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
DISCLAIMER

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publications. With respect to particular circumstances, local, state, and federal laws and regulations should be
reviewed. It is not the intent of GPA to assume the duties of employers, manufacturers, or suppliers to warn and
properly train employees, or others exposed, concerning health and safety risks or precautions.

GPA makes no representation, warranty, or guarantee in connection with this publication and hereby expressly
disclaims any liability or responsibility for loss or damage resulting from its use or for the violation of any federal,
state, or municipal regulation with which this publication may conflict, or for any infringement of letters of patent
regarding apparatus, equipment, or method so covered.
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
> 30
SCOPE

This standard covers the determination of the chemical

composition of natural gas and similar gaseous mixtures Isobutane
within the ranges listed in Table 1, using a Gas 0.01 - 0.25
Chromatograph (GC). The three columns represent the
original Table 1, but separate the values to three distinct 0.25 - 4
groups. The first group is concentrations lower than the data >4
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 Methane
0.01 - 40
the round-robin project (RR-188).

40 - 100
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 N/A
applies only to values listed in Section 10, Table 6. n-Butane
0.01 - 0.25
1.2 Components sometimes associated with natural gases,
i.e., helium, hydrogen sulfide, water, carbon monoxide, 0.25 - 4
hydrogen and other compounds are excluded from the main >4
body of the method. These components may be determined
and made a part of the complete compositional data. Refer
to Appendix A.

Table I Ranges of Natural Gas Components Covered Ethane

0.01 - 0.1

0.1 - 10
> 10
Lower
Round
Isopentane
Higher
0.01 - 0.12
Component
0.12 - 1.5
Region
Robin > 1.5

Region
Propane

Nitrogen
0.01 - 0.1
0.01 - 0.1

0.1 - 10
0.1 - 30
> 30
> 10

Carbon Dioxide

0.01 - 0.1 n-Pentane

0.01 - 0.12
0.1 - 30
0.12 - 1.5
> 1.5
SUMMARY OF
METHOD
Components to be
determined in a gaseous
sample are physically
separated by gas
chromatography and
compared to calibration
data obtained under
* Hexanes Plus identical operating
0.01 - 0.1 conditions. A fixed volume
of sample in the gaseous
phase is isolated in a
0.1 - 1.5
suitable inlet sample
> 1.5
system and entered onto
the column.
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,
* Heptanes Plus
carbon dioxide, ethane and
heavier hydrocarbons.
0.01 - 0.1 When oxygen/argon
content is critical in the
0.1 - 1.5 unknown sample, or is
suspected as a
> 1.5 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
*Data from round –robin was only obtained for Hexanes Plus
secondary run should be
made to determine helium
Table Note: Uncertainty in the Lower region can easily be ten
times greater and in the higher region two to three times greater and/or hydrogen.
than the center column.
These analyses are
NOTE 1 – Components not listed in Table 1 may be determined independent and may be
by procedures outlined in Appendix A or other applicable made in any order, or may
analytical procedures. Refer to Appendix A. be made separately to
1
sample volume should be repeatable such that Section 10.
successive runs meet the precision requirements of
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.
Response factors or
response curves derived
from calibration data are
essential to accurately
determine the composition
of an unknown sample.
The reference standard
blend and the unknown
samples must be run using
identical GC operating
conditions.
APPARATUS
Chromatograph - Any Gas
Chromatograph may be
used as long as the
specifications for
repeatability and
reproducibility stated in
Section 10 within the
round-robin test
component ranges listed in
Table 1 are met or
exceeded. The equipment
described in this section
has been proven to meet
the above requirements;
however other
configurations including
portable and online may
be acceptable.
Detector - The Thermal
Conductivity Detector
(TCD) has proven to be a
reliable and universal
detector for this method.
Sample Inlet System - A
gas sampling valve
capable of introducing
sample volumes of up to
0.500 ml may be used to
introduce a fixed volume
into the carrier gas stream
at the head of the
analyzing column. The
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

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.

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 Figure 1A Chromatogram of early backflush of
column for grouping the hexanes and heavier (heptanes hexanes and heavier (C6+).
and heavier in Figure 1B).

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
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.

Precision Test - Section 10 of this document establishes

the precision requirements of this standard.

SAMPLE INTRODUCTION

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
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.

NATURAL GAS QUALITY ASSURANCE

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.

