Gpa 2286

~
G P A STD*(<228b 95
3824b99 00LiLbA 214

GPA Standard 2286-95
Tentative Method of Extended Analysis

for Natural Gas and Similar Gaseous
Mixtures by Temperature Programmed
Gas Chromatography
Adopted as Tentative Standard 1986

Reprinted 1989, 1991, 1995
Revised 1995
Gas Processors Association

6526 East 60th Street
Tulsa, Oklahoma 74145
COPYRIGHT Gas Processors Association (GPA)

Licensed by Information Handling Services
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G P A STDr228b 95 W 3824b99 0017169 150 W
DISCLAIMER
GPA publications necessarily address problems of a general nature and may be used by anyone desiring
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contained in its publications. With respect to particular circumstances, local, state, and federal laws
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GPA makes no representation, warranty, or guarantee in connection with this publication and hereby
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any infringement of letters of patent regarding apparatus, equipment, or method so covered.
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G P A STDa2286 95
3824677 0017170 772
Tentative Method of Extended Analysis for Natural Gas and Similar Gaseous
Mixtures by Temperature Programmed Gas Chromatography
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 is0 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 sulfide 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.
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 i n 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 suljde 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 three
r------I
I
I
NOTE 2-The TCD and FID may be run in series $desired

instead of using an efluent splitter.
N O T E 3-The times listed in this method are f o r
informational purposes only and may vary with changes in
operating parameters.
IfII------
-1
I
I
I
I
I
col. 1
Mol Sebu\
13% Cd.
. -
I
I
Hdium in.
6P Y2
I
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I
- -
Gas Sample Loop
I
cids B
side A
I
I
I
I
Hdiun in
Gas Sample Oui
L - - - - - - - -- - - - -
Gas Sample In
Vacuum Saum
Figure 1 - Suggested Flow System Using an Effluent Splitter.

1
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G P A STD*228b 95
3 8 2 4 6 9 9 OOL7L7L 809
Table I
Natural Gas Components and Range of Components Covered
Peak
Number
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
Component
Oxygen
Nitrogen
Carbon Dioxide
Methane
Ethane
Hydrogen Sulfide
Propane
Iso-Butane
n-Butane
iso-Pentane
n-Pentane
2,Z-Dimethylbutane
2-Methylpentane
23-Dimethylbutane
3-Methylpentane
Cyclopentane
n-Hexane
Methylcyclopentane
2.2-Dimethylpentane
2,CDimethylpentane
2.2.3-Trimethylbutane
Benzene
3.3-Dimethylpentane
Cyclohexane
ZMethylhexane
2,3-Dimethylpentane
3-Methylhexane
1,l-Dimthylcyclopentane
1t,3-Dimethylcyclopentane
1c,3-Dimethylcyclopentane
1t, 2-Dimethylcyclopentane
3-Ethylpentane
n-Heptane
Methylcyclohexane
2,2-Dimethylhexane
1,1,3-Trimethylcyclopentane
Ethylcyclopentane
2,CDimethylhexane
2,5-Dimethylhexane
Conc. Range
Mol %
Peak
Number
0.005 - 20
0.005 - 100
0.005 - 100
0.001 - 100
0.001 - 100
0.10 - loo
0.001 - 100
0.001 - 10
0.001 - 10
0.001 - 5
0.001 - 5
0.001 - 5
16
17
18
19
20
0.001 - 5
21
0.001 - 5
22
0.001 - 5
23
0.001 - 2
24
25
0.001 - 2
26
0.001 - 2
0.001 - 2
27
0.001 - 2
28
0.001 - 2
29
30
31
32
33
34
35
0.001 - 2
0.001 - 2
0.001 - 2
Component
1c,2t,4-Trimethylcyclopentane
lc,2t,3-Trimethylcyclopentane
2,3,4-Trimethylpentane
Toluene
2,3-Dimethylhexane
2-Methylheptane
CMethylheptane
3-Methylheptane
3,4-Dimethylhexane
1c,2c,4-Trimethylcyclopentane
1c,3-Dimethylcyclohexane
1t,4-Dimethylcyclohexane
1.1-Dimethylcyclohexane
1-Methyl-cis-3-ethylcyclopentane
1-Methyl-trans-2-ethylcyclopentane
1-Methyl- 1-ethylcyclopentane
n-Octane
1c,2c,3-Trimethylcyclopentane
2,s-Dimethylheptane
3,s-Dimethylheptane
Ethylbenzene
1,3-Dimethylbenzene
1,CDimethylbenzene
2,3-Dimethylheptane
3,4-Dimethylheptane
2-Methyloctane
3-Methyloctane
1,2-Dimethylbenzene
n-Nonane
Decanes
Undecanes
Dodecanes
Tridecanes
Tetradecanes
Conc. Range
Mol %
0.001 - 2
0.001 - 2
0.001 - 2
0.001 - 2
0.001 - 2
0.001 - 2
0.001 - 2
0.001 - 2
0.001 - 2
0.001 - 2
0.001 - 2
0.001 - 2
0.001 - 2
0.001 - 2
0.001 - 2
0.001 - 1
0.001 - 1
0.001 -1
0.001 - 1
0.001 - 1
CAUTION: Peak identification and component groupings are based on the spec@ column arrangement and operating conditions
used in the development of this method.
volumes up to 0.5 ml will normally be required. The sample
volume should be reproducible such that successive runs agree
to HIS% of the counts on each component peak.
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.
NOTE &The sample size limitation of 0.5 ml or smaller is

selected with the linearity of detector response and ejjciency of
the column separation in mind. Larger samples may
occasionally be used to improve measurement accuracy in low
concentration components.
APPARATUS
3.1 Chromatograph-Any gas chromatograph may be used

which has the following specifications:
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.
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
2
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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.
Column - 12 ft. 13X Mol Sieve

