Standard Test Method for Hydrocarbon Types, Oxygenated Compounds, Benzene, and Toluene in Spark Ignition Engine Fuels by Multidimensional Gas Chromatography

SIGNIFICANCE AND USE
5.1 A knowledge of spark-ignition engine fuel composition is useful for regulatory compliance, process control, and quality assurance.  
5.2 The quantitative determination of olefins and other hydrocarbon types in spark-ignition engine fuels is required to comply with government regulations.  
5.3 This test method is not applicable to M85 fuels, which contain 85 % methanol.
SCOPE
1.1 This test method covers the quantitative determination of saturates, olefins, aromatics, and oxygenates in spark-ignition engine fuels by multidimensional gas chromatography. Each hydrocarbon type can be reported either by carbon number (see Note 1) or as a total.
Note 1: There can be an overlap between the C9 and C10 aromatics; however, the total is accurate. Isopropyl benzene is resolved from the C8 aromatics and is included with the other C9 aromatics.  
1.2 This test method is not intended to determine individual hydrocarbon components except benzene and toluene.  
1.3 This test method is divided into two parts, Part A and Part B.  
1.3.1 Part A is applicable to the concentration ranges for which precision (Table 10 and Table 11) has been obtained:    
Property  
Units  
Applicable range  
Total aromatics  
Volume %  
19.32 to 46.29  
Total saturates  
Volume %  
26.85 to 79.31  
Total olefins  
Volume %  
0.40 to 26.85  
Oxygenates  
Volume %  
0.61 to 9.85  
Oxygen Content  
Mass %  
2.01 to 12.32  
Benzene  
Volume %  
0.38 to 1.98  
Toluene  
Volume %  
5.85 to 31.65  
Methanol  
Volume %  
1.05 to 16.96  
Ethanol  
Volume %  
0.50 to 17.86  
MTBE  
Volume %  
0.99 to 15.70  
ETBE  
Volume %  
0.99 to 15.49  
TAME  
Volume %  
0.99 to 5.92  
TAEE  
Volume %  
0.98 to 15.59
1.3.1.1 This test method is specifically developed for the analysis of automotive motor gasoline that contains oxygenates, but it also applies to other hydrocarbon streams having similar boiling ranges, such as naphthas and reformates.  
1.3.2 Part B describes the procedure for the analysis of oxygenated groups (ethanol, methanol, ethers, C3 to C5 alcohols) in ethanol fuels containing an ethanol volume fraction between 50 % and 85 % (17 % to 29 % oxygen). The gasoline is diluted with an oxygenate-free component to lower the ethanol content to a value below 20 % before the analysis by GC. The diluting solvent should not be considered in the integration, this makes it possible to report the results of the undiluted sample after normalization to 100 %.  
1.4 Oxygenates as specified in Test Method D4815 have been verified not to interfere with hydrocarbons. Within the round robin sample set, the following oxygenates have been tested: MTBE, ethanol, ETBE, TAME, iso-propanol, isobutanol, tert-butanol and methanol. Applicability of this test method has also been verified for the determination of n-propanol, acetone, and di-isopropyl ether (DIPE). However, no precision data have been determined for these compounds.  
1.4.1 Other oxygenates can be determined and quantified using Test Method D4815 or D5599.  
1.5 The method is harmonized with ISO 22854.  
1.6 This test method includes a relative bias section for U.S. EPA spark-ignition engine fuel regulations for total olefins reporting based on Practice D6708 accuracy assessment between Test Method D6839 and Test Method D1319 as a possible Test Method D6839 alternative to Test Method D1319. The Practice D6708 derived correlation equation is only applicable for fuels in the total olefins concentration range from 0.2 % to 18.2 % by volume as measured by Test Method D6839. The applicable Test Method D1319 range for total olefins is from 0.6 % to 20.6 % by volume as reported by Test Method D1319.  
1.7 This test method includes a relative bias section for reporting benzene based on Practice D6708 accuracy assessment between Test Method D6839 and Test Method D3606 (Procedure B) as a possible Test Method D6839 alternativ...

