ASTM D5845-01(2016)

Standard Test Method for Determination of MTBE, ETBE, TAME, DIPE, Methanol, Ethanol and <emph type="ital">tert</emph>-Butanol in Gasoline by Infrared Spectroscopy

SIGNIFICANCE AND USE
5.1 Alcohols and ethers are added to gasoline to produce a reformulated lower emissions gasoline. Alcohols and ethers may also be added to gasoline to increase the octane number. Type and concentration of various oxygenates are specified and regulated to ensure acceptable commercial gasoline quality. Driveability, vapor pressure, phase separation, and evaporative emissions are some of the concerns associated with oxygenated fuels.  
5.2 This test method is faster, simpler, less expensive and more portable than current methods.  
5.3 This test method may be applicable for quality control in the production of gasoline.  
5.4 This test method is not suitable for testing for compliance with federal regulations.3  
5.5 False positive readings for some of the samples tested in the round robin were sometimes observed. As only extreme base gasolines were tested in the round robin, no definitive statement can be made as to the expected frequency or magnitude of false positives expected in a wider range of base gasolines.
SCOPE
1.1 This test method covers the determination of methanol, ethanol, tert-butanol, methyl tert-butyl ether (MTBE), ethyl tert-butyl ether (ETBE), tert-amyl methyl ether (TAME), and diisopropyl ether (DIPE) in gasoline by infrared spectroscopy. The test method is suitable for determining methanol from 0.1 to 6 mass %, ethanol from 0.1 to 11 mass %, tert-butanol from 0.1 to 14 mass %, and DIPE, MTBE, ETBE and TAME from 0.1 to 20 mass %.  
1.2 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.  
1.3 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-2016
• ICS: 75.160.20 - Liquid fuels
• Technical Committee: D02 - Petroleum Products, Liquid Fuels, and Lubricants
• Drafting Committee: D02.04.0F - Absorption Spectroscopic 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NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.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: D5845 − 01 (Reapproved 2016)
Standard Test Method for
Determination of MTBE, ETBE, TAME, DIPE, Methanol,
Ethanol and tert-Butanol in Gasoline by Infrared
Spectroscopy
This standard is issued under the fixed designation D5845; 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 hols in Gasoline by Gas Chromatography
D5599 Test Method for Determination of Oxygenates in
1.1 This test method covers the determination of methanol,
Gasoline by Gas Chromatography and Oxygen Selective
ethanol, tert-butanol, methyl tert-butyl ether (MTBE), ethyl
Flame Ionization Detection
tert-butyl ether (ETBE), tert-amyl methyl ether (TAME), and
E1655 Practices for Infrared Multivariate Quantitative
diisopropyl ether (DIPE) in gasoline by infrared spectroscopy.
Analysis
The test method is suitable for determining methanol from 0.1
to 6 mass %, ethanol from 0.1 to 11 mass %, tert-butanol from 2.2 Other Standard:
0.1 to 14 mass %, and DIPE, MTBE, ETBE and TAME from GC/OFID EPATest Method—Oxygen and Oxygenate Con-
0.1 to 20 mass %. tent Analysis (by way of gas chromatography with
oxygen-selective flame ionization detection)
1.2 The values stated in SI units are to be regarded as
standard. No other units of measurement are included in this
3. Terminology
standard.
3.1 Definitions:
1.3 This standard does not purport to address all of the
3.1.1 multivariate calibration, n—a process for creating a
safety concerns, if any, associated with its use. It is the
calibration model in which multivariate mathematics is applied
responsibility of the user of this standard to establish appro-
to correlate the absorbances measured for a set of calibration
priate safety and health practices and determine the applica-
samples to reference component concentrations or property
bility of regulatory limitations prior to use.
values for the set of samples. The resultant multivariate
2. Referenced Documents
calibration model is applied to the analysis of spectra of
2 unknown samples to provide an estimate of the component
2.1 ASTM Standards:
concentration or property values for the unknown sample.
