An American National Standard

Designation: D 2163 – 07

Standard Test Method for

Determination of Hydrocarbons in Liquefied Petroleum (LP)
Gases and Propane/Propene Mixtures by Gas
Chromatography1
This standard is issued under the fixed designation D 2163; 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 (e) indicates an editorial change since the last revision or reapproval.

1. Scope D 6729 Test Method for Determination of Individual Com-

1.1 This test method covers the quantitative determination ponents in Spark Ignition Engine Fuels by 100 Metre
of individual hydrocarbons in liquefied petroleum (LP) gases Capillary High Resolution Gas Chromatography
and mixtures of propane and propene, excluding high-purity E 355 Practice for Gas Chromatography Terms and Rela-
propene in the range of C1 to C5. Component concentrations tionships
are determined in the range of 0.01 to 100 volume percent. E 594 Practice for Testing Flame Ionization Detectors Used
1.2 This test method does not fully determine hydrocarbons in Gas or Supercritical Fluid Chromatography
heavier than C5 and non-hydrocarbon materials, and additional E 1510 Practice for Installing Fused Silica Open Tubular
tests may be necessary to fully characterize an LPG sample. Capillary Columns in Gas Chromatographs
1.3 The values stated in SI units are to be regarded as the 2.2 Canadian General Standards Board Publications:3
standard. The values given in parentheses are for information CAN/CGSB 3.0 No. 14.3 Standard Test Method for the
only. Identification of Hydrocarbon Components in Automotive
1.4 This standard does not purport to address all of the Gasoline Using Gas Chromatography
safety concerns, if any, associated with its use. It is the 2.3 Gas Processors Association:4
responsibility of the user of this standard to establish appro- GPA Std 2145-03 for hexane
priate safety and health practices and determine the applica- 3. Terminology
bility of regulatory limitations prior to use.
3.1 Definitions:
2. Referenced Documents 3.1.1 Additional terminology related to the practice of gas
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2.1 ASTM Standards: 2 chromatography can be found in Practice E 355.

D 1265 Practice for Sampling Liquefied Petroleum (LP) 3.1.2 liquefied petroleum gas (LPG), n—hydrocarbon gases
Gases, Manual Method that can be stored or handled in the liquid phase through
D 1835 Specification for Liquefied Petroleum (LP) Gases compression or refrigeration, or both.
D 2421 Practice for Interconversion of Analysis of C5 and 3.1.2.1 Discussion—LPG’s generally consist of C3 and C4
Lighter Hydrocarbons to Gas-Volume, Liquid-Volume, or alkanes and alkenes or mixtures thereof and containing less
Mass Basis than 10 volume percent of higher carbon number material.
D 2598 Practice for Calculation of Certain Physical Prop- Vapor pressure does not normally exceed 2000 kPa at 40ºC.
erties of Liquefied Petroleum (LP) Gases from Composi- 3.2 Definitions of Terms Specific to This Standard:
tional Analysis 3.2.1 propane/propene mixtures, n—mixtures primarily
D 3700 Practice for Obtaining LPG Samples Using a Float- composed of propane and propene where one of these compo-
ing Piston Cylinder nents is usually in the concentration range of 30 to 85 mass %
with the other comprising the majority of the remainder.
“Commercial Propane in Specification D 1835 is typically this
1
This test method is under the jurisdiction of ASTM Committee D02 on sort of product mixture.
Petroleum Products and Lubricants and is the direct responsibility of Subcommittee 3.2.1.1 Discussion—Other components may be present,
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D02.D0.03 on Propylene.
Current edition approved Dec. 1, 2007. Published February 2008. Originally
usually at less than 10 mass %.
approved in 1963. Last previous edition approved in 1996 as D 2163–91(1996)
which was withdrawn December 2004 and reinstated in December 2007.
2 3
For referenced ASTM standards, visit the ASTM website, www.astm.org, or Available from CGSB, Canadian General Standards Board, Gatineau, Canada
contact ASTM Customer Service at [email protected]. For Annual Book of ASTM K1A 1G6. Visit the CGSB website, www.pwgsc.gc.ca/cgsb/
4
Standards volume information, refer to the standard’s Document Summary page on Available from Gas Processors Association (GPA), 6526 E. 60th St., Tulsa, OK
the ASTM website. 74145, http://www.gasprocessors.com.

