Designation: D7833 − 14

Standard Test Method for

Determination of Hydrocarbons and Non-Hydrocarbon
Gases in Gaseous Mixtures by Gas Chromatography1
This standard is issued under the fixed designation D7833; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.

1. Scope analyzer used, pentenes, if present, may either be separated or

1.1 This test method is intended to quantitatively determine grouped with the C6+ components.
the non-condensed hydrocarbon gases with carbon numbers 1.7 The values stated in SI units are to be regarded as
from C1 to C5+ and non-hydrocarbon gases, such as H2, CO2, standard. No other units of measurement are included in this
O2, N2, and CO, in gaseous samples. This test method is a standard.
companion standard test method to Test Method D1945 and 1.8 This standard does not purport to address all of the
Practice D1946 differing in that it incorporates use of capillary safety concerns, if any, associated with its use. It is the
columns instead of packed columns and allows other techno- responsibility of the user of this standard to establish appro-
logical differences. priate safety and health practices and determine the applica-
1.2 Hydrogen sulfide can be detected but may not be bility of regulatory limitations prior to use.
accurately determined by this procedure due to loss in sample
containers or sample lines and possible reactions unless special 2. Referenced Documents
precautions are taken. 2.1 ASTM Standards:2
1.3 Non-hydrocarbon gases have a lower detection limit in D1945 Test Method for Analysis of Natural Gas by Gas
the concentration range of 0.03 to 100 mole percent using a Chromatography
thermal conductivity detector (TCD) and C1 to C6 hydrocar- D1946 Practice for Analysis of Reformed Gas by Gas
bons have a lower detection limit in the range of 0.005 to 100 Chromatography
mole percent using a flame ionization detector (FID); using a D3588 Practice for Calculating Heat Value, Compressibility
TCD may increase the lower detection limit to approximately Factor, and Relative Density of Gaseous Fuels
0.03 mole percent. E355 Practice for Gas Chromatography Terms and Relation-
1.3.1 Hydrocarbon detection limits can be reduced with the ships
use of pre-concentration techniques and/or cryogenic trapping. E1510 Practice for Installing Fused Silica Open Tubular
Capillary Columns in Gas Chromatographs
1.4 This test method does not fully determine individual
F307 Practice for Sampling Pressurized Gas for Gas Analy-
hydrocarbons heavier than benzene, which are grouped to-
sis
gether as C7+ When detailed analysis is not required the
compounds with carbon number greater than C5 may be 2.2 ASTM Publication:
grouped as either C6+, or C7+. Accurate analysis of C5+ ASTM DS 4B, 1991 Physical Constants of Hydrocarbon and
components depends on proper vaporization of these com- Non-Hydrocarbon Compounds
pounds during sampling at process unit sources as well as in
3. Terminology
the sample introduction into the analyzer in the laboratory.
3.1 Terminology related to the practice of gas chromatog-
1.5 Water vapor may interfere with the C6+ analysis if a
raphy can be found in Practice E355.
TCD detector is used.
3.2 Definitions:
1.6 Helium and argon may interfere with the determination
3.2.1 sample set—a collection of samples taken from the
of hydrogen and oxygen respectively. Depending on the
same source or at similar component composition and concen-
trations.
1
This test method is under the jurisdiction of ASTM Committee D03 on Gaseous
Fuels and is the direct responsibility of Subcommittee D03.07 on Analysis of
2
Chemical Composition of Gaseous Fuels. For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Current edition approved June 1, 2014. Published June 2014. Originally contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
approved in 2012. Last previous edition approved in 2012 as D7833-12. DOI: Standards volume information, refer to the standard’s Document Summary page on
10.1520/D7833-14. the ASTM website.

Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States

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 D7833 − 14
4. Summary of Test Method TABLE 1 List of Components Typically Analyzed
Component FID TCD
4.1 Components in a representative sample are physically
C5 olefin / C6+ composite X X
separated by gas chromatography (GC) and compared to oxygen/argon composite X
calibration data obtained under identical operating conditions hydrogen X
from a reference standard mixture of known composition. The carbon dioxide X
hydrogen sulfide X
numerous heavy-end components of a sample can be grouped nitrogen X
into irregular peaks by reversing the direction of the carrier gas carbon monoxide X
through the column at such time as to group the heavy ends methane X X
ethane X X
either as C5 and heavier, C6 and heavier, or C7 and heavier or ethylene X X
alternatively elute them in the non-backflushed mode and propane X X
summed accordingly. The composition of the sample is calcu- propylene X X
acetylene X X
lated by comparing the peak areas with the corresponding isobutane X X
values obtained with the reference standard. propadiene X X
n-butane X X
trans-2-butene X X
5. Significance and Use 1-butene X X
isobutylene X X
5.1 The hydrocarbon component distribution of gaseous cis-2-butene X X
mixtures is often required for end-use sale of this material. neopentane X X
Applications such as chemical feedstock or fuel require precise cyclopentane X X
isopentane X X
compositional data to ensure uniform quality. Trace amounts of methyl acetylene X X
some hydrocarbon impurities in these materials can have n-pentane X X
adverse effects on their use and processing. Certain regulations 1,3-butadiene X X
may require use of such method.
5.2 The component distribution data of gaseous mixtures
can be used to calculate physical properties such as relative
density, vapor pressure, and heating value calculations found in 6.1.3 Other detectors or combination of detectors may be
Practice D3588. Precision and accuracy of compositional data used provided that they have sufficient response, linearity, and
is extremely important when this data is used to calculate sensitivity to measure the components of interest at the
various properties of petroleum products. concentration levels required for this application and meeting
all of the quality controls specified in this method. Some
6. Apparatus analyzers, such as micro-analyzers, may contain up to
4-channels and separation systems to accomplish the analysis
6.1 Gas Chromatograph (GC)—This method allows the use described in this method.
of most gas chromatographic analyzers designed for gas
analysis. Generally, any gas chromatographic instrument with 6.2 Data Acquisition—Any commercial computerized data
a linear temperature programmable column oven or adequate acquisition system may be used for display of the chromato-
temperature control to provide the required separation of graphic detector signal and peak area integration from all of the
gaseous compounds being analyzed may be used. The tem- detectors used in the analysis. The device should be capable of
perature control must be capable of obtaining retention time generating and storing a calibration and reporting the final
repeatability within 5% of the retention time for each compo- corrected response factor results.
nent throughout the scope of this analysis for hydrocarbon and 6.3 Sample Introduction and System Configurations—
non-hydrocarbon gas analyses. Sample introduction is typically performed with automated
6.1.1 Detector—The type and number of detectors em- valves containing sampling ‘loops’ of appropriate sizes. Fig. 1
ployed is dependent on gas analyzer model and vendor used. gives a suggested configuration, although systems may vary
Detectors that can be used include, but are not limited to FID, slightly among gas analyzers. The combination of valve
TCD, AED (Atomic Emission Detector), HID (Helium Ioniza- injection size and/or splitting inlet ratio must be selected such
tion Detector), and MS(Mass Spectrometer). Many systems use that the required sensitivity for the application is achieved and
a 3 detector system: also that no component concentration in a sample is greater
(1) One FID (Flame Ionization Detector) for the determi- than the detector upper linearity limit. The sample inlet system
nation of the hydrocarbon gases for the compounds listed in shall be constructed of materials that are inert and non-
Table 1, adsorptive with respect to the components in the sample. The
(2) One TCD (Thermal Conductivity Detector) dedicated preferred material of construction is stainless steel. Copper,
to the determination of hydrogen utilizing nitrogen or argon as brass, and other copper-bearing alloys are unacceptable. The
a carrier gas, and sample size limitation of 0.5 mL or smaller is selected relative
(3) One TCD for the determination of all other required to the linearity of the detector response, and efficiency of
non-hydrocarbon gases using helium as the carrier gas. column separation. Larger samples may be used to determine
6.1.2 A TCD may also be used for the analysis of the low-quantity components to increase measurement accuracy.
hydrocarbon gases (replacing the FID) when high sensitivity (< Sample sizes may be determined by experimentation or as
0.03 mole percent) for trace analysis is not required. recommended by analyzer vendors.

