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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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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
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 roundrobin 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).

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.

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.

2.2.1 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 GCs to accomplish this.
Refer to Appendix A.
2.3 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.

Table I Ranges of Natural Gas Components Covered


Component
Nitrogen
Carbon Dioxide
Methane
Ethane
Propane
Isobutane
n-Butane
Isopentane
n-Pentane
* Hexanes Plus
* Heptanes Plus

Lower
Region

Round
Robin

Higher
Region

0.01 - 0.1
0.01 - 0.1
0.01 - 40
0.01 - 0.1
0.01 - 0.1
0.01 - 0.25
0.01 - 0.25
0.01 - 0.12
0.01 - 0.12
0.01 - 0.1
0.01 - 0.1

0.1 - 30
0.1 - 30
40 - 100
0.1 - 10
0.1 - 10
0.25 - 4
0.25 - 4
0.12 - 1.5
0.12 - 1.5
0.1 - 1.5
0.1 - 1.5

> 30
> 30
N/A
> 10
> 10
>4
>4
> 1.5
> 1.5
> 1.5
> 1.5

3. APPARATUS
3.1 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.

*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
for this method.

Table Note: Uncertainty in the Lower region can easily be


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


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 1 Components not listed in Table 1 may be


determined by procedures outlined in Appendix A or other
applicable analytical procedures. Refer to Appendix A.
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.)

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.

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.

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.

3.2 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

3.4 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.

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.
2

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.

Figure 2A Two Six port valves used for sample


injection and precut backflush.

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.

Figure 2B One Ten port valve used for sample


injection and precut backflush.

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.

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.

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.

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.

NOTE 5 To ensure representative samples are


obtained in the field, refer to GPA Publication 2166.

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.

5.2.1 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.

5. SAMPLE INTRODUCTION

6. CALIBRATION PROCEDURE

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

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
3

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.

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.)

6.2.2.2 The calibrated range, when within the ranges


listed in Section 10, must meet the precision requirements
listed in the column Reproducibility.

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.

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 npentane with hexanes and heavier eluting as the first peak
in the chromatogram.

6.1.4 Fidelity plots and Control Charts, as described


in GPA 2198, are excellent tools to monitor instruments
and calibration blends.

7.1.1 This is accomplished by the GC system


configured as shown in Figures 2A and 2B.

6.2 Calibration types


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 precolumn 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.

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.

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.

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.

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.

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.

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.

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.

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.

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

8. CALCULATIONS

Table IV Example of Weight %


Calculated from Mole %

8.1 Determine the peak areas of each component for


the reference standard blend and unknown sample.

Component
Nitrogen
Methane
Carbon Dioxide
Ethane
Propane
Isobutane
n-Butane
Isopentane
n-Pentane
Hexanes Plus

8.2 Response factors are calculated for each


component using peak areas from the reference standard
blend in accordance with the following relationship:
K = Ms / Ps where:
K - Response factor
Ms Mol % of component in reference standard
Ps -Peak area in arbitrary units for reference
standard

Fnorm = unnormalized / desired


where:

Table II Example of Response Factors


Determined from Reference Standard Blend
Area
3140
106874
1174
6389
4944
2962
3038
1053
1098
749

Fnorm = normalization factor


unnorm = unnormalized total
desired = desired total

Response Factor
0.0006465
0.0008398
0.0004514
0.0004821
0.0003843
0.0003275
0.0003193
0.0002849
0.0002641
0.0002403

9.2 Normally the desired total is 100%, except in


cases such as secondary analyses such as those described
in Appendix A, Section A-1.2. Refer to Appendix A and
Table 5 below.
Table V Calculation of Concentration in Unknown Sample
Using Response Factors

Table III Calculation of Molar Concentration in


Unknown Sample Using Response Factors

Component
Nitrogen
Methane
Carbon Dioxide
Ethane
Propane
Isobutane
n-Butane
Isopentane
n-Pentane
Hexanes Plus

Area
Resp. Factor
1050
0.0006465
95153
0.0008398
1255
0.0004514
21470
0.0004821
13623
0.0003843
2253
0.0003275
4324
0.0003193
1398
0.0002849
1321
0.0002641
2080
0.0002403

