GPA Standard 2261-13

Analysis for Natural Gas and Similar Gaseous

Mixtures by Gas Chromatography

Adopted as Tentative Standard, 1961

Revised and Adopted as a Standard, 1964
Revised 1972, 1986, 1989, 1990, 1995, 1999, 2000 and 2013

Gas Processors Association

6526 East 60th Street
Tulsa, Oklahoma 74145
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 FOREWARD

GPA 2261 provides the gas processing industry a method for determining the chemical composition of natural gas
and similar gaseous mixtures using a Gas Chromatograph (GC).

The precision statements contained in this standard are based on the statistical analysis of round-robin laboratory
data obtained by Section B.

This standard was developed by the cooperative efforts of many individuals from industry under the sponsorship of
GPA Section B, Analysis and Test Methods.

Throughout this publication, the latest appropriate GPA Standards are referenced

“Copyright© 2013 by Gas Processors Association. All rights reserved.

No part of this Report may be reproduced without the written consent
of the Gas Processors Association.”
 Analysis for Natural Gas and Similar Gaseous Mixtures by Gas Chromatography

1. SCOPE 2. SUMMARY OF METHOD

1.1 This standard covers the determination of the
chemical composition of natural gas and similar gaseous
mixtures within the ranges listed in Table 1, using a Gas
Chromatograph (GC). The three columns represent the
original Table 1, but separate the values to three distinct
groups. The first group is concentrations lower than the
data obtained from the round-robin project (RR-188).
The second group is concentrations used in the round-
robin project (RR-188). The equations listed in the
precision statement in this standard cover the range listed
in the middle column, after outliers were removed. The
third group is concentrations higher than the data obtained
from the round-robin project (RR-188).
The precision statement in this standard utilizes
equations derived from a regression of the data in RR-188
and is detailed in GPA TP-31. The precision statement
criterion applies only to values listed in Section 10, Table
6.
1.2 Components sometimes associated with natural
gases, i.e., helium, hydrogen sulfide, water, carbon
monoxide, hydrogen and other compounds are excluded
from the main body of the method. These components
may be determined and made a part of the complete
compositional data. Refer to Appendix A.
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. A fixed volume of sample in the
gaseous phase is isolated in a suitable inlet sample system
and entered onto the column.
2.2 The full range analysis of a gaseous sample may
require multiple runs to properly determine all
components of interest. The primary run is on a partition
column to determine air, methane, carbon dioxide, ethane
and heavier hydrocarbons. When oxygen/argon content is
critical in the unknown sample, or is suspected as a
contaminant, a secondary run should be made to
determine oxygen/argon and nitrogen in the air peak on
the partition column. When carbon dioxide content in the
unknown sample does not fall within the calibrated range
on the partition column, a secondary run should be made
to determine carbon dioxide content. When helium and/or
hydrogen content are critical in the unknown sample, a
secondary run should be made to determine helium and/or
hydrogen.
2.2.1 These analyses are independent and may be
made in any order, or may be made separately to obtain
less than the full range analysis. The configuration can
consist of a single or multiple GC’s to accomplish this.
Refer to Appendix A.

Table I Ranges of Natural Gas Components Covered 2.3 Response factors or response curves derived
from calibration data are essential to accurately determine
Lower Round Higher the composition of an unknown sample. The reference
Component Region Robin Region standard blend and the unknown samples must be run
using identical GC operating conditions.
Nitrogen 0.01 - 0.1 0.1 - 30 > 30
Carbon Dioxide 0.01 - 0.1 0.1 - 30 > 30
Methane 0.01 - 40 40 - 100 N/A 3. APPARATUS
Ethane 0.01 - 0.1 0.1 - 10 > 10
Propane 0.01 - 0.1 0.1 - 10 > 10 3.1 Chromatograph - Any Gas Chromatograph may
Isobutane 0.01 - 0.25 0.25 - 4 >4 be used as long as the specifications for repeatability and
n-Butane 0.01 - 0.25 0.25 - 4 >4 reproducibility stated in Section 10 within the round-robin
Isopentane 0.01 - 0.12 0.12 - 1.5 > 1.5 test component ranges listed in Table 1 are met or
n-Pentane 0.01 - 0.12 0.12 - 1.5 > 1.5 exceeded. The equipment described in this section has
been proven to meet the above requirements; however
* Hexanes Plus 0.01 - 0.1 0.1 - 1.5 > 1.5
other configurations including portable and online may be
* Heptanes Plus 0.01 - 0.1 0.1 - 1.5 > 1.5
acceptable.
*Data from round –robin was only obtained for Hexanes
Plus 3.1.1 Detector - The Thermal Conductivity Detector
(TCD) has proven to be a reliable and universal detector
Table Note: Uncertainty in the Lower region can easily be for this method.
ten times greater and in the higher region two to three
times greater than the center column.
3.1.2 Sample Inlet System - A gas sampling valve
NOTE 1 – Components not listed in Table 1 may be capable of introducing sample volumes of up to 0.500 ml
determined by procedures outlined in Appendix A or other may be used to introduce a fixed volume into the carrier
applicable analytical procedures. Refer to Appendix A. gas stream at the head of the analyzing column. The

1
sample volume should be repeatable such that successive
runs meet the precision requirements of Section 10.