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 D7833 − 14

FIG. 1 Example of a Three Detector System for Analysis of Hydrocarbons and Non-Hydrocarbon Gases

FIG. 2 Example Chromatogram of Non-Hydrocarbon and Light Hydrocarbon Gases from System Configuration in Fig. 1

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 D7833 − 14

NOTE 1—For the hydrocarbon analysis, the Al2O3 PLOT was used.
FIG. 3 Example Chromatogram of Hydrocarbons from System Configuration in Fig. 1

6.3.1 Hydrogen Sulfide and Other Reactive Gases— 6.4 Hydrogen Gas Analysis (Thermal Conductivity
Samples containing hydrogen sulfide and trace reactive gases Detector)—A 10-port gas-sampling valve or equivalent may be
may benefit from use of surface treated metal surfaces, such as used with nitrogen or argon carrier gas. Nitrogen or argon
Silcosteel3 or Sulfinert4 processes. Such specially treated carrier gas is used to ensure that the hydrogen ‘peak’ remains
surfaces are also recommended for sample containers that may positive over the concentration range of interest. Any column
contain such reactive species. or multiple columns may be used, as long as helium and
6.3.2 With Capillary Columns—The gas chromatograph hydrogen are separated and also separated from the other
must include a heated splitting type inlet that is operated components. Typically, a dedicated TCD is used for this
isothermally, or if appropriate, direct connection to the valve analysis. The gas-sampling valve shall provide a repeatability
may be possible as long as sample sizes are adjusted of at least 6 2% relative to the sample volume introduction for
accordingly, the calibrations are linear in the range of interest, major compounds present at >5 vol%.
and the required resolution of the compounds of interest is NOTE 1—When helium is not expected to be present in samples the
maintained. When using a split injection, split ratios in the resolution of hydrogen from helium is not critical.
range of 5:1 to 200:1, with a typical value of 100:1, have been
used successfully depending upon the sample injection volume 6.5 Non-Hydrocarbon and Light Hydrocarbon Gas Analysis
and sensitivity required. (Except Hydrogen) (Thermal Conductivity Detector)—A 10-
6.3.3 With Pre-concentrator and/or Cryogenic Trapping— port gas sampling valve in combination with a 6-port switching
Pre-concentrator and/or cryogenic trapping can be used prior to valve or equivalent is used with helium or hydrogen carrier to
sample introduction into the gas chromatograph. These items analyze for CO2, O2, N2, CH4, C2H6, and CO and in some
may enable lower detection limits on the components detailed cases H2S. Any column or multiple columns may be used as
by the manufacturer to be concentrated. long as the desired components are well separated. A TCD may
also be used for the analysis of the hydrocarbon gases
(replacing the FID) when high sensitivity (<300 ppm) for trace
3
Silcosteel is a trademarked of SilcoTek, 112 Benner Circle, Bellefonte, PA analysis is not required. The gas-sampling valve shall provide
16823.
4
Sulfinert is a trademarked of Restek Corporation 110 Benner Circle Bellefonte, a repeatability of at least 6 2% relative to the sample volume
PA 16823. introduction for major compounds present at >5 vol%.

