Designation: D6159 − 97 (Reapproved 2012)

Standard Test Method for

Determination of Hydrocarbon Impurities in Ethylene by Gas
Chromatography1
This standard is issued under the fixed designation D6159; 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 3. Summary of Test Method

1.1 This test method covers the determination of methane, 3.1 A gaseous ethylene sample is analyzed as received. The
ethane, propane, propene, acetylene, iso-butane, propadiene, gaseous sample is injected into a capillary gas chromatograph.
butane, trans-2-butene, butene-1, isobutene, cis-2-butene, A split-injector may or may not be used. The gas chromato-
methyl acetylene and 1,3-butadiene in high-purity ethylene. graph is provided with a 6–port sampling valve and two wide
The purity of the ethylene can be calculated by subtracting the bore capillary columns connected in series. These columns are
total percentage of all impurities from 100.00 %. Since this test a dimethyl silicone column and a (porous layer open tubular
method does not determine all possible impurities such as CO, column (PLOT) Al2O3/KCl column.3 A flame ionization detec-
CO2, H2O, alcohols, nitrogen oxides, and carbonyl sulfide, as tor is used for detection. The integrated detector signal (peak
well as hydrocarbons higher than decane, additional tests may areas) are corrected for detector response. The hydrocarbon
be necessary to fully characterize the ethylene sample. impurities are determined and the total impurities are used to
1.2 Data are reported in this test method as ppmV (parts per determine the ethylene content.
million by volume). This test method was evaluated in an 4. Significance and Use
interlaboratory cooperative study in the concentration range of
4 to 340 ppmV (2 to 204 mg/kg). The participants in the 4.1 High-purity ethylene is required as a feedstock for some
interlaboratory cooperative study reported the data in non-SI manufacturing processes and the presence of trace amounts of
units. Wherever possible, SI units are included. certain hydrocarbon impurities can have deleterious effects.
This test method is suitable for setting specifications, for use as
1.3 This standard dose not purport to address all of the an internal quality control tool, and for use in development or
safety concerns, if any, associated with its use. It is the research work.
responsibility of the user of this standard to establish appro-
priate safety and health practices and determine the applica- 4.2 This test method does not detect such impurities as H2O,
bility of regulatory limitations prior to use. CO, CO2, and alcohols that may be present in the sample.
Hydrocarbons higher than n-decane cannot be analyzed by this
2. Referenced Documents test method, if present in the sample. Test Method D2504
addresses the analysis of noncondensable gases and Test
2.1 ASTM Standards:2 Method D2505 addresses the analysis of CO2. Guide D5234
D2504 Test Method for Noncondensable Gases in C2 and describes all potential impurities present in ethylene. These
Lighter Hydrocarbon Products by Gas Chromatography standards should be consulted when determining the total
D2505 Test Method for Ethylene, Other Hydrocarbons, and concentration of impurities in ethylene.
Carbon Dioxide in High-Purity Ethylene by Gas Chroma-
tography 5. Apparatus
D5234 Guide for Analysis of Ethylene Product
5.1 Gas Chromatograph (GC), a gas chromatographic in-
strument provided with a temperature programmable column
oven and a flame ionization detector (FID). Regulate the carrier
1
This test method is under the jurisdiction of ASTM Committee D02 on gas by pressure control.
Petroleum Products and Lubricants and is the direct responsibility of Subcommittee
D02.D0.02 on Ethylene. 5.2 Detector—Use a flame ionization detector (FID) having
Current edition approved Dec. 1, 2012. Published December 2012. Originally a sensitivity of approximately 2.0 ppmV (1.2 mg/kg) or less for
approved in 1997. Last previous edition approved in 2007 as D6159–97(2007). the compounds listed in 1.1. An FID was exclusively used in
DOI: 10.1520/D6159-97R12.
2
For referenced ASTM standards, visit the ASTM website, [Link], or the interlaboratory cooperative study.
contact ASTM Customer Service at service@[Link]. For Annual Book of ASTM
Standards volume information, refer to the standard’s Document Summary page on
3
the ASTM website. This column is supplied by major column manufacturers.

