An American National Standard

Designation: D 5845 – 01

Standard Test Method for

Determination of MTBE, ETBE, TAME, DIPE, Methanol,
Ethanol and tert-Butanol in Gasoline by Infrared
Spectroscopy1
This standard is issued under the fixed designation D 5845; 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 (e) indicates an editorial change since the last revision or reapproval.

1. Scope Flame Ionization Detection4

1.1 This test method covers the determination of methanol, E 1655 Practice for Infrared Multivariate Quantitative
ethanol, tert-butanol, methyl tert-butyl ether (MTBE), ethyl Analysis5
tert-butyl ether (ETBE), tert-amyl methyl ether (TAME), and 2.2 Other Standard:
diisopropyl ether (DIPE) in gasoline by infrared spectroscopy. GC/OFID EPA Test Method—Oxygen and Oxygenate Con-
The test method is suitable for determining methanol from 0.1 tent Analysis6 (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 3. Terminology
0.1 to 20 mass %.
1.2 SI units of measurement are preferred and used through- 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
samples to reference component concentrations or property
2. Referenced Documents values for the set of samples. The resultant multivariate
2.1 ASTM Standards: calibration model is applied to the analysis of spectra of
D 1298 Practice 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 Method2 4. Summary of Test Method
D 4052 Test Method for Density and Relative Density of
Liquids by Digital Density Meter3 4.1 A sample of gasoline is introduced into a liquid sample
D 4057 Practice for Manual Sampling of Petroleum and cell. A beam of infrared light is imaged through the sample
Petroleum Products3 onto a detector, and the detector response is determined.
D 4307 Practice for Preparation of Liquid Blends for Use as Regions of the infrared spectrum are selected for use in the
Analytical Standards3 analysis by either placing highly selective bandpass filters
D 4815 Test Method for Determination of MTBE, ETBE, before or after the sample or mathematically selecting the
TAME, DIPE, tert-Amyl Alcohol, and C1 to C4 Alcohols regions after the whole spectrum is obtained. A multivariate
in Gasoline by Gas Chromatography3 mathematical analysis is carried out which converts the detec-
D 5599 Test Method for Determination of Oxygenates in tor response for the selected regions in the spectrum of an
Gasoline by Gas Chromatography and Oxygen Selective unknown to a concentration for each component.
5. Significance and Use
5.1 Alcohols and ethers are added to gasoline to produce a
1
This test method is under the jurisdiction of ASTM Committee D02 on reformulated lower emissions gasoline. Alcohols and ethers
Petroleum Products and Lubricants and is the direct responsibility of Subcommittee
D02.04.0F on Absorption Spectroscopic Methods.
Current edition approved Dec. 10, 2001. Published February 2002. Originally
published as D 5845 – 95. Last previous edition D 5845 – 95 (2000)e1. 4
Annual Book of ASTM Standards, Vol 05.03.
2 5
Annual Book of ASTM Standards, Vol 05.01. Annual Book of ASTM Standards, Vol 03.06.
3 6
Annual Book of ASTM Standards, Vol 05.02. 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.

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 D 5845
may also be added to gasoline to increase the octane number. 8. Sampling and Sample Handling
Type and concentration of various oxygenates are specified and 8.1 General Requirements:
regulated to ensure acceptable commercial gasoline quality. 8.1.1 Gasoline samples must be handled with meticulous
Driveability, vapor pressure, phase separation, and evaporative care to prevent evaporative loss and composition changes.
emissions are some of the concerns associated with oxygenated 8.1.2 Gasoline samples to be analyzed by the test method
fuels. shall be obtained using method(s) specified by governmental
5.2 This test method is faster, simpler, less expensive and regulatory agencies or by the procedures outlined in Practice
more portable than current methods. D 4057 (or equivalent). Do not use the “Sampling by Water
5.3 This test method may be applicable for quality control in Displacement” method as some alcohols or ethers might be
the production of gasoline. extracted into the water phase.
5.4 This test method is not suitable for testing for compli- 8.1.3 Protect samples from excessive temperatures prior to
ance with federal regulations.6 testing. This can be accomplished by storage in an appropriate
5.5 False positive readings for some of the samples tested in ice bath or refrigerator at 0 to 5°C.
the round robin were sometimes observed. As only extreme 8.1.4 Do not test samples stored in leaky containers. Discard
base gasolines were tested in the round robin, no definitive and obtain a new sample if leaks are detected.
statement can be made as to the expected frequency or 8.1.5 Perform the oxygenate determination on fresh samples
magnitude of false positives expected in a wider range of base from containers that are at least 80 % full. If sample containers
gasolines. 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, an A-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 E 1655. 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, an A-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
qualified according to the procedure in Annex A1 to ensure that
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).
7.1.1 Base gasolines containing no oxygenates, 10. Quality Control Standards
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 D 4307 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 individual oxygenate values obtained must agree
harmful if ingested or inhaled. within 6 5 % relative of the values in the prepared quality