NOTE 2 – The sample size limitation of 0.500 ml or

smaller is selected relative to linearity of detector
response and efficiency of column separation. Larger
samples may be used to determine low-quantity
components in order to increase measurement accuracy.

3.1.3 Chromatographic Columns

3.1.3.1 Partition Column - This column must separate

nitrogen (air), carbon dioxide, and the hydrocarbons
methane through n-Pentane. (or n-Hexane when a C7 plus
analysis is performed). Silicone DC 200/500, 30% by
weight on 80/100 mesh Chromosorb P, acid washed,
packed into 30’ x 1/8” SS tubing has proven to be
satisfactory for this purpose. Figure 1A Chromatogram of early backflush of
hexanes and heavier (C6+).
3.1.3.2 Precut Column – A backflush column similar
to the partition column described in 3.1.3.1. This column
must be of the same diameter and long enough to clearly
separate the hexanes plus or heptanes plus fraction from
the lighter components. Figure 1A shows an example
chromatogram of a natural gas mixture using the precut
column for grouping the hexanes and heavier (heptanes
and heavier in Figure 1B).

3.1.3.3 Pressure Buffer Column - A lightly loaded

column placed between the detector inlet and the column
switching/sampling valve (Figure 2A, Column 3) may
help to position the hexanes and heavier peak to provide
better resolution. This column is usually 1 wt% Silicone
200/500 between 12” and 40” long. (Figures 2A and 2B
show a typical column switching/sampling valve
arrangement).

NOTE 3 – The arrangements of columns, detectors

and valves depicted in Figure 2A and 2B have been
determined to meet or exceed the performance criteria of
this standard. (See Section 10, “Precision”.)
3.1.4 Temperature Control -The chromatographic
columns and the detector should be maintained at
temperatures consistent enough to provide repeatable peak
retention times and compositional precision within the
limits described in Section 10 during the reference
standard and corresponding sample runs.
3.2 Carrier Gas - The contaminants in the carrier gas
must be limited to levels that are known not to interfere
with the analysis or cause maintenance problems with the
GC. Refer to manufacturer for recommendations
regarding carrier gas quality
3.2.1 Pressure and Flow Control Devices - These
devices should maintain flow rate consistent enough to
provide repeatable peak retention times and compositional
precision within the limits described in Section 10 during
the reference standard and corresponding sample runs.
Two Stage regulators with stainless steel diaphragms have
been shown to be satisfactory for this purpose.
Figure 1B Chromatogram of early backflush of
heptanes and heavier (C7+).
3.3 Sample Conditioning Systems - GPA 2166 gives
guidance for proper design and use of sample
conditioning systems. The sample conditioning system
should not cause the GC precision to fall outside the
requirements in Section 10.
NOTE 4 – Valves and sample introduction system
must be maintained at a temperature above the
hydrocarbon dew point of the calibration blend and
unknown samples. Supplemental heating may be required
to accomplish this. Refer to GPA 2166 for guidance.
3.4 Integration System - The integration system
should be configured to properly integrate all peaks of
interest. Integration systems can not correct for
inadequate component separation. The integration system
should not cause the GC precision to fall outside the
requirements in Section 10.