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 D7833 − 14
6.6 Hydrocarbon Gas Analysis (Flame Ionization C5+/C6+ components through the use of the sequence reversal/
Detector)—A 6-port gas-sampling valve in combination with a backflush valve is desired, a second column is required. Any
6-port pre-column switching valve (backflush) for the C6+ or pre-column that provides separation between the components
C7+ hydrocarbons is typically used. These valves shall be of interest and the composite heavier components may be used.
contained in a heated enclosure and operated at a sufficiently Choices may include lengths of column such as a 10 to 30 m
high temperature, and within the limits of the valve operating section of 0.53 mm (I.D.) 3-µm film thickness dimethyl
temperature as specified by manufacturer, to prevent conden- polysiloxane or a 9 to 15 cm section of the same column
sation of the C6+ components in the sample. The use of a frit material as the analytical column or any pre-column that
or packed-screen type filter ahead of the sample introduction provides the desired retention of pentenes, hexanes, and
port is recommended with use of PLOT columns. The gas- heavier components. This pre-column acts to keep the heavier
sampling valve shall provide a repeatability of at least 6 2% components away from the analytical alumina PLOT column
relative to the sample volume introduction for major com- and to backflush the heavier components as a composite peak
pounds present at >5 vol%. to the detector for quantification. If analysis of individual
6.7 Column Series/Reversal Switching Valve—If desired, a C6-C7 components is required, extend the backflush valve time
multi-port valve may be used to provide the C5 olefin/C6+ or until the desired components have eluted and prior to back-
C7+ determination for this analysis. Other switching valve flushing the remaining heavier compounds.
configurations may be used to allow the elution of the gaseous 6.12 Analytical Columns for Hydrogen Analysis—Generally
compounds. Consult instrument manufacturer for optimum hydrogen analysis consists of a pre-column to remove most of
configuration. the hydrocarbons, H2S and CO2 and a Molecular Sieve 5A or
NOTE 2—If a dimethylsilicone capillary column or equivalent is used equivalent for separation of hydrogen from oxygen and nitro-
for the hydrocarbon analysis, then the capillary column may be used in the
foreflush mode (no-backflush) until all of the hydrocarbons have eluted
gen. Follow vendor’s recommendations.
using temperature programming or equivalent. 6.13 Analytical Columns for Other Non-Hydrocarbon
6.8 Gas Controls—The gas chromatograph shall be pro- Gases—Generally a series-bypass two-valve configuration is
vided with suitable facilities for delivery and control of carrier used, consisting of porous polymer-molecular sieve 5A or 13X
gases and detector gases. This will consist of the appropriate combination. Follow vendor’s recommendations.
gas supply, down-stream regulators, and supply tubing as well
as the mass or pressure controls for the precise regulation of the 7. Reagents and Materials
instrument operation.
NOTE 3—Most gas chromatograph suppliers will provide these devices
7.1 All chemicals are reagent grade unless specified
or recommend the proper suppliers. Ensure that the analyzer when heated otherwise, and all water used is distilled or deionized.
and in-use does not run out of carrier gases. In addition, running out of Warning—Hydrogen sulfide contained in calibration stan-
carrier gas will require flushing out any air introduced into the sample inlet dards may be flammable and harmful or fatal if ingested or
system, column and/or detector. inhaled. Calibration standards or samples containing hydrogen
6.9 Columns—Condition all columns used according to the sulfide should be handled in well ventilated locations away
manufacturer’s suggestions prior to putting the system in from sparks and flames.
service.
7.2 Carrier Gases—For carrier gases, it is strongly recom-
6.10 Analytical Column for Hydrocarbon Analysis—A rec- mended to install commercial active oxygen scrubbers and
ommended analytical column for the hydrocarbon analysis in water dryers, such as molecular sieves, ahead of the instrument
Fig. 1 is a 50 m × 0.53 mm (I.D.) deactivated alumina (Al2O3) to protect the chromatographic columns. Follow supplier
porous layer open tubular (PLOT) column used with a FID instructions in the use of such gas purifiers and replace as
detector for lowest detection limits. Relative retention order for necessary.
the alumina PLOT column is dependent upon the deactivation
7.2.1 Chromatographic Grade Hydrogen, 99.995% mini-
method for the column and moisture content. Warning—
mum purity, <0.1 ppm H2O. The use of appropriate scrubbers
Specifically test the alumina PLOT column to ensure that the
may be sufficient to obtain the desired purity.
column does not adsorb propadiene, methyl acetylene, and
7.2.2 Chromatographic Grade Helium, 99.995 % minimum
butadiene when such compounds need to be determined. This
purity, <0.1 ppm H2O. The use of appropriate scrubbers may be
condition can exist depending upon the degree of column
sufficient to obtain the desired purity.
deactivation.
6.10.1 Routine re-conditioning of the alumina PLOT col- 7.2.3 Chromatographic Grade Nitrogen, 99.995 % mini-
umn may be required to maintain column performance. It is mum purity, <0.1ppm H2O. The use of appropriate scrubbers
recommended that a standby method be used when the system may be sufficient to obtain the desired purity. Warning—
is idle to maintain the PLOT column at a temperature of at least Improper handling of compressed gas cylinders containing air,
130ºC or as recommended by the manufacturer. nitrogen, hydrogen, or helium can result in an explosion. Rapid
6.10.2 Alternatively, any column or combination of col- release of nitrogen or helium can result in asphyxiation.
umns that provides the appropriate component C1-C5 separa- 7.3 FID Detector Gases:
tions may be used. 7.3.1 Chromatographic Grade Hydrogen, 99.995 % mini-
6.11 Pre-column for Hydrocarbon Gas Analysis—When mum purity. The use of appropriate scrubbers may be sufficient
using the alumina PLOT column, if an initial backflush of the to obtain the desired purity.