D1298 Test Method for Density, Relative Density, or API
3.1.2 oxygenate, n—an oxygen-containing organic
Gravity of Crude Petroleum and Liquid Petroleum Prod-
ucts by Hydrometer Method compound,whichmaybeusedasafuelorfuelsupplement,for
example, various alcohols or ethers.
D4052 Test Method for Density, Relative Density, and API
Gravity of Liquids by Digital Density Meter
D4057 Practice for Manual Sampling of Petroleum and 4. Summary of Test Method
Petroleum Products
4.1 A sample of gasoline is introduced into a liquid sample
D4307 Practice for Preparation of Liquid Blends for Use as
cell. A beam of infrared light is imaged through the sample
Analytical Standards
onto a detector, and the detector response is determined.
D4815 Test Method for Determination of MTBE, ETBE,
Regions of the infrared spectrum are selected for use in the
TAME, DIPE, tertiary-Amyl Alcohol and C to C Alco-
1 4
analysis by either placing highly selective bandpass filters
before or after the sample or mathematically selecting the
regions after the whole spectrum is obtained. A multivariate
This test method is under the jurisdiction of ASTM Committee D02 on
Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of
mathematical analysis is carried out which converts the detec-
Subcommittee D02.04.0F on Absorption Spectroscopic Methods.
tor response for the selected regions in the spectrum of an
Current edition approved Oct. 1, 2016. Published November 2016. Originally
unknown to a concentration for each component.
approved in 1995. Last previous edition approved in 2011 as D5845 – 01 (2011).
DOI: 10.1520/D5845-01R16.
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 Code of Federal Regulations, Part 80 of Title 40, Section 80.46(g); also
the ASTM website. published in the Federal Register, Volume 59, No. 32, February 16, 1994, p 7828.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D5845 − 01 (2016)
5. Significance and Use 7.1.6 Ethyl tert-butyl ether, ETBE,
7.1.7 tert-Amyl methyl ether, TAME, and
5.1 Alcohols and ethers are added to gasoline to produce a
7.1.8 Diisopropyl ether, DIPE.
reformulated lower emissions gasoline. Alcohols and ethers
may also be added to gasoline to increase the octane number.
7.2 Warning—These materials are flammable and may be
Typeandconcentrationofvariousoxygenatesarespecifiedand
harmful if ingested or inhaled.
regulated to ensure acceptable commercial gasoline quality.
Driveability, vapor pressure, phase separation, and evaporative
8. Sampling and Sample Handling
emissionsaresomeoftheconcernsassociatedwithoxygenated
8.1 General Requirements:
fuels.
8.1.1 Gasoline samples must be handled with meticulous
5.2 This test method is faster, simpler, less expensive and
care to prevent evaporative loss and composition changes.
more portable than current methods.
8.1.2 Gasoline samples to be analyzed by the test method
shall be obtained using method(s) specified by governmental
5.3 Thistestmethodmaybeapplicableforqualitycontrolin
regulatory agencies or by the procedures outlined in Practice
the production of gasoline.
D4057 (or equivalent). Do not use the “Sampling by Water
5.4 This test method is not suitable for testing for compli-
Displacement” method as some alcohols or ethers might be
ance with federal regulations.
extracted into the water phase.
5.5 False positive readings for some of the samples tested in
8.1.3 Protect samples from excessive temperatures prior to
the round robin were sometimes observed. As only extreme
testing. This can be accomplished by storage in an appropriate
base gasolines were tested in the round robin, no definitive
ice bath or refrigerator at 0 °C to 5 °C.
statement can be made as to the expected frequency or
8.1.4 Donottestsamplesstoredinleakycontainers.Discard
magnitude of false positives expected in a wider range of base
and obtain a new sample if leaks are detected.
gasolines.