2

Figure 2A Two Six port valves used for sample
injection and precut backflush.
Figure 2B One Ten port valve used for sample
injection and precut backflush.
4. NATURAL GAS QUALITY ASSURANCE
4.1 Determination of Linear Range - GPA 2198
describes procedures to establish the linear range of a GC
system. This process is necessary to determine the proper
calibration and analytical procedures for each instrument.
4.2 Fidelity Plot - GPA 2198 describes the procedure
to create a Fidelity Plot. The Fidelity Plot is a tool that
can be used to monitor the validity of calibration
standards and performance of GC systems.
4.3 Control Charts - GPA 2198 describes the use of
Control Charts. Control Charts can be used to monitor
each component in the calibration blend and the GC
performance over time.
4.4 Precision Test - Section 10 of this document
establishes the precision requirements of this standard.
5. SAMPLE INTRODUCTION
5.1 Sample Introduction -The sample introduction
must be performed in the same manner for calibration and
subsequent unknown samples. It is acceptable to either
perform a purged or evacuated introduction. Successive
runs must be repeatable and not contain contamination
3
from the previous injection. Refer to Appendix A for
discussions on linearity, calibration and other related
topics.
5.1.1 Purged Introduction - Determine the rate and
duration of the purge. Perform alternate injections using a
suitable reference blend and instrument carrier gas.
Perform alternate injections of each material at various
purge rates and purge durations. Note the rate and
duration of each purge test and the component
concentrations from each run. Repeatability of each
component must meet the criteria listed in Section 10,
“Repeatability” on the sample runs for the purge rate to be
acceptable. Results from the carrier gas blank run must
not contain carryover (individual peaks) greater than 0.01
un-normalized mol % from the previous injection of
sample for the duration to be sufficient. Once this has
been established, this rate and duration should be used for
all calibration and analytical runs.
5.1.2 Evacuated Introduction - Evacuate the sample
entry system and observe the vacuum gage or manometer
for pressure changes indicating a leak. Leaks must be
repaired before proceeding. Determine the pressure to be
used for injections. Perform alternate injections of a
suitable reference blend and carrier gas. Make replicate
runs at the selected pressure. Repeatability of each
component must meet the criteria listed in Section 10,
“Repeatability”. Use this pressure for calibration and
analytical runs. Results from the carrier gas blank run
must not contain carryover (individual peaks) greater than
0.01 un-normalized mol % from the previous injection of
sample.
5.1.3 Equilibration - All sample injections must be
performed in the same manner for known and unknown
sample compositions. The sample introduction system
must be allowed to equilibrate prior to operation of the
gas sample valve.
5.2 Preparation and Introduction of Sample –
Samples must be properly conditioned prior to analysis.
GPA 2166 gives guidance on proper heating of sample
containers and sampling systems. Refer to GPA 2166.
NOTE 5 – To ensure representative samples are
obtained in the field, refer to GPA Publication 2166.
5.2.1 Sample connections and tubing used in the
sample entry system of the GC must be composed of
material that does not cause sample distortion. Stainless
Steel and Nylon 11 have proven to perform in this
manner. Rubber and other plastic tubing must not be used
since these materials readily absorb hydrocarbons.
6. CALIBRATION PROCEDURE
6.1 Calibration
6.1.1 Response factors for the components of interest
are determined in accordance with the calculations
discussed in Section 8. This can be accomplished by
various means. Either single level calibration(s) using one
or more certified reference blend(s) or a multi-level
calibration using at least three certified reference blends is
acceptable.
6.1.2 Procedures discussed in Section 4 and the
calibration type will determine the calibrated range. All
components in the unknown samples should lie within the
calibrated range for a specific GC. (See Section 10,
“Precision”.)
6.1.3 Calibration should be verified on a set
frequency. Verifications can utilize a single blend or
multiple blends. At least two runs should be made to
verify repeatability. If the calculated concentrations
deviate by more than the precision requirements for
repeatability listed in Section 10, or the un-normalized
total deviates by more than 1% from 100 %, instrument
maintenance or recalibration may be necessary. First
verify the calibration blend is valid, then verify the
instrument is operating properly (repair as required), and
then recalibrate if necessary.
6.1.4 Fidelity plots and Control Charts, as described
in GPA 2198, are excellent tools to monitor instruments
and calibration blends.
6.2 Calibration types
6.2.1 Single Level Calibration(s)
6.2.1.1 One or more certified gas reference standard
blends of known composition are used to determine
response factors for anticipated component ranges in the
unknown samples. The results from the “Linearity
Check” and the response factors determined for each
component can be used to identify the calibrated range for
concentrations anticipated in the unknown samples.
6.2.1.2 One gas reference standard blend of known
composition may be used to determine response factors
for each component. Unknown samples are analyzed and
the results determined from the response factors derived
from the reference standard blend.
6.2.1.3 More than one gas reference standard blend of
known composition may be used to determine response
factors for each component. The composition of these
standards should cover the anticipated range of
compositions in the unknown samples. Unknown samples
are analyzed and the results determined from the certified
reference blend more closely matching the unknown.
6.2.1.4 The calibrated range, when within the ranges
listed in Section 10, must meet the precision requirements
listed in the column “Reproducibility”.
6.2.2 Multi-level Calibration
6.2.2.1 Multi-level calibrations may be used for
single components, select components, or the full range of
4
components in each standard. A multi-level calibration
with three or more gas reference standard may be used to
determine response factors for component(s) of interest.
The results from the “Linearity Check” and response
factors determined for each component can be used to
identify the calibrated range for concentrations anticipated
in the unknown samples.
6.2.2.2 The calibrated range, when within the ranges
listed in Section 10, must meet the precision requirements
listed in the column “Reproducibility”.
NOTE 6 – See Appendix A for more information on
linearity, calibrations, and other related topics.
7. ANALYTICAL PROCEDURE
7.1 Precut Backflush Method for Nitrogen, Carbon
Dioxide, Methane, and Heavier Hydrocarbons - Using the
same instrument conditions and sample introduction
technique that were used in the calibration run(s) for the
unknown sample, obtain a chromatogram through n-
pentane with hexanes and heavier eluting as the first peak
in the chromatogram.
7.1.1 This is accomplished by the GC system
configured as shown in Figures 2A and 2B.
7.1.2 The sample is loaded into the sample loop as
determined in Section 5 and allowed to equilibrate. The
sample is injected by valve actuation. The lighter
components, including n-pentane, move through the pre-
column and into the analytical column. Column switching
must occur before hexanes and heavier material exit the
pre-column. The exact valve timing must be determined
for each GC system.
7.1.3 The pre-column is initially in series upstream of
the analytical column to isolate the hexanes plus. After the
valve switch the pre-column is in series downstream of the
analytical column, with flow reversed to back-flush the
hexanes plus into a single peak. See Figure 1A.
7.1.4 This recommended approach to the hexanes and
heavier separation has two distinct advantages: (1) better
precision of measuring the peak area, and (2) a reduction
in analysis time over the non-precut (single) column
approach.
7.1.5 To perform this procedure as a heptanes plus
analysis the valve timing must be adjusted so that the
valve switch occurs after the elution of normal hexane
from the pre-column onto the analytical column. See
Figure 1B.
7.1.6 In order to reduce the pressure disturbance from
the valve actuation on the plus fraction peak, a delay or
buffer column may be utilized. A column between 12”
and 40”, with 1% DC 200/500 on Chromosorb P has been
found effective.
 8. CALCULATIONS Table IV Example of Weight %
Calculated from Mole %
8.1 Determine the peak areas of each component for
Component Mole % Mole Wt. Lbs./Mole Wt. %
the reference standard blend and unknown sample.
Nitrogen 0.68 28.013 0.1905 0.91
Methane 79.81 16.043 12.8039 61.27
8.2 Response factors are calculated for each Carbon Dioxide 0.57 44.01 0.2509 1.20
component using peak areas from the reference standard Ethane 10.34 30.07 3.1092 14.88
blend in accordance with the following relationship: Propane 5.23 44.097 2.3063 11.04
Isobutane 0.74 58.123 0.4301 2.06
K = Ms / Ps where:
n-Butane 1.38 58.123 0.8021 3.84
K - Response factor Isopentane 0.40 72.15 0.2886 1.38
Ms – Mol % of component in reference standard n-Pentane 0.35 72.15 0.2525 1.21
Ps -Peak area in arbitrary units for reference Hexanes Plus 0.50 92.489 0.4624 2.21
standard 20.8966 100.00