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 D 5845
TABLE 1 Recommended Concentrations for Individual Quality Df = relative density of the fuel at 15.56°C under study as
Control Standards
determined by Practice D 1298 or Test Method
Concentration to Attain
Oxygenate D 4052. If the density has not been measured, an
2.0 mass % O 2.7 mass % O 3.5 mass % O assumed density of 0.742 should be used.
Methanol 4.00 mass % 5.41 mass % 12.2 Total Mass % Oxygen—To determine the total oxygen
Ethanol 5.76 mass % 7.77 mass % 10.1 mass %
tert-Butanol 9.26 mass % 12.5 mass %
content of the fuel, sum the mass % oxygen contents of all
MTBE 11.0 mass % 14.9 mass % oxygenate components determined above according to Eq 2:
TAME 12.8 mass % 17.2 mass %
DIPE 12.8 mass % 17.2 mass %
Wtot 5 ( @~mi 3 16.0 3 Ni!/Mi# (2)
ETBE 12.8 mass % 17.2 mass %

where:
Wtot = total mass % oxygen in the fuel,
mi = mass % for each oxygenate,
control standard (for example, MTBE 14.0 6 0.7 mass %) or 16.0 = atomic mass of oxygen,
to within6 0.3 mass % absolute, whichever is greater (for Ni = number of oxygen atoms in the oxygenate mol-
example, methanol 4.06 0.3 mass % ). If the individual values ecule, and
are outside the specified range, recalibrate the instrument Mi = molecular mass of the oxygenate molecule as given
according to the procedures in 9.2. The quality control stan- in Table 2.
dards should not be used for the calibration or recalibration of
the instrument. Do not analyze samples without meeting the 13. Report
quality control specifications. 13.1 Report results of each oxygenate and the total oxygen
to the nearest 0.1 mass %.
11. Procedure 14. Precision and Bias 7
11.1 Equilibrate the samples to between 15 and 38°C before 14.1 The precision of the method as obtained by statistical
analysis. examination of interlaboratory results is as follows:
11.2 Follow the manufacturer’s instructions for establishing 14.2 Repeatability—The difference between successive test
a baseline for the instrument, introducing a sample into the results, obtained by the same operator with the same apparatus
sample cell and operating the instrument. If the instructions under constant operating conditions on identical test material
call for a non-oxygenated gasoline to be used in establishing would, in the long run, in the normal and correct operation of
the baseline, use a non-oxygenated gasoline that is different the test method exceed the following values only in one case in
from the non-oxygenated gasolines used in the preparation of twenty:
either calibration standards, validation of qualification samples, Oxygenate Repeatability (mass %)
MTBE 0.13
or quality control standards. TAME 0.13
11.3 Thoroughly clean the sample cell by introducing ETBE 0.15
Ethanol 0.13
enough sample to the cell to ensure the cell is washed a Methanol 0.07
minimum of three times with the test solution. t-Butanol 0.10
DIPE 0.14
11.4 Establish that the equipment is running properly by Total Oxygen Content 0.05
running the quality control standards prior to the analysis of
14.3 Reproducibility—The difference between two single
unknown test samples (see Section 10).
and independent results, obtained by different operators work-
11.5 Introduce the sample in the manner established by the ing in different laboratories on identical test materials would, in
manufacturer. Obtain the concentration reading produced by the long run, exceed the following values only in one case in
the instrument. twenty:

12. Calculation 7
Supporting data available from ASTM International Headquarters. Request
12.1 Conversion to Mass Concentration of Oxygenates—If D02-1374.
the instrument readings are in volume % for each component,
convert the results to mass % according to Eq 1: TABLE 2 Pertinent Physical Constants
Relative Density,
mi 5 Vi ~Di/Df! (1) Component CAS Number Molecular Mass
15.56°C
Methanol 67-56-1 32.04 0.7963
where: Ethanol 64-17-5 46.07 0.7939
tert-Butanol 75-65-0 74.12 0.7922
mi = mass % for each oxygenate to be determined, MTBE 1634-04-4 88.15 0.7460
Vi = volume % of each oxygenate, DIPE 108-20-3 102.18 0.7300
Di = relative density at 15.56°C of the individual oxygen- ETBE 637-92-3 102.18 0.7452
TAME 994-05-8 102.18 0.7758
ate as found in Table 2,

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 D 5845
Oxygenate Reproducibility (mass %) base gasolines was not tested, it is not possible to offer a
MTBE 0.98 definitive statement of bias except to note that biases were
TAME 1.36
ETBE 0.77 observed in the round robin.
Ethanol 0.59
Methanol 0.37
t-Butanol 0.59
15. Keywords
DIPE 0.79
Total Oxygen Content 0.30
15.1 alcohols; diisopropyl ether; ethanol; ethers; ethyl tert-
butyl ether; methanol; methyl tert-butyl ether; motor gasoline;
14.4 Bias—No consistent bias was observed with the oxygenate; tert-amyl methyl ether; tert-butanol
samples tested in the round robin and since a wide range of