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.
from the previous injection. Refer to Appendix A for
discussions on linearity, calibration and other related
topics.
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.
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
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.
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”.)
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.
Fidelity plots and Control Charts, as described in GPA
2198, are excellent tools to monitor instruments and
calibration blends.
un-normalized mol % from the previous injection of
sample.
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.
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.
CALIBRATION PROCEDURE
Calibration
Response factors for the components of interest are
determined in accordance with the calculations
discussed in Section 8. This can be accomplished by
3
Calibration types
Single Level Calibration(s)
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.
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.
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.

The calibrated range, when within the ranges listed in
Section 10, must meet the precision requirements listed
in the column “Reproducibility”.
Multi-level Calibration
Multi-level calibrations may be used for single
components, select components, or the full range of
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.
ANALYTICAL PROCEDURE
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.
This is accomplished by the GC system configured as
shown in Figures 2A and 2B.
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.
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.
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.
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.
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.
 4
CALCULATIONS 0.2509
1.20
Ethane
Determine the peak areas of each component for the 10.34
reference standard blend and unknown sample. 30.07
3.1092
14.88
Response factors are calculated for each component Propane
using peak areas from the reference standard blend in 5.23
44.097
accordance with the following relationship: 2.3063
11.04
K = Ms / Ps where: K - Response factor Isobutane
Ms – Mol % of component in reference standard 0.74
58.123
0.4301
Ps -Peak area in arbitrary units for reference standard 2.06
n-Butane
1.38
8.3 Concentrations are calculated for each component 58.123
in accordance with the following relationship: 0.8021
3.84
Isopentane
Mu = Pu x K where: 0.40
72.15
0.2886
Mu - Mol% of component in unknown 1.38
n-Pentane
0.35
Pu- Peak area of each component in unknown sample 72.15
K - Response factor as determined in 8.2 0.2525
1.21
Table IV Example of Weight % Hexanes Plus
0.50
92.489
Calculated from Mole % 0.4624
2.21
Component
Mole %
Mole Wt.
Lbs./Mole
Wt. % 20.8966
Nitrogen 100.00
0.68
28.013
0.1905 REPORTING AND NORMALIZATION
0.91
Methane
79.81 Normalization is the process of forcing the sum of the
16.043 concentrations of components to the desired total. This is
12.8039 accomplished by multiplying each component by the
61.27
normalization factor. This factor is determined as follows:
Carbon Dioxide
0.57
44.01 Fnorm = Σunnormalized / Σdesired
Ethane 2962
Table II Example of 0.0006465 3.08
Response Factors 0.0003275
Methane 6389
Determined from Reference 89.75 n-Butane
Standard Blend 0.0004821 0.97
106874
Component Propane 3038
Mole % 0.0008398 1.90
0.0003193
Area Carbon Dioxide 4944
0.53 Isopentane
Response Factor 0.0003843 0.30
Nitrogen 1174
2.03 Isobutane 1053
0.0004514 0.97
3140 0.0002849
 Carbon Dioxide Appendix A, Section A-1.2.
1255
n-Pentane Refer to Appendix A and
0.0004514
0.29 0.57 Table 5 below.

1098 0.57
Ethane Table V Calculation of Concentration
0.0002641 21470 in Unknown Sample
0.0004821
10.35
Hexanes Plus Using Response Factors
0.18
10.34
Component
Propane
Area
749 13623 Resp. Factor
0.0003843 Unnorm.
5.24
0.0002403
Norm. Mole
5.23
Isobutane
100.00 2253
0.0003275
0.74

0.74 Mole %
n-Butane %
4324
0.0003193 Nitrogen
1.38
Table III Calculation of 1050
Molar Concentration in 1.38 0.0006465
Isopentane 0.68
1398 0.68
0.0002849
Unknown Sample Using 0.40 Methane
Response Factors
0.40 95153
n-Pentane 0.0008398
1321 79.91
0.0002641 79.77
0.35
Carbon Dioxide
0.35
Hexanes Plus
1255
2080 0.0004514
0.0002403 0.57
0.50 0.57

0.50 Ethane

21470
0.0004821
10.35
10.33
Unnorm.
Norm. 100.12
Component Hydrogen Sulfide
Area 100.00
Resp. Factor

Mole % where:
Mole % 0.05
Nitrogen
1050 Fnorm = normalization factor
0.05
0.0006465
0.68
Σunnorm = unnormalized total Propane

