample Btu/lb. mass should not be adjusted for any pressure base corrections. 19 D-7. Conversion of Known Btu Value to Btu Value at Different Condition. Btu Conversion Factors Conditions Required Btu Conditions of 14.650 psia 14.696 psia 14.730 psia

Known Dry Sat Dry Sat Dry Sat Btu Multiply By: 14.735 psia 15.025 psia Dry Sat Dry Sat 14.650 Dry 1.000 0.9825 1.0031 0.9856 1.0055 0.9880 1.0058 0.9883 1.0256 1.0081 psia Sat 1.0178 1.0000 1.0210 1.0032 1.0234 1.0056 1.0237 1.0059 1.0439 1.0261 14.696 Dry 0.9969 0.9794 1.0000 0.9826 1.0023 0.9849 1.0027 0.9852 1.0224 1.0049 psia Sat 1.0146 0.9968 1.0178 1.0000 1.0201 1.0024 1.0205 1.0027 1.0405 1.0228 14.730 Dry 0.9946 0.9772 0.9977 0.9803 1.0000 0.9826 1.0003 0.9829 1.0200 1.0026 psia Sat 1.0122 0.9945 1.0154 0.9977 1.0177 1.0000 1.0181 1.0003 1.0381 1.0204 14.735 Dry 0.9942 0.9768 0.9974 0.9800 0.9997 0.9823 1.0000 0.9826 1.0197 1.0023 psia Sat 1.0118 0.9941 1.0150 0.9973 1.0174 0.9997 1.0177 1.0000 1.0377 1.0200 15.025 Dry 0.9750 0.9580 0.9781 0.9610 0.9804 0.9633 0.9807 0.9636 1.0000 0.9829 psia Sat 0.9920 0.9746 0.9951 0.9777 0.9974 0.9800 0.9977 0.9804 1.0174 1.0000 Note: Sat (saturation) assumes that the gas contains all of the water vapor it can hold at 60F and the indicated pressure base. Formulas Used to Derive Btu Conversion Factors 1. Dry to Dry: PB Required x Known Dry Btu Known Dry Btu PB 2. Dry to Sat: PB Required - 0.25636 x Known Dry Btu Known Dry Btu PB 3. Sat to Dry: PB Required x Known Sat Btu Known Sat Btu PB - 0.25636 4. Sat to Sat: PB Required - 0.25636 x Known Sat Btu Known Sat Btu PB - 0.25636 Where: PB = pressure base (psia) 20 0 0 0