8.3 Concentrations are calculated for each component
in accordance with the following relationship:
Mu = Pu x K where:
Mu - Mol% of component in unknown
Pu- Peak area of each component in unknown
sample
K - Response factor as determined in 8.2
9. REPORTING AND NORMALIZATION
9.1 Normalization is the process of forcing the sum of
the concentrations of components to the desired total.
This is accomplished by multiplying each component by
the normalization factor. This factor is determined as
follows:
Fnorm = Σunnormalized / Σdesired

Table II Example of Response Factors where:

Determined from Reference Standard Blend
Fnorm = normalization factor
Component Mole % Area Response Factor Σunnorm = unnormalized total
Nitrogen 2.03 3140 0.0006465
Σdesired = desired total
Methane 89.75 106874 0.0008398
Carbon Dioxide 0.53 1174 0.0004514
Ethane 3.08 6389 0.0004821 9.2 Normally the desired total is 100%, except in
Propane 1.90 4944 0.0003843
cases such as secondary analyses such as those described
in Appendix A, Section A-1.2. Refer to Appendix A and
Isobutane 0.97 2962 0.0003275
Table 5 below.
n-Butane 0.97 3038 0.0003193
Isopentane 0.30 1053 0.0002849
n-Pentane 0.29 1098 0.0002641 Table V Calculation of Concentration in Unknown Sample
Hexanes Plus 0.18 749 0.0002403 Using Response Factors
100.00
Unnorm. Norm. Mole
Component Area Resp. Factor Mole % %
Nitrogen 1050 0.0006465 0.68 0.68
Table III Calculation of Molar Concentration in
Methane 95153 0.0008398 79.91 79.77
Unknown Sample Using Response Factors Carbon Dioxide 1255 0.0004514 0.57 0.57
Ethane 21470 0.0004821 10.35 10.33
Unnorm. Norm. Hydrogen Sulfide 0.05 0.05
Component Area Resp. Factor Mole % Mole % Propane 13623 0.0003843 5.24 5.23
Nitrogen 1050 0.0006465 0.68 0.68 Isobutane 2253 0.0003275 0.74 0.74
Methane 95153 0.0008398 79.91 79.81 n-Butane 4324 0.0003193 1.38 1.38
Carbon Dioxide 1255 0.0004514 0.57 0.57 Isopentane 1398 0.0002849 0.40 0.40
Ethane 21470 0.0004821 10.35 10.34 n-Pentane 1321 0.0002641 0.35 0.35
Propane 13623 0.0003843 5.24 5.23 Hexanes Plus 2080 0.0002403 0.50 0.50
Isobutane 2253 0.0003275 0.74 0.74 100.12 100.00
n-Butane 4324 0.0003193 1.38 1.38
Isopentane 1398 0.0002849 0.40 0.40 9.3 Reporting is commonly to two decimal places
n-Pentane 1321 0.0002641 0.35 0.35 due to limitations on equipment. TCD detectors typically
Hexanes Plus 2080 0.0002403 0.50 0.50 have a linear dynamic range of 10,000:1. Numbers are
100.12 100.00 calculated to three decimal places and then rounded up
when the third digit is 5 or higher.