Unnorm.
Mole %
0.68
79.91
0.57
10.35
5.24
0.74
1.38
0.40
0.35
0.50
100.12

Wt. %
0.91
61.27
1.20
14.88
11.04
2.06
3.84
1.38
1.21
2.21
100.00

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:

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

Mole %
2.03
89.75
0.53
3.08
1.90
0.97
0.97
0.30
0.29
0.18
100.00

Mole Wt.
Lbs./Mole
28.013
0.1905
16.043
12.8039
44.01
0.2509
30.07
3.1092
44.097
2.3063
58.123
0.4301
58.123
0.8021
72.15
0.2886
72.15
0.2525
92.489
0.4624
20.8966

9. REPORTING AND NORMALIZATION

8.3 Concentrations are calculated for each component


in accordance with the following relationship:

Component
Nitrogen
Methane
Carbon Dioxide
Ethane
Propane
Isobutane
n-Butane
Isopentane
n-Pentane
Hexanes Plus

Mole %
0.68
79.81
0.57
10.34
5.23
0.74
1.38
0.40
0.35
0.50

Norm.
Mole %
0.68
79.81
0.57
10.34
5.23
0.74
1.38
0.40
0.35
0.50
100.00

Component
Nitrogen
Methane
Carbon Dioxide
Ethane
Hydrogen Sulfide
Propane
Isobutane
n-Butane
Isopentane
n-Pentane
Hexanes Plus

Area
Resp. Factor
1050
0.0006465
95153
0.0008398
1255
0.0004514
21470
0.0004821
13623
2253
4324
1398
1321
2080

0.0003843
0.0003275
0.0003193
0.0002849
0.0002641
0.0002403

Unnorm.
Norm. Mole
Mole %
%
0.68
0.68
79.91
79.77
0.57
0.57
10.35
10.33
0.05
0.05
5.24
5.23
0.74
0.74
1.38
1.38
0.40
0.40
0.35
0.35
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.

10. PRECISION

Example 1
Mol %

10.1 The repeatability and reproducibility statements


for this standard are from the statistical data obtained in a
GPA RR-188. The testing program included ten samples
comprised of ten components analyzed by six laboratories.
The standard as revised has been statistically evaluated
under ISO and ASTM protocols. The documentation of
the statistical evaluation may be found in GPA TP-31.
10.2 To determine the precision for any component
at a specific concentration, use the formulae shown in
Table 6 and substitute the mole percent of the component
for x.
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
precision when the same method is used by different
laboratories using different equipment and different
analysts. Reproducibility is the difference between two
analyzed values. Neither value represents the difference
between an analyzed value and the certified value listed
on a blend. (Refer to 10.6 and 10.7).

Repeatability
1/4

Nitrogen

0.04

0.16

Methane

71.6

0.03

0.25

CO2

0.14

0.01

0.06

Ethane

4.9

0.02

0.05

Propane

2.3

0.01

0.04

Iso-butane

0.26

0.01

0.01

N-butane

0.6

0.01

0.03

Iso-pentane

0.12

0.01

0.01

N-pentane

0.14

0.01

0.01

Hexanes Plus

0.1

0.01

0.02

Example 2

Table VI Component Ranges for Precision Limits


Range

Repeatability Reproducibility

Reproducibility
1/2

Mol %

Repeatability

Reproducibility

Nitrogen

7.7

0.06

0.44

Methane

86.4

0.03

0.14

CO2

7.9

0.01

0.24

Ethane

9.7

0.03

0.07

Propane

4.3

0.01

0.05

Iso-butane

0.01

0.02

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

0.01

0.03

.02 15

0.026x1/2

0.35

Propane

0.0084x1/8

Hexanes Plus

Iso-butane

.02 8

0.01x1/5

0.018x1/2

N-butane

.02 8

0.0117x2/5

0.033x1/2

1/4

10.6 Performance evaluations commonly use the


repeatability and reproducibility of laboratory results
compared to a certified blend. This precision statement is
based on the data contained in GPA RR-188 and the
statistical evaluation described in GPA TP-31. This
treatment of data compared laboratory results independent
of the certified blend values. Therefore, performance
evaluations must either compare the laboratory results in
the same manner by using the reproducibility values
described in Table 6 and subsequent example calculations,
or use the Performance Evaluation Acceptance Criteria
listed below.