ANNEX

(Mandatory Information)

A1. QUALIFICATION OF INSTRUMENT

A1.1 Preparation of Qualification Samples —The mini- chromatographic analysis of the base gasolines must be per-
mum matrix of qualification standards is presented in Table formed to ensure the absence of oxygenates (use Test Methods
A1.1. Additional qualification standards may be added. Prepare D 4815, D 5599, or GC-OFID). To ensure the insensitivity of
multicomponent qualification standards of the oxygenates by the calibration to the hydrocarbon matrix of the base gasolines,
mass according to Practice D 4307 or appropriately scaled for the base gasolines used for preparation of the qualification
larger blends. To ensure that there is minimum interference samples should be different from the base gasoline(s) used for
from any oxygenate present in the base gasolines, a gas preparation of the calibration standards. To minimize the
TABLE A1.1 Minimum Matrix for Qualification Samples

NOTE 1—All concentrations are mass %.

Sample Base GasA MTBE TAME ETBE Ethanol Methanol t-Butanol DIPE
1 A 10
2 A 5
3 A 16.5
4 A 9 1.5 2
5 A 18.5
6 A 4 12 1.25
7 A 17
8 A 9.5 4
9 A 5.5
10 A 3 3.5
11 A 12
12 A 9 6
13 A 16.5
14 A 7 10
15 A 7 3 6
16 A 5 5 3 3 5
17 A 1.5 2 2
18 A 2 7
19 B 9
20 B 6
21 B 14
22 B 10 2 1.5
23 B 16.5
24 B 4 11 2
25 B 15.5
26 B 8 5
27 B 5
28 B 3 3.5
29 B 12
30 B 5 8
31 B 16.5
32 B 6 9
33 B 6 3 4
34 B 2 8 2 4
35 B 1.5 1.5 1.5 7
36 B 8 4
A
Base gasoline A should be a gasoline with at least 60 % alkylate. A suggested recipe for base gasoline A is 60 % alkylate, 30 % full range reformate, and 10 % light
straight run. Base gasoline B should be a gasoline with at least 60 % full range reformate. A suggested recipe for base gasoline B is 60 % full range reformate, 30 % FCC
gasoline, and 10 % light straight run.

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 D 5845
evaporation of light components, adjust the temperature of all TABLE A1.2 Maximum Error Allowed for Qualification of
chemicals and gasolines used to prepare standards to between Instrument
5 and 20°C. None of the samples or base gasolines used in the Error When
Error When
Oxygenate Is
qualification of calibration may be used for the calibration (or Oxygenate Known To Be
Oxygenate Is Not
Present, mass %,
recalibration) of an instrument. Present, mass %,
max
max
A1.1.1 Analysis of Qualification Samples—The qualifica-
MTBE 1.5 0.9
tion samples should be analyzed by the procedure specified in TAME 2.0 1.8
Section 11. If necessary, results should be converted from ETBE 1.2 1.9
volume to mass % by the calculations described in Section 12. Ethanol 0.9 0.6
Methanol 0.6 0.3
A1.1.2 Criteria for Qualification of Instrument—The in- t-Butanol 0.9 0.9
strument is considered to be qualified if the following specifi- DIPE 1.2 0.9
cations are all met:
A1.1.2.1 Accuracy of Each Oxygenate—Analysis of each
of the oxygenates in each of the qualification standards must be TABLE A1.3 Maximum Standard Error of Prediction Allowed for
within the criteria established in Table A1.2. If it is known that Qualification of Instrument
an analyte is not present in a particular qualification sample, SEQ Summed Over SEQ Summed Over
Oxygenate Samples Containing All Samples In The
the value determined for that analyte must be less than the The Oxygenate, max Qualification Set, max
criteria also established in Table A1.2.
MTBE 0.9 0.5
A1.1.2.2 Overall Accuracy—The standard error of qualifi- TAME 1.2 0.9
cation (SEQ) for each analyte summed over all samples in the ETBE 0.75 0.6
qualification set must be within the criteria established in Table Ethanol 0.4 0.25
Methanol 0.25 0.15
A1.3. t-Butanol 0.55 0.45
A1.1.2.3 Overall Repeatability—Each sample of the quali- DIPE 0.6 0.35
fication set must be run twice. Repeat determinations of any
sample can differ by no more than 0.3 mass %.
A1.1.3 Frequency of Qualification—Once the calibration of or when the quality control check samples are outside of the
the instrument has been qualified, it need only be requalified test tolerance.
when either the instrument has been recalibrated due to repair

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