5
 10. PRECISION Example 1
Mol % Repeatability Reproducibility
10.1 The repeatability and reproducibility statements
for this standard are from the statistical data obtained in a Nitrogen 1 0.04 0.16
GPA RR-188. The testing program included ten samples Methane 71.6 0.03 0.25
comprised of ten components analyzed by six laboratories.
CO2 0.14 0.01 0.06
The standard as revised has been statistically evaluated
under ISO and ASTM protocols. The documentation of Ethane 4.9 0.02 0.05
the statistical evaluation may be found in GPA TP-31. Propane 2.3 0.01 0.04
Iso-butane 0.26 0.01 0.01
10.2 To determine the precision for any component
at a specific concentration, use the formulae shown in N-butane 0.6 0.01 0.03
Table 6 and substitute the mole percent of the component Iso-pentane 0.12 0.01 0.01
for x. N-pentane 0.14 0.01 0.01
Hexanes Plus 0.1 0.01 0.02
10.3 Repeatability is the expected precision within a
laboratory using the same equipment and same analyst.
Repeatability is the difference in analyzed values between
two sequential runs. Reproducibility is the expected Example 2
precision when the same method is used by different
laboratories using different equipment and different Mol % Repeatability Reproducibility
analysts. Reproducibility is the difference between two Nitrogen 7.7 0.06 0.44
analyzed values. Neither value represents the difference
Methane 86.4 0.03 0.14
between an analyzed value and the certified value listed
on a blend. (Refer to 10.6 and 10.7). CO2 7.9 0.01 0.24
Ethane 9.7 0.03 0.07
Table VI Component Ranges for Precision Limits
Propane 4.3 0.01 0.05
Range Repeatability Reproducibility Iso-butane 1 0.01 0.02
1/4 1/2
Nitrogen .02 – 15 0.039x 0.158x N-butane 1.9 0.02 0.05
Methane 50 – 100 0.0079x1/3 91000x-3 Iso-pentane 0.45 0.01 0.02
CO2 .02 – 15 0.0042x1/3 0.12x1/3 N-pentane 0.42 0.01 0.02
Ethane .02 – 15 0.0124x1/3 0.0315x1/3
Hexanes Plus 0.35 0.01 0.03
Propane .02 – 15 0.0084x1/8 0.026x1/2
Iso-butane .02 – 8 0.01x1/5 0.018x1/2
N-butane .02 – 8 0.0117x2/5 0.033x1/2 10.6 Performance evaluations commonly use the
Iso-pentane .02 – 4 0.009x 1/4
0.025x1/4 repeatability and reproducibility of laboratory results
N-pentane .02 – 4 0.01x1/5 0.026x1/3
compared to a certified blend. This precision statement is
based on the data contained in GPA RR-188 and the
Hexanes Plus .02 – 2 0.0135x1/4 0.051x1/2
statistical evaluation described in GPA TP-31. This
treatment of data compared laboratory results independent
10.4 The following example calculations show the of the certified blend values. Therefore, performance
repeatability and reproducibility for two different blends. evaluations must either compare the laboratory results in
The Ranges from the previous precision statement are the same manner by using the reproducibility values
used in the two examples. Example 1 lists the lower
concentration from the original precision statement range described in Table 6 and subsequent example calculations,
of each component and Example 2 lists the higher or use the Performance Evaluation Acceptance Criteria
concentration from the original precision statement range listed below.
for each component along with the repeatability and
reproducibility calculated for those values. 10.7 The ability of an instrument to match the
certified values from a gravimetric blend referred to as is
10.5 The values shown in these calculations are in the Performance Evaluation Acceptance Criteria. The
mol percent. These values are the mol % of the blend uncertainty must be known to use this approach.
component plus or minus the value determined from the The reproducibility and the uncertainty of the calibration
appropriate equation. That is to say, if the value is 1.00 blend are used to determine the Performance Evaluation
and the precision value is 0.02, results that are between Acceptance Criteria.
0.98 and 1.02 are acceptable and values that are above or
below that range are not acceptable and fail to meet the
precision criteria of this standard. When the result is less
than 0.01, use 0.01 as the lowest precision value.