Temperature - 60C
Inlet Pressure - 25 psig
Sample Size - 0.25 cc
Type Detector - Thermal Conductivity
Carrier Gas - Helium
W
e
c
NOTE 7-The preparation of a suitable exfended 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.
.ze c=
o
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 andor 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 &The preparation of a suitable partition column to
perform this separation is described in Appendix C.2.
3.1.7 Temperature Control-During the iso-thermal part of

the method the analyzer columns shall be maintained at a
temperature within +0.2"C 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 performance during the course of the run.
Column Silicone Composite

Temperature - Programmed
60C - 170C
Inlet Pressure 50 psig
Type Detector See Fig. 3
)c-
TCD Signal Plot

FID Sional Plot
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G P A STDm228b 75
= 3824b
O O L i L 7 3 b8L
Column - 15 t. UCL-45
Temperature - Programmed
60C - 170C
Inlet Pressure - 80 psig
Type Detector - Flame Ionization
i
II I
w
Figure 4.
4. LINEARITY CHECK PROCEDURE
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 c d m i n and minimum chart width IO cm.
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).
3.3.2 Integrator/Computers-Wide range, 0-1 volt/O-IO volt,

with both printing and plotting capabilities, baseline tracking
and tangent skim peak detection. Integratorkomputers should
have sufficient memory to handle the large number of
components and have a minimum of 12 programmable external
event relays.
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.
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3.4 Manometer-May be either U-tube type or well type

equipped with an accurately graduated and easily read scale
covering the range O 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.
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, elute 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 10-Dry air can be used f o r the calibration of

oxygen and nitrogen, using composition values of 21.87 mol 96
for oxygen (includes argon which is eluted with oxygen on a
molecular sieve column at these conditions) and 78.08 mol %
for nitrogen.
NOTE 8-A suggested mangold 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.
G P A STD*228b 95
= 3824699 001717Y
Table II
Range of Partial Pressures Used to Determine Pure Component
Linearity Response Data on Partition Column (Column 2) by
Thermal Conductivity Detection
Component
Nitrogen
Methane
Carbon Dioxide
Ethane
Hydrogen Sulfide*
TO
VACLILIM
...- -..
PUMP
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Methane
Carbon Monoxide
50 - Atmosphere
50 - Atmosphere
50 - Atmosphere
50 - Atmosphere
50 - Atmosphere
U
W I
4.3.3 Record exact partial pressure, operate appropriate gas

sample valve to place sample on Column 1,
Partial Pressure Range

mm of Mercury
50 - Atmoshpere
50 - Atmoshpere
50 - Atmoshpere
20 - 200
Helium
II
Figure 5 - Suggested Manifold Arrangement for Entering

Vacuum Samples.
Table III
Range of Partial Pressures Used to Determine Pure Component
Linearity Response Data on Adsorption Column (Column 1)
by Thermal Conductivity Detection
Oxygen
Nitrogen
VAIVF
Partial Pressure Range

m m of Mercury
T A UTION: Exercise appropriate handling procedures when

using pure hydrogen sulfide. See Appendix B-3.
Component
518
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 f o r 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 f o r a i r 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 linearig curve for oxygen over the range O to 21.9
mol % and a linearig curve for nitrogen over the range O to
78.1 mol %.
20- 100
NOTE II-Procedures for the calibration and analysis of

helium and carbon monoxidefound 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.
4.4 From experimental data developed in accordance with

4.2, 4.3, response curves shall be prepared in the following
manner:
4.2.2 Carefully open metering valve to admit pure

component up to approximately 50 mm mercury absolute (2 in.
Hg).
4.4.1 Determine area counts of all peaks of interest.
4.2.3 Record exact partial pressure, operate appropriate gas

sample valve to place sample onto Column 2.
4.4.2 Tabulate peak area counts opposite the appropriate

partial pressure used for each calibration run.
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).
4.4.3 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.
4.3 For each of the compounds oxygen, nitrogen and

methane separated on the adsoption column (Column 1) proceed
as follows:
5. CALIBRATION PROCEDURE
4.3.1 Connect sample source to gas sampling valve of
chromatograph. Evacuate manifold system, including sample
loop and check for leaks.
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.
4.3.2 Carefully open metering valve to admit pure

component up to approximately 50 mm absolute (2 in. of Hg).
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.)
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.
Evacuate V1 and V2 and then fill with fresh sample using

the manifold arrangement shown in Figure 5. This pari 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
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
Molecular Sieve Column
Silicone Comoosite Column

TCIFID Split Effluent
Part isothermal - part temperature programmed
TCD (Coi. 2)
TC-Isothermal
FID (Coi. 2)
TCD (Col. I)
Oxygen
Nitrogen
Methane
Nitrogen (Air Free)

