ASTM D5599-15

Standard Test Method for Determination of Oxygenates in Gasoline by Gas Chromatography and Oxygen Selective Flame Ionization Detection

SIGNIFICANCE AND USE
5.1 In gasoline blending, the determination of organic oxygenated compounds is important. Alcohols, ethers, and other oxygenates are added to gasoline to increase the octane number and to reduce tailpipe emissions of carbon monoxide. They must be added in the proper concentration and ratios to meet regulatory limitations and to avoid phase separation and problems with engine performance or efficiency.  
5.2 This test method provides sufficient oxygen-to-hydro-carbon selectivity and sensitivity to allow determination of oxygenates in gasoline samples without interference from the bulk hydrocarbon matrix.
SCOPE
1.1 This test method covers a gas chromatographic procedure for the quantitative determination of organic oxygenated compounds in gasoline having a final boiling point not greater than 220 °C and oxygenates having a boiling point limit of 130 °C. It is applicable when oxygenates are present in the 0.1 % to 20 % by mass range.  
1.2 This test method is intended to determine the mass concentration of each oxygenate compound  present in a gasoline. This requires knowledge of the identity of each oxygenate being determined (for calibration purposes). However, the oxygen-selective detector used in this test method exhibits a response that is proportional to the mass of oxygen. It is, therefore, possible to determine the mass concentration of oxygen  contributed by any oxygenate compound in the sample, whether or not it is identified. Total oxygen content in a gasoline may be determined from the summation of the accurately determined individual oxygenated compounds. The summed area of other, uncalibrated or unknown oxygenated compounds present, may be converted to a mass concentration of oxygen and summed with the oxygen concentration of the known oxygenated compounds.  
1.3 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.  
1.4 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-May-2015
• 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 D5599-00(2010) - Standard Test Method for Determination of Oxygenates in Gasoline by Gas Chromatography and Oxygen Selective Flame Ionization Detection
• Effective Date: 01-Jun-2015
• Replaced By: ASTM D5599-17 - Standard Test Method for Determination of Oxygenates in Gasoline by Gas Chromatography and Oxygen Selective Flame Ionization Detection
• Effective Date: 01-May-2017
• Referred By: ASTM D8071-21 - Standard Test Method for Determination of Hydrocarbon Group Types and Select Hydrocarbon and Oxygenate Compounds in Automotive Spark-Ignition Engine Fuel Using Gas Chromatography with Vacuum Ultraviolet Absorption Spectroscopy Detection (GC-VUV)
• Effective Date: 01-Jun-2015
• 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-Jun-2015
• Referred By: ASTM D6227-18(2023) - Standard Specification for Unleaded Aviation Gasoline Containing a Non-hydrocarbon Component
• Effective Date: 01-Jun-2015
• Referred By: ASTM D5845-21 - Standard Test Method for Determination of MTBE, ETBE, TAME, DIPE, Methanol, Ethanol and <emph type="ital">tert</emph>-Butanol in Gasoline by Infrared Spectroscopy
• Effective Date: 01-Jun-2015
• Referred By: ASTM D1319-20a - Standard Test Method for Hydrocarbon Types in Liquid Petroleum Products by Fluorescent Indicator Adsorption
• Effective Date: 01-Jun-2015
• 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-Jun-2015
• Referred By: 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
• Effective Date: 01-Jun-2015
• Referred By: ASTM D4814-23 - Standard Specification for Automotive Spark-Ignition Engine Fuel
• Effective Date: 01-Jun-2015
• Referred By: ASTM D7753-12(2020) - Standard Test Method for Hydrocarbon Types and Benzene in Light Petroleum Distillates by Gas Chromatography
• Effective Date: 01-Jun-2015
• 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-Jun-2015
• Referred By: ASTM D6122-22 - Standard Practice for Validation of the Performance of Multivariate Online, At-Line, Field and Laboratory Infrared Spectrophotometer, and Raman Spectrometer Based Analyzer Systems
• Effective Date: 01-Jun-2015
• Referred By: ASTM D8076-21b - Standard Specification for 100 Research Octane Number Test Fuel for Automotive Spark-Ignition Engines
• Effective Date: 01-Jun-2015
• Referred By: ASTM D7794-21 - Standard Practice for Blending Mid-Level Ethanol Fuel Blends for Flexible-Fuel Vehicles with Automotive Spark-Ignition Engines
• Effective Date: 01-Jun-2015