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

Copyright by ASTM Int'l (all rights reserved); 1

 D6159 − 97 (2012)

FIG. 1 Valve Off – Sample Loading FIG. 2 Valve On – Injection

5.3 Column Temperature Programmer—The chromatograph

shall be capable of linear programmed temperature operation
over a range sufficient for separation of the components of
interest. Section 8 lists the recommended operating conditions.
The programming rate shall be sufficiently reproducible to
obtain retention repeatability of 0.05 min (3 s) throughout the
scope of this analysis.
5.4 Columns—Couple the two columns in series with either
a glass press tight connector or a mini-connector equipped with
graphite ferrules.
5.4.1 Column 1, 50 m, 0.53 mm inside diameter (ID) KCl
deactivated Al2O3 PLOT column.3 Relative retention is depen-
dent on the deactivation method of the column. Other deacti- FIG. 3 Valve Off – Sample Loading
vated Al2O3 plot columns using sulfates as the deactivating
agent were also used in the interlaboratory comparison.
5.4.2 Column 2, 30 m, 0.53 mm ID, 5µm film thickness
methyl silicone. This column improves the separation of
methyl acetylene, iso-pentane, and n-pentane.
5.5 Sample Inlet System—Two injection modes were used
for the interlaboratory cooperative study.
5.5.1 A gas sampling valve placed in an unheated zone of
the gas chromatograph injecting the sample directly into the
column.
5.5.2 A gas sampling valve placed in an unheated zone of
the gas chromatograph in conjunction with a splitter injector
heated with a variable temperature control.
5.6 Gas Sampling Valve and Injection System—Use a 6-port FIG. 4 Valve On – Injection
valve provided with 1⁄16 in. fittings as the sample injection
system. A typical valve arrangement is shown in Fig. 1 and Fig.
2. Use a 10–60µL loop as shown in Fig. 1. Use good valve 5.7 Data Acquisition System—Use any integrator or com-
maintenance techniques to avoid such problems as dead puterized data acquisition system for peak area integration, as
volumes, cold spots, long connections, and non-uniform heated well as for recording the chromatographic trace.
zones. The preferred carrier gas arrangement for sample
introduction is pressure regulation. Use a 6-port valve in 6. Reagent Materials
conjunction with a splitter injector. A typical arrangement is 6.1 Standard Mixture—Use a gravimetrically blended gas
shown in Fig. 3 and Fig. 4. Use split ratios of 50:1 to 100:1 at standard containing levels of 2 to 204 mg/kg (4 to 340 ppmV)
temperatures of 150°C to 200°C. Loop sizes of 200–500µL of each of the trace components listed in Table 1 to calibrate
were used in the interlaboratory study. When using a splitter it the detector’s response. The standard gas mixture shall be
is important to check linearity of the splitter. Inject the standard prepared gravimetrically from known raw materials, and cross
blend at 50:1, 75:1, and 100:1 split ratios. Check the response contaminants shall be taken into account. The mixtures should
factors as determined in 9.1, and the factors shall not vary more be certified analytically such that the gravimetric and analyti-
than 3 %. cally derived values agree to an acceptable tolerance; that is 6