Methane
Carbon Dioxide
t Briged in Mol Yo t
c Briged in Mol % c
Ethane
Hydrogen Sulfide
UCL-45 Column
FID (Col. 3)
Weight Percent
Methane
-
Propane
so-Butane
n-Butane
so-Pentane
n-Pentane
so-Pentane
n-Pentane
2,2-Dimethylbutane
2-Methylpentane
2.3-Dimethylbutane
3-Methylpentane
Cyclopentane
n-Hexane
Methylcyclopentane
2,P-Dimethylpentane
2,4-Dimethylpentane
2.2,3-Trimethylbutane
Benzene
3,3-Dimethylpentane
Cyclohexane
2-Methylhexane
2,3-Dimethylpentane
3-Methylhexane
1,I -Dimethylcyclopentane
3-Ethylpentane
n-Heptane
Methylcyclohexane
2.2-Dimethylhexane
1,I ,3-Tnmethylcyclopentane
Ethylcyclopentane
2.4-Dimethylhexane
2,5-Dimethylhexane
1c,2t,4-Trimethylcyclopentane
1c,2t,3-Tnmethylcyclopentane
2,3,4-Tnmethylpentane
Toluene
- 2.3-Dimethylhexane
In Weight Percent
Converted to
Mol Relationship
+ Briged in Weight % +
YCL-45 Column
FID (Col. 3)
Weight Percent -
2-Methylheptane
4-Methylheptane
3-Methylheptane
3,4-Dimethylhexane
1~,2~,4-Trimethylcyclopentane
1,l -Dimethylcyclohexane
1-Methyl-trans-2-ethylcyclopentane
1-Methyl-1-ethylcyclopentane
n-Octane
1c,2~,3-Trimethylcyclopentane
Ic,2-Dimethylcyclohexane
2,5-Dimethylheptane
3.5-Dimethylheptane
Ethylbenzene
1,3-Dimethylbenzene
1,4-Dimethylbenzene
2,3-Dirnethylheptane
3.4-Dimethylheptane
2-Methyloctane
3-Methyloctane
1,2-Dimethylbenzene
n-Nonane
Decanes
Undecanes
Dodecanes
Tridecanes
Tetradecanes
Figure 6 - Calculation Procedure.
NOTE 13-Bridge
2 al). (See 7.2)
FID (Col. 3) in weight % to FID (Col. 2). Convert both data columns to moles and then bridge to TCD (Col.
6
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G P A S T D W 2 8 b 95 M 3824699 OOl17l175 454
G P A STD*228b 95
3824699 00LLb 390

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 hat the gas shall not be allowed to drop below its dew
point and shall be representative of the gas that was sampled.
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 themal 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.
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
Sandard and Pure Components by Thermal Conductivity
At this time the oven temperature heating program

commences and adds heat at approximately 2C per minute,
reaching the final temperamre 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
cell, 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 equiiibriated at 6O"C, ail valves are
back to the starting position of the cycle and a new sample may
be charged to the system.
component
Mol %
Response Factor
oxrsen
2.73
17795
0.W1534
Nitrogen
29.282
252925
o.Ooo1158
Methane (Mol Sieve)
69.97
498116
= 0.0001405
Methane ( S i i i iComposite)
52.42
1337500
= 0.00003919
Carbon Dioxide
7.37
280215
= 0.00OZ630
Hydrogen Culide
2.5
-
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.
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 partiai 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.
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 moi 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
Compooent
Methane
Ethane
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 ail lines
connecting the sample to the GC be made of stainless steel and
that these lines should be permanenrly heated to a tempemure
Weight %
47.69
6926850
11.89
1670658
Responce Factor
0.00000688
0.00000712
ProPane
11.32
1547536
0.00000732
Ico-BUtane
7.46
919943
0.00000810
0.00000806
0.00000893
n-8utane
iso-Pentane
Mentane
7.28
902966
3.04
340424
3.06
340528
7
0.00002857
87500
//^:^^#^~^^""~:""~#*^~@^"#:$@""~^"~"~:~:^::#^^*^~@^~:\\
= 0.00000899
by TC from the following formula:
M (or W)
P
K - Response factor on either mol 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
Where K =
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)
NOTE 15-Some integrators determine a response factor
Be sure to use the approach that is consistent with your

integration equipment.
Component
//^:^^#^~^^""~:""~#*^~@^"#:$@""~^"~"~:~:^::#^^*^~@^~:\\
soPentane
n-Pentane
2,2-Dirnethylbutane
2-Methylpntane
2,3-Dimethylbutane
3-Methylpentane
Cyclopntane
n-Hexane
Methylcyclopentane
2,2-Dmethylpentane
2,4-Dmthylpentane
2,2,3-Tnmethylbutane
Benzene
3,3-Dimethylpentane
Cyclohexane
2-Methylhexane
2.3-Dimethylpentane
3-Methylhexane
1.l-Dimethylcyclopentane
11,3-Dimethylcyclopentane
1t ,2-Dimethylcyclopentane
3-Ethylpentane
n-Heptane
Methylcyclohexane
2,2-Dimethylhexane
1,1,3-Trimethylcyclopentane
Ethylcyclopentane
2.4-Dimethylhexane
2.5-Dimethylhexane
1c,21,4-Trimethylcyclopentane
1c,21,3-Trimethylcyclopentane
2.3.4-Trimethylpentane
Toluene
2.3-Dimethylhexane
2-Methylheptane
4-Methylheptane
3-Methylheptane
3,4-Dimethylhexane
1~,2~,4-Trimethylcyclopentane
1c.3-Dimethylcyclohexane
1t.4-Dimethylcyclohexane
1-Methyl-trans-2-ethyIcyclopentane
1-Methyl-14hylcyclopentane
n-Octane
1c.2c.3-Trimethylcyclopentane
1c,2-Dimethylcyclohexe
2,5-Dimethylheptane
3,5-Dimethylheptane
Ethylbenzene
1,3-Dirnethylbenzene
1,4-Dimethylbenzene
2,3-Dimethylheptane
3,4-Dimethylheptane
2-Methyloctane
3-Methyloctane
1,2-Dimethylbenzene
n-Nonane
Decanes
Undecanes
Dodecanes
Tridecanes
Tetradecanes
7.2 Response factors for a flame ionization detector from