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 D7833 − 14
7.3.2 Chromatographic Grade Air, less than 10 ppm-mol used as long as the repeatability for these systems meets or
each of total hydrocarbons and water. The use of appropriate exceeds those stated in this method. Calibration standards are
scrubbers may be sufficient to obtain the desired purity. injected under similar temperature and pressures as the samples
Warning—Compressed air supports combustion. to be analyzed. Generally the sampling pressure is approxi-
7.4 Reference Standards: mately atmospheric. The temperature of sampling is such as to
7.4.1 Purity of Reagents—Reagent grade chemicals shall be avoid condensation of the compounds to be analyzed. For
used in all tests. Unless otherwise indicated, all reagents should hexanes and higher, heat the sample loop. Most modern
conform to the specifications of the Committee on Analytical chromatographs have valve ovens that can be temperature
Reagents of the American Chemical Society where such controlled. It is strongly recommended in the absence of valve
specifications are available. Other grades may be used, pro- ovens to mount the gas-sampling valve in the chromatograph
vided it is first ascertained that the reagent is of sufficiently oven and operate at the column temperature. Sub-ambient
high purity to permit its use without lessening the accuracy of sampling can be performed if a pressure transducer is used to
the determination. measure the sampling line pressure and make the appropriate
7.4.2 Calibration Standards—Individual and mixed compo- correction.
nent reference materials are commercially available and may 8.5 Switching (backflush) Valve for Alumina PLOT Hydro-
be used to establish qualitative and quantitative calibration. carbon Analysis (optional)—The valve rests in the “OFF”
The calibration standard mixture should be gravimetrically state, allowing a continuous backflush flow through the pre-
prepared, supplied with both gravimetric and calculated volu- column. Before or upon injection of the sample, the valve
metric and mole% concentrations, and at least NIST traceable should be rotated to the “ON” position so that the pre-column
or Van Swinden Laboratorium, National Metrology Institute of is placed at the head of the flow path from the sample valve
the Netherlands (VSL) certified. The calibration standard (see Fig. 1). At a time which must be empirically determined
mixture should have analytical uncertainty of <1% relative. and which is dependant upon the length and type of pre-column
7.4.3 Secondary Reference Standards—A mixture or mix- used, the valve must be returned to the “OFF” position, causing
tures of known composition that is (or are) independent of the the flow to backflush through the pre-column and flush to the
calibration standards and similar wherever possible in concen- detector ahead of components eluting from the analytical
tration to the samples being analyzed. The secondary reference column (see Fig. 1). The switch time of the valve should be
standards are used as check standards to monitor testing determined such that the areas of 2-methyl butane, pentane,
precision and accuracy. and 1,3-butadiene are not diminished, but so that pentene
components are not allowed to elute to and through the
8. Preparation of Apparatus analytical column (where they would elute after the pentanes
8.1 Install the valves for the hydrogen, other non- and 1,3-butadiene). Determining this switch time may require
hydrocarbon gases analysis, and/or the hydrocarbon analysis. If iterative attempts and interpolation. However, once the time
a turn-key analyzer is used follow manufacturer’s instructions. has been determined, it should remain repeatable for all
Fig. 1 gives an example of a three-detector system using the samples of similar composition. For other system configura-
Al2O3 column for the hydrocarbons, and individual analyses tions consult the analyzer vendor.
for hydrogen and other non-hydrocarbon gases. 9. Calibration and Standardization
8.2 If using the alumina PLOT column for the hydrocarbon 9.1 Qualitative—After the analyzer is installed, at least
analysis, it is recommended that the PLOT column undergo annually, after major repair, or after extended shutdown,
routine baking at the maximum method temperature in order to determine the retention times of components by analyzing
maintain conditioning. See Practice E1510 for recommended known reference mixtures in the same manner as samples
installation procedures. If multiple columns for this analysis (Section 11). Table 1 gives a summary of components com-
are placed into the same oven with the alumina PLOT, ensure monly determined according to this standard using TCD or FID
that the bake out temperature does not exceed the maximum detection. The stated elution order of the hydrocarbons is that
allowable temperature of any of the other columns. for an alumina PLOT column. In general, elution order will
8.3 Set the GC instrument to the operating parameters. vary by column used and the configuration of the analyzer.
Allow the instrument to stabilize before proceeding with Note that some PLOT columns do not separate neopentane
calibration and sample injections. When using an alumina from butenes.
PLOT column, recommended operating conditions are listed in 9.2 Verification of Linearity—Ensure that the response of
Appendix X1. However, conditions may vary if other column each component of interest is linear bracketing the expected
systems are used or if tubing is different. concentration of analytes. Use at least three concentration
8.4 Gas Sampling Valves—Set valve on and off times to ranges for each component of interest. This is typically
comply with manufacturer’s instructions. When using a three accomplished using a multi-component gas standard(s) con-
detector system, sample introduction into the analyzer for taining analytes of interest analyzed with and without dilution
hydrogen, non-hydrocarbon gases, and hydrocarbons may be or by using gas standards with components at each of the
accomplished using valve injections that are synchronized such concentrations needed to prepare a calibration curve. Ensure
that samples are injected simultaneously into the system using that the linearity regression coefficient is at least 0.999 for each
computer controlled valves. Other sample introduction may be compound calibrated. Special care should be used to verify that