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4. Summary of Test Method 6.2.1 Other detectors may be used (alone or in series)
4.1 An LPG sample is analyzed via either liquid or gas provided that they have sufficient response, linearity, and
sampling valves by gas chromatography and compared to sensitivity to measure the components of interest at the
corresponding components separated under identical operating concentration levels required.
conditions from a reference standard mixture of known com- 6.3 Data Acquisition—Any commercial integrator or com-
position or from use of pure hydrocarbons. The chromatogram puterized data acquisition system may be used for display of
of the sample is interpreted by comparing peak retention times the chromatographic detector signal and peak area integration.
and areas with those obtained for the reference standard The device should be capable of calibration and reporting of

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mixture or pure hydrocarbons. the final response corrected results.
6.4 Sample Introduction—Whether liquid or vapor sam-
5. Significance and Use pling, the combination of valve injection size and split ratio
5.1 The hydrocarbon component distribution of liquefied must be selected such that the required sensitivity is achieved
petroleum gases and propene mixtures is often required for and also that no component concentration in a sample is greater
end-use sale of this material. Applications such as chemical than the detector upper linearity limit.
feed stocks or fuel require precise compositional data to ensure 6.4.1 If capillary columns will be used, then the GC must
uniform quality. Trace amounts of some hydrocarbon impuri- include a heated splitting type injector that is operated isother-
ties in these materials can have adverse effects on their use and mally. Split ratios in the range of 5:1 to 200:1, with a typical
processing. value of 100:1, will be used dependent upon the sample
5.2 The component distribution data of liquefied petroleum injection volume and sensitivity required. If packed columns
gases and propene mixtures can be used to calculate physical will be used, then a splitting type injector is not required and a
properties such as relative density, vapor pressure, and motor suitable packed inlet port may be used.
octane (see Practice D 2598). Precision and accuracy of 6.4.2 Liquid Sampling (recommended)—The GC should be
compositional data are extremely important when these data equipped with a liquid sampling valve for introduction of the
are used to calculate various properties of these petroleum sample aliquot to the splitting injector. Liquid sampling valves
products. with an internal fixed sample volume between 0.2 to 0.5 µL or
a size to provide the minimum detection limits given in 1.1
6. Apparatus have been used satisfactorily. The valve shall be rated for at
6.1 Gas Chromatograph (GC)—Any gas chromatographic least 1380 kPa (200 psi) above the vapor pressure of the sample
instrument provided with a linear temperature programmable at the valve operating temperature. A shut-off valve shall be
column oven. The temperature control must be capable of provided at the exit of the sampling valve waste port. A 2 to 7
obtaining a retention time repeatability of 0.05 min (3 s) µm packed-screen type filter should be provided at the sample
throughout the scope of this analysis. inlet port of the sampling valve to remove possible particulate
6.2 Detector—A flame ionization detector (FID) having a material from the sample. The valve shall provide for a
sensitivity of 0.5 ppm (mole) or less for the compounds listed repeatability of at least 2% relative sample volume introduc-
in Table 1 is strongly recommended (see Practice E 594). tion. The sampling valve shall be located at the GC such that

TABLE 1 Expected Retention Order and Times

Estimated Retention Time (min) Estimated Retention Time (min)
Component (using typical Al2O3 (using typical 100 m Dimethylpolysiloxane FID TCD
PLOT operating conditions) column operating conditions)
C5 Olefin/C6+ Composite (backflush) NAA ... x x
Air Composite (O2, Ar, N2, Co) NAA ... ... x
Methane 1.9 6.5 x x
Ethane 2.1 6.7 x x
Propane 2.7 7.3 x x
Cyclopropane 3.4 ... x x
Propene 3.5 7.2 x x
2-Methyl Propane (Isobutane) 4.0 8.4 x x
Butane 4.2 9.5 x x
Propadiene 4.7 ... x x
Ethyne (Acetylene) 5.0 ... x x
Trans-2-Butene 5.5 9.9 x x
1-Butene 5.6 9.2 x x
2-Methyl Propene (Isobutene) 5.7 9.1 x x
2,2-Dimethylpropane (Neopentane) 5.9 10.1 x x
Cis-2-Butene 6.2 10.6 x x
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Cyclopentane 6.7 25.8 x x