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ASTM D6839-21a - Standard Test Method for Hydrocarbon Types, Oxygenated Compounds, Benzene, and Toluene in Spark Ignition Engine Fuels by Multidimensional Gas Chromatography
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This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the
Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
Designation: D6839 − 21a
Standard Test Method for
Hydrocarbon Types, Oxygenated Compounds, Benzene, and
Toluene in Spark Ignition Engine Fuels by Multidimensional
1
Gas Chromatography
This standard is issued under the fixed designation D6839; 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* is diluted with an oxygenate-free component to lower the
ethanol content to a value below 20 % before the analysis by
1.1 This test method covers the quantitative determination
GC. The diluting solvent should not be considered in the
of saturates, olefins, aromatics, and oxygenates in spark-
integration, this makes it possible to report the results of the
ignitionenginefuelsbymultidimensionalgaschromatography.
undiluted sample after normalization to 100 %.
Each hydrocarbon type can be reported either by carbon
number (see Note 1) or as a total.
1.4 Oxygenates as specified in Test Method D4815 have
NOTE 1—There can be an overlap between the C and C aromatics;
9 10
been verified not to interfere with hydrocarbons. Within the
however, the total is accurate. Isopropyl benzene is resolved from the C
8
round robin sample set, the following oxygenates have been
aromatics and is included with the other C aromatics.
9
tested: MTBE, ethanol, ETBE, TAME, iso-propanol,
1.2 This test method is not intended to determine individual
isobutanol, tert-butanol and methanol.Applicability of this test
hydrocarbon components except benzene and toluene.
method has also been verified for the determination of
1.3 This test method is divided into two parts, Part A and n-propanol, acetone, and di-isopropyl ether (DIPE). However,
no precision data have been determined for these compounds.
Part B.
1.3.1 Part A is applicable to the concentration ranges for
1.4.1 Other oxygenates can be determined and quantified
which precision (Table 10 and Table 11) has been obtained:
using Test Method D4815 or D5599.
Property Units Applicable range
1.5 The method is harmonized with ISO 22854.
Total aromatics Volume % 19.32 to 46.29
Total saturates Volume % 26.85 to 79.31
1.6 ThistestmethodincludesarelativebiassectionforU.S.
Total olefins Volume % 0.40 to 26.85
EPA spark-ignition engine fuel regulations for total olefins
Oxygenates Volume % 0.61 to 9.85
Oxygen Content Mass % 2.01 to 12.32
reporting based on Practice D6708 accuracy assessment be-
Benzene Volume % 0.38 to 1.98
tween Test Method D6839 and Test Method D1319 as a
Toluene Volume % 5.85 to 31.65
possible Test Method D6839 alternative to Test Method
Methanol Volume % 1.05 to 16.96
Ethanol Volume % 0.50 to 17.86
D1319. The Practice D6708 derived correlation equation is
MTBE Volume % 0.99 to 15.70
onlyapplicableforfuelsinthetotalolefinsconcentrationrange
ETBE Volume % 0.99 to 15.49
from 0.2 % to 18.2 % by volume as measured by Test Method
TAME Volume % 0.99 to 5.92
TAEE Volume % 0.98 to 15.59
D6839. The applicable Test Method D1319 range for total
olefins is from 0.6 % to 20.6 % by volume as reported by Test
1.3.1.1 This test method is specifically developed for the
Method D1319.
analysis of automotive motor gasoline that contains
oxygenates, but it also applies to other hydrocarbon streams
1.7 This test method includes a relative bias section for
havingsimilarboilingranges,suchasnaphthasandreformates.
reporting benzene based on Practice D6708 accuracy assess-
1.3.2 Part B describes the procedure for the analysis of
ment between Test Method D6839 and Test Method D3606
oxygenated groups (ethanol, methanol, ethers, C to C alco-
3 5
(Procedure B) as a possible Test Method D6839 alternative to
hols) in ethanol fuels containing an ethanol volume fraction
Test Method D3606 (Procedure B). The Practice D6708
between 50 % and 85 % (17 % to 29 % oxygen). The gasoline
derived correlation equation is only applicable for fuels in the
benzeneconcentrationrangefrom0.52 %to1.67 %byvolume
as measured by Test Method D6839.
1
This test method is under the jurisdiction of ASTM Committee D02 on
Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of
1.8 This test method includes a relative bias section for
Subcommittee D02.04.0L on Gas Chromatography Methods.
reporting benzene based on Practice D6708 accuracy assess-
CurrenteditionapprovedMay1,2021.PublishedJuly2021.Originallyapproved
ment between Test Method D6839 and Test Method D5580 as
in 2002. Last previous edition approved in 2021 as D6839 – 21. DOI: 10.1520/
D6839-21A. a possible Te
...