6
 D7833 − 14
low concentration values do not deviate significantly from the temperature as the samples (Section 11). For each component
calibration curve. If low concentration points do not conform present in the calibration standard, calculate the response factor
to linearity as defined by higher concentration points, it is according to Eq 1.
necessary to prepare a second calibration curve for low RF i 5 C i ⁄A i (1)
concentration analytes when samples contain components at
levels approaching the low level of the initial curve are where:
expected. The linearity is confirmed upon analyzer start-up and RFi = the response factor for component i,
whenever major changes are made to the analyzer, such as Ci = the known concentration of i, and
changing columns, replacing detectors etc. Ensure the TCD Ai = the integrated area of peak i.
analyzing hydrogen exhibits a positive response (peak area) 9.3.1 If desired for C6 and C7+ hydrocarbons (if split) the
over the range of interest. RF’s can be estimated from isopentane and n-pentane as
9.2.1 Introduction of Standards—Open the outlet valve of follows:
the sample cylinder and purge the sample through the inlet RF C6 5 RF C5AV 3 72⁄86 (2)
system and sample loop or tube. The amount of purging
RF C7 5 RF C5AV 3 72⁄100 (3)
required must be established and verified for each instrument.
9.2.1.1 When purging the valve, sample loops, and the where:
general inlet system with calibration standard do not expose the RFC5AV = average RFs of i-C5 and n-C5.
calibration standards to high flows as this may change the 9.3.2 In cases where the C6+ are backflushed as one
composition of the standard over time. Initiating flows of composite and the average molecular weight of the composite,
approximately 10–30 mL/min of gas standard should be if desired the C6+ RF can be estimated as follows:
adequate. Use appropriate regulators on standard cylinders and
RF C61 5 RF C5AV 3 72⁄93 (4)
slowly increase the flow from a zero flow. Once the correct
flow has been established the cylinder regulator may be set to 9.3.3 The standard should contain all of the components
the required setting. The cylinder may be isolated from the typically observed in the samples.
system by using the shut-off valve when not in use. The sample
NOTE 4—Hydrocarbons with a boiling point greater than isopentane in
loop pressure should be near atmospheric during injection. the standard have a potential for condensation. Consult with gas standard
Close the cylinder valve and allow the pressure of the sample manufacturer for proper sizing and pressure of standard cylinder to
in the loop or tube to stabilize. Then immediately inject the minimize condensation. In some cases where a FID is used, an adjacent
contents of the loop or tube into the gas chromatograph. Such eluting hydrocarbon of the same carbon number for which a calibration
gauges may be used to adjust the pressure to close to standard is not available may be estimated from a hydrocarbon that is
present in the standard, e.g., isobutane may be estimated from the RF of
atmospheric pressure. Flow meters and bubble meters may also n-butane, 1-butene, or isobutylene.
be used to monitor and set the flow standards and verify
pressures prior to injection. If injecting sub-ambient pressure 9.4 Quality Monitoring—After determining the response
samples, the proper equipment must be used to ensure the factor for each component using the primary standard(s),
sample has been properly introduced into the gas chromato- analyze a secondary check standard(s) that approximates
graph. composition of samples being analyzed (see 7.4.3) every 24 hrs
or at a frequency determined through a statistical TPI assess-
9.2.1.2 Standards containing hydrogen sulfide should use ment when samples are analyzed. Verify that the concentra-
corrosive resistant regulators. Vents from gas sampling valves tions agree within the acceptable values for the standard(s). If
need to be vented to a well ventilated hood to avoid exposure the test method is used only occasionally, reanalyze the
to hydrogen sulfide. Some systems may contain a pressure calibration standard(s) and secondary standard before each set
gauge to measure the actual pressure in the loop. of analyses. Results should agree within 2% relative of the
9.2.2 If it is not possible to obtain information on the certified value for components present at >5 vol%. Failure to
linearity of the available gas chromatograph detector for all of compare may result from lack of injection splitter (if used)
the test gas components, then as a minimum the linearity data linearity or use of a standard that has not been maintained
must be obtained for any gas component that exceeds a according to the standard manufacturer’s recommendations. It
concentration of 5 mol%. GC detectors have a lower detection is necessary to compare calculated results to the certified
limit and are not truly linear over wide concentration ranges. values for a known standard before accepting the calibration.
Linearity should be established over the range of interest and
confirmed annually. 10. Sampling
9.3 Calibration and Primary Standardization—Once linear- 10.1 Sampling at the sample source, the use of appropriate
ity has been established a single standard may be used to sample containers that are stored and transported properly, and
perform a recalibration of the analyzer as necessary. Recali- introduction into a chromatograph must be done in a manner
bration should be performed when hardware is changed, there that ensures that a representative sample is being analyzed. See
is a failure of the QC check, or as needed to meet raw recovery Practice F307 for the recommended procedures. Lack of
requirements. Determine the experimental response factors of precision and accuracy in using this method can most often be
components detected by the detectors used by analyzing known attributed to improper sampling, sample containment, or
calibration mixtures under the same conditions of pressure and sample introduction procedures.

