ASTM D4815-15b

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 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 % to14.39 % 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 must 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 and health practices and determine the applicability of regulatory limitations prior to use.

General Information

• Status: Historical
• Publication Date: 30-Nov-2015
• 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)

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 − 15b
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 must be analyzed by alternate methodology
propylether (DIPE), methanol, ethanol, isopropanol,
(see Test Method D3606).
n-propanol, isobutanol, tert-butanol, sec -butanol, n-butanol,
and tert-pentanol (tert-amylalcohol). 1.6 The values stated in SI units are to be regarded as
standard. Alternate units, in common usage, are also provided
1.2 Individual ethers are determined from 0.20 mass % to
to increase clarity and aid the users of this test method.
20.0 mass %. Individual alcohols are determined from
0.20 mass % to 12.0 mass %. Equations used to convert to
1.7 This standard does not purport to address all of the
mass % oxygen and to volume % of individual compounds are
safety concerns, if any, associated with its use. It is the
provided. At concentrations <0.20 mass %, it is possible that
responsibility of the user of this standard to establish appro-
hydrocarbons may interfere with several ethers and alcohols.
priate safety and health practices and determine the applica-
The reporting limit of 0.20 mass % was tested for gasolines
bility of regulatory limitations prior to use.
containing a maximum of 10 volume % olefins. It may be
possible that for gasolines containing >10 volume % olefins,
2. Referenced Documents
the interference may be >0.20 mass %. Annex A1 gives a
2
chromatogram showing the interference observed with a gaso-
2.1 ASTM Standards:
line containing 10 volume % olefins.
D1298 Test Method for Density, Relative Density, or API
Gravity of Crude Petroleum and Liquid Petroleum Prod-
1.3 This test method includes a relative bias correlation for
ethanol in spark-ignition engine fuels for the U.S. EPA ucts by Hydrometer Method
regulationsreportingbasedonPracticeD6708accuracyassess- D1744 Test Method for Water in Liquid Petroleum Products
3
ment between Test Method D4815 and Test Method D5599 as
by Karl Fischer Reagent
a possible Test Method D4815 alternative to Test Method
D3606 Test Method for Determination of Benzene and
D5599. The Practice D6708 derived correlation equation is
Toluene in Finished Motor and Aviation Gasoline by Gas
only applicable for ethanol in fuels in the concentration range
Chromatography
from 2.28 % to 14.42 % by mass as measured by Test Method
D4052 Test Method for Density, Relative Density, and API
D4815.TheapplicableTestMethodD5599rangeforethanolis
Gravity of Liquids by Digital Density Meter
from 2.16 % to14.39 % by mass as reported by Test Method
D4057 Practice for Manual Sampling of Petroleum and
D5599.
Petroleum Products
1.4 Alcohol-based fuels, such as M-85 and E-85, MTBE
D4307 Practice for Preparation of Liquid Blends for Use as
product, ethanol product, and denatured alcohol, are specifi-
Analytical Standards
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
2
Subcommittee D02.04.0L on Gas Chromatography Methods. For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Current edition approved Dec. 1, 2015. Published December 2015. Originally contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM
approved in 1989. Last previous edition approved in 2015 as D4815 – 15a. DOI: Standards volume information, refer to the standard’s Document Summary page on
10.1520/D4815-15B. 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 − 15b
TABLE 1 Pertinent Physical Constants and Retention
D4420 Test Method for Determination of Aromatics in
Characteristics for TCEP/WCOT Column Set Conditions
Finished Gasoline by Gas Chromatogr
...

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 − 15a D4815 − 15b
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 0.20 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 <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 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 % to14.39 % 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 must 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 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
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, 2015Dec. 1, 2015. Published May 2015December 2015. Originally approved in 1989. Last previous edition approved in 2015 as
D4815 – 15.D4815 – 15a. DOI: 10.1520/D4815-15A.10.1520/D4815-15B.
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or contact ASTM 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 − 15b
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 Met
...