ASTM D4815-22

Standard Test Method for Determination of MTBE, ETBE, TAME, DIPE, tertiary-Amyl Alcohol and C<inf>1</inf> to C<inf>4</inf> Alcohols in Gasoline by Gas Chromatography

SIGNIFICANCE AND USE
5.1 Ethers, alcohols, and other oxygenates can be added to gasoline to increase octane number and to reduce emissions. Type and concentration of various oxygenates are specified and regulated to ensure acceptable commercial gasoline quality. Drivability, vapor pressure, phase separation, exhaust, and evaporative emissions are some of the concerns associated with oxygenated fuels.  
5.2 This test method is applicable to both quality control in the production of gasoline and for the determination of deliberate or extraneous oxygenate additions or contamination.
SCOPE
1.1 This test method covers the determination of ethers and alcohols in gasolines by gas chromatography. Specific compounds determined are methyl tert-butylether (MTBE), ethyl tert-butylether (ETBE), tert-amylmethylether (TAME), diisopropylether (DIPE), methanol, ethanol, isopropanol, n-propanol, isobutanol, tert-butanol, sec-butanol, n-butanol, and tert-pentanol (tert-amylalcohol).  
1.2 Individual ethers are determined from 0.20 % to 20.0 % by mass. Individual alcohols are determined from 0.20 % to 12.0 % by mass. Equations used to convert to mass percent oxygen and to volume percent of individual compounds are provided. At concentrations 10 % by volume olefins, the interference may be >0.20 % by mass. Annex A1 gives a chromatogram showing the interference observed with a gasoline containing 10 % by volume olefins.  
1.3 This test method includes a relative bias correlation for ethanol in spark-ignition engine fuels for the U.S. EPA regulations reporting based on Practice D6708 accuracy assessment between Test Method D4815 and Test Method D5599 as a possible Test Method D4815 alternative to Test Method D5599. The Practice D6708 derived correlation equation is only applicable for ethanol in fuels in the concentration range from 2.28 % to 14.42 % by mass as measured by Test Method D4815. The applicable Test Method D5599 range for ethanol is from 2.16 % to 14.39 % by mass as reported by Test Method D5599.  
1.4 Alcohol-based fuels, such as M-85 and E-85, MTBE product, ethanol product, and denatured alcohol, are specifically excluded from this test method. The methanol content of M-85 fuel is considered beyond the operating range of the system.  
1.5 Benzene, while detected, cannot be quantified using this test method and shall be analyzed by alternate methodology (see Test Method D3606).  
1.6 The values stated in SI units are to be regarded as standard. Alternate units, in common usage, are also provided to increase clarity and aid the users of this test method.  
1.7 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety, health, and environmental practices and determine the applicability of regulatory limitations prior to use.  
1.8 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.

General Information

• Status: Published
• Publication Date: 31-Mar-2022
• ICS: 75.160.20 - Liquid fuels
• Technical Committee: D02 - Petroleum Products, Liquid Fuels, and Lubricants
• Drafting Committee: D02.04.0L - Gas Chromatography Methods

Standards Content (Sample)

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: D4815 − 22
Standard Test Method for
Determination of MTBE, ETBE, TAME, DIPE, tertiary-Amyl
Alcohol and C to C Alcohols in Gasoline by Gas
1 4
1
Chromatography
This standard is issued under the fixed designation D4815; 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.
This standard has been approved for use by agencies of the U.S. Department of Defense.
1. Scope* cally excluded from this test method. The methanol content of
M-85 fuel is considered beyond the operating range of the
1.1 This test method covers the determination of ethers and
system.
alcohols in gasolines by gas chromatography. Specific com-
pounds determined are methyl tert-butylether (MTBE), ethyl 1.5 Benzene, while detected, cannot be quantified using this
tert-butylether (ETBE), tert-amylmethylether (TAME), diiso- test method and shall be analyzed by alternate methodology
propylether (DIPE), methanol, ethanol, isopropanol, (see Test Method D3606).
n-propanol, isobutanol, tert-butanol, sec-butanol, n-butanol,
1.6 The values stated in SI units are to be regarded as
and tert-pentanol (tert-amylalcohol).
standard. Alternate units, in common usage, are also provided
1.2 Individual ethers are determined from 0.20 % to 20.0 %
to increase clarity and aid the users of this test method.
by mass. Individual alcohols are determined from 0.20 % to
1.7 This standard does not purport to address all of the
12.0 % by mass. Equations used to convert to mass percent
safety concerns, if any, associated with its use. It is the
oxygen and to volume percent of individual compounds are
responsibility of the user of this standard to establish appro-
provided. At concentrations <0.20 % by mass, it is possible
priate safety, health, and environmental practices and deter-
that hydrocarbons may interfere with several ethers and alco-
mine the applicability of regulatory limitations prior to use.
hols. The reporting limit of 0.20 % by mass was tested for
1.8 This international standard was developed in accor-
gasolines containing a maximum of 10 % by volume olefins. It
dance with internationally recognized principles on standard-
maybepossiblethatforgasolinescontaining>10 %byvolume
ization established in the Decision on Principles for the
olefins, the interference may be >0.20 % by mass. Annex A1
Development of International Standards, Guides and Recom-
gives a chromatogram showing the interference observed with
mendations issued by the World Trade Organization Technical
a gasoline containing 10 % by volume olefins.
Barriers to Trade (TBT) Committee.
1.3 This test method includes a relative bias correlation for
2. Referenced Documents
ethanol in spark-ignition engine fuels for the U.S. EPA
2
regulationsreportingbasedonPracticeD6708accuracyassess-
2.1 ASTM Standards:
ment between Test Method D4815 and Test Method D5599 as
D1298 Test Method for Density, Relative Density, or API
a possible Test Method D4815 alternative to Test Method
Gravity of Crude Petroleum and Liquid Petroleum Prod-
D5599. The Practice D6708 derived correlation equation is
ucts by Hydrometer Method
only applicable for ethanol in fuels in the concentration range
D1744 Test Method for Determination of Water in Liquid
from 2.28 % to 14.42 % by mass as measured by Test Method
Petroleum Products by Karl Fischer Reagent (Withdrawn
3
D4815.TheapplicableTestMethodD5599rangeforethanolis
2016)
from 2.16 % to 14.39 % by mass as reported by Test Method
D3606 Test Method for Determination of Benzene and
D5599.
Toluene in Spark Ignition Fuels by Gas Chromatography
D4052 Test Method for Density, Relative Density, and API
1.4 Alcohol-based fuels, such as M-85 and E-85, MTBE
product, ethanol product, and denatured alcohol, are specifi-
1 2
This test method is under the jurisdiction of ASTM Committee D02 on For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM
Subcommittee D02.04.0L on Gas Chromatography Methods. Standards volume information, refer to the standard’s Document Summary page on
Current edition approved April 1, 2022. Published April 2022. Originally the ASTM website.
3
approved in 1989. Last previous edition approved in 2019 as D4815 – 15b (2019). The last approved version of this historical standard is referenced on
DOI: 10.1520/D4815-22. www.astm.org.
*A Summary
...

