An American National Standard

Designation: D 5622 – 95 (Reapproved 2005)

Standard Test Methods for

Determination of Total Oxygen in Gasoline and Methanol
Fuels by Reductive Pyrolysis1
This standard is issued under the fixed designation D 5622; 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 D 4057 Practice for Manual Sampling of Petroleum and

1.1 These test methods cover the quantitative determination Petroleum Products
of total oxygen in gasoline and methanol fuels by reductive D 4815 Test Method for Determination of MTBE, ETBE,
pyrolysis. TAME, DIPE, tertiary-Amyl Alcohol and C1 to C4 Alco-
1.2 Precision data are provided for 1.0 to 5.0 mass % hols in Gasoline by Gas Chromatography
oxygen in gasoline and for 40 to 50 mass % oxygen in 2.2 Other Standards:
methanol fuels. Clean Air Act (1992) 3
1.3 Several types of instruments can be satisfactory for 3. Summary of Test Method
these test methods. Instruments can differ in the way that the
oxygen-containing species is detected and quantitated. How- 3.1 A fuel specimen of 1 to 10 µL is injected by syringe into
ever, these test methods are similar in that the fuel is pyrolyzed a 950 to 1300°C high-temperature tube furnace that contains
in a carbon-rich environment. metallized carbon. Oxygen-containing compounds are pyro-
1.4 The values stated in SI units are to be regarded as the lyzed, and the oxygen is quantitatively converted into carbon
standard. The values given in parentheses are for information monoxide.
only. 3.2 A carrier gas, such as nitrogen, helium, or a helium/
1.5 This standard does not purport to address all of the hydrogen mixture, sweeps the pyrolysis gases into any of four
safety concerns, if any, associated with its use. It is the downstream systems of reactors, scrubbers, separators, and
responsibility of the user of this standard to establish appro- detectors for the determination of the carbon monoxide con-
priate safety and health practices and determine the applica- tent, hence of the oxygen in the original fuel sample. The result
bility of regulatory limitations prior to use. is reported as mass % oxygen in the fuel.

2. Referenced Documents 4. Significance and Use

2.1 ASTM Standards: 2 4.1 These test methods cover the determination of total
D 1298 Test Method for Density, Relative Density (Specific oxygen in gasoline and methanol fuels, and they complement
Gravity), or API Gravity of Crude Petroleum and Liquid Test Method D 4815, which covers the determination of
Petroleum Products by Hydrometer Method several specific oxygen-containing compounds in gasoline.
D 4052 Test Method for Density and Relative Density of 4.2 The presence of oxygen-containing compounds in gaso-
Liquids by Digital Density Meter line can promote more complete combustion, which reduces
carbon monoxide emissions. The Clean Air Act (1992) requires
that gasoline sold within certain, specified geographical areas
1
These test methods are under the jurisdiction of Committee D02 on Petroleum contain a minimum percent of oxygen by mass (presently 2.7
Products and Lubricants and are the direct responsibility of Subcommittee D02.03 mass %) during certain portions of the year. The requirement
on Elemental Analysis.
Current edition approved May 1, 2005. Published June 2005. Originally
can be met by blending compounds such as methyl tertiary
approved in 1994. Last previous edition approved in 2000 as D 5622–95(2000). butyl ether, ethyl tertiary butyl ether, and ethanol into the
2
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
3
the ASTM website. Federal Register, Vol 57, No. 24, Feb. 5, 1992, p. 4408.

Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.

