ASTM D4815-09

Standard Test Method for Determination of MTBE, ETBE, TAME, DIPE, tertiary-Amyl Alcohol and C₁ to C₄ Alcohols in Gasoline by Gas Chromatography

SIGNIFICANCE AND USE
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.
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 mass %. Individual alcohols are determined from 0.20 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.

General Information

• Status: Historical
• Publication Date: 30-Sep-2009
• ICS: 75.160.20 - Liquid fuels
• Technical Committee: D02 - Petroleum Products, Liquid Fuels, and Lubricants
• Drafting Committee: D02.04.0L - Gas Chromatography Methods

Relations

• Replaces: ASTM D4815-04 - Standard Test Method for Determination of MTBE, ETBE, TAME, DIPE, tertiary-Amyl Alcohol and C₁ to C₄ Alcohols in Gasoline by Gas Chromatography
• Effective Date: 01-Oct-2009
• Referred By: ASTM D6729-20 - Standard Test Method for Determination of Individual Components in Spark Ignition Engine Fuels by 100 Metre Capillary High Resolution Gas Chromatography
• Effective Date: 01-Oct-2009
• Referred By: ASTM D6733-01(2020) - Standard Test Method for Determination of Individual Components in Spark Ignition Engine Fuels by 50-Metre Capillary High Resolution Gas Chromatography
• Effective Date: 01-Oct-2009
• Referred By: ASTM D6839-21a - Standard Test Method for Hydrocarbon Types, Oxygenated Compounds, Benzene, and Toluene in Spark Ignition Engine Fuels by Multidimensional Gas Chromatography
• Effective Date: 01-Oct-2009
• Referred By: ASTM D6984-18e1 - Standard Test Method for Evaluation of Automotive Engine Oils in the Sequence IIIF, Spark-Ignition Engine
• Effective Date: 01-Oct-2009
• Referred By: ASTM D7753-12(2020) - Standard Test Method for Hydrocarbon Types and Benzene in Light Petroleum Distillates by Gas Chromatography
• Effective Date: 01-Oct-2009
• Referred By: ASTM D6227-18(2023) - Standard Specification for Unleaded Aviation Gasoline Containing a Non-hydrocarbon Component
• Effective Date: 01-Oct-2009
• Referred By: ASTM D7717-11(2021) - Standard Practice for Preparing Volumetric Blends of Denatured Fuel Ethanol and Gasoline Blendstocks for Laboratory Analysis
• Effective Date: 01-Oct-2009
• Referred By: ASTM D4814-23 - Standard Specification for Automotive Spark-Ignition Engine Fuel
• Effective Date: 01-Oct-2009
• Referred By: ASTM D6730-22 - Standard Test Method for Determination of Individual Components in Spark Ignition Engine Fuels by 100-Metre Capillary (with Precolumn) High-Resolution Gas Chromatography
• Effective Date: 01-Oct-2009
• Referred By: ASTM D1319-20a - Standard Test Method for Hydrocarbon Types in Liquid Petroleum Products by Fluorescent Indicator Adsorption
• Effective Date: 01-Oct-2009
• Referred By: ASTM D5501-20 - Standard Test Method for Determination of Ethanol and Methanol Content in Fuels Containing Greater than 20 % Ethanol by Gas Chromatography
• Effective Date: 01-Oct-2009
• Referred By: ASTM D5622-17 - Standard Test Methods for Determination of Total Oxygen in Gasoline and Methanol Fuels by Reductive Pyrolysis
• Effective Date: 01-Oct-2009
• Referred By: ASTM D8076-21b - Standard Specification for 100 Research Octane Number Test Fuel for Automotive Spark-Ignition Engines
• Effective Date: 01-Oct-2009
• Referred By: ASTM D7096-19 - Standard Test Method for Determination of the Boiling Range Distribution of Gasoline by Wide-Bore Capillary Gas Chromatography
• Effective Date: 01-Oct-2009

Standards Content (Sample)

NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Contact ASTM International (www.astm.org) for the latest information
Designation: D4815 − 09
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 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 (Specific
1.2 Individual ethers are determined from 0.20 to 20.0
Gravity), or API Gravity of Crude Petroleum and Liquid
mass %. Individual alcohols are determined from 0.20 to 12.0
Petroleum Products by Hydrometer Method
mass %. Equations used to convert to mass % oxygen and to
D1744 Test Method for Water in Liquid Petroleum Products
3
volume % of individual compounds are provided. At concen-
by Karl Fischer Reagent
trations <0.20 mass %, it is possible that hydrocarbons may
D3606 Test Method for Determination of Benzene and
interfere with several ethers and alcohols. The reporting limit
Toluene in Finished Motor and Aviation Gasoline by Gas
of0.20mass %wastestedforgasolinescontainingamaximum
Chromatography
of 10 volume % olefins. It may be possible that for gasolines
D4052 Test Method for Density, Relative Density, and API
containing >10 volume % olefins, the interference may be
Gravity of Liquids by Digital Density Meter
>0.20 mass %. Annex A1 gives a chromatogram showing the
D4057 Practice for Manual Sampling of Petroleum and
interference observed with a gasoline containing 10 volume %
Petroleum Products
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 and Lubricantsand is the direct responsibility of Subcommittee contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM
D02.04.0L on Gas Chromatography Methods. Standards volume information, refer to the standard’s Document Summary page on
Current edition approved Oct. 1, 2009. Published November 2009. Originally the ASTM website.
3
approved in 1989. Last previous edition approved in 2004 as D4815–04. DOI: The last approved version of this historical standard is referenced on
10.1520/D4815-09. 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 − 09
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 sample inlet versus the
as
...

This document is not anASTM standard and is intended only to provide the user of anASTM 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:D4815–04 Designation:D4815–09
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 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).
1.2Individual1.2 Individual ethers are determined from 0.20 to 20.0 mass %. Individual alcohols are determined from 0.20 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 (Specific Gravity), orAPI 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
Chromatography
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
D4420 Test Method for Determination of Aromatics in Finished Gasoline by Gas Chromatography
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-mm inside diameter and smaller.
1
This test method is under the jurisdiction ofASTM Committee D02 on Petroleum Products and Lubricants and is the direct responsibility of Subcommittee D02.04.0L
on Hydrocarbon Analysis. Gas Chromatography Methods.
Current edition approved Nov.Oct. 1, 2004.2009. Published February 2005.November 2009. Originally approved in 1989. Last previous edition approved in 20032004 as
D4815–03.D4815–04. DOI: 10.1520/D4815-049.
2
For referencedASTM standards, visit theASTM website, www.astm.org, or contactASTM Customer Service at [e-mail]. For Annual Book of ASTM Standards
volume information, refer to the standard’s Document Summary page on the ASTM website.
*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 ----------------------
D4815–09
Sometimes this is referred to as zero dead volume union.
3.1.2 oxygenate—any oxygen-containing organic compound that can be used as a fuel or fuel supplement, for example, v
...