C5 to C, can be determined relative to the response of pentane
by analyzing a liquid blend of aliphatic, aromatic, and
naphthenic hydrocarbons from C5 to C,. (Examples of relative
sensitivity values for the FID are shown in Table VI.) Weight
sensitivities relative to i-Cs and n-Cs for the above components
are very close to 1.o0so making peak area percent almost equal
to weight percent.l 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 Cl through Cs unnormalized weight percent distribution
by the bridge components iCs and nCs and an unnormalized
weight percent for the components C6 to C, 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 fl.O% 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 VIL)
7.2.1 Response factors for the liquid blend C5 to C, are
calculated by the following formula:
W
K= 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 7.2.1
0.94
0.97
0.93
0.93
0.97
0.97
0.93
1.o2
0.93
0.93
0.93
0.93
0.93
0.97
0.97
0.97
0.97
0.97
0.97
0.97
0.93
0.97
0.97
0.97
0.93
0.93
0.99
0.98
0.98
0.94
0.94
0.94
0.94
0.98
0.94
0.95
0.94
0.95
0.95
0.95
NOTE Z6-Each area count is divided by the relative

sensitivity vahe to get the true area count.1
7.2.3 Calculate the moi % of oxygen, nitrogen, methane,

carbon dioxide and hydrogen sulfide in unknown as determined
8
Relative Sensitivity
1.o0
1.o0
0.99
0.99
0.98
0.98
0.98
0.99
0.97
0.98
0.98
0.98
1.O7
0.96
0.97
0.96
0.96
0.96
0.97
0.97
0.97
0.97
0.96
0.96
0.97
0.93
~~
3824699 O O L L 8 L b 3
G P A STD*<228b 95
Table VI1
Calculation of Unknown Sample using Response Factors
Adsorption Column Thermal Conductivity Detection
Comoonent
Counts
Oxygen
Nitrogen
Methane
210
237928
378759
Response
Factor
fr Containing
Unnormalized
Mol %
0.0001534
0.0001 158
0.0001405
0.032
27.545
53.21 5
Air Containing
Air Free
Air Free
Mol %
Corrected Mol % Corrected Mol Yo
(Unnormalized) Wnnormalized) (Normalized)
0.032
27.545
53.21 5
27.429
53.215
27.435
53.225
Composite Silicone Column Thermal Conductivity Detection

Component
counts
Response
Factor
Methane
Carbon Dioxide
Hydrogen Sulfide
1351682
240863
98732
0.00003919
0.00002630
0.00002857
Unnormalized
Mol %
52.972
6.335
2.821
Air Containing
Corrected Mol YO
(Unnormalized)
53.21 5
6.364
2.834
Air Free
Air Free
Corrected Mol Yo
Mol %
(Unnormalized) (Normalized)
53.21 5
6.364
2.834
6.365
2.835
Composite Silicone Column Flame ionization Detection

Component
Counts
Response
Factor
Methane
Ethane
Propane
iso-Butane
n-Butane
iso-Pentane
n-Pentane
5322628
849288
596340
228233
286869
135164
104274
0.00000688
0.00000712
0.00000732
0.00000810
0.00000806
0.00000893
0.00000899
Unnormalized
Weight % Mol wt.
36.620'
6.047'
4.365'
1.849'
2.312'
1.207
0.937'
Mdes
Air Containing
Corrected Mol %
(Unnormalized)
2.28304
0.201 10
0.09900
0.031 81
0.03978
0.01673
0.01299
16.04
30.07
44.09
58.12
58.12
72.15
7215
53.215
4.687
2.308
0.742
0.927
0.390
0.303
Air Free
Corrected Mol Yo
(Unnormalized)
53.215
4.687
2.308
0.742
0.927
0.390
0.303
Air Free
MOI%
(Normalized]
4.688
2.309
0.742
0.927
0.390
0.303
Silicone UCL-45 Column Flame ionization Detection

Relative Corrected Unnormalized
Sensitivitv Counts
Weipht % Mol Wt.
Air Containing
Air Free
Air Free
Corrected Mol % Corrected Moi Yo Mol %
Moles (Unnormalized) (Unnormalized) (Normalized
Component
Counts
iso-Pentane
n-Pentane
2,2-Dimethyibutane
332181
268065
18200
1.o0
1.o0
0.99
332181
268065
18384
1.207
0.937
0.066*
86.1 8
0.00077
0.01 8
0.01 8
0.018
2-Methylpentane
2,3-Dimethylbutane
93830
0.99
94778
0.339'
86.18
0.00393
0.092
0.092
0.092
3-Methylpentane
Cyclopentane
64900
0.98
66224
0.237'
78.16
0.00303
0.071
0.071
0.071
145200
0.99
146667
0.524'
86.18
0.00608
O. 142
0.142
0.142
Methylcyclopentane
2,2-Dimethyipentane
2,4-dimethyl pentane
2.2.3-Trimethylbutane
33916
0.98
34608
0.124'
85.76
0.00145
0.034
0.034
0.034
Benzene
3,SDimethyipentane
20550
1.O6
19387
0.069'
80.31
0.00086
0.020
0.020
0.020
Cyclohexane
11352
0.97
11703
0.042'
84.16
0.00050
0.01 2
0.012
0.012
2-Methylhexane
2,3-Dirnethylpentane
16190
0.96
16865
0.060'
100.20
0.00060
0.014
0.014
0.014
3-Methylhexane
1,l -Dimethylcyclopentane
8250
0.96
8594
0.031'
99.76
0.00031
0.007
0.007
0.007
1c,3-Dimethyicyclopentane
3-Ethylpentane
15110
0.97
15577
0.056'
98.19
0.00057
0.013
0.013
0.013
101176
0.96
105392
0.376'
100.20
0.00375
0.087
0.087
0.087
21448
0.96
22342
0.080'
99.78
0.00080
0.01 9
0.019
0.019
Ethyicyclopentane
2,4-Dimethylhexane
2,BDimethyl hexane
7982
0.94
8492
0.030'
110.22
0.00027
0.006
0.006
0.006
1c,2t,4-Tnmethylcyclopentane
4940
0.97
5093
0.018'
112.22
0.0001 6
0.004
0.004
0.004
N-Hexane
n-Heptane
Methyicyclohexane
2,2-Dimethyl hexane
1.1,3-Tnrnethylcyclopentane
9
//^:^^#^~^^""~:""~#*^~@^"#:$@""~^"~"~:~:^::#^^*^~@^~:\\
G P A STDa228b 95
m 3824699 OOL7L79
OTT
Table VI1 - Continued
Silicone UCL-45 Column Flame Ionization Detection
Component
Counts
lc,2t,3-Trimethyicyclopentane
5420
2,3,4-Trimethylpentane
Relative Corrected Unnormalized