7
 D7833 − 14
10.2 Higher boiling components such as C5+ may condense where:
during sampling of the process unit if the sample vessel is not SCi = concentration of component i in the sample,
at the same or greater temperature as the sample stream. This RFi = response factor for component i, and
will result in an inaccurate collection of sample components. A SAi = integrated area for peak i.
representative sample must be collected to obtain valid results. 12.2 The summation of all components from Eq 5 must
Please reference API MPMS 14.1 for additional information. agree within 100 6 5 %.
10.3 It is recommended that samples be equilibrated in the 12.3 Normalize the final results to 100%.
laboratory at –6.7 to 10°C (20 to 50°F) above the source
temperature of the field sampling. If the hydrocarbon dew point 13. Reporting
of the sample is known to be lower than the lowest temperature
to which the sample has been exposed, it is not necessary to 13.1 Report the concentration of each component as mole
heat the sample. percent to the nearest 0.01%.
13.2 Report the C6+ (C5 olefins+C6+ components) as “C6+
10.4 Connections from the sample container to the sample
hydrocarbons.” If the C5 olefins are resolved they may be
inlet of the instrument should be made with stainless steel or
reported separately.
with short pieces of TFE-fluorocarbon or inert tubing coated
with Silcosteel3 or Sulfinert4. Copper, vinyl, or rubber connec- 13.3 For systems that are set-up to calculate a split C6 and
tions are not acceptable. Heated lines may be necessary for C7+ hydrocarbons report them individually as separate groups
samples containing C6+ hydrocarbon content samples. as “C6+ hydrocarbons” and “C7+ hydrocarbons.”
10.5 Samples should be clean and free of liquid prior to
14. Quality Control
injection. It is recommended that filters be placed between the
sampling device and the analytical equipment to minimize the 14.1 Confirm the performance of the GC analysis and test
risk of damage to the analytical equipment. procedure by analyzing a secondary reference standard(s) of
10.5.1 If the sample is known to have excessive liquid or known composition (see 7.4.3) according to the frequencies
particulates, the sampling device may need to be tilted or stood identified in 9.4. The secondary reference standard(s) are used
in an upright position to place the contamination away from the as check standards to monitor testing precision and accuracy.
sample being drawn from the sampling device. Other prepara- 14.2 In addition, the analysis of other quality control (QC)
tory techniques may need to be employed to reduce the samples from plant production that are representative of the
potential for damaging the analytical equipment. samples typically analyzed is recommended. An ample supply
of such QC sample material should be available and stored
11. Procedure without undergoing composition changes for the intended
11.1 The sample cylinder should be oriented vertically with period of use. It is recommended that a QC sample be analyzed
the valve to be used for sampling located at the top. Open the with each batch of samples to ensure data quality relative to the
outlet valve of the sample cylinder and purge the sample statistical control limits established.
through the inlet system and sample loop or tube at flows <50 14.3 Blank Analysis—Confirmation of lack of carry-over or
mL/min. The amount of purging required must be established contamination is recommended and may be required for certain
and verified for each instrument. The sample loop pressure applications. This is accomplished through analysis of ultra
should be near atmospheric unless sub-ambient sampling is pure hydrogen, helium, methane blank, nitrogen, or zero air
performed. blank as appropriate. Blank analysis results may be subtracted
NOTE 5—Vents from gas sampling valves need to be directed to a from sample results as necessary.
well-ventilated hood to avoid exposure to hydrogen sulfide.
14.4 Spiked Samples—For some applications it may be
11.2 Close the cylinder valve and allow the pressure of the necessary to analyze spiked sample for each sample set as part
sample in the loop or tube to stabilize. Immediately inject the of a QA/QC program. Spikes are prepared by quantitative
contents of the loop or tube into the chromatograph. Some addition of a mixed component calibration gas to a known
systems may contain a pressure gauge to measure the actual volume of sample gas. Acceptable recoveries for components
pressure in the loop. Such gauges may be used to adjust present at greater than 5 ppmv should fall within 10% of the
pressure to close to atmospheric or to measure the injection theoretical amounts to verify nominal system performance.
pressure if your sampling system requires it. In addition to Unacceptable recoveries indicate matrix interference or system
pressure gauges, gas bubblers and flow meters may also be malfunction.
used.
14.5 Calibration Standard Reanalysis—For some applica-
tions a standard is reanalyzed after each sample set to assess
12. Calculations instrument drift. All components of interest should be within
12.1 External Standard Calibration Calculation—Calculate 2% of the theoretical amounts based on the original standards.
the concentration of each component according to Eq 5. 14.6 It is recommended that a duplicate analysis be per-
Determine the total amount of all components by summing the formed every tenth sample or one for each sample set. All
component concentrations. components of interest should be within 2% of the averaged
SC i 5 RF i 3 SA i (5) concentration of each component.