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: D5599 − 15
Standard Test Method for
Determination of Oxygenates in Gasoline by Gas
Chromatography and Oxygen Selective Flame Ionization
1
Detection
This standard is issued under the fixed designation D5599; 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.
1. Scope* 2. Referenced Documents
2
1.1 This test method covers a gas chromatographic proce- 2.1 ASTM Standards:
dure for the quantitative determination of organic oxygenated D1744 Test Method for Determination of Water in Liquid
compounds in gasoline having a final boiling point not greater Petroleum Products by Karl Fischer Reagent
than 220 °C and oxygenates having a boiling point limit of D4175 Terminology Relating to Petroleum, Petroleum
130 °C. It is applicable when oxygenates are present in the Products, and Lubricants
0.1 % to 20 % by mass range. D4307 Practice for Preparation of Liquid Blends for Use as
Analytical Standards
1.2 This test method is intended to determine the mass
E594 Practice for Testing Flame Ionization Detectors Used
concentration of each oxygenate compound present in a gaso-
in Gas or Supercritical Fluid Chromatography
line.This requires knowledge of the identity of each oxygenate
E1064 Test Method for Water in Organic Liquids by Coulo-
being determined (for calibration purposes). However, the
metric Karl Fischer Titration
oxygen-selective detector used in this test method exhibits a
E1510 Practice for Installing Fused Silica Open Tubular
response that is proportional to the mass of oxygen.Itis,
Capillary Columns in Gas Chromatographs
therefore, possible to determine the mass concentration of
oxygen contributed by any oxygenate compound in the sample,
3. Terminology
whether or not it is identified. Total oxygen content in a
3.1 Definitions:
gasoline may be determined from the summation of the
3.1.1 independent reference standards—calibration samples
accurately determined individual oxygenated compounds. The
of the oxygenates which are purchased or prepared from
summed area of other, uncalibrated or unknown oxygenated
materials independent of the quality control check standards
compounds present, may be converted to a mass concentration
and used for intralaboratory accuracy.
of oxygen and summed with the oxygen concentration of the
3.1.2 oxygenate, n—an oxygen-containing compound, such
known oxygenated compounds.
as an alcohol or ether, which may be used as a fuel or fuel
1.3 The values stated in SI units are to be regarded as
supplement.
standard. No other units of measurement are included in this
3.1.3 quality control check standards—calibration samples
standard.
of the oxygenates for intralaboratory repeatability.
1.4 This standard does not purport to address all of the
safety concerns, if any, associated with its use. It is the
4. Summary of Test Method
responsibility of the user of this standard to establish appro-
4.1 An internal standard of a noninterfering oxygenate, for
priate safety and health practices and determine the applica-
example, 1,2-dimethoxyethane (ethylene glycol dimethyl
bility of regulatory limitations prior to use.
ether) is added in quantitative proportion to the gasoline
sample. A representative aliquot of the sample and internal
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
CurrenteditionapprovedJune1,2015.PublishedJuly2015.Originallyapproved contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM
in 1994. Last previous edition approved in 2010 as D5599 – 00 (2010). DOI: Standards volume information, refer to the standard’s Document Summary page on
10.1520/D5599-15. 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 ----------------------
D5599 − 15
standard is injected into a gas chromatograph equipped with a tubing containing a nickel-based catalyst. It is installed within
capillary column operated to ensure separation of the oxygen- or before the FID and is operated in the range from 350 °C to
ates. Hydrocarbons and oxygenates are eluted from the 450 °C, depending on the instrument’s manufacturer.
column, but only oxygenates are detected with the oxygen-
NOTE 2—Gasolines with high sulfur content may cause a loss in
selective flame ionization detector
...

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: D5599 − 00 (Reapproved 2010) D5599 − 15
Standard Test Method for
Determination of Oxygenates in Gasoline by Gas
Chromatography and Oxygen Selective Flame Ionization
1
Detection
This standard is issued under the fixed designation D5599; 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.
1. Scope Scope*
1.1 This test method covers a gas chromatographic procedure for the quantitative determination of organic oxygenated
compounds in gasoline having a final boiling point not greater than 220°C220 °C and oxygenates having a boiling point limit of
130°C.130 °C. It is applicable when oxygenates are present in the 0.10.1 % to 20 % by mass range.
1.2 This test method is intended to determine the mass concentration of each oxygenate compound present in a gasoline. This
requires knowledge of the identity of each oxygenate being determined (for calibration purposes). However, the oxygen-selective
detector used in this test method exhibits a response that is proportional to the mass of oxygen. It is, therefore, possible to determine
the mass concentration of oxygen contributed by any oxygenate compound in the sample, whether or not it is identified. Total
oxygen content in a gasoline may be determined from the summation of the accurately determined individual oxygenated
compounds. The summed area of other, uncalibrated or unknown oxygenated compounds present, may be converted to a mass
concentration of oxygen and summed with the oxygen concentration of the known oxygenated compounds.
1.3 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.4 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:
D1744 Test Method for Determination of Water in Liquid Petroleum Products by Karl Fischer Reagent
D4175 Terminology Relating to Petroleum, Petroleum Products, and Lubricants
D4307 Practice for Preparation of Liquid Blends for Use as Analytical Standards
E594 Practice for Testing Flame Ionization Detectors Used in Gas or Supercritical Fluid Chromatography
E1064 Test Method for Water in Organic Liquids by Coulometric Karl Fischer Titration
E1510 Practice for Installing Fused Silica Open Tubular Capillary Columns in Gas Chromatographs
3. Terminology
3.1 Definitions:
3.1.1 independent reference standards—calibration samples of the oxygenates which are purchased or prepared from materials
independent of the quality control check standards and used for intralaboratory accuracy.
3.1.2 oxygenate, n—an oxygen-containing compound, such as an alcohol or ether, which may be used as a fuel or fuel
supplement. D4175
3.1.3 quality control check standards—calibration samples of the oxygenates for intralaboratory repeatability.
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 Oct. 1, 2010June 1, 2015. Published November 2010July 2015. Originally approved in 1994. Last previous edition approved in 20052010 as
D5599 – 00 (2005).(2010). DOI: 10.1520/D5599-00R10.10.1520/D5599-15.
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 ----------------------
D5599 − 15
4. Summary of Test Method
4.1 An internal standard of a noninterfering oxygenate, for example, 1,2-dimethoxyethane (ethylene glycol dimethyl ether) is
added in quantitative proportion to the gasoline sample. A representative aliquot of the sample and internal standard is injected into
a gas chromatograph equipped with a capillary column operated to ensure separation of the oxy
...