Sensitivity Counts
Weight % Mol Wt.
Moles
Air Free
Air Containing
Air Free
Corrected Mol % Corrected Mol % Mol %
(Unnormalized) . .(Unnormalized) (Normalized)
0.97
5588
0.020'
113.22
0.00018
0.004
0.004
0.004
Toluene
34318
1.o2
33645
o. 120*
92.1 3
0.00130
0.030
0.030
0.030
2,3-Dimethylhexane
2-Methylheptane
4-Methylheptane
15722
0.93
16905
0.060*
114.23
0.00053
0.012
0.012
0.012
5249
0.93
5644
0.020*
114.23
0.00018
0.004
0.004
0.004
10651
0.97
10980
0.039'
112.21
0.00035
0.008
0.008
0.008
0.97
2322
0.008'
112.21
0.00007
0.002
0.002
0.002
43566
0.93
46845
0.167'
114.23
0.00146
0.034
0.034
0.034
1453
0.97
1498
0.005'
112.21
0.00005
0.001
0.001
0.001
2251
0.97
2321
0.008'
112.21
0.00007
0.002
0.002
0.002
2,5-Dimethylheptane
3,5-Dimethylheptane
10519
0.93
11311
0.040"
128.25
0.00031
0.007
0.007
0.007
Ethylbenzene
1,3-Dimethylbenzene
1,4-Dirnethylbenzene
2,3-Dimethylheptane
3P-Dimethylheptane
35740
0.96
37229
0.133'
117.23
0.001 14
0.027
0.027
0.027
2-Methyloctane
3-Methyloctane
15482
0.94
16470
0.059"
128.25
0.00046
0.01 1
0.01 1
0.01 1
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
0.1 15'
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
3-Meth ylheptane
3,4-Dimethylhexane
1t,4--Dimethylcyclohexane
1-1-Dimethylcyclohexane
1-Methvl-Trans-2-ethvlcvclo~entane 2252
1-Meth;l-l -ethylcyclopentane
I
n-Octane
'
0.032
0.032
0.032
100.128'
99.980
100.000
*NOTE 17-if all components are measured, the unnomlized total should not vary more than & 1.00%from 100.00%.
APPENDIX A
Supplementary Procedures
A. 1 Extended Analysis by Capillary Gas Chromatography
Table A-I
GPA Standard 2261
A.l.l 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.
1. Hexanes and heavier

2. Nitrogen
3. Methane
4. Carbon Dioxide
5. Ethane
6. Propane
7. Ico-butane
8. nButane
9. Iso-pentane
10. n-Pentane
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 char-
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

//^:^^#^~^^""~:""~#*^~@^"#:$@""~^"~"~:~:^::#^^*^~@^~:\\
acterization 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.
G P A STD*228b 95
3 8 2 4 b 9 9 O O L 7 L B O 811
A.2.4 Capillary Column-A 60 meter x 0.26 mm ID fused
silica capillary coated with a 1.O micron film thickness of DB- 1
has been found by experiment to be suitable for this analysis.
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 1 1
through 33 in Table A-II and normalized to 1OO.ooO%.
A.2.5 Integratorkomputer-Wide range, O- 1 VIO-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.
Table A-II
Capillary Extended Analysis
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
30.
31.
32.
33.
Iso-pentane
n-Pentane
Neohexane
2-Methylpentane
3-Methylpentane
n-Hexane
Methylcyclopentane
Benzene
Cyclohexane
2-Methylhexane
3-Methylhexane
Dimethylcyclopentanes
n-Heptane
Methylcyclohexane
Tnmethylcyclopentanes
Toluene
2-Methylheptane
3-Methylheptane
Dimethylcyclohexanes
n-Octane
C, Aromatics
C, Naphthenes
C, Paraffins
n-Nonane
Decanes and heavier
A.2.7 Pressure Reducing a n d 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
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.
NOTE A-2-Before the capillary column is inserted into the

detector inlet, the carrier gas flow through this column should
be measured at 30"C, using a soap bubble meter or similar
technique to measure flow as a function of time. A t 30"C,
establish a flow of 1.8-2.0 cc/minute by adjusting the column
inlet pressure up or down until the desiredflow rate is achieved.
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.
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 so- 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.
NOTE A-1-A vacuum sample entry system, such a s

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 mrn partial pressure would greatly reduce
the possibility of condensation of heavier sample components,
11
(15-30) (Nominal Range)

30C for 3.0 min.
6"C/min. for 20.0 min.
150C for 1 min.
175C
175C
1:400 (nominal)
//^:^^#^~^^""~:""~#*^~@^"#:$@""~^"~"~:~:^::#^^*^~@^~:\\
3824694 O O L 7 L 8 L 758
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 f l % relative.
A S 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 A-
Ii 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 mol percent as follows:
NOTE A-3-This blend can be used f o r guidance in