2-Methyl Butane (Isopentane) 6.8 14.0 x x
Pentane 7.2 16.9 x x
1,3-Butadiene 7.5 9.3 x x
Propyne (Methyl Acetylene) 7.9 ... x x
>nC5(Sum C5 Olefins and Heavier)B 8.1 until end of run ... x x
A
Not applicable.
B
>nC5 components may be speciated and reported individually.

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 D 2163 – 07
it can be operated at ambient temperature. The use of floating separation between the components of interest and the com-
piston sample cylinders is encouraged to minimize or eliminate posite heavier components may be used. Choices may include
the volatilization of lighter components into the headspace. lengths of column such as a 10 to 30 m section of 0.53 mm
Common 80% filled LPG storage cylinders should be pressur- (I.D.) 1 µm film thickness dimethylpolysiloxane or polyethyl-
ized with an inert gas such as helium to facilitate liquid transfer ene glycol capillary column or a 9 to 15 cm section of the same
and accurate liquid injections. A minimum pressure of 200 psi column material as the analytical column or any pre-column
above sample vapor pressure is recommended. A pressure that provides the desired retention of C5 olefins, hexanes, and
gauge may be used to make this determination. Before pres- heavier components. This pre-column acts to keep the heavier
surization, verify that the sample cylinder, transfer lines and components away from the analytical column and to back flush
valves are rated to safely contain the pressurized sample. It is the heavier components as a composite peak to the detector for
customary to add a check valve between the helium cylinder quantitation. A pre-column that also has the ability to retain
and the sample cylinder to prevent contamination in the event water and oxygenated hydrocarbon compounds is recom-
the sample cylinder is higher in pressure than the pressurizing mended to keep those materials from entering the analytical
cylinder. column.
6.4.3 Vapor Sampling (optional)—A six-port gas sampling
valve or a ten-port sampling/column switching valve with 7. Reagents and Materials
1.6 mm (1⁄16 in.) fittings and a 200 µL fixed sampling loop may 7.1 Carrier Gases—For carrier gases, it is recommended to
be provided. This valve shall be contained in a heated install commercial active oxygen scrubbers and water dryers,
enclosure and operated at a temperature above the boiling point such as molecular sieves, ahead of the instrument to protect the
of the highest boiling component in the sample. The use of a 2 system’s chromatographic columns. Follow supplier instruc-
to 7 µm frit or packed-screen type filter ahead of the sample tions in the use of such gas purifiers and replace as necessary.
introduction port is recommended. The valve shall provide for 7.1.1 Hydrogen, 99.995% minimum purity, <0.1 ppm H2O.
a repeatability of at least 2% relative sample volume introduc- (Warning—Hydrogen is a flammable gas under high pres-
tion. sure.)
6.5 Gas Controls—The GC shall be provided with suitable 7.1.2 Helium, 99.995 % minimum purity, <0.1 ppm H2O.
facilities for delivery and control of carrier gas and the detector (Warning—These materials are flammable and may be harm-
gases. This will consist of the appropriate tank and down- ful or fatal if ingested or inhaled.)
stream regulators and supply tubing as well as the mass or 7.2 Detector Gases:
pressure controls for the precise regulation of the instrument 7.2.1 Hydrogen, 99.99 % minimum purity. (Warning—
operation. Hydrogen is a flammable gas under high pressure.)
NOTE 1—Most GC suppliers will provide these devices or recommend
7.2.2 Air, less than 10 ppm each of total hydrocarbons and
the proper supplies. water. (Warning—These materials are flammable and may be
harmful or fatal if ingested or inhaled.
6.6 Column Series/Reversal Switching Valve—If desired, a 7.3 Reference Standards:
multi-port valve mentioned may be used to provide the C5 7.3.1 Purity of Reagents—Reagent grade chemicals shall be
olefin/C6+ determination for this analysis. The back-flush used in all tests. Unless otherwise indicated, all reagents should
configuration should be configured according to the manufac- conform to the specifications of the Committee on Analytical
turer’s recommendations. Reagents of the American Chemical Society where such
6.7 Columns—Condition all columns used according to the specifications are available.5 Other grades may be used, pro-
manufacturers’ suggestions prior to use. vided it is first ascertained that the reagent is of sufficiently
6.7.1 Analytical Column—The recommended analytical high purity to permit its use without lessening the accuracy of
column is a 50 m by 0.53 mm (I.D) Na2SO4 deactivated Al2O3 the determination.
porous layer open tubular (PLOT) column. Relative retention 7.3.2 Reference Gas Mixture—Individual and mixed com-
order is dependent upon the deactivation method for the ponent reference materials are commercially available and may
column. (Warning—Specifically test the column to ensure that be used to establish qualitative and quantitative calibration.
the column does not adsorb propadiene and butadienes. This The calibration standard mixture should be gravimetrically
condition can exist depending upon the degree of column prepared, supplied with both gravimetric and calculated volu-
deactivation.) metric concentrations, and certified. Due to the high partial
6.7.1.1 Routine re-conditioning of the column may be pressure exerted by methane and ethylene, it is recommended
required to maintain column performance. that these components be limited to no greater than 0.2 vol% of
6.7.1.2 Alternatively, any column(s) that provides the ap- the mixture composition. It is strongly recommended that the
propriate component separations may be used. Columns (100 calibration standards be contained in floating piston cylinders
m by 0.25 mm (ID) by 0.5 µm film thickness) employed in
standard methods Test Method D 6729 and CGSB 3.0 No. 14.3
have been successfully used. 5
Reagent Chemicals, American Chemical Society Specifications, American
6.7.2 Pre-column (optional)—If an initial back flush of the Chemical Society, Washington, DC. For suggestions on the testing of reagents not
listed by the American Chemical Society, see Analar Standards for Laboratory
C5 olefins or hexane plus (C6+) components, or both, through Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
the use of the sequence reversal/back flush valve is desired, a and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
second column is required. Any pre-column that provides MD.