Copyright by ASTM Int'l (all rights reserved); 2

 D6159 − 97 (2012)
TABLE 1 Typical Compounds and Retention Times for Common Final time: 15 min.
Hydrocarbon Impurities in EthyleneA Carrier Gas
Components Retention Time, min Helium at 6 to 8 mL/min
Methane 7.02
Ethane 8.12 Injection System with Splitter
Ethene 9.00 Sample valve loop volume = 200–500µl
Propane 12.41
Propene 16.93
Sample valve temperature = 35° to 45°C
Ethyne 19.52 Splitter temperature = 150° to 200°C
Isobutane 19.76 Split ratio = 50:1 to 100:1
Propadiene 20.48
Butane 20.78
Flame Ionization Detector, 300°C
t-2-Butene 24.99 Air = 300mL/min (see Note 6)
Butene-1 25.23
Isobutylene 25.90 NOTE 6—Follow the values suggested by instrument manufacturer.
c-2-Butene 26.71 H2 = 30mL/min
Propyne 29.14
1,3-Butadiene 30.37 Makeup = N2 at 20mL/min
A
Conditions as specified in Section 8.
Range = suitable to obtain measurable counts for the
impurities
Injection System using a Valve Directly
Sample valve loop volume = 10–60µl
1 or 6 2 %. The concentration of the minor components in the Sample valve temperature = 35 to 45°C
calibration standard shall be within 20 to 50 % above the
8.2 When the G.C. has achieved a ready status, proceed with
concentration of the process stream or samples.
analysis.
6.2 Compressed Helium, gas having purity of 99.999 %, or
better, with a total hydrocarbon level of < 1ppmV. 9. Calibration
NOTE 1—Compressed helium is a gas under high pressure. 9.1 Proceed to inject the standard mixture. Connect the
gaseous sample to the sample port and flush the sample loop
6.3 Compressed Hydrogen, gas used as fuel in the FID for a period of 30 s. Close the standard sample cylinder outlet
detector (less than 1.0 ppmV hydrocarbon impurities). and when the pressure drops to atmospheric pressure and no
NOTE 2—Hydrogen is an extremely flammable gas under high pressure. sample elutes, inject the standard sample and proceed with the
6.4 Compressed Air—Air having less than 1.0 ppmV of analysis. At least three standard determinations should be made
hydrocarbon impurities for the operation of the FID is recom- to obtain a relative standard deviation of the measurements.
mended. 9.2 Determination of Calibration Factors—For each impu-
NOTE 3—Compressed air is a gas under high pressure and supports
rity present in the standard, calculate the calibration factor as
combustion. follows:
6.5 Compressed Nitrogen—Nitrogen having less than 1.0 Cf 5 Ci/Ai (1)
ppmV of hydrocarbon impurities is used as make up gas in where:
order to increase the response of the FID.
Cf = the calibration factor,
NOTE 4—Compressed nitrogen is a gas under high pressure. Ci = the concentration of the impurity i in the standard
(usually expressed as ppmV), and
7. Sampling Ai = the area counts obtained for that impurity as integrated
7.1 Gas samples are collected in 1000 mL stainless steel by the data acquisition system.
cylinders equipped with a rupture disk capable of sustaining 9.2.1 It is important that the system linearity is checked by
5500 to 6900 kPa (800 to 1000 psi) in order to protect against injecting standard gas samples of varying impurity concentra-
dangerous pressure build up. It is important to thoroughly flush tion over a range covering the impurity concentration range in
the cylinder with the sample prior to sealing, thus excluding air the samples analyzed. Verify that the system responds linearly
and other contaminants that may be present in the cylinder. and that the response is of the type y = mx + b with b = 0. Use
a linear calibration forced through the origin.
8. Preparation of Apparatus
8.1 Instrument Conditions—Adjust the instrumental param- 10. Procedure
eters to the following conditions: 10.1 The sample shall be injected under the same tempera-
Column Temperature ture and pressure conditions as the standard mixture.
Equilibration time: 2.0 min
10.2 Connect the gas sample to the G.C. sample port. Flush
Initial: 35°C
the loop for a period of 30 s. Close the sample cylinder shut-off
Final: 190°C (see Note 5)
valve and inject the sample the moment the loop reaches
NOTE 5—PLOT Al2O3 columns should not be heated above 200°C atmospheric pressure. Integrate the areas of the impurities.
since above this temperature the column activity is changed. Identify the impurities by comparing their retention time to that
Rate: 4°C/min obtained with the standard mixture. A typical sample chro-
Initial time: 2.0 min matogram is shown in Fig. 5.

Copyright by ASTM Int'l (all rights reserved); 3

 D6159 − 97 (2012)

