ASTM D4815-15a
(Test Method)Standard Test Method for Determination of MTBE, ETBE, TAME, DIPE, tertiary-Amyl Alcohol and C1 to C4 Alcohols in Gasoline by Gas Chromatography
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 mass % to 20.0 mass %. Individual alcohols are determined from 0.20 mass % to 12.0 mass %. Equations used to convert to mass % oxygen and to volume % of individual compounds are provided. At concentrations 10 volume % olefins, the interference may be >0.20 mass %. Annex A1 gives a chromatogram showing the interference observed with a gasoline containing 10 volume % olefins.
1.3 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.
1.4 Benzene, while detected, cannot be quantified using this test method and must be analyzed by alternate methodology (see Test Method D3606).
1.5 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.
1.6 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 and health practices and determine the applicability of regulatory limitations prior to use.
General Information
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Designation: D4815 − 15a
StandardTest 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* 1.6 This standard does not purport to address all of the
safety concerns, if any, associated with its use. It is the
1.1 This test method covers the determination of ethers and
responsibility of the user of this standard to establish appro-
alcohols in gasolines by gas chromatography. Specific com-
priate safety and health practices and determine the applica-
pounds determined are methyl tert-butylether (MTBE), ethyl
bility of regulatory limitations prior to use.
tert-butylether (ETBE), tert-amylmethylether (TAME), diiso-
propylether (DIPE), methanol, ethanol, isopropanol,
2. Referenced Documents
n-propanol, isobutanol, tert-butanol, sec -butanol, n-butanol,
2
2.1 ASTM Standards:
and tert-pentanol (tert-amylalcohol).
D1298 Test Method for Density, Relative Density, or API
1.2 Individual ethers are determined from 0.20 mass % to
Gravity of Crude Petroleum and Liquid Petroleum Prod-
20.0 mass %. Individual alcohols are determined from
ucts by Hydrometer Method
0.20 mass % to 12.0 mass %. Equations used to convert to
D1744 Test Method for Water in Liquid Petroleum Products
3
mass % oxygen and to volume % of individual compounds are
by Karl Fischer Reagent
provided. At concentrations <0.20 mass %, it is possible that
D3606 Test Method for Determination of Benzene and
hydrocarbons may interfere with several ethers and alcohols.
Toluene in Finished Motor and Aviation Gasoline by Gas
The reporting limit of 0.20 mass % was tested for gasolines
Chromatography
containing a maximum of 10 volume % olefins. It may be
D4052 Test Method for Density, Relative Density, and API
possible that for gasolines containing >10 volume % olefins,
Gravity of Liquids by Digital Density Meter
the interference may be >0.20 mass %. Annex A1 gives a
D4057 Practice for Manual Sampling of Petroleum and
chromatogram showing the interference observed with a gaso-
Petroleum Products
line containing 10 volume % olefins.
D4307 Practice for Preparation of Liquid Blends for Use as
Analytical Standards
1.3 Alcohol-based fuels, such as M-85 and E-85, MTBE
D4420 Test Method for Determination of Aromatics in
product, ethanol product, and denatured alcohol, are specifi-
Finished Gasoline by Gas Chromatography (Withdrawn
cally excluded from this test method. The methanol content of
3
2004)
M-85 fuel is considered beyond the operating range of the
system.
3. Terminology
1.4 Benzene, while detected, cannot be quantified using this
3.1 Definitions of Terms Specific to This Standard:
test method and must be analyzed by alternate methodology
3.1.1 low volume connector—a special union for connecting
(see Test Method D3606).
two lengths of tubing 1.6 mm inside diameter and smaller.
1.5 The values stated in SI units are to be regarded as Sometimes this is referred to as zero dead volume union.
standard. Alternate units, in common usage, are also provided
3.1.2 oxygenate—anyoxygen-containingorganiccompound
to increase clarity and aid the users of this test method.
that can be used as a fuel or fuel supplement, for example,
various alcohols and ethers.
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 Lubricantsand is the direct responsibility of contact ASTM Customer Service at service@astm.org. 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, 2015. Published May 2015. Originally the ASTM website.
3
approved in 1989. Last previous edition approved in 2015 as D4815 – 15. DOI: The last approved version of this historical standard is referenced on
10.1520/D4815-15A. www.astm.org.
*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 ----------------------
D4815 − 15a
TABLE 1 Pertinent Physical Constants and Retention
3.1.3 split ratio—in capillary gas chromatography, the ratio
Characteristics for TCEP/WCOT Column Set Conditions
of the total flow of carrier gas to the
...
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 − 15 D4815 − 15a
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*
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 0.200.20 mass % to 20.0 mass %. Individual alcohols are determined from
0.200.20 mass % to 12.0 mass %. Equations used to convert to mass % oxygen and to volume % of individual compounds are
provided. At concentrations <0.20 mass %, it is possible that hydrocarbons may interfere with several ethers and alcohols. The
reporting limit of 0.20 mass % was tested for gasolines containing a maximum of 10 volume % olefins. It may be possible that
for gasolines containing >10 volume % olefins, the interference may be >0.20 mass %. Annex A1 gives a chromatogram showing
the interference observed with a gasoline containing 10 volume % olefins.
1.3 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.
1.4 Benzene, while detected, cannot be quantified using this test method and must be analyzed by alternate methodology (see
Test Method D3606).
1.5 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.
1.6 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 and health practices and determine the applicability of regulatory
limitations prior to use.
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
D1744 Test Method for Water in Liquid Petroleum Products by Karl Fischer Reagent
D3606 Test Method for Determination of Benzene and Toluene in Finished Motor and Aviation Gasoline by Gas Chromatog-
raphy
D4052 Test Method for Density, Relative Density, and API Gravity of Liquids by Digital Density Meter
D4057 Practice for Manual Sampling of Petroleum and Petroleum Products
D4307 Practice for Preparation of Liquid Blends for Use as Analytical Standards
3
D4420 Test Method for Determination of Aromatics in Finished Gasoline by Gas Chromatography (Withdrawn 2004)
1
This test method is under the jurisdiction of ASTM Committee D02 on Petroleum Products, Liquid Fuels, and Lubricantsand is the direct responsibility of Subcommittee
D02.04.0L on Gas Chromatography Methods.
Current edition approved Feb. 1, 2015April 1, 2015. Published March 2015May 2015. Originally approved in 1989. Last previous edition approved in 20132015 as
D4815 – 13.D4815 – 15. DOI: 10.1520/D4815-15.10.1520/D4815-15A.
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM Standards
volume information, refer to the standard’s Document Summary page on the ASTM website.
3
The last approved version of this historical standard is referenced on www.astm.org.
*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 ----------------------
D4815 − 15a
3. Terminology
3.1 Definitions of Terms Specific to This Standard:
3.1.1 low volume connector—a special union for connecting two lengths of tubing 1.6-mm1.6 mm inside diameter and smaller.
Sometimes this is referred to as zero dead volume un
...
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