6
Where:
CVB is the certified value of component in blend
PE is the Acceptance Criteria for component
R is the method reproducibility for component
UB is the blend uncertainty of component
In Example 3, we use the blend from Example 2, with
a 1% Certified Reference Blend used in an audit. For
more information, refer to Section 11, “Definitions”.
Column – The part(s) of the GC system used to separate
components from each other.
Detector – The device used to detect the presence and
determine the amount of each component within a
mixture.
Effluent – A component that has exited the analytical
column.

Example 3 Elute – The act of a component leaving the column.

Mol % UB Reproducibility PE GC System – The equipment used in gas chromatography,

Nitrogen 7.70 0.077 0.44 0.45 including the sample inlet system, sample conditioning
Methane 86.40 0.86 0.14 0.88 system, outlet tubing, analytical columns, carrier gas
CO2 7.90 0.079 0.24 0.25 tubing, and detectors.
Ethane 9.70 0.097 0.067 0.12
Propane 4.30 0.043 0.054 0.07 Hydrocarbon Dew Point – The temperature (pressure) at a
Iso-butane 1.00 0.010 0.018 0.02 given pressure (temperature) at which a particular gaseous
N-butane 1.90 0.019 0.045 0.05 hydrocarbon mixture begins to condense into the liquid
Iso-pentane 0.45 0.0045 0.020 0.02 phase.
N-pentane 0.42 0.0042 0.020 0.02
Hexanes Integration System – The hardware and software used to
Plus 0.35 0.0035 0.030 0.03 calculate peak areas.

From the example above, if the laboratory result for
methane is between 85.52 and 87.28 mol % it would be
deemed acceptable. For hexanes plus, a result between
0.32 and 0.38 mol % would be acceptable.
10.8 If the Blend Uncertainty is not known, this
approach is not acceptable. Instead, compare the
individual laboratory results to the robust mean of those
results plus or minus the reproducibility of the method.
Using the values from Example 2, if the mean result for
methane is 86.66 mol %, then acceptable results will be
between 86.52 and 86.8 mol %. In example 2, if the
hexanes plus mean result is 0.37, acceptable results will
be between 0.34 and 0.40 mol %. Refer to TP-31.
Linearity – The ability to obtain test results within the
precision limits of the standard for components of interest,
using a single response factor for each component.
Linear Range – The range of concentrations where the
peak area is proportional to the component mol % for a
particular component.
Linearity Check –A process that verifies the degree of
nonlinearity for an analytical instrument (Refer to GPA
2198)
Molecular Sieve – A device used to separate a particular
component from the rest of a mixture.

Normalized Mol % – The sum of mol % determined for a

11. DEFINITIONS mixture, adjusted to 100 %.

Analytical Column – The column in the early backflush
configuration that separates all compounds of interest
except the “Plus” fraction. This is the longer of the two
DC200/500columns.
Calibrated Linear Range – An experimentally determined
range of concentrations for a component on a particular
instrument. (Refer to GPA 2198”)
Carrier Gas – The gas used to deliver the sample to the
detector.
Carryover – Components that are left in the GC system
from a previous run.
Partition Column – A column that separates by liquid
partitioning, gas-liquid chromatography, such as the
DC200/500.
Peak Windows – The expected time period for a particular
component to elute from the column.
Performance Evaluation Acceptance Criteria – A range
that acceptable instrument test result must fall within
defined by the root sum square of the method
reproducibility and uncertainties of the performance
evaluation blend. Refer to GPA 2198.
Plus Fraction – A group of components that are lumped
together after the last speciated component. In a “C6

7
Plus” analysis, this is all components that elute after
normal pentane on frontal flow.
Porous Polymer Column – A column that separates
utilizing polymer beads, gas solid chromatography, such
as Porapak Q or Hayesep Q.
Pre-Column – The column in the early backflush
configuration that lumps the “Plus” fraction components
into a single peak. This is the shorter of the two
DC200/500 columns.
Retention Time – The amount of time between sample
introduction and elution for a particular component.
Repeatability – The expected precision for a test result
when the same method is used utilizing the same
equipment and analyst. Values for “Repeatability” can be
found in Section 10, “Precision”.
Reproducibility – The expected precision for a test result
when the same method is used utilizing different
equipment and/or analysts. Values for “Reproducibility”
can be found in Section 10, “Precision”.
Response Factor – The response factor is calculated by
dividing the peak area for a particular component by the
corresponding mol % of the reference standard blend.
This factor is then used to determine the mol % of the
component in an unknown gas sample.
Robust Mean – The statistical mean of a set of values after
outliers have been removed. Refer to TP-31 for guidance
on outlier rejection.
8
Sample/Calibration Run – The act of analyzing a gaseous
mixture, from sample introduction to elution.
Sample Conditioning System – The portion of the sample
system that removes contaminants from the sample.
Sample Inlet/Entry System – The portion of the sample
system where the sample is received from a sample
container.
Sample System – The equipment used to prepare and
introduce a sample onto the pre-column, including the
sample inlet/entry system and the sample conditioning
system
Thermal Conductivity Detector (TCD) – A detector that
may use a wheat-stone bridge to determine the amount of
each component. The carrier gas passes over an element
with a current running through it, and the sample stream
passes over a similar element with the same current
running through it. The resistance of each element is
measured and the difference between the two coupled with
expected retention times is used to determine the amount
of each component present.
Un-Normalized Mol % - Un-normalized mol % is the sum
total mol % of the components determined for a mixture.
(See Normalized Mol %.)
 APENDIX A - Calibrations