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: D4815 − 15b (Reapproved 2019) D4815 − 22
Standard Test Method for
Determination of MTBE, ETBE, TAME, DIPE, tertiary-Amyl
Alcohol and C to C Alcohols in Gasoline by Gas
1 4
1
Chromatography
This standard is issued under the fixed designation D4815; 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.
This standard has been approved for use by agencies of the U.S. Department of Defense.
1. Scope Scope*
1.1 This test method covers the determination of ethers and alcohols in gasolines by gas chromatography. Specific compounds
determined are methyl tert-butylether (MTBE), ethyl tert-butylether (ETBE), tert-amylmethylether (TAME), diisopropylether
(DIPE), methanol, ethanol, isopropanol, n-propanol, isobutanol, tert-butanol, sec-butanol, n-butanol, and tert-pentanol (tert-
amylalcohol).
1.2 Individual ethers are determined from 0.20 % to 20.0 % by mass. Individual alcohols are determined from 0.20 % to 12.0 %
by mass. Equations used to convert to mass %mass percent oxygen and to volume %volume percent of individual compounds are
provided. At concentrations <0.20 % by mass, it is possible that hydrocarbons may interfere with several ethers and alcohols. The
reporting limit of 0.20 % by mass was tested for gasolines containing a maximum of 10 % by volume olefins. It may be possible
that for gasolines containing >10 % by volume olefins, the interference may be >0.20 % by mass. Annex A1 gives a chromatogram
showing the interference observed with a gasoline containing 10 % by volume olefins.
1.3 This test method includes a relative bias correlation for ethanol in spark-ignition engine fuels for the U.S. EPA regulations
reporting based on Practice D6708 accuracy assessment between Test Method D4815 and Test Method D5599 as a possible Test
Method D4815 alternative to Test Method D5599. The Practice D6708 derived correlation equation is only applicable for ethanol
in fuels in the concentration range from 2.28 % to 14.42 % by mass as measured by Test Method D4815. The applicable Test
Method D5599 range for ethanol is from 2.16 % to 14.39 % by mass as reported by Test Method D5599.
1.4 Alcohol-based fuels, such as M-85 and E-85, MTBE product, ethanol product, and denatured alcohol, are specifically excluded
from this test method. The methanol content of M-85 fuel is considered beyond the operating range of the system.
1.5 Benzene, while detected, cannot be quantified using this test method and mustshall be analyzed by alternate methodology (see
Test Method D3606).
1.6 The values stated in SI units are to be regarded as standard. Alternate units, in common usage, are also provided to increase
clarity and aid the users of this test method.
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 Dec. 1, 2019April 1, 2022. Published December 2019April 2022. Originally approved in 1989. Last previous edition approved in 20152019 as
D4815 – 15b.D4815 – 15b (2019). DOI: 10.1520/D4815-15BR19.10.1520/D4815-22.
*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

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D4815 − 22
1.7 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility
of the user of this standard to establish appropriate safety, health, and environmental practices and determine the applicability of
regulatory limitations prior to use.
1.8 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.
2. Referenced Documents
2
2.1 ASTM Standards:
D1298 Test Method for Density, Relative Density, or API Gravity of Crude Petroleum and Liquid Petroleum Products by
Hydrometer Method
3 3
D1744 Test Method for Determination of Water in Liquid Petroleum Products by Karl Fischer Reagent (Withdrawn 2016)
D3606 Tes
...