ASTM D5845-01(2006)
(Test Method)Standard Test Method for Determination of MTBE, ETBE, TAME, DIPE, Methanol, Ethanol and tert-Butanol in Gasoline by Infrared Spectroscopy
Standard Test Method for Determination of MTBE, ETBE, TAME, DIPE, Methanol, Ethanol and <i>tert</i>-Butanol in Gasoline by Infrared Spectroscopy
SIGNIFICANCE AND USE
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.
This test method is faster, simpler, less expensive and more portable than current methods.
This test method may be applicable for quality control in the production of gasoline.
This test method is not suitable for testing for compliance with federal regulations.3
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 SI units of measurement are preferred and used throughout this standard.
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
Relations
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NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.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 2006)
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 Gasoline by Gas Chromatography and Oxygen Selective
Flame Ionization Detection
1.1 This test method covers the determination of methanol,
E1655 Practices for Infrared Multivariate Quantitative
ethanol, tert-butanol, methyl tert-butyl ether (MTBE), ethyl
Analysis
tert-butyl ether (ETBE), tert-amyl methyl ether (TAME), and
2.2 Other Standard:
diisopropyl ether (DIPE) in gasoline by infrared spectroscopy.
GC/OFID EPATest Method—Oxygen and Oxygenate Con-
The test method is suitable for determining methanol from 0.1
tent Analysis (by way of gas chromatography with
to 6 mass %, ethanol from 0.1 to 11 mass %, tert-butanol from
oxygen-selective flame ionization detection)
0.1 to 14 mass %, and DIPE, MTBE, ETBE and TAME from
0.1 to 20 mass %.
3. Terminology
1.2 SIunitsofmeasurementarepreferredandusedthrough-
3.1 Definitions:
out this standard.
3.1.1 oxygenate, n—an oxygen-containing organic com-
1.3 This standard does not purport to address all of the
pound, which may be used as a fuel or fuel supplement, for
safety concerns, if any, associated with its use. It is the
example, various alcohols or ethers.
responsibility of the user of this standard to establish appro-
3.1.2 multivariate calibration, n—a process for creating a
priate safety and health practices and determine the applica-
calibration model in which multivariate mathematics is applied
bility of regulatory limitations prior to use.
to correlate the absorbances measured for a set of calibration
2. Referenced Documents samples to reference component concentrations or property
values for the set of samples. The resultant multivariate
2.1 ASTM Standards:
calibration model is applied to the analysis of spectra of
D1298 Test Method for Density, Relative Density (Specific
unknown samples to provide an estimate of the component
Gravity), or API Gravity of Crude Petroleum and Liquid
concentration or property values for the unknown sample.
Petroleum Products by Hydrometer Method
D4052 Test Method for Density and Relative Density of
4. Summary of Test Method
Liquids by Digital Density Meter
4.1 A sample of gasoline is introduced into a liquid sample
D4057 Practice for Manual Sampling of Petroleum and
cell. A beam of infrared light is imaged through the sample
Petroleum Products
onto a detector, and the detector response is determined.
D4307 Practice for Preparation of Liquid Blends for Use as
Regions of the infrared spectrum are selected for use in the
Analytical Standards
analysis by either placing highly selective bandpass filters
D4815 Test Method for Determination of MTBE, ETBE,
before or after the sample or mathematically selecting the
TAME, DIPE, tertiary-Amyl Alcohol and C to C Alco-
1 4
regions after the whole spectrum is obtained. A multivariate
hols in Gasoline by Gas Chromatography
mathematical analysis is carried out which converts the detec-
D5599 Test Method for Determination of Oxygenates in
tor response for the selected regions in the spectrum of an
unknown to a concentration for each component.
This test method is under the jurisdiction of ASTM Committee D02 on
5. Significance and Use
Petroleum Products and Lubricants and is the direct responsibility of Subcommittee
D02.04.0F on Absorption Spectroscopic Methods.
5.1 Alcohols and ethers are added to gasoline to produce a
Current edition approved Dec. 1, 2006. Published January 2007. Originally
reformulated lower emissions gasoline. Alcohols and ethers
approved in 1995. Last previous edition approved in 2001 as D5845 – 01. DOI:
may also be added to gasoline to increase the octane number.
10.1520/D5845-01R06.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at service@astm.org. 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 (2006)
Typeandconcentrationofvariousoxygenatesarespecifiedand 8. Sampling and Sample Handling
regulated to ensure acceptable commercial gasoline quality.
8.1 General Requirements:
Driveability, vapor pressure, phase separation, and evaporative
8.1.1 Gasoline samples must be handled with meticulous
emissionsaresomeoftheconcernsassociatedwithoxygenated
care to prevent evaporative loss and composition changes.
fuels.