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 D 5622 – 95 (2005)
gasoline. These test methods cover the quantitative determina- 5.3 For instruments that measure carbon monoxide only,
tion of total oxygen which is the regulated parameter. pyrolysis conditions must be established to quantitatively
convert oxygen to carbon monoxide.
5. Apparatus 5.4 A system of scrubbers and separators must be estab-
5.1 Oxygen Elemental Analyzer4,5,6,7,8—A variety of instru- lished to effectively remove pyrolysis products that interfere
mentation can be satisfactory. However, the instrument must with the detection of carbon monoxide or carbon dioxide, or
reductively pyrolize the specimen and convert oxygen to both.
carbon monoxide. 5.5 The detector responses must be linear with respect to
concentration, or nonlinear responses must be detectable and
5.1.1 Test Method A4,8—Helium carrier gas transports the
accurately related to concentration.
pyrolysis products through a combination scrubber to remove
5.6 Selected items are available from the instrument manu-
acidic gases and water vapor. The products are then transported
facturer.
to a molecular sieve gas chromatographic column where the
5.6.1 Pyrolysis Tubes,
carbon monoxide is separated from the other pyrolysis prod-
5.6.2 Scrubber Tubes, and
ucts. A thermal conductivity detector generates a response that
5.6.3 Absorber Tubes.
is proportional to the amount of carbon monoxide.
5.1.2 Test Method B5,8—Nitrogen carrier gas transports the 6. Reagents
pyrolysis products through a scrubber to remove water vapor.
6.1 Purity of Reagents9—Reagent grade chemicals shall be
The pyrolysis products then flow through tandem infrared
used in all tests. Unless otherwise indicated, it is intended that
detectors that measure carbon monoxide and carbon dioxide,
all reagents conform to the specifications of the Committee on
respectively.
Analytical Reagents of the American Chemical Society where
5.1.3 Test Method C6,8—A mixture of helium and hydrogen such specifications are available. Other grades may be used,
(95:5 %), helium, or argon transports the pyrolysis products provided it is first ascertained that the reagent is of sufficiently
through two reactors in series. The first reactor contains heated high purity to permit its use without lessening the accuracy of
copper which removes sulfur-containing products. The second the determination.
reactor contains a scrubber which removes acidic gases and a 6.2 Calibration Standards:
reactant which oxidizes carbon monoxide to carbon dioxide 6.2.1 NIST SRM 1837,10 which contains certified concen-
(optional). The product gases are then homogenized in a trations of methanol and t-butanol in reference fuel, can be
mixing chamber, which maintains the reaction products at used to calibrate the instrument for the analysis of oxygenates
absolute conditions of temperature, pressure, and volume. The in gasoline.
mixing chamber is subsequently depressurized through a 6.2.2 Anhydrous methanol, 99.8 % minimum assay, can be
column that separates carbon monoxide (or carbon dioxide, if used to calibrate the instrument for the analysis of methanol
operating in the oxidation mode) from interfering compounds. fuels.
A thermal conductivity detector measures a response propor- 6.2.3 Isooctane, or other hydrocarbons, can be used as the
tional to the amount of carbon monoxide or carbon dioxide. blank provided the purity is satisfactory.
5.1.4 Test Method D7,8—Nitrogen carrier gas transports the 6.3 Quality Control Standard—NIST SRM 183810 can be
pyrolysis products through scrubbers to remove acidic gases used to check the accuracy of the calibration.
and water vapor. A reactor containing cupric oxide at 325°C 6.4 The instrument manufacturers require additional re-
oxidizes the carbon monoxide to carbon dioxide, which in turn agents.
is transported into a coulometric carbon dioxide detector. 6.4.1 Test Method A: 4,8
Coulometrically generated base titrates the acid formed by 6.4.1.1 Anhydrone (anhydrous magnesium perchlorate),
reacting carbon dioxide with monoethanolamine. 6.4.1.2 Ascarite II (sodium hydroxide on silica),
5.2 A technique must be established to make a quantitative 6.4.1.3 Helium carrier gas, 99.995 % pure,
introduction of the test specimen into the analyzer. Specimen 6.4.1.4 Molecular sieve, 5Å, 60 to 80 mesh,
vials and transfer labware must be clean and dry. 6.4.1.5 Nickel wool,
6.4.1.6 Nickelized carbon, 20 % loading,
6.4.1.7 Quartz chips, and
4
6.4.1.8 Quartz wool.
The sole source of supply of the apparatus (Carlo Erba Models 1106 and 1108)
known to the committee at this time is CE Elantech, Inc., 170 Oberlin Ave. N., Ste 6.4.2 Test Method B:5,8
5, Lakewood, NJ 08701. 6.4.2.1 Anhydrone (anhydrous magnesium perchlorate),
5
The sole source of supply of the apparatus (Leco Model RO-478) known to the
committee at this time is Leco Corp., 3000 Lakeview Ave., St. Joseph, MI 49085.
6
The sole source of supply of the apparatus (Perkin-Elmer Series 2400) known
9
to the committee at this time is Perkin-Elmer Corp., 761 Main Ave., Norwalk, CT Reagent Chemicals, American Chemical Society Specifications, American
06859. Chemical Society, Washington, DC. For suggestions on the testing of reagents not
7
The sole source of supply of the apparatus (UIC, Inc./Coulometrics Model 5012 listed by the American Chemical Society, see Analar Standards for Laboratory
CO2 coulometer and Model 5220 autosampler-furnace) known to the committee at Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
this time is UIC Inc., Box 863, Joliet, IL 60434. and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
8
If you are aware of alternative suppliers, please provide this information to MD.
10
ASTM International Headquarters. Your comments will receive careful consider- Available from the National Institute of Standards and Technology, Gaithers-
ation at a meeting of the responsible technical committee,1 which you may attend. burg, MD 20899.