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15. Precision and Bias 15.2 Reproducibility—The difference between two single
15.1 Repeatability—The difference between successive test and independent results obtained by different operators work-
results obtained by the same operator with the same apparatus ing in different laboratories on identical test materials.
under constant operating conditions on identical test materials. 15.2.1 Reproducibility data to be added within 5 years of
15.1.1 The difference between two successive results ob- method approval.
tained by the same operator with the same apparatus under
15.3 Bias—A statement of bias will be developed through
constant operating conditions on identical test materials should
be considered suspect if they differ by more than the following inter-laboratory testing by the responsible study group.
amounts:
16. Keywords
Component Concentration Repeatability
Range (mol %) (mol %) 16.1 gas analysis; gas chromatography; gas sampling valve;
0 to 0.1 0.01
0.1 to 1.0 0.04 hydrocarbons; non-hydrocarbon gases
1.0 to 5.0 0.09
5.0 to 10 0.10
10 to 50 0.40
50 to 100 0.50

APPENDIX

(Nonmandatory Information)

X1. RECOMMENDED OPERATING CONDITIONS

Typical Operating Conditions for Hydrocarbon Analysis

Column dimensions 50 meter × 0.53 mm Al2O3
Backflush Yes
Initial temperature 75°C (167°F)
Initial hold time 3 min
Program rate 10°C/min (18°F/min)
Final temperature 180°C
Final hold time 2 min
Injector temperature 225°C
Sample size 200 µL
Split ratio 100:1
Typical detector FID
Detector temperature 250°C (482°F)
Fuel gas hydrogen flow 35–45 mL/min
Oxidizing gas air flow 400–450 mL/min
Make-up gas type He or N2
Make-up gas flow 35 mL/min
Capillary column carrier gas type Constant or programmed flow or pressure helium or hydrogen at 5 mL/min
Capillary column average linear velocity 45 cm/sec
Data rate 5–10 Hz
Packed pre-column flow rate for C5+ or C6+ heart-cutting away from 30–40 mL/min
Al2O3 column
Packed pre-column temperature for C5+ or C6+ heart-cutting away Approximately 90°C (194°F). Pre-column usually installed in an auxiliary
from Al2O3 column secondary oven
Typical Operating Conditions for Non-hydrocarbon Gas Analysis
Backflush Yes
Isothermal temperature 75°C (167°F)
Typical detector TCD
Detector temperature 250°C (482°F)
Make-up gas type He or H2
Column carrier gas type Constant or programmed flow or pressure helium or hydrogen
Data rate 5–10 Hz
Typical Operating Conditions for Hydrogen Analysis
Backflush Yes
Isothermal temperature 75°C (167°F)
Typical detector TCD
Detector temperature 250°C (482°F)
Column carrier gas type Constant or programmed flow or pressure nitrogen or argon
Data rate 5–10 Hz

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