FIG. 5 Typical Chromatogram

11. Calculations 12.1.1 An interlaboratory cooperative study was adopted

11.1 Calculate the concentration of each impurity to the with 7 laboratories participating. Fourteen hydrocarbon impu-
nearest ppmV as follows: rities in ethylene were measured; the results obtained are
shown in Table 2.
Ci 5 ~ Cfi!~ Ai! (2)
12.1.2 Repeatability—The difference between successive
where results obtained by the same operator with the same apparatus
Ci = concentration of the impurity in the sample in ppmV, under constant operating conditions on identical test materials
Cfi = calibration factor previously calculated in Eq 1 (units would, in the long run, and in the normal and correct operation
are usually ppmV/counts), and of the test method exceed the values only one case in twenty as
Ai = integrated area of the impurity from the data acquisi- shown in Table 2, where r is the repeatability and X is the
tion system. concentration (ppmV) of the component.
11.2 Determine the total amount of hydrocarbon impurities 12.1.3 Reproducibility—The difference between two single
by summing the concentrations of the individual impurities. and independent results obtained by different operators work-
Calculate the concentration of the ethylene by subtracting the ing in different laboratories on identical material would, in the
total impurities concentration from 100.00 %. Since this test long run, exceed the values in only one case in twenty as
method cannot measure such impurities as CO, CO2, O2, N2, shown in Table 2, where R is the reproducibility and X is the
H2O and alcohols, it will be necessary to analyze the ethylene
mean concentration (ppmV) of the component.
for these impurities as described in Test Methods D2504 and
D2505. The sum total of all impurities analyzed should be used 12.2 Bias—There is, at this time, no accepted reference
in reporting the ethylene concentration. material suitable for measuring bias for this test method.
12. Precision and Bias4
13. Keywords
12.1 Precision:
13.1 ethylene; gas chromatography; hydrocarbon impurities
4
Supporting data have been filed at ASTM International Headquarters and may
be obtained by requesting Research Report RR:D02-1412.

Copyright by ASTM Int'l (all rights reserved); 4

 D6159 − 97 (2012)
TABLE 2 Repeatability and Reproducibility
Component Range, ppmV Repeatability, (r) Reproducibility (R)
Methane 5.57 - 62.3 0.02277 X ˆ 0.6 1.408 X ˆ 0.6
Ethane 35.1 - 338 0.03811 X 0.3165 X
Propane 8.07 - 59.7 0.03273 (X + 21.23) 0.2277 (X + 4.558)
Propene 4.67 - 49.2 0.04780 X ˆ 1.15 0.4849 X ˆ 1.15
Ethyne 4.14 - 34.4 0.1189 X 0.8 5.471 X 0.8
isobutane 7.74 - 48.4 0.04370 X ˆ 1.07 0.6728 X ˆ 1.07
Propadiene 4.53 - 67.6 0.05091 (X + 0.7831) 0.7256 (X + 0.7831)
Butane 4.97 - 56.1 0.1156 X ˆ 0.85 0.4399 X ˆ 0.85
t-2-Butene 7.20 - 55.9 0.063960 X ˆ 0.95 0.2196 X ˆ 0.95
Butene-1 6.18 - 56.9 0.03992 (X + 17.14) 0.1600 (X + 7.028)
isobutylene 4.13 - 55.6 0.1229 X ˆ 0.85 0.3174 X ˆ 0.85
C-2-Butene 8.16 - 56.6 0.08350 X ˆ 0.93 0.3017 X ˆ 0.93
Propyne 5.57 - 62.3 0.07518 ˆ 0.9 1.136 X ˆ 0.90
1,3 Butadiene 5.80 - 49.1 0.05205 X ˆ 1.1 0.4613 X ˆ 1.1

ASTM International takes no position respecting the validity of any patent rights asserted in connection with any item mentioned
in this standard. Users of this standard are expressly advised that determination of the validity of any such patent rights, and the risk
of infringement of such rights, are entirely their own responsibility.

This standard is subject to revision at any time by the responsible technical committee and must be reviewed every five years and
if not revised, either reapproved or withdrawn. Your comments are invited either for revision of this standard or for additional standards
and should be addressed to ASTM International Headquarters. Your comments will receive careful consideration at a meeting of the
responsible technical committee, which you may attend. If you feel that your comments have not received a fair hearing you should
make your views known to the ASTM Committee on Standards, at the address shown below.

This standard is copyrighted by ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959,
United States. Individual reprints (single or multiple copies) of this standard may be obtained by contacting ASTM at the above
address or at 610-832-9585 (phone), 610-832-9555 (fax), or service@[Link] (e-mail); or through the ASTM website
([Link]). Permission rights to photocopy the standard may also be secured from the ASTM website ([Link]/
COPYRIGHT/).

Copyright by ASTM Int'l (all rights reserved); 5