8.1.5 Performtheoxygenatedeterminationonfreshsamples
from containers that are at least 80 % full. If sample containers
6. Apparatus
are less than 80 % full or have been opened and sampled
6.1 Mid-IR Spectrometric Analyzer, of one of the following
multiple times, a new sample shall be obtained.
types:
8.2 Sample Handling During Analysis:
6.1.1 Filter-based Mid-IR Test Apparatus—The type of
8.2.1 Prior to the analysis of samples by infrared
apparatus suitable for use in this test method minimally
spectroscopy, the samples should be allowed to equilibrate to
employs an IR source, an infrared transmission cell or a liquid
the temperature at which they should be analyzed (15 °C to
attenuated total internal reflection cell, wavelength discrimi-
38 °C).
nating filters, a chopper wheel, a detector, anA-D converter, a
8.2.2 After withdrawing the sample, reseal the container,
microprocessor, and a sample introduction system.
and store the sample in an ice bath or a refrigerator at 0 °C to
6.1.2 Fourier Transform Mid-IR Test Apparatus—The type
5 °C.
of apparatus suitable for use in this test method employs an IR
source, an infrared transmission cell or a liquid attenuated total
9. Preparation, Calibration, and Qualification of the
internal reflection cell, a scanning interferometer, a detector, an
Infrared Test Apparatus
A-D converter, a microprocessor and a sample introduction
system.
9.1 Preparation—Prepare the instrument for operation in
6.1.3 Dispersive Mid-IR Test Apparatus—The type of appa-
accordance with the manufacturer’s instructions.
ratus suitable for use in this test method minimally employs an
9.2 Calibration—Each instrument must be calibrated by the
IR source, an infrared transmission cell or a liquid attenuated
manufacturer or user in accordance with Practice E1655. This
total internal reflection cell, a wavelength dispersive element
practice serves as a guide for the multivariate calibration of
such as a grating or prism, a chopper wheel, a detector, anA-D
infrared spectrometers used in determining the physical char-
converter, a microprocessor and a sample introduction system.
acteristics of petroleum and petrochemical products. The
7. Reagents and Materials procedures describe treatment of the data, development of the
calibration, and qualification of the instrument. Note that bias
7.1 Samples for Calibration and Quality Control Check
and slope adjustments are specifically not recommended to
Solutions—Use of chemicals of at least 99 % purity is highly
improve calibration or prediction statistics for IR multivariate
recommended when preparing calibration and quality control
models.
check samples. If reagents of high purity are not available, an
accurate assay of the reagent must be performed using a 9.3 Qualification of Instrument—The instrument must be
properly calibrated GC or other techniques (for example, water qualifiedaccordingtotheprocedureinAnnexA1toensurethat
determination). the instrument accurately and precisely measures each oxygen-
7.1.1 Base gasolines containing no oxygenates, ate in the presence of typical gasoline compounds or other
7.1.2 Methanol, oxygenates that, in typical concentrations, present spectral
7.1.3 Ethanol, interferences. General classes of compounds that will cause
7.1.4 tert-Butanol, interferences include aromatics, branched aliphatic
7.1.5 Methyl tert-butyl ether, MTBE, hydrocarbons, and other oxygenates.
D5845 − 01 (2016)
TABLE 1 Recommended Concentrations for Individual Quality TABLE 2 Pertinent Physical Constants
Control Standards
Relative Density,
Component CAS Number Molecular Mass
15.56 °C
Concentration to Attain
Oxygenate
Methanol 67-56-1 32.04 0.7963
2.0 mass % O 2.7 mass % O 3.5 mass % O
Ethanol 64-17-5 46.07 0.7939
Methanol 4.00 mass % 5.41 mass %
tert-Butanol 75-65-0 74.12 0.7922
Ethanol 5.76 mass % 7.77 mass % 10.1 mass %
MT
...

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: D5845 − 01 (Reapproved 2011) D5845 − 01 (Reapproved 2016)
Standard Test Method for
Determination of MTBE, ETBE, TAME, DIPE, Methanol,
Ethanol and tert-Butanol in Gasoline by Infrared
Spectroscopy
This standard is issued under the fixed designation D5845; 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
1.1 This test method covers the determination of methanol, ethanol, tert-butanol, methyl tert-butyl ether (MTBE), ethyl
tert-butyl ether (ETBE), tert-amyl methyl ether (TAME), and diisopropyl ether (DIPE) in gasoline by infrared spectroscopy. The
test method is suitable for determining methanol from 0.1 to 6 mass %, ethanol from 0.1 to 11 mass %, tert-butanol from 0.1 to
14 mass %, and DIPE, MTBE, ETBE and TAME from 0.1 to 20 mass %.