0.68 Σdesired = desired total

Methane
95153
0.0008398 9.2 Normally the desired
79.91 total is 100%, except in cases
such as secondary analyses
79.81 such as those described in
13623
0.0003843
5.24
5.23

Isobutane

2253
0.0003275
0.74
0.74

n-Butane

4324
0.0003193
1.38
1.38

Isopentane

1398
0.0002849
0.40
0.40

n-Pentane

1321
0.0002641
0.35
0.35

Hexanes Plus

2080
0.0002403
0.50
0.50

100.12
100.00

9.3 Reporting is
commonly to two
decimal places due to
limitations on equipment.
TCD detectors typically
have a linear dynamic
range of 10,000:1.
Numbers are calculated
to three decimal places
and then rounded up
when the third digit is 5
or higher.
 5
PRECISION Iso-pentane
.02 – 4
1/4
The repeatability and reproducibility statements for this 0.009x
1/4
standard are from the statistical data obtained in a GPA 0.025x
RR-188. The testing program included ten samples N-pentane
comprised of ten components analyzed by six laboratories. .02 – 4
1/5
The standard as revised has been statistically evaluated 0.01x
1/3
under ISO and ASTM protocols. The documentation of the 0.026x
statistical evaluation may be found in GPA TP-31. Hexanes Plus
.02 – 2
1/4
To determine the precision for any component at a 0.0135x
1/2
specific concentration, use the formulae shown in Table 0.051x
6 and substitute the mole percent of the component for
x. The following example calculations show the repeatability
and reproducibility for two different blends. The Ranges
Repeatability is the expected precision within a from the previous precision statement are used in the two
laboratory using the same equipment and same analyst. examples. Example 1 lists the lower concentration from the
Repeatability is the difference in analyzed values original precision statement range of each component and
between two sequential runs. Reproducibility is the Example 2 lists the higher concentration from the original
expected precision when the same method is used by precision statement range for each component along with
different laboratories using different equipment and the repeatability and reproducibility calculated for those
different analysts. Reproducibility is the difference values.
between two analyzed values. Neither value represents
the difference between an analyzed value and the The values shown in these calculations are in mol percent.
certified value listed on a blend. (Refer to 10.6 and These values are the mol % of the component plus or
10.7). minus the value determined from the appropriate equation.
That is to say, if the value is 1.00 and the precision value is
Table VI Component Ranges for Precision Limits 0.02, results that are between

and 1.02 are acceptable and values that are above or below
Range that range are not acceptable and fail to meet the precision
Repeatability criteria of this standard. When the result is less than 0.01,
Reproducibility use 0.01 as the lowest precision value.
Nitrogen
.02 – 15
0.039x
1/4 Example 1
1/2
0.158x
Methane
50 – 100 Mol %
1/3 Repeatability
0.0079x
-3 Reproducibility
91000x
Nitrogen
CO2
1
.02 – 15
1/3 0.04
0.0042x 0.16
1/3
0.12x Methane
Ethane 71.6
.02 – 15 0.03
1/3 0.25
0.0124x
0.0315x
1/3 CO2
Propane
0.14
.02 – 15 0.01
1/8 0.06
0.0084x
1/2
Ethane
0.026x 4.9
Iso-butane 0.02
.02 – 8 0.05
1/5
0.01x Propane
0.018x
1/2 2.3
N-butane 0.01
.02 – 8 0.04
2/5 Iso-butane
0.0117x
1/2 0.26
0.033x 0.01
0.01 0.01
N-butane 0.05
0.6 Iso-butane
0.01 1
0.03 0.01
Iso-pentane 0.02
0.12 N-butane
0.01 1.9
0.01 0.02
N-pentane 0.05
0.14 Iso-pentane
0.01 0.45
0.01 0.01
Hexanes Plus 0.02
0.1 N-pentane
0.01 0.42
0.02 0.01
0.02
Hexanes Plus
0.35
Example 2 0.01
0.03

Mol %
Repeatability Performance evaluations commonly use the repeatability
Reproducibility
Nitrogen
and reproducibility of laboratory results compared to a
7.7 certified blend. This precision statement is based on the
0.06 data contained in GPA RR-188 and the statistical
0.44 evaluation described in GPA TP-31. This treatment of data
Methane compared laboratory results independent of the certified
86.4 blend values. Therefore, performance evaluations must
0.03 either compare the laboratory results in the same manner
0.14 by using the reproducibility values described in Table 6 and
CO2
subsequent example calculations, or use the Performance
7.9
0.01 Evaluation Acceptance Criteria listed below.
0.24
Ethane The ability of an instrument to match the certified values
9.7 from a gravimetric blend referred to as is the Performance
0.03 Evaluation Acceptance Criteria. The blend uncertainty
0.07 must be known to use this approach. The reproducibility
Propane
and the uncertainty of the calibration blend are used to
4.3
determine the Performance Evaluation Acceptance Criteria.
6