This document is not an ASTM standard and is intended only to provide the user of an ASTM standard an indication of what changes have been made to the previous version. Because
it may not be technically possible to adequately depict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current version
of the standard as published by ASTM is to be considered the official document.
Designation: D6839 − 21 D6839 − 21a
Standard Test Method for
Hydrocarbon Types, Oxygenated Compounds, Benzene, and
BenzeneToluene in Spark Ignition Engine Fuels by
1
Multidimensional Gas Chromatography
This standard is issued under the fixed designation D6839; 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*
1.1 This test method covers the quantitative determination of saturates, olefins, aromatics, and oxygenates in spark-ignition engine
fuels by multidimensional gas chromatography. Each hydrocarbon type can be reported either by carbon number (see Note 1) or
as a total.
NOTE 1—There can be an overlap between the C and C aromatics; however, the total is accurate. Isopropyl benzene is resolved from the C aromatics
9 10 8
and is included with the other C aromatics.
9
1.2 This test method is not intended to determine individual hydrocarbon components except benzene.benzene and toluene.
1.3 This test method is divided into two parts, Part A and Part B.
1.3.1 Part A is applicable to automotive motor gasolinethe concentration ranges for which precision (Table 9) (Table 10 and Table
11) has been obtained obtained:
Property Units Applicable range
Total aromatics Volume % 19.32 to 46.29
Total saturates Volume % 26.85 to 79.31
Total olefins Volume % 0.40 to 26.85
Oxygenates Volume % 0.61 to 9.85
Oxygen Content Mass % 2.01 to 12.32
Benzene Volume % 0.38 to 1.98
Toluene Volume % 5.85 to 31.65
Methanol Volume % 1.05 to 16.96
Ethanol Volume % 0.50 to 17.86
MTBE Volume % 0.99 to 15.70
ETBE Volume % 0.99 to 15.49
TAME Volume % 0.99 to 5.92
TAEE Volume % 0.98 to 15.59
for total volume fraction of aromatics of up to 50 %; a total volume fraction of olefins from about 1.5 % up to 30 %; a
volume fraction of oxygenates, from 0.8 % up to 15 %; a total mass fraction of oxygen from about 1.5 % to about 3.7 %; and
a volume fraction of benzene of up to 2 %. Although this test method can be used to determine higher-olefin contents of up to
50 % volume fraction, the precision for olefins was tested only in the range from about 1.5 % volume fraction to about 30 %
volume fraction. The method has also been tested for an ether content up to 22 % volume fraction but no precision data has
been determined.
1
This test method is under the jurisdiction of ASTM Committee D02 on Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of Subcommittee
D02.04.0L on Gas Chromatography Methods.
Current edition approved April 1, 2021May 1, 2021. Published July 2021. Originally approved in 2002. Last previous edition approved in 20182021 as
D6839 – 18.D6839 – 21. DOI: 10.1520/D6839-21.10.1520/D6839-21A.
*A Summary of Changes section appears at the end of this standard
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
1

---------------------- Page: 1 ----------------------
D6839 − 21a
1.3.1.1 This test method is specifically developed for the analysis of automotive motor gasoline that contains oxygenates, but it
also applies to other hydrocarbon streams having similar boiling ranges, such as naphthas and reformates.
1.3.2 Part B describes the procedure for the analysis of oxygenated groups (ethanol, methanol, ethers, C to C alcohols) in ethanol
3 5
fuels containing an ethanol volume fraction between 50 % and 85 % (17 % to 29 % oxygen). The gasoline is diluted with an
oxygenate-free component to lower the ethanol content to a value below 20 % before the analysis by GC. The diluting solvent
should not be considered in the integration, this makes it possible to report the results of the undiluted sample after normalization
to 100 %.
1.4 Oxygenates as specified in Test Method D4815 have been verified not to interfere with hydrocarbons. Within the round robin
sample set, the following oxygenates have been tested: MTBE, ethanol, ETBE, TAME, iso-propanol, isobutanol, tert-butanol and
methanol. The derived precision data for methanol do not comply with the precision calculation as presented in this International
Standard. Applicability of this test method has also been verified for the determination of n-propanol, acetone, and di-isopropyl
ether (DIPE). However, no precision data have been determined for these compounds.
1.4.1 Other oxygenates can be determined and quantified using Te
...

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