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 D 2163 – 07
pressurized to at least 1380 kPa (200 psi) above the vapor 2%. Use the same sample size (split ratio) and range for all
pressure of the mixture at all times (a constant pressure source runs. Example chromatograms are provided in Figs. 1 and 2.
is suggested). Common LPG storage cylinders may also be 8.5 Liquid Sampling Valve (recommended)—Set valve on
used provided they can be maintained at the required pressure. and off times to comply with manufacturer’s instructions.
Liquid mixtures containing levels of each of the analytes listed 8.6 Gas Sampling Valve (optional)—Set valve on and off
in Table 1 in a balance of the type of LPG that is being times to comply with manufacturer’s instructions.
analyzed should be used to calibrate the instrumentation. 8.7 Switching (Backflush) Valve (optional)—The valve rests
(Warning—These materials are flammable and may be harm- in the “off” state, allowing a continuous back flush flow
ful or fatal if ingested or inhaled.) through the pre-column. Before or upon injection of the
7.3.3 Calibration Gas Mixture—A mixture of known com- sample, the valve should be rotated to the “on” position so that
position similar in concentration to the samples being analyzed the pre-column is placed at the head of the flow path from the
may be used to monitor precision and accuracy. For liquid sample valve. At a time which must be empirically determined
sampling, it is strongly recommended that the mixture be and which is dependant upon the length and type of pre-column
contained in floating piston or other cylinders pressurized to at used, the valve must be returned to the “off” position, causing
least 1380 kPa (200 psi) above the vapor pressure of the the flow to back flush through the pre-column and flush to the
mixture at all times (a constant pressure source is suggested). detector ahead of components eluting from the analytical
column. Determining this switch time may require iterative
8. Preparation of Apparatus attempts and interpolation. However, once the time has been
8.1 Set up the instrumentation in accordance with the determined, it should remain repeatable for all samples of
manufacturer’s instructions or as specified herein. similar composition.
8.2 Install and condition the column according to manufac-
turer’s instructions. See Practice E 1510 for recommended 9. Calibration and Standardization
installation and conditioning procedures. 9.1 Qualitative—Determine the retention times of compo-
8.3 Set the GC instrument to the operating parameters. nents by analyzing known reference mixtures in the same
Allow the instrument to stabilize before proceeding with manner as the samples (Section 10). Typical retention times are
calibration and sample injections. Typical operating conditions given in Table 1.
for both PLOT and 100% dimethylpolysiloxane columns are 9.2 Quantitative, Hydrocarbons—Use response factors for
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provided in Table 2. The conditions provided for the dimeth- correction of the detector response of hydrocarbons determined
ylpolysiloxane column are equivalent to those described in Test by this test method. Experimental or theoretical response
Method D 6729. factors may be used.
8.4 Obtain duplicate chromatograms of the standard or 9.2.1 Experimental Response Factors—Determine the ex-
sample, or both. Ensure that none of the peaks obtained have perimental response factor of components by analyzing known
exceeded the upper range limit of the data handling device (at calibration mixtures under the same conditions of pressure and
full scale on the data handling device, all peaks are on scale temperature as the samples (Section 10). For each component
and display symmetrical, Gaussian shapes as opposed to flat present in the calibration standard, calculate the response factor
peak tops). Peak areas of like components shall agree within according to Eq 1. (Note that some integrators or computer