A-1 Linearity
Section 4, Appendix C and GPA 2198 discuss Linearity
and list procedures to determine the linear range and
calibration requirements of GC systems. When it is
anticipated that the range of concentrations of components
in the unknown samples will not fall in the linear
calibrated range of the instrument, it is necessary to make
corrections for this. Two means of accomplishing this are
through multi-level calibration (calibration curve) or
secondary analysis.
A-1.1 Calibration Curves (Multi-level Calibration)
Where
K = Response factor
Pi = Partial pressure of pure component in mm of
mercury to nearest 0.5 mm
Po = Barometric pressure in mm of mercury to
nearest 0.5 mm
A = Peak area of pure component in arbitrary
units
Calibration curves can now be developed by plotting
response factors versus concentration. Most integration
software packages have this feature built-in, but if this
feature is not available, other programs capable of
generating a polynomial curve fit may be used.

A-1.1.1 Calibration Curves Using Multiple Calibration

Blends Table A-1
Once linearity has been determined for a GC, as described
in Section 4, and the linear range is found to be Component Partial Barometric Pi/Po * 100
inadequate for the range of unknown sample Pressure mm Pressure mm of
of Hg (Pi) Hg (Po)
concentrations anticipated, calibration curves for any Oxygen 100 750 13.33
component may be determined by using multiple Nitrogen 100 750 13.33
calibration blends. Methane 500 750 66.67
Duplicate injections of at least three concentration levels Carbon 100 750 13.33
for the desired component should be made. If the values Monoxide
Carbon Dioxide 100 (650)* 750 13.33
on duplicate runs agree within the tolerances in Section
Ethane 200 (450)* 750 26.67
10, “Repeatability”, the response factor should be Propane 100 (200)* 750 13.33
calculated as follows for each concentration level: Isobutane 100 (100)* 750 13.33
K= Cn n-Butane 100 (100)* 750 13.33
An Isopentane 50 (50)* 750 6.67
where n-Pentane 50 (50)* 750 6.67
K = Response factor
Cn = Concentration of component n *Partial Pressures in parentheses are the maximum pressures to be
used to determine response factors. Exceeding these pressures could
An = Peak area in arbitrary units of component n
result in low response factors caused by compressibility of the pure
component.
Calibration curves may now be developed by plotting
response factors versus concentration. Any program A-1.2 Secondary Analyses
capable of generating a polynomial curve fit may be used. Secondary analyses may be used instead of calibration
curves (as in the case of Carbon Dioxide on a Porous
A-1.1.2 Calibration Curves Using Partial Pressures of Polymer column.) or for determination of compounds not
Pure Components determined by the partition column run. The secondary
Once linearity has been established for the instrument as analysis or run may occur separately or simultaneously to
described in Section 4, calibration curves for any the primary analysis or run. When more than one
component to be measured in the unknown sample may be component is determined, add all component
determined by using pure components. concentrations and normalize to 100%. When a single
Attach the pure component to the sample entry system and component is determined, it is acceptable to keep that
evacuate the entry system to less than 1 mm of mercury. component concentration whole as described below:
Using the partial pressure range suggested in Table A-l,
inject at least three partial pressures in duplicate and Fnorm= 100- Cn
capture data including Barometric Pressure at the time of 100
the injection. When concentrations on duplicate runs meet Where
the criteria listed in Section 10, “Repeatability”, calculate Fnorm = Normalization Factor
the response factor as follows: Cn = Concentration of component n

K= (Pi) (100)
(Po) (A)
9
All components determined in the primary analyses or run
are then multiplied by N, and the single component held
whole.

A-1.3 Other Documentation – Instrument logbooks,

Maintenance logbooks, User Manuals, Calibration

Records, QA/QC records, Analytical Methods and SOP’s

are documents that form the analytical audit trail. These
documents may either be maintained electronically or in
written form.