1/4

Iso-pentane

.02 4

0.009x

0.025x

N-pentane

.02 4

0.01x1/5

0.026x1/3

Hexanes Plus

.02 2

0.0135x1/4

0.051x1/2

10.4 The following example calculations show the


repeatability and reproducibility for two different blends.
The Ranges from the previous precision statement are
used in the two examples. Example 1 lists the lower
concentration from the original precision statement range
of each component and Example 2 lists the higher
concentration from the original precision statement range
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
the Performance Evaluation Acceptance Criteria. The
blend uncertainty must be known to use this approach.
The reproducibility and the uncertainty of the calibration
blend are used to determine the Performance Evaluation
Acceptance Criteria.

10.5 The values shown in these calculations are in


mol percent. These values are the mol % of the
component plus or minus the value determined from the
appropriate equation. That is to say, if the value is 1.00
and the precision value is 0.02, results that are between
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:

Column The part(s) of the GC system used to separate


components from each other.

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

Detector The device used to detect the presence and


determine the amount of each component within a
mixture.

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.

Effluent A component that has exited the analytical


column.
Elute The act of a component leaving the column.

Example 3

Nitrogen
Methane
CO2
Ethane
Propane
Iso-butane
N-butane
Iso-pentane
N-pentane
Hexanes
Plus

Mol %

UB

Reproducibility

PE

7.70
86.40
7.90
9.70
4.30
1.00
1.90
0.45
0.42

0.077
0.86
0.079
0.097
0.043
0.010
0.019
0.0045
0.0042

0.44
0.14
0.24
0.067
0.054
0.018
0.045
0.020
0.020

0.45
0.88
0.25
0.12
0.07
0.02
0.05
0.02
0.02

0.35

0.0035

0.030

0.03

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.

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.

Linear Range The range of concentrations where the


peak area is proportional to the component mol % for a
particular component.

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.

Molecular Sieve A device used to separate a particular


component from the rest of a mixture.

11. DEFINITIONS

Normalized Mol % The sum of mol % determined for a


mixture, adjusted to 100 %.

Linearity Check A process that verifies the degree of


nonlinearity for an analytical instrument (Refer to GPA
2198)

Partition Column A column that separates by liquid


partitioning, gas-liquid chromatography, such as the
DC200/500.

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.

Peak Windows The expected time period for a particular


component to elute from the column.

Calibrated Linear Range An experimentally determined


range of concentrations for a component on a particular
instrument. (Refer to GPA 2198)

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.

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.

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.

Sample/Calibration Run The act of analyzing a gaseous


mixture, from sample introduction to elution.

Porous Polymer Column A column that separates


utilizing polymer beads, gas solid chromatography, such
as Porapak Q or Hayesep Q.

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.

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.

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

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.

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.

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.

Un-Normalized Mol % - Un-normalized mol % is the sum


total mol % of the components determined for a mixture.
(See Normalized Mol %.)

Robust Mean The statistical mean of a set of values after


outliers have been removed. Refer to TP-31 for guidance
on outlier rejection.

APENDIX A - Calibrations
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

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.

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 Calibration Curves (Multi-level Calibration)


A-1.1.1 Calibration Curves Using Multiple Calibration
Blends
Once linearity has been determined for a GC, as described
in Section 4, and the linear range is found to be
inadequate for the range of unknown sample
concentrations anticipated, calibration curves for any
component may be determined by using multiple
calibration blends.
Duplicate injections of at least three concentration levels
for the desired component should be made. If the values
on duplicate runs agree within the tolerances in Section
10, Repeatability, the response factor should be
calculated as follows for each concentration level:
K= Cn
An
where
K = Response factor
Cn = Concentration of component n
An = Peak area in arbitrary units of component n

Table A-1
Component

Oxygen
Nitrogen
Methane
Carbon
Monoxide
Carbon Dioxide
Ethane
Propane
Isobutane
n-Butane
Isopentane
n-Pentane