adjusting instrumentparameters for optimum analysis time since
n-decane is usually the last significant component in natural
gas.
AcxMsxRn)
C n = ( (As x Mc)
Where
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 120'C or above,
record the unnormalized mol percent values for nitrogen through
n-butane, the peak areas and unnormalized mol percent for isoand normal pentane, and the peak area for hexanes and heavier.
For an analysis made below 120'C, do not record the peak area
for hexanes and heavier.
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-4-At temperatures above 120"C, 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.
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 responsefactors of 1.000. (Refer to Table VI, main text.)
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.
-+\
Time - Minutes
Figure A-I - Natural Gas Residue by Capillary Gas Chromatography.
12
//^:^^#^~^^""~:""~#*^~@^"#:$@""~^"~"~:~:^::#^^*^~@^~:\\
G P A STD*:228b 95
3824699 0017182 b 9 4
Table A-III
Example Calculations (above 120C)
Table A-IV
Example Calculations (below 120C)
TABLE A-I
TABLE A4
Area
1. 4400
2.
3.
4.
5.
6.
7.
8.
9. 5500
10. 5000
Unnorm.
Mol %
Norm.
Mol %
4.031
71.456
1.O62
9.843
5.462
2.998
3.014
1.012
,921
4.012
71.129
1.O57
9.797
5.437
2.984
3.000
1.O07
.SI 7
Area
-
600
18500
14250
21350
15600
9500
17890
6500
6450
7540
11840
22. 10560
23.
1200
24.
4560
25.
1100
26.
905
27.
1360
28.
826
29.
425
30.
100
31.
100
32.
75
33.
50
151281
Norm.
4.031
71.456
1.O62
9.843
5.462
2.998
3.01 4
1.012
.921
4.012
71.129
1.O57
9.797
5.437
2.984
3.000
1.O07
.917
3.
4.
5.
6.
7.
8.
9. 5500
10. 5000
Mol %
TABLE A-Il
Nom. x Area(1) Apportioned
Area (1)
Area %
x A-I (9)(10) Adjusted for

A-Il (9)(10) Sample Size
crl
-
.o03
.o05
.O03
.o01
c.001
<.o01
c.001
<.o01
9. 186700
10. 167900
11.
600
12. 18500
13. 14250
14. 21350
15. 15600
16.
9500
17. 17890
18.
6500
6450
19.
20.
7540
21. 11840
22. 10560
23.
1200
24.
4560
25.
1100
26.
905
27.
1360
826
28.
29.
425
100
30.
31.
100
75
32.
33.
50
100.000
151281
9.
1o.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
Unnorm.
Mol %
1.
2.
TABLE A-Il
Area
-
.397
12.229
9.41 9
14.113
10.312
6.280
11.826
4.297
4.263
4.984
7.826
6.980
.793
3.014
.727
.598
.a99
,546
.281
.O66
.O66
.O49
.O33
100.000
4400
17.468
538.076
414.436
620.972
453.728
276.320
520.344
189.068
187.572
219.296
344.344
.O03
.O83
.O64
.O96
.O72
.O42
.O82
.O25
.O25
.O29
.o45
.O41
.O04
.O18
.O04
307.120
34.892
132.616
31.988
26.316
.O03
.O05
39.556
.O03
24.024
12.364
.o01
<.o01
2.904
2.904
c.001
2.156
c.001
1.452
c.001
___4400.000 100.450
.O03
.o83
.o64
.O96
.O72
.O42
.O82
.O25
.O25
.O29
.O45
.O41
.o04
.O18
.o04
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.
.O2961
17.766
547.785
421.942
632.1 74
461.816
281.295
529.723
192.465
190.984
223.259
350.582
312.682
35.532
135.022
32.571
26.970
40.269
24.458
12.584
2.961
2.961
2.221
1.480
.O03
.o01
<.o01
<.o01
<.o01
<.o01
.042
.004
.o18
.004
.003
.005
.003
,001
<.001
<.001
c.001
c.001
4479.502
100.455
100.000
.O03
.O84
.O65
.O97
.O73
.O43
.O84
.O25
.O25
.O30
.O47
.O42
.O04
.O18
.O04
.O03
.O05
.003
.084
.065
.097
.073
.o43
.o84
.025
.025
.O30
,047
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.
A.5.4 GPA Standard 2261 below 120C- The summed

areas of is0 and normal pentane in Table A-II are divided
into the summed areas of is0 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 mol % data are summed into the n-pentane and lighter
data from GPA Standard 2261 and the combined data is
normalized to lOO.ooO%. An example calculation is shown in
Table A-IV.
B.2 Determination of Hydrogen and Helium-If hydrogen is to

be separated from helium, a 40 ft. molecular sieve 13X column
13
crl
//^:^^#^~^^""~:""~#*^~@^"#:$@""~^"~"~:~:^::#^^*^~@^~:\\
GPA STDx2286 95 M 3824699 QOLL83 520 M
30# nitrogen carrier

40C even
1/2 cc. loop
250 m.a.
40-foot mol sieve 13X
(1/8- inch col.)
Thermal conductivitydetection
-5
z
I
3
Tima, minules
~~
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.
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 initation to
the eyes and respiratory tract if the exposure lasts through the
working day. Exposure of 800 to 1,ooO 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.
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 need 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.
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.
B.3 Determination of Hydrogen Sulfide
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.
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.)
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 mm) stainless steel column tubing with
14
//^:^^#^~^^""~:""~#*^~@^"#:$@""~^"~"~:~:^::#^^*^~@^~:\\
Figure B-1-Separation of Helium and Hydrogen.
95
= 3824b99
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 112 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 QI1 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 mm) 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.

0037384 467
C.4 Preparation of a Reference Standard by Weigh?-Materials

required:
a. Five gallon cylinder.
b. 2,000 gram balance, sensitivity I O 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-1-Maintain the GPA Reference Standard at 21C

or above, which is safely above the hydrocarbon dew point. Ifit
should be exposed to lower temperature, heat the bottom of the
cylinder for several hours before using.
REFERENCE
Dietz. W. A., J of GC, February, 1967, Pages 68-71.
NIOSH No. MX1225000.
//^:^^#^~^^""~:""~#*^~@^"#:$@""~^"~"~:~:^::#^^*^~@^~:\\
GPA STD*228b
G P A STD*228b 95
= 3824b
0017185 3T3
Appendix D
Calculations Performed in
Association with Gas Analyses
PREFACE
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 H,O (psia) @ 60F (reference: U.S. Bureau of Standards)
1230 = vapor pressure of CO, (psia) @ 100F
5000 = vapor pressure of N, (psia) @ 100F