Where:
7.70
0.077
CVB is the certified value of component in blend PE is the 0.44
Acceptance Criteria for component 0.45

R is the method reproducibility for component UB is the Methane

86.40
blend uncertainty of component
0.86
0.14
In Example 3, we use the blend from Example 2, with a 0.88
1% Certified Reference Blend used in an audit. For more
information, refer to Section 11, “Definitions”. CO2
7.90
0.079
Example 3 0.24
0.25
Nitrogen
Mol % Ethane
9.70
UB 0.097
Reproducibility
0.067
PE
0.12 configuration that separates all compounds of interest
except the “Plus” fraction. This is the longer of the two
Propane DC200/500columns.
4.30
0.043
0.054 Calibrated Linear Range – An experimentally
0.07 determined range of concentrations for a component on
a particular instrument. (Refer to GPA 2198”)
Iso-butane
1.00
0.010
Carrier Gas – The gas used to deliver the sample to the
0.018 detector.
0.02
Carryover – Components that are left in the GC system
N-butane from a previous run.
1.90
0.019
0.045
0.05

Iso-pentane
0.45
0.0045
0.020
0.02

N-pentane
0.42
0.0042
0.020
0.02

Hexanes

Plus
0.35
0.0035
0.030
0.03

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

and 0.38 mol % would be acceptable.

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.

DEFINITIONS

Analytical Column – The column in the early backflush

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.
Elute – The act of a component leaving the column.
GC System – The equipment used in gas
chromatography, including the sample inlet system,
sample conditioning system, outlet tubing, analytical
columns, carrier gas tubing, and detectors.
Hydrocarbon Dew Point – The temperature (pressure) at
a given pressure (temperature) at which a particular
gaseous hydrocarbon mixture begins to condense into the
liquid phase.
Integration System – The hardware and software used to
calculate peak areas.
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.
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.
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 mixture, adjusted to 100 %.
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
Robust Mean – The statistical mean of a set of values
after outliers have been removed. Refer to TP-31 for
guidance on outlier rejection.

