Standard Test Method for Determination of MTBE, ETBE, TAME, DIPE, tertiary-Amyl Alcohol and C<sub>1</sub> to C<sub>4</sub> 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 %. 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 D 3606).
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.
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
31-Oct-2004
Current Stage
Ref Project

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ASTM D4815-04 - Standard Test Method for Determination of MTBE, ETBE, TAME, DIPE, tertiary-Amyl Alcohol and C<sub>1</sub> to C<sub>4</sub> Alcohols in Gasoline by Gas Chromatography
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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:D4815–04
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* priate safety and health practices and determine the applica-
bility of regulatory limitations prior to use.
1.1 This test method covers the determination of ethers and
alcohols in gasolines by gas chromatography. Specific com-
2. Referenced Documents
pounds determined are methyl tert-butylether (MTBE), ethyl
2
2.1 ASTM Standards:
tert-butylether (ETBE), tert-amylmethylether (TAME), diiso-
D1298 Test Method for Density, Relative Density (Specific
propylether (DIPE), methanol, ethanol, isopropanol,
Gravity), or API Gravity of Crude Petroleum and Liquid
n-propanol, isobutanol, tert-butanol, sec-butanol, n-butanol,
Petroleum Products by Hydrometer Method
and tert-pentanol (tert-amylalcohol).
D1744 TestMethodforWaterinLiquidPetroleumProducts
1.2 Individual ethers are determined from 0.20 to 20.0
3
by Karl Fischer Reagent
mass %. Individual alcohols are determined from 0.20 to 12.0
D3606 Test Method for Determination of Benzene and
mass %. Equations used to convert to mass % oxygen and to
Toluene in Finished Motor and Aviation Gasoline by Gas
volume % of individual compounds are provided. At concen-
Chromatography
trations <0.20 mass %, it is possible that hydrocarbons may
D4052 Test Method for Density and Relative Density of
interfere with several ethers and alcohols. The reporting limit
Liquids by Digital Density Meter
of0.20mass %wastestedforgasolinescontainingamaximum
D4057 Practice for Manual Sampling of Petroleum and
of 10 volume % olefins. It may be possible that for gasolines
Petroleum Products
containing >10 volume % olefins, the interference may be
D4307 Practice for Preparation of Liquid Blends for Use as
>0.20 mass %. Annex A1 gives a chromatogram showing the
3
Analytical Standards
interference observed with a gasoline containing 10 volume %
D4420 Test Method for Determination of Aromatics in
olefins.
4
Finished Gasoline by Gas Chromatography
1.3 Alcohol-based fuels, such as M-85 and E-85, MTBE
product, ethanol product, and denatured alcohol, are specifi-
3. Terminology
cally excluded from this test method. The methanol content of
3.1 Definitions of Terms Specific to This Standard:
M-85 fuel is considered beyond the operating range of the
3.1.1 low volume connector—aspecialunionforconnecting
system.
two lengths of tubing 1.6-mm inside diameter and smaller.
1.4 Benzene, while detected, cannot be quantified using this
Sometimes this is referred to as zero dead volume union.
test method and must be analyzed by alternate methodology
3.1.2 oxygenate—any oxygen-containing organic com-
(see Test Method D3606).
pound that can be used as a fuel or fuel supplement, for
1.5 The values stated in SI units are to be regarded as
example, various alcohols and ethers.
standard. Alternate units, in common usage, are also provided
3.1.3 split ratio—in capillary gas chromatography, the ratio
to increase clarity and aid the users of this test method.
of the total flow of carrier gas to the sample inlet versus the
1.6 This standard does not purport to address all of the
flow of the carrier gas to the capillary column, expressed by
safety concerns, if any, associated with its use. It is the
responsibility of the user of this standard to establish appro-
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
1
This test method is under the jurisdiction of ASTM Committee D02 on contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
Petroleum Products and Lubricants and is the direct responsibility of Subcommittee Standards volume information, refer to the standard’s Document Summary page on
D02.04 on Hydrocarbon Analysis. the ASTM website.
3
Current edition approved Nov. 1, 2004. Published February 2005. Originally Withdrawn.
4
approved in 1989. Last previous edition approved in 2003 as D4815 – 03. DOI: Withdrawn. The last approved version of this historical standard is referenced
10.1520/D4815-04. 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.
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D4815–04
TABLE 1 Pertinent Physical Constants and Retention
split ratio 5
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