-
R = Gas Constant = 1545.3504 ft. - lbplb - mol OR

Cu.ft./lb - mol of any gas at 14.696 psia and 60F = 1
n
=E
P
(1545,3504)(459.67+ 60)
(144)(14.696)
= 379.48357
Constant values for hexanes plus ((2,)'
or heptanes plus (C,')
mutually agreed upon by all concerned parties.
if not actually determined by extended analysis should be
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 calculations 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.
I t 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, moi fraction shall be equal to: mo1%/100.
16
//^:^^#^~^^""~:""~#*^~@^"#:$@""~^"~"~:~:^::#^^*^~@^~:\\
G P A STD*2'28b 95 W 3824699 001718b 23T
Calculation of Physical Properties from Mol Fraction

D.1
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.
0.2
Calculation of GPM (Liquid Volume Equivalent Expressed as Gallons per 1000 CU. fi. of Gas) of Natural Gas.
Column 1
Mol Fraction
Component
Nitrogen
Methane
Carbon Dioxide
Ethane
Propane
Iso-Butane
N-Butane
Iso-Pentane
N-Pentane
Hexanes Plus
0.0068
0.7987
0.0056
O. 1034
0.0523
0.0074
0.0138
0.0040
0.0035
0.0045
Totals
1.o000
Column 2
Cu. Ft./Gallon
d 14.696 psia
GPA-2145
91.413
59.135
58.807
37.476
36.375
30.639
31.791
27.380
27.673
23.235*
Column 3
GPM Q 14.696 Dsia
(Col. 1 x 1ooo)/col. 2
Column 4
GPM Q 14.650 psia
Col. 3 x 14.650
14.696
2.759
1.438
0.242
0.434
0.146
O. 126
0.1 94
2.7504
1.4335
0.2412
0.4326
0.1 455
0.1 256
0.1934
C
+, GPM =
C+
, GPM =
IC5+ GPM =
5.339
2.580
0.466
5.3222
2.5718
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.
0.3
Calculation of 26-70 Gasoline Content of Natural Gas.

Column 1
Mol Fraction
Column 2
Vapor Pressure
Column 3
Partial Pressure
GPA-2145
Col. 1 x Col. 2
20.450
15.580
3.683*
0.0818
0.0545
0.01 66
Component
Iso-Pentane
N-Pentane
Hexanes Plus
Total
0.0040
0.0035
0.0045
B = 0.1529
A = 0.0120
Note: 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
//^:^^#^~^^""~:""~#*^~@^"#:$@""~^"~"~:~:^::#^^*^~@^~:\\
= 3824699 0037387 176 m

~
G P A STDx2286 95
Mol Fraction of NC, Required to Produce 26 PSI Gasoline:

[(27.5 x A) - B ] t 24.22 = mol fraction of NC, 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, Vapor Pressure (51.72) - required pressure (27.5)

Sum of mol fractions of C,+ components.
Sum of Partial Pressures of C,+ components.
Column 1
Mol Fraction
Column 2
Cu. Ft./Gallon
Column 3
GPM Q 14.696 psia
GPA-2145
Col. 1 x 1000
Col. 2
31.791
27.380
27.673
23.235*
0.2296
0.1461
0.1265
0.1937
Component
N-Butane
Iso-Pentane
N-Penatane
Hexanes Plus
0.0073
0.0040
0.0035
0.0045
Total 26 psi Reid V.P. Gasoline GPM = 0.6959

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 NC4 True Vapor Pressure and required pressure.
D. 5
Calculation of Actual Btu (Based on Field Determined H 2 0 Content) of Natural Gas.
//^:^^#^~^^""~:""~#*^~@^"#:$@""~^"~"~:~:^::#^^*^~@^~:\\
Actual Btdcu. ft. = Dry Btu @ PB x
Where:
(21.0649 CU. ft.Ab x 14.696PB)I
PB = Pressure Base (psia) of Dry Btu

Pounds = Field determined H,O Content in pounds per MMcf
21.0649 = 379.48357 (CU. ft. per mol H,O)
18.015 (mol wt. H,O)
18
G P A S T D t 2 2 8 b 95
0.6.
m 3824699 0017188
002
Calculation of Btu per pound of Natural Gas.
D.6a
Calculation of Weight Fraction.
//^:^^#^~^^""~:""~#*^~@^"#:$@""~^"~"~:~:^::#^^*^~@^~:\\
Column 1
Mol Fraction
Column 2
Molecular Wt.
GPA-2145
Column 3
Comp. Pounds
Col. 1 x Col. 2
Column 4
WeinM Fraction
Col. 3
Sample Mol. Wt.
Nitrogen
Methane
Carbon Dioxide
Ethane
Propane
Iso-Butane
N-Butane
Iso-Pentane
N-Pentane
Hexanes Plus
0.0068
0.7987
0.0056
0.1 o34
0.0523
0.0074
0.01 38
O.Oo40
0.0035
0.0045
28.01 3
16.043
44.01 o
30.070
44.097
58.123
58.123
72.1 50
72.1 50
92.489*
O. 1905
12.8135
0.2465
3.1 092
2.3063
0.4301
0.8021
0.2886
0.2525
0.41 62
0.0091
0.61 44
0.01 18
0.1491
0.1106
0.0206
0.0385
0.01 38
0.0121
0.0200
Totals
1.oOOo
Sample mol wt. = 20.8555
1.moo
Component
* Arbitrarily assumed value (used 1 average value not determined).
D.6b
Calculation of Bhlb.
Column 1
Weight F r a c t x
Component
Nitrogen
Methane
Carbon Dioxide
Ethane
Propane
Iso-Butane
N-Butane
IsoPentane
N-Pentane
Hexanes Plus
0.0091
0.61 44
0.01 18
0.1491
0.1 106
0.0206
0.0385
0.01 38
0.0121
0.0200
Total
1.o000
Column 2
BtuAb. Mass
Column 3
Comp. Btu/lb.
GPA-2145
Col. 1 x Col. 2
O
14679
O
3330
2395
437
820
290
255
41 8
23891
22333
21653
21232
21300
21o43
21085
20899'
BtuAb. mass = 22624
Arbitrarily assumed value (used if average value not determined).
Notes: 1. Bhlb. mass constantsporn GPA-2145 are fuel as ideal gas.