8.1.2 Gasoline samples to be analyzed by the test method
5.2 This test method is faster, simpler, less expensive and
shall be obtained using method(s) specified by governmental
more portable than current methods.
regulatory agencies or by the procedures outlined in Practice
5.3 Thistestmethodmaybeapplicableforqualitycontrolin
D4057 (or equivalent). Do not use the “Sampling by Water
the production of gasoline.
Displacement” method as some alcohols or ethers might be
5.4 This test method is not suitable for testing for compli-
extracted into the water phase.
ance with federal regulations.
8.1.3 Protect samples from excessive temperatures prior to
5.5 False positive readings for some of the samples tested in
testing. This can be accomplished by storage in an appropriate
the round robin were sometimes observed. As only extreme
ice bath or refrigerator at 0 to 5°C.
base gasolines were tested in the round robin, no definitive
8.1.4 Donottestsamplesstoredinleakycontainers.Discard
statement can be made as to the expected frequency or
and obtain a new sample if leaks are detected.
magnitude of false positives expected in a wider range of base
8.1.5 Performtheoxygenatedeterminationonfreshsamples
gasolines.
from containers that are at least 80 % full. If sample containers
are less than 80 % full or have been opened and sampled
6. Apparatus
multiple times, a new sample shall be obtained.
8.2 Sample Handling During Analysis:
6.1 Mid-IR Spectrometric Analyzer, of one of the following
8.2.1 Prior to the analysis of samples by infrared spectros-
types:
copy, the samples should be allowed to equilibrate to the
6.1.1 Filter-based Mid-IR Test Apparatus—The type of
temperature at which they should be analyzed (15 to 38°C).
apparatus suitable for use in this test method minimally
8.2.2 After withdrawing the sample, reseal the container,
employs an IR source, an infrared transmission cell or a liquid
and store the sample in an ice bath or a refrigerator at 0 to 5°C.
attenuated total internal reflection cell, wavelength discrimi-
nating filters, a chopper wheel, a detector, anA-D converter, a
9. Preparation, Calibration, and Qualification of the
microprocessor, and a sample introduction system.
Infrared Test Apparatus
6.1.2 Fourier Transform Mid-IR Test Apparatus—The type
9.1 Preparation—Prepare the instrument for operation in
of apparatus suitable for use in this test method employs an IR
accordance with the manufacturer’s instructions.
source, an infrared transmission cell or a liquid attenuated total
9.2 Calibration—Each instrument must be calibrated by the
internal reflection cell, a scanning interferometer, a detector, an
manufacturer or user in accordance with Practice E1655. This
A-D converter, a microprocessor and a sample introduction
practice serves as a guide for the multivariate calibration of
system.
infrared spectrometers used in determining the physical char-
6.1.3 Dispersive Mid-IR Test Apparatus—The type of appa-
acteristics of petroleum and petrochemical products. The
ratus suitable for use in this test method minimally employs an
procedures describe treatment of the data, development of the
IR source, an infrared transmission cell or a liquid attenuated
calibration, and qualification of the instrument. Note that bias
total internal reflection cell, a wavelength dispersive element
and slope adjustments are specifically not recommended to
such as a grating or prism, a chopper wheel, a detector, anA-D
improve calibration or prediction statistics for IR multivariate
converter, a microprocessor and a sample introduction system.
models.
9.3 Qualification of Instrument—The instrument must be
7. Reagents and Materials
qualifiedaccordingtotheprocedureinAnnexA1toensurethat
7.1 Samples for Calibration and Quality Control Check
the instrument accurately and precisely measures each oxygen-
Solutions—Use of chemicals of at least 99 % purity is highly
ate in the presence of typical gasoline compounds or other
recommended when preparing calibration and quality control
oxygenates that, in typical concentrations, present spectral
check samples. If reagents of high purity are not available, an
interferences. General classes of compounds that will cause
accurate assay of the reagent must be performed using a
interferences include aromatics, branched aliphatic hydrocar-
properly calibrated GC or other techniques (for example, water
bons, and other oxygenates.
determination).
10. Quality Control Standards
7.1.1 Base gasolines containing no oxygenates,
7.1.2 Methanol,
10.1 Confirm the proper operation of the instrument each
7.1.3 Ethanol,
day it is used by analyzing at least one quality control standard
7.1.4 tert-Butanol,
of known oxygenate content for each oxygenate to be deter-
7.1.5 Methyl tert-butyl ether, MTBE,
mined. These standards should be made up by mass according
7.1.6 Ethyl tert-butyl ether, ETBE, to Practice D4307 and should be at the expected concentration
7.1.7 tert-Amyl methyl ether, TAME, and
level for that oxygenate. The recommended quality control
7.1.8 Diisopropyl ether, DIPE. standard concentrations are found in Table 1.
7.2 Warning—These materials are flammable and may be 10.2 The individua
...
Questions, Comments and Discussion
Ask us and Technical Secretary will try to provide an answer. You can facilitate discussion about the standard in here.