10
 APENDIX B – Linearity Discussion

An ideal GC detector will provide a linear response across However, many chromatograph detectors are not linear in
all sample component concentrations. In this case, a their response. A graph of Mole % concentration to peak
calibration standard with any concentration of the area would not be linear:
component of interest could be run and a calibration
response factor could be determined: In this example,

Example: A calibration standard has 80 Mole % Methane. Calibrating to 80 Mole % would yield the following
When the sample is run on the GC, it generated a peak response factor:
area of 80,000. The response factor for Methane at 80%
KFMethane = Mole % Methane ÷ Peak
concentration is:

Kmethane = Mole % Methane ÷ Peak Area Methane

Area = 80 ÷ 80,000 = 0.001 = 80 ÷ 96,000 = 0.000833
When the detector was perfectly linear, and an unknown Using the above calibration factor to analyze a sample
sample was run and generated a peak area for Methane of with 40% Methane would yield the following result:
40,000, the Methane concentration in Mole % would be:
Mole% Methane = Peak Area
Peak Area x Kmethane = 40,000 x 0.001 =
Methane * KFMethane
40 Mole % Methane
= 64,000 * 0.000833 = 53.333 Mole %
A graph of Mole % concentration to peak area would be Methane
linear (a straight line):
Since the difference between the actual value (40%) and
the reported value from calibration to 80% Methane
Linear Methane Response (53.333%) exceeds the reproducibility limits established
in Section 10 it would be necessary to have separate
120000 calibration standards for samples containing 80%
100000 Methane and samples containing 40% Methane.
Peak Area

80000
The linearity check is used to determine the number of
60000 calibration standards that are needed to analyze all the
40000 expected sample compositions.
20000
When more than one calibration is required, this can be
0 achieved by having a separate calibration method for each
0 20 40 60 80 100 120 expected sample composition, a multi-level calibration for
Mole% Methane all components or a multi-level calibration for the
components that are not linear.

Non - Linear Methane Response Whether a GC detector is linear for a component or not
linear for a component is determined by whether it can be
120000 analyzed within the reproducibility limits outlined in
100000 Section 10.
80000
Peak Area

Linearity curves can be established by running multiple

60000 calibration standards of various compositions. In this case,
40000 the actual Mole% is plotted against the peak area.
20000
Linearity curves can also be established by running the
0
same calibration standard under various partial pressures.
0 20 40 60 80 100 120
In this case, the Mole% value is determined by the
Mole% Methane following formula (see Appendix A, A-1.1.2):

11
Partial Pressure Mole % Equivalent =
Mole % x Inj P / Max P
Where:
Max P = the normal sample loop
pressure that samples are injected in
absolute pressure
Inj P = the sample loop pressure that
the sample was injected in absolute
pressure
Notes:
The above calculation does not take compressibility into
account. To be accurate, the compressibility factor should
be included in the calculation.
Max P and Inj P must be expressed in the same absolute
pressure units.

Refer to GPA 2198 for more detailed instruction in

calibrating with non-linearity in mind

12
 APENDIX C – Supplementary Procedures
C-1 Run Analysis for Nitrogen, Methane, Carbon
Dioxide, and Ethane
The porous polymer column must completely separate
methane, carbon dioxide and ethane to baseline as shown
in the example chromatogram. The linearity of this
system must be determined to be linear to be an
acceptable alternative to the calibration curve technique
described in Appendix B. This system can be used as part
of a multi-column GC, as in the case of some portable
GC’s.
C-2. 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 gases. No extra equipment
is necessary to determine carbon monoxide since it elutes
shortly after methane on the molecular sieve run. 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.
C-3 Determination of Hydrogen and Helium
When hydrogen is to be separated from helium, a 20’
molecular sieve 5A column using nitrogen or argon as a
carrier gas may be used. Low temperature, 40°C (104°F)
or less is necessary to effect this separation.
When hydrogen is present, it will elute on the standard
molecular sieve run, using helium as a carrier gas, just
before oxygen. The hydrogen response is downscale
(negative) rather than upscale (positive). Signal polarity
must be reversed for the hydrogen peak to be recorded
upscale. The sensitivity and precision of measurement will
be poor under these conditions due to similar thermal
conductivity values for hydrogen and helium. If a
calibration gas blend is available containing hydrogen and
13
helium, it should be used to obtain response factors
however, if this is not the case, the pure components,
hydrogen and helium, may be used to develop response
factors in the manner set forth in Appendix A, A-1.
C-4. Determination of Hydrogen Sulfide
As indicated earlier in this text, to be absolutely sure of
the hydrogen sulfide content of a gas, determinations
should be made at the sample source. However, in the
case where a field measurement has not been made and
although corrosion of the sample bottle may have resulted
in some loss of hydrogen sulfide, a measurement 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.) 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 determining the hydrocarbons
in a natural gas analysis. Hydrogen sulfide elutes between
ethane and propane with good resolution.
CAUTION - 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. The Maximum
Allowable Concentration that a person may be
exposed to without approved respiratory protection
equipment is 10 ppm for an eight hour working
period. When the exposure lasts through the working
day, concentrations as low as 15 ppm may cause severe
irritation to the eyes and respiratory tract. Exposure
of 800 to 1,000 ppm may be fatal in a few minutes. The
nose must not be depended upon to detect the presence
of hydrogen sulfide, as 2-15 minutes of exposure will
cause the loss of smell.