2. Since mass is not pressure dependent the final sample Btdlb. mass should not be adjusted for any pressure base
corrections.

19
95 W 3824699 0037189 T 4 9 W
GPA STD*228b
Conversion of Known Btu Value to Btu Value at Different Condition.
0-7.
Btu Conversion Factors

Conditions
14.650 psia
of
14.696 psia
-Dry
. . - Sat
D r y - p
Known
Required Btu Conditions

14.730 psia
Sat
Dry
Btu
14.735 psia
15.025 psia
Sat
Dry
Sat
Dry
Sat
1.0081
1.O261
Multiply By:
14.650
mia
Dry
Sat
1.000
1.O178
0.9825
1.O000
1.0031
1.O21O
0.9856
1.O032
1.0055
1.O234
0.9880
1.O056
1.0058
1.O237
0.9883
1.O059
1.0256
1.O439
14.696
psia
Dry
Sat
0.9969
1.0146
0.9794
0.9968
1.0000
1.0178
0.9826
1.0000
1.0023
1.0201
0.9849
1.0024
1.0027
1.0205
0.9852
1.0027
1.0224 1.0049
1.0405 1.0228
14.730
psia
Dry
Sat
0.9946
1.O122
0.9772
0.9945
0.9977
1.O154
0.9803
0.9977
1.0000
1.O177
0.9826
1.O000
1.0003
1.O181
0.9829
1.O003
1.0200 1.0026
1.O381 1.O204
14.735
psia
Dry
Sat
0.9942
1.O118
0.9768
0.9941
0.9974
1.O150
0.9800
0.9973
0.9997
1.O174
0.9823
0.9997
1.0000
1.O177
0.9826
1.O000
1.0197 1.0023
1.O377 1.O200
15.025
psia
Dry
Sat
0.9750
0.9920
0.9580
0.9746
0.9781
0.9951
0.9610
0.9777
0.9804
0.9974
0.9633
0.9800
0.9807
0.9977
0.9636
0.9804
1.0000 0.9829
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
Known Dry Btu PB
Known Dry Btu
2. Dry to Sat: PB Required - 0.25636
Known Dry Btu
Known Dry Btu PB

3. Sat to Dry:
4.
Sat to Sat:
Where:
PB Required
x Known Sat Btu
Known Sat Btu PB - 0.25636
PB Required - 0.25636
Known Sat Btu PB - 0.25636
Known Sat Btu
PB = pressure base (psia)

20
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3824b99 00LiLbA 214

Tentative Method of Extended Analysis

Adopted as Tentative Standard 1986

Gas Processors Association

COPYRIGHT Gas Processors Association (GPA)

G P A STDr228b 95 W 3824b99 0017169 150 W

COPYRIGHT Gas Processors Association (GPA)

3824677 0017170 772

NOTE 1-Hydrogen suljde is eluted in a well defined peak

2.1 Components to be determined in a gaseous sample are

NOTE 2-The TCD and FID may be run in series $desired

Gas Sample Loop

Gas Sample Oui

Figure 1 - Suggested Flow System Using an Effluent Splitter.

COPYRIGHT Gas Processors Association (GPA)

2.2 An equally acceptable method using a packed column/

NOTE &The sample size limitation of 0.5 ml or smaller is

3.1 Chromatograph-Any gas chromatograph may be used

3.1.3 Adsorption Column (Column 1)-This column must

3.1.1 Detectors-The instrument should be equipped with

capable of introducing gas

3.1.5 Extended Analysis Packed Column (Column 3)-This

Column - 12 ft. 13X Mol Sieve

NOTE 7-The preparation of a suitable exfended analysis

3.1.6 Attenuator-The chromatograph should be equipped

Figure 2 - Separation of Oxygen, Nitrogen and Methane.

NOTE 5-The preparation of a suitable adsorption column

3.1.4 Partition Column (Column 2)-This column must

3.1.7 Temperature Control-During the iso-thermal part of

3.2 Carrier Gas-Pressure reducing and flow control

3.3 Recording Instruments-Either strip-chart recorders or

Column Silicone Composite

TCD Signal Plot

COPYRIGHT Gas Processors Association (GPA)

FID Sional Plot

4. LINEARITY CHECK PROCEDURE

3.3.1 .Recorders-Recorders shall be strip-chart types with

4. 1 For any specific chromatograph, the linear range of the

3.3.2 Integrator/Computers-Wide range, 0-1 volt/O-IO volt,

In order to determine the range of linearity it is necessary to

3.4 Manometer-May be either U-tube type or well type

NOTE 9-To generate pure component data necessary to

NOTE 10-Dry air can be used f o r the calibration of

NOTE 8-A suggested mangold arrangement for entering

3.5 Vacuum Pump-Must have the capability of producing

4.3.3 Record exact partial pressure, operate appropriate gas

Partial Pressure Range

Figure 5 - Suggested Manifold Arrangement for Entering

Partial Pressure Range

T A UTION: Exercise appropriate handling procedures when

4.3.4 Repeat steps 4.3.2 and 4.3.3 above at partial pressures

NOTE 12-Dry air can be used f o r the calibration of

NOTE II-Procedures for the calibration and analysis of

4.4 From experimental data developed in accordance with

4.2.2 Carefully open metering valve to admit pure

4.4.1 Determine area counts of all peaks of interest.

4.2.3 Record exact partial pressure, operate appropriate gas

4.4.2 Tabulate peak area counts opposite the appropriate

4.2.4 Repeat steps 4.2.2 and 4.2.3 above at partial

4.4.3 Plot the data in 4.4.2. Use rectangular coordinate

4.3 For each of the compounds oxygen, nitrogen and

5.1 The routine method of calibration is to use the response