TABLE 2 Typical Operating Conditions

Column Type 100% Dimethylpolysiloxane Al2O3 PLOT - Na2SO4 deactivated
Column Dimensions 100 m by 0.25 mm by 0.5 µm 50 m by 0.53 mm by 15 µm
Backflush No No
Initial Temperature 0°C 80°C
Initial Hold Time 15 min 1 min
Program Rate 1 1°C/min 10°C/min
Final Temperature 50°C 200°C
Program Rate 2 2°C/min ...
Final Temperature 130°C ...
Program Rate 3 4°C/min ...
Final Temperature 270°C ...
Final Hold Time 0 min 12 min
Injector Temperature 250°C 250°C
Sample Size 0.2 to 0.5 µL 0.2 µL
Split Ratio 175:1 to 275:1 100:1
Detector Temperature 300 to 350°C 250°C
Fuel Gas Hydrogen Flow 30 to 40 mL/min 40 mL/min
Oxidizing Gas Air Flow 300 to 450 mL/min 400 mL/min
Make-up Gas Type N2 or He He
Make-up Gas Flow 30 mL/min 35 mL/min
Carrier Gas He @ 2 mL/min (H2 optional) Helium at 6 mL/min
Average Linear Velocity 25 cm/s 45 cm/s
Data Rate 10 to 20 Hz 5 Hz
Approximate Run Time 140 min 25 min

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FIG. 1 Example Chromatogram Using the PLOT Column (without back-flush)

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FIG. 2 Example Chromatogram Using the Dimethylpolysiloxane Column

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 D 2163 – 07
data systems may use another formula (inverse of the formula 10. Procedure
given, in some cases) for calculating response factors.) After
10.1 Sampling—Sampling at the sample source and at the
determining the response factors for each component, analyze
chromatograph shall always be done in a manner that ensures
a secondary standard as a sample and verify that the concen-
that a representative sample is being analyzed. Lack of
trations agree with the values for the standard within the
precision and bias for this test method as determined by precision and accuracy in using this test method can most often
interlaboratory testing. be attributed to improper sampling procedures. (See Practice
D 3700 and Practice D 1265.)
RFi 5 Ci /Ai (1)
10.2 Liquid Sample Valve Injection—For propene concen-
where: trates, butane samples, or other LPG samples, the sample may
RFi = the response factor for component i, be introduced as a liquid by means of a liquid sample valve. It
Ci = the known concentration of i, and is strongly suggested that the use of a floating piston type
Ai = the integrated area of peak i. sample cylinder be used and that the sample be pressurized to
9.2.2 Theoretical Response Factors—If the samples to be 1380 kPa (200 psi) above the vapor pressure of the sample
assayed contain only hydrocarbons and a FID is employed for prior to sampling.
the determination of those components, then theoretical re-
sponse factors may be applied. The results shall then be 10.2.1 In a hood, prior to connecting the cylinder, invert the