1.2 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.3 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
2.1 ASTM Standards:
D1298 Test Method for Density, Relative Density, or API Gravity of Crude Petroleum and Liquid Petroleum Products by
Hydrometer Method
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
D4815 Test Method for Determination of MTBE, ETBE, TAME, DIPE, tertiary-Amyl Alcohol and C to C Alcohols in
1 4
Gasoline by Gas Chromatography
D5599 Test Method for Determination of Oxygenates in Gasoline by Gas Chromatography and Oxygen Selective Flame
Ionization Detection
E1655 Practices for Infrared Multivariate Quantitative Analysis
2.2 Other Standard:
GC/OFID EPA Test Method—Oxygen and Oxygenate Content Analysis (by way of gas chromatography with oxygen-selective
flame ionization detection)
3. Terminology
3.1 Definitions:
3.1.1 multivariate calibration, n—a process for creating a calibration model in which multivariate mathematics is applied to
correlate the absorbances measured for a set of calibration samples to reference component concentrations or property values for
the set of samples. The resultant multivariate calibration model is applied to the analysis of spectra of unknown samples to provide
an estimate of the component concentration or property values for the unknown sample.
3.1.2 oxygenate, n—an oxygen-containing organic compound, which may be used as a fuel or fuel supplement, for example,
various alcohols or ethers.
This test method is under the jurisdiction of ASTM Committee D02 on Petroleum Products Products, Liquid Fuels, and Lubricants and is the direct responsibility of
Subcommittee D02.04.0F on Absorption Spectroscopic Methods.
Current edition approved Oct. 1, 2011Oct. 1, 2016. Published November 2011November 2016. Originally approved in 1995. Last previous edition approved in 20062011
as D5845–01(2006).D5845 – 01 (2011). DOI: 10.1520/D5845-01R11.10.1520/D5845-01R16.
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.
Code of Federal Regulations, Part 80 of Title 40, Section 80.46(g); also published in the Federal Register, Volume 59, No. 32, February 16, 1994, p 7828.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D5845 − 01 (2016)
4. Summary of Test Method
4.1 A sample of gasoline is introduced into a liquid sample cell. A beam of infrared light is imaged through the sample onto
a detector, and the detector response is determined. Regions of the infrared spectrum are selected for use in the analysis by either
placing highly selective bandpass filters before or after the sample or mathematically selecting the regions after the whole spectrum
is obtained. A multivariate mathematical analysis is carried out which converts the detector response for the selected regions in
the spectrum of an unknown to a concentration for each component.
5. Significance and Use
5.1 Alcohols and ethers are added to gasoline to produce a reformulated lower emissions gasoline. Alcohols and ethers may also
be added to gasoline to increase the octane number. Type and concentration of various oxygenates are specified and regulated to
ensure acceptable commercial gasoline quality. Driveability, vapor pressure, phase separation, and evaporative emissions are some
of the concerns associated with oxygenated fuels.
5.2 This test method is faster, simpler, less expensive and more portable than current methods.
5.3 This test method may be applicable for quality control in the production of gasoline.
5.4 This test method is not suitable for testing for compliance with federal regulations.
5.5 False positive readings for some of the samples tested in the round robin were sometimes observed. As only extreme base
gasolines were tested in the round robin, no definitive statement can be made as to the expected frequency or magnitude of false
positives expected in a wider range of base gasolines.
6. Apparatus
6.1 Mid-IR Spectrometric Analyzer, of one of the following types:
6.1.1 Filter-based Mid-IR Test Apparatus—The type of apparatus suitable for use in this test method minimally employs an IR
source, an infrared transmission cell or a liquid attenuated total internal reflection cell, wavelength discriminating filters, a chopper
wheel, a detector, an A-D converter, a microprocessor, and a sample introduction system.