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.
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 %.)
8
APENDIX A - Calibrations
(calibratio desired
n curve) or component
secondary should be
analysis. made. If the
A-1 values on
Linearity duplicate
A-1.1
Calibratio runs agree
Section n Curves within the
4, (Multi- tolerances
Appendix level in Section
C and Calibratio 10,
GPA n) “Repeatabil
2198 ity”, the
discuss response
Linearity A-1.1.1 factor
and list Calibratio should be
procedur n Curves calculated
es to Using
as follows
determin Multiple for each
e the Calibratio
n Blends concentrati
linear on level:
range and
calibratio Once
n linearity K= Cn An
requirem has been where
ents of determined
GC for a GC, K=
systems. as Response
When it described factor
is in Section Cn =
anticipate 4, and the Concentrati
d that the linear on of
range of range is component
concentra found to be n
tions of inadequate An = Peak
compone for the area in
nts in the range of arbitrary
unknown unknown units of
samples sample component
will not concentrati n
fall in the ons
linear anticipated
Calibration
calibrated ,
curves may
range of calibration
curves for now be
the
developed
instrume any
by plotting
nt, it is component
response
necessary may be
factors
to make determined
versus
correctio by using
multiple concentrati
ns for
on. Any
this. Two calibration
program
means of blends.
capable of
accompli
generating
shing this Duplicate
a
are injections
polynomial
through of at least
curve fit
multi- three
may be
level concentrati
used.
calibratio on levels
n for the
A-1.1.2 least three area of pure
Calibrati partial component
on pressures in arbitrary
Curves in units
Using duplicate
Partial and Calibration
Pressures capture curves can
of Pure data now be
Compone including developed
nts Barometric by plotting
Pressure at response
Once the time of factors
linearity the versus
has been injection. concentrati
establishe When on. Most
d for the concentrati integration
instrume ons on software
nt as duplicate packages
described runs meet have this
in the criteria feature
Section listed in built-in, but
4, Section 10, if this
calibratio “Repeatabi feature is
n curves lity”, not
for any calculate available,
compone the other
nt to be response programs
measured factor as capable of
in the follows: generating
unknown a
sample K= (Pi) polynomial
may be (100) curve fit
determin may be
ed by (Po) (A) used.
using
pure Table A-1
compone
nts. Where
Component
Partial
Attach K = Barometric
Pi/Po * 100
the pure Response
compone factor Pressure mm
nt to the Pressure mm
sample Pi = Partial of
entry pressure of
system pure
and component of Hg (Pi)
evacuate in mm of Hg (Po)
the entry mercury to
system to nearest 0.5 Oxygen
less than mm 100
750
1 mm of 13.33
mercury. Po = Nitrogen
Using the Barometric 100
partial pressure in 750
13.33
pressure mm of Methane
range mercury to 500
suggested nearest 0.5 750
in Table mm 66.67
Carbon
A-l, 100
inject at A = Peak 750
13.33 response analysis or
Monoxide factors
run. When
caused by
compressibili more than
ty of the pure one
component. component
Carbon is
Dioxide A-1.2 determined,
100 (650)*
Secondary add all
750
13.33 Analyses component
Ethane concentrati
200 (450)* ons and
750
Secondary
26.67 analyses normalize
Propane may be to 100%.
100 (200)* used When a
750 single
13.33
instead of
Isobutane calibration component
100 (100)* curves (as is
750 in the case determined,
13.33 it is
n-Butane
of Carbon
100 (100)* Dioxide on acceptable
750 a Porous to keep that
13.33 Polymer component
Isopentane concentrati
50 (50)*
column.)
750 or for on whole as
6.67 determinati described
n-Pentane on of below:
50 (50)*
750
compound
6.67 s not Fnorm= 100-
determined
Cn
*Partial by the
Pressures partition
in column 100
parentheses
are the run. The
maximum secondary Where
pressures to analysis or Fnorm =
be used to run may
determine
Normalizati
response occur on Factor
factors. separately Cn =
Exceeding or
these Concentrati
simultaneo on of
pressures
could result usly to the component
in low primary n
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
Mole % linear:
An ideal GC
detector will
Methane In this
provide a linear ÷ Peak example,
response across
all sample Calibrating to
component
Area =
80 Mole %
concentrations. 80 ÷ would yield
In this case, a 80,000 = the following
calibration response
standard with 0.001 factor:
any
concentration When the
of the detector was KFMethane
component of perfectly = Mole
interest could linear, and an
be run and a unknown %
calibration sample was Methane
response factor run and
could be generated a
÷ Peak
determined: peak area for
Methane of Area
40,000, the
Example: A
Methane
Methane
calibration
standard has 80 concentration = 80 ÷
Mole % in Mole % 96,000 =
Methane. Whenwould be: 0.000833
the sample is
run on the GC, However,
it generated a many Using the
peak area of chromatograp above
calibration
80,000. The h detectors
factor to
response factor are not linear analyze a
for Methane at in their sample with
80% response. A 40% Methane
concentration graph of would yield
is: Mole % the following
concentration result:
to peak area
Kmethane = would not be
Met straig
ht
Peak han line):
Area e 100000
x Line
60000
A ar
Kmeth graph Meth
of ane
ane = Mole Resp
40,00 % onse
0 x conce
ntratio
0.001 n to 120000 Area
= peak 80000 Peak
area
would
40 be
Mole linear
(a
%
 53.33 The
linearit
3 y check
Mole is used
to
% determi
40000 ne the
Meth number
of