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normalized to 100%. cylinder and purge a small aliquot of the sample through the
9.2.2.1 Table 3 provides theoretical mass response factors valve on the sample cylinder to remove any moisture or
relative to methane (RRF). Use of these response factors will particulate matter which might be present.
produce results in mass percent units, which may be converted 10.2.2 Connect the pressurized liquid standard to the
to other units (liquid volume percent or mole percent) by the “sample in” port of the liquid sampling valve and close the
user as needed. Alternately, the theoretical response factors waste vent shut-off valve. Open the outlet valve on the standard
may be converted to other units prior to quantification. Indi- cylinder and open the waste shut-off valve for 10 to 15 s to
vidually eluting C5 olefins or hexane-plus components, or both, allow sample to flow through the sampling valve. Flushing the
may be quantified using the same RRF as the C5=/C6+ valve several times prior to injection provides some local
composite peak. cooling, and it provides for more repeatable liquid injections.
9.2.2.2 It is necessary to compare calculated results to the When liquid is flowing through the valve, quickly close the
certified values for a known standard before adopting the waste shut-off valve, then rotate the liquid sampling valve to
calibration. The standard should contain all of the components inject the sample.
typically observed in the samples. Results should agree within
5% of the certified value. Failure to compare may result from 10.2.3 If the back flush option is being used, switch the back
lack of injection split linearity or use of a standard that has not flush valve at the pre-determined time to elute the C5=/C6+
been maintained under pressure. composite to the detector.
9.3 Quality Monitoring—The primary or secondary stan- 10.3 Gas Sample Valve Injection (optional)—Vaporize the
dard should be analyzed at least once a week to verify system liquid sample according to the procedure given in 10.3.1
accuracy, when the test method is in regular use. If the test through 10.3.5, or using an on-line heated vaporizing device
method is used only occasionally, analyze a primary or that is heat-traced to the gas sampling valve, as described in
secondary standard before each set of analyses. 10.3.6. Flush a gas sample loop with 5 to 10 mL of sample,

TABLE 3 Theoretical Mass Relative Response FactorsA

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Component RRFi Component RRFi
Methane 1.0 1-butene 0.874
Ethane 0.937 2-methylpropene (isobutene) 0.874
Ethene (Ethylene) 0.874 cis-2-butene 0.874
Propane 0.916 2,2-dimethyl propane (neopentane) 0.895
Propene (Propylene) 0.874 2-methyl butane (isopentane) 0.899
Cyclopropane 0.874 propyne (methyl acetylene) 0.834
2-Methylpropane (Isobutane) 0.906 cyclopentane 0.849
Ethyne (Acetylene) 0.813 n-pentane 0.899
Propadiene 0.834 1,3-butadiene 0.843
Butane 0.906 C5=/C6+ composite (backflush only) 0.885
Trans-2-Butene 0.874 >nC5(C5= and heavier) 0.885
A
RF values obtained from Test Method D 6729.
All response factors are relative to that of methane according to the following equation:
RRFi 5 ~MWi / NCi! 3 ~1 / MWmethane!

where:
RRFi = relative response factor of each component with respect to methane,
MWi = the molecular weight of the component,
NCi = the number of carbon atoms in the component molecule, and
MWmethane = the molecular weight of methane.