6.1.2 Fourier Transform Mid-IR Test Apparatus—The type of apparatus suitable for use in this test method employs an IR
source, an infrared transmission cell or a liquid attenuated total internal reflection cell, a scanning interferometer, a detector, an
A-D converter, a microprocessor and a sample introduction system.
6.1.3 Dispersive Mid-IR Test Apparatus—The type of apparatus suitable for use in this test method minimally employs an IR
source, an infrared transmission cell or a liquid attenuated total internal reflection cell, a wavelength dispersive element such as
a grating or prism, a chopper wheel, a detector, an A-D converter, a microprocessor and a sample introduction system.
7. Reagents and Materials
7.1 Samples for Calibration and Quality Control Check Solutions—Use of chemicals of at least 99 % purity is highly
recommended when preparing calibration and quality control check samples. If reagents of high purity are not available, an
accurate assay of the reagent must be performed using a properly calibrated GC or other techniques (for example, water
determination).
7.1.1 Base gasolines containing no oxygenates,
7.1.2 Methanol,
7.1.3 Ethanol,
7.1.4 tert-Butanol,
7.1.5 Methyl tert-butyl ether, MTBE,
7.1.6 Ethyl tert-butyl ether, ETBE,
7.1.7 tert-Amyl methyl ether, TAME, and
7.1.8 Diisopropyl ether, DIPE.
7.2 Warning—These materials are flammable and may be harmful if ingested or inhaled.
8. Sampling and Sample Handling
8.1 General Requirements:
8.1.1 Gasoline samples must be handled with meticulous care to prevent evaporative loss and composition changes.
8.1.2 Gasoline samples to be analyzed by the test method shall be obtained using method(s) specified by governmental
regulatory agencies or by the procedures outlined in Practice D4057 (or equivalent). Do not use the “Sampling by Water
Displacement” method as some alcohols or ethers might be extracted into the water phase.
8.1.3 Protect samples from excessive temperatures prior to testing. This can be accomplished by storage in an appropriate ice
bath or refrigerator at 00 °C to 5°C.5 °C.
8.1.4 Do not test samples stored in leaky containers. Discard and obtain a new sample if leaks are detected.
8.1.5 Perform the oxygenate determination on fresh samples from containers that are at least 80 % full. If sample containers are
less than 80 % full or have been opened and sampled multiple times, a new sample shall be obtained.
D5845 − 01 (2016)
8.2 Sample Handling During Analysis:
8.2.1 Prior to the analysis of samples by infrared spectroscopy, the samples should be allowed to equilibrate to the temperature
at which they should be analyzed (15(15 °C to 38°C).38 °C).
8.2.2 After withdrawing the sample, reseal the container, and store the sample in an ice bath or a refrigerator at 00 °C to
5°C.5 °C.
9. Preparation, Calibration, and Qualification of the Infrared Test Apparatus
9.1 Preparation—Prepare the instrument for operation in accordance with the manufacturer’s instructions.
9.2 Calibration—Each instrument must be calibrated by the manufacturer or user in accordance with Practice E1655. This
practice serves as a guide for the multivariate calibration of infrared spectrometers used in determining the physical characteristics
of petroleum and petrochemical products. The procedures describe treatment of the data, development of the calibration, and
qualification of the instrument. Note that bias and slope adjustments are specifically not recommended to improve calibration or
prediction statistics for IR multivariate models.
9.3 Qualification of Instrument—The instrument must be qualified according to the procedure in Annex A1 to ensure that the
instrument accurately and precisely measures each oxygenate in the presence of typical gasoline compounds or other oxygenates
that, in typical concentrations, present spectral interferences. General classes of compounds that will cause interferences include
aromatics, branched aliphatic hydrocarbons, and other oxygenates.
10. Quality Control Standards
10.1 Confirm the proper operation of the instrument each day it is used by analyzing at least one quality control standard of
known oxygenate content for each oxygenate to be determined. These standards should be made up by mass according to Practice
D4307 and should be at the expected concentration level for that oxygenate. The recommended quality control standard
concentrations are found in Table 1.
10.2 The individual oxygenate values obtained must
...