100000 0 ane calibrat
ion
Since standar
the ds that
differen are
ce needed
between to
the analyze
20000
actual all the
Area
80000
value expecte
0 (40%)
20
d
40
and the sample
60 reported compos
80 value itions.
100 from
120
calibrati
When
on to
more
80%
Mole% Methan than
0
Metha one
e
60000
ne calibrat
(53.333
ion is
%)
Mol exceeds require
d, this
e% the can be
reprodu
Met cibility achieve
d by
han limits having
e = establis
hed in
a
0 separat
20 Peak Pea Section
e
40 k 10 it calibrat
60
80 Are would
be
ion
100 method
120
a necessa for
Met ry to each
have
han separate expecte
d
e * calibrati sample
Mole%
Methane KF on standar
compos
ition, a
40000 Meth ds for multi-
samples
level
Non - ane containi calibrat
Linear ng 80%
ion for
Methan Methan
e = e and all
Respon compo
se
64,0 samples nents
00 * containi
ng 40%
or a
multi-
0.00 Methan level
120000
20000
083 e. calibrat
3= ion for
the it can establiMole% various
compone be shed is partial
nts that analyz by plotted pressur
are not ed runni against es. In
linear. within ng the peak this
the multiparea. case,
Whether repro le the
a GC ducibi calibr Linearit Mole%
detector lity ation y curves value is
is linear limits standa can also determi
for a outlin rds of be ned by
compone ed in variou establis the
nt or not Sectio s hed by followi
linear for n 10. comp running ng
a ositio the formul
compone Linear ns. In same a (see
nt is ity this calibrati Appen
determin curve case, on dix A,
ed by s can the standar A-
whether be actual d under 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
sieve column. precision of
C-1 Run Analysis for However, measurement
Nitrogen, Methane, should a gas will be poor
Carbon Dioxide, blend not be under these
and Ethane available, a conditions due
The porous polymer calibration to similar
column must curve should be thermal
completely separate developed using conductivity
methane, carbon pure carbon values for
dioxide and ethane monoxide to hydrogen and
to baseline as shown determine the helium. If a
in the example extent of the calibration gas
chromatogram. The nonlinearity, if blend is
linearity of this present. available
system must be containing
determined to be C-3 hydrogen and
linear to be an Determination
acceptable of Hydrogen helium, it
alternative to the and Helium should be used
calibration curve to obtain
technique described When hydrogen response factors
in Appendix B. This is to be however, if this
system can be used separated from is not the case,
as part of a multi- helium, a 20’ the pure
column GC, as in the molecular sieve components,
case of some 5A column hydrogen and
portable GC’s. using nitrogen helium, may be
or argon as a used to develop
C-2. Determination carrier gas may response factors
of Carbon Monoxide be used. Low in the manner
temperature, set forth in
This component is 40°C (104°F) or Appendix A, A-
encountered in less is necessary 1.
association with to effect this
oxygen, nitrogen, separation. C-4.
carbon dioxide and Determination
the conventional When hydrogen of Hydrogen
hydrocarbons in the is present, it will Sulfide
effluent streams elute on the
from combustion standard As indicated
processes such as molecular sieve earlier in this
insitu combustion, run, using text, to be
manufactured gas helium as a absolutely sure
and many varied carrier gas, just of the hydrogen
types of stack gases. before oxygen. sulfide content of
No extra equipment The hydrogen a gas,
is necessary to response is determinations
should be made
determine carbon downscale
at the sample
monoxide since it (negative) rather source. However,
elutes shortly after than upscale in the case where
methane on the (positive). a field
molecular sieve run. Signal polarity measurement has
If a calibration gas is must be not been made
available containing reversed for the and although
carbon monoxide, hydrogen peak corrosion of the
obtain a response to be recorded sample bottle
factor as for methane upscale. The may have
on the molecular sensitivity and resulted in some
loss of hydrogen determining the protection
sulfide, a hydrocarbons in equipment is
measurement of the a natural gas 10 ppm for an
in-place component analysis. eight hour
may be made by gas Hydrogen sulfide working
chromatography. It is elutes between period. When
necessary to charge a ethane and the exposure
sample of pure propane with lasts through
hydrogen sulfide to good resolution.
the working
the column prior to
day,
charging the unknown CAUTION -
gas. As soon as the Extreme care concentrations
pure hydrogen sulfide must be taken as low as 15
has cleared the ppm may cause
when working severe
column, the unknown
with hydrogen irritation to the
gas should be
charged. (All sulfide due to eyes and
calibrations should be the very toxic respiratory
done the same way, nature of the tract. Exposure
that is, each partial gas. The best of 800 to 1,000
pressure charge of ventilation ppm may be
pure hydrogen sulfide possible must fatal in a few
must be preceded by a be maintained minutes. The
full sample loop of in the nose must not
pure hydrogen laboratory. The be depended
sulfide.) A column Maximum upon to detect
that has proved Allowable the presence of
satisfactory for this Concentration
hydrogen
type of analysis is the that a person
sulfide, as 2-15
Silicone 200/500 may be
column. It is most minutes of
exposed to exposure will
convenient since this without
is the recommended cause the loss
approved of smell.
column for
respiratory

13