Partial
Pressure mm
of Hg (Pi)
100
100
500
100

Barometric
Pressure mm of
Hg (Po)
750
750
750
750

Pi/Po * 100

100 (650)*
200 (450)*
100 (200)*
100 (100)*
100 (100)*
50 (50)*
50 (50)*

750
750
750
750
750
750
750

13.33
26.67
13.33
13.33
13.33
6.67
6.67

13.33
13.33
66.67
13.33

*Partial Pressures in parentheses are the maximum pressures to be


used to determine response factors. Exceeding these pressures could
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
capable of generating a polynomial curve fit may be used.

A-1.2 Secondary Analyses


Secondary analyses may be used instead of calibration
curves (as in the case of Carbon Dioxide on a Porous
Polymer column.) or for determination of compounds not
determined by the partition column run. The secondary
analysis or run may occur separately or simultaneously to
the primary analysis or run. When more than one
component is determined, add all component
concentrations and normalize to 100%. When a single
component is determined, it is acceptable to keep that
component concentration whole as described below:

A-1.1.2 Calibration Curves Using Partial Pressures of


Pure Components
Once linearity has been established for the instrument as
described in Section 4, calibration curves for any
component to be measured in the unknown sample may be
determined by using pure components.
Attach the pure component to the sample entry system and
evacuate the entry system to less than 1 mm of mercury.
Using the partial pressure range suggested in Table A-l,
inject at least three partial pressures in duplicate and
capture data including Barometric Pressure at the time of
the injection. When concentrations on duplicate runs meet
the criteria listed in Section 10, Repeatability, calculate
the response factor as follows:

Fnorm= 100- Cn
100
Where
Fnorm = Normalization Factor
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 SOPs
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
all sample component concentrations. In this case, a
calibration standard with any concentration of the
component of interest could be run and a calibration
response factor could be determined:

However, many chromatograph detectors are not linear in


their response. A graph of Mole % concentration to peak
area would not be linear:

Example: A calibration standard has 80 Mole % Methane.


When the sample is run on the GC, it generated a peak
area of 80,000. The response factor for Methane at 80%
concentration is:

Calibrating to 80 Mole % would yield the following


response factor:

In this example,

KFMethane = Mole % Methane Peak


Area Methane
= 80 96,000 = 0.000833

Kmethane = Mole % Methane Peak


Area = 80 80,000 = 0.001
When the detector was perfectly linear, and an unknown
sample was run and generated a peak area for Methane of
40,000, the Methane concentration in Mole % would be:

Using the above calibration factor to analyze a sample


with 40% Methane would yield the following result:

Mole% Methane = Peak Area


Methane * KFMethane
= 64,000 * 0.000833 = 53.333 Mole %
Methane

Peak Area x Kmethane = 40,000 x 0.001 =


40 Mole % Methane
A graph of Mole % concentration to peak area would be
linear (a straight line):

Since the difference between the actual value (40%) and


the reported value from calibration to 80% Methane
(53.333%) exceeds the reproducibility limits established
in Section 10 it would be necessary to have separate
calibration standards for samples containing 80%
Methane and samples containing 40% Methane.

Linear Methane Response


120000

Peak Area

100000
80000

The linearity check is used to determine the number of


calibration standards that are needed to analyze all the
expected sample compositions.

60000
40000
20000

When more than one calibration is required, this can be


achieved by having a separate calibration method for each
expected sample composition, a multi-level calibration for
all components or a multi-level calibration for the
components that are not linear.

0
0

20

40

60

80

100

120

Mole% Methane

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
analyzed within the reproducibility limits outlined in
Section 10.

120000

Peak Area

100000
80000

Linearity curves can be established by running multiple


calibration standards of various compositions. In this case,
the actual Mole% is plotted against the peak area.

60000
40000
20000

Linearity curves can also be established by running the


same calibration standard under various partial pressures.
In this case, the Mole% value is determined by the
following formula (see Appendix A, A-1.1.2):

0
0

20

40

60

80

100

120

Mole% Methane

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
GCs.

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-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-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 inplace 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.

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, 40C (104F)
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

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.

13