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close cylinder valve, and allow the sample pressure to equili- The device should consist of a volume of tubing of approxi-
brate to atmospheric pressure (stopped flow) before introduc- mately 10 mL that is encased in a heated block (the block
ing the sample into the carrier gas stream. should be a high-mass block heated to approximately 60ºC).
10.3.1 In a hood, prior to connecting the cylinder, invert the The outlet of the tubing should be heat-traced and connected to
cylinder and purge a small aliquot of the sample through the the gas sampling valve. Connect the liquid sample cylinder to
valve on the sample cylinder to remove any moisture or the inlet of the heated tubing. Using the sample cylinder outlet
particulate matter which might be present. valve, pulse several small aliquots of the liquid sample through
10.3.2 Attach a secondary sampling vessel, consisting of the tubing successively. Allow the sample loop of the gas
two ball valves joined together and having an internal volume sampling valve to equilibrate to ambient pressure, and then
of approximately one mL to the liquid outlet on the sample rotate the gas sampling valve to inject the vaporized sample.
vessel.
10.3.3 Evacuate the secondary vessel to approximately 11. Calculation
0.13 kPa (1 mm Hg), including the connection to the liquid 11.1 External Standard Calibration Calculation
outlet of the sample vessel. Close all valves. (recommended)—Calculate the concentration of each compo-

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10.3.4 Slowly open the sample outlet valve of the sample nent according to Eq 2. Determine the total amount of
cylinder to fill the connection with liquid. Open the inlet ball hydrocarbons by summing the component concentrations. If
valve of the secondary vessel and fill the vessel with liquid. the sample is known to contain only hydrocarbons, then the
Holding the liquid sample vessel vertically with the secondary results shall be normalized to 100.00%. Occasionally, normal-
vessel on the bottom, open the outlet ball valve and allow a ized results will not equal precisely 100.00% due to rounding.
portion of the liquid to purge through the secondary vessel. In this case, small differences are typically added to the largest
Shut the outlet ball valve, followed by the inlet ball valve and component. As stated in 1.2, this test method does not fully
the sample cylinder outlet valve, in that order. Disconnect the determine non-hydrocarbon materials and normalization could
secondary vessel. cause skewed data.
10.3.5 Connect the secondary vessel to a container with an SCi 5 RFi 3 SAi (2)
approximate volume of 100 mL which is fitted with needle
valves or shut-off valves. Open the container valves and where:
evacuate the container and connecting pipe work. Close the SCi = concentration of component i in the sample,
container outlet valve and slowly open the secondary vessel RFi = response factor for component i, and
outlet valve to allow the liquid sample to vaporize into the SAi = integrated area for peak i.
evacuated vessel. Close all valves. The 100 mL container will 11.2 Theoretical Relative Response Calibration
contain a vapor that is representative of the liquid sample and Calculation—If a FID is being employed for the determination
have a gauge pressure of 69 to 138 kPa (10 to 20 psi). This gas of those components, then theoretical response factors, as listed
may be used to purge the sample loop of the gas sampling in Table 3, may be applied in place of RFi. The results shall
valve as described in 11.1. then be normalized to 100%. Use of these response factors will
10.3.6 Alternatively, an on-line heated vaporizing device, produce results in mass percent units, which may be converted
which is heat-traced to the gas sampling valve, may be used. to other units (liquid volume percent or mole percent) by the
user as needed. Alternately, the theoretical response factors
TABLE 4 Repeatability Standard Deviation may be converted to other units prior to quantitation. Quanti-
Component Repeatability Standard Deviation tation using theoretical response factors does not account for
Vol % the presence of non-hydrocarbon components. Example unit
Methane 0.0014 conversion calculations are found in Practice D 2421. If
Ethane 0.0009 non-hydrocarbon components are present, the results using this
Ethylene 0.0018
Propane 0.0731
calculation method will not be representative or valid.
Propylene 0.0854
Isobutane 0.0043 12. Report
n-butane 0.0071
Propadiene 0.0004
12.1 Report the concentration of each component as liquid
Acetylene 0.0004 volume percent (vol%) to the nearest 0.01%.
t2-butene 0.0036 12.2 Individually eluted C5 olefins and hexanes-plus com-
1-butene 0.0057
Isobutylene 0.0025
ponents may be speciated and reported separately or summed
c2-butene 0.0195 together into groups.
Cyclopentane 0.0132
Isopentane 0.0023 13. Precision and Bias
n-pentane 0.0048
1,3 butadiene 0.0006 13.1 The precision of this test method (Table 4) was
Methyl acetylene 0.0001 determined by statistical examination of limited interlaboratory
3m 1-butene 0.0014
t2-pentene 0.0018 results. The precision data are provisional, and further data are
2m 2-butene 0.0008 to be developed in a interlaboratory cooperative test program
1-pentene 0.0013 before the five-year reapproval required by the society.
2m 1-butene 0.0010
c2-pentene 0.0007 13.2 No information can be presented on the bias of this test
method at present, since no reference material is available.

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14. Keywords
14.1 floating piston cylinder; gas chromatography; gas sam-
pling valve; liquid sampling valve; liquefied petroleum gases;
LP gases; propane; propene

APPENDIX

(Nonmandatory Information)

X1. THEORETICAL RESPONSE FACTORS

X1.1 Conversion of From Mass to Volume Basis—Example to meet this criterion is typically attributed to a standard that no
conversion of theoretical mass response factors to volume longer has sufficient pressure to keep the lighter components in
response factors are provided in Table X1.1. Since methane is the liquid phase. If this is the case, calibrating with the standard
difficult to maintain reliably in an LPG standard, these re- would result in inaccurate sample analyses. If the standard is
sponse factors are presented relative to n-butane. confirmed to be good, the results may differ due to hardware
problems. In this case, the hardware problems should be
X1.2 Comparison of Experimental and Theoretical Re-
corrected before continuing with the calibration.
sponse Factors—Whether employing experimental or theoreti-
cal response factors for quantitation, an initial evaluation of X1.2.1 If LPG standards are reported in liquid volume
experimental response factors is recommended. The experi- percent, the following conversion may be helpful to determine
mental values should compare to theoretical within 5%. Failure the theoretical relative mass response factors. See Table X1.2.

TABLE X1.1 Conversion of Theoretical Mass RRF to Theoretical Volume RRF Relative to n-Butane
Component Theoretical Mass RRFi Relative Density 15.6/15.6°C (60/60°F)A Theoretical Vol. RRF Theoretical Vol. RRFi
(Mass RRF/Density) (relative to butane)
Methane 1.000 0.3000 3.3333 2.149
Ethane 0.937 0.3564 2.6291 1.695
Ethene (Ethylene) 0.874 0.3700B 2.3622 1.523
Propane 0.916 0.5074 1.8053 1.164
Propene (Propylene) 0.874 0.5226 1.6724 1.078
2-Methyl Propane (Isobutane) 0.906 0.5629 1.6095 1.038
Ethyne (Acetylene) 0.811 0.4180 1.9402 1.251
Propadiene 0.831 0.6000 1.3850 0.893
n-Butane 0.906 0.5841 1.5511 1.000
Trans-2-Butene 0.874 0.6112 1.4300 0.922
1-Butene 0.874 0.6004 1.4557 0.938
2-Methyl Propene (Isobutene) 0.874 0.6015 1.4530 0.937
Cis-2-Butene 0.874 0.6286 1.3904 0.896
2,2-Dimethyl Propane (Neopentane) 0.899 0.5967 1.5066 0.971
2-Methyl Butane (Isopentane) 0.899 0.6246 1.4393 0.928
Propyne (Methyl Acetylene) 0.843 0.6210 1.3575 0.875
n-Pentane 0.899 0.6311 1.4245 0.918
1,3-Butadiene 0.843 0.6272 1.3441 0.867
C5=/C6+ Composite 0.885 0.6641C 1.3326 0.859
A
See DS4B, Physical Constants of Hydrocarbon and Non-Hydrocarbon Compounds, ASTM International, 1991.
B
See Practice D 2421–95.
C
See GPA Std 2145-03 for hexane. Note that the value has been rounded to four decimals from the five decimal value in the GPA standard.

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TABLE X1.2 Theoretical Mass Response Factor Evaluation for Liquefied Petroleum Gas
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