2
 D 5622 – 95 (2005)
6.4.2.2 Carbon pyrolysis pellets, and = volume of the SRM (µL) 3 density of the SRM
6.4.2.3 Nitrogen carrier gas, 99.99 % pure. (g/mL), and
6.4.3 Test Method C:6,8 Ravg = average of the blank corrected responses.
6.4.3.1 Anhydrone (anhydrous magnesium perchlorate),
6.4.3.2 Ascarite II (sodium hydroxide on silica), NOTE 1—Density can be determined by Test Method D 1298 or Test
Method D 4052.
6.4.3.3 Carrier gas, either helium (95 %)/hydrogen (5 %),
mixture, 99.99 % pure; helium, 99.995 % pure; or argon, 9.2 Calibration for Test Methods A, B, and C, Methanol
99.98 % pure, Fuels—Repeat procedure 9.1; however, substitute anhydrous
6.4.3.4 Copper plus, wire form, and methanol for the SRM. For methanol fuels, a unique K-factor
6.4.3.5 Platinized carbon. can be necessary.
6.4.4 Test Method D:7,8 9.3 Calibration for Test Method D—This test method does
6.4.4.1 Anhydrone (anhydrous magnesium perchlorate), not require calibration; however, a quality control standard
6.4.4.2 Ascarite II (sodium hydroxide on silica), must be analyzed to ensure proper operation of the instrument.
6.4.4.3 Copper (II) oxide, A blank must also be analyzed periodically to ensure consistent
6.4.4.4 Coulometric cell solutions, including a cathode so- responses.
lution of monoethanolamine in dimethyl sulfoxide and an
anode solution of water and potassium iodide in dimethyl 9.4 Quality Control (QC):
sulfoxide, 9.4.1 Introduce the QC standard SRM 183810 in the same
6.4.4.5 Nickelized carbon, 20 % loading, and manner as the calibration standards. Calculate the percent
6.4.4.6 Nitrogen carrier gas, 99.99 % pure. oxygen (m/m) as described in Section 10.
9.4.2 When results obtained on the QC standard do not
7. Sampling agree with the certified values within 2 % relative, take
7.1 Take samples in accordance with the instructions in corrective action and repeat the calibration and quality control.
Practice D 4057. 9.4.3 For Test Method D, when the recovery of oxygen from
7.2 Visually inspect the samples, and when there is evidence the QC SRM is less than 0.85 (that is, 85 %), take corrective
of nonuniformity, take fresh samples. action and repeat the quality control. Recoveries that are
7.3 Store the samples in a cold room or a laboratory greater than 0.85 but less than unity can be used to correct the
refrigerator designed for storage of chemicals. calculated result (refer to the r parameter in Section 10).
9.5 Procedure:
8. Preparation of Apparatus
9.5.1 Introduce the samples, and record the instrument
8.1 Prepare the instrument in accordance with the manufac- response. Calculate the results as described in Section 10. Use
turer’s recommendations. These test methods require that
the appropriate K-factor for oxygenates in gasoline and metha-
correct operating procedures are followed for the model used.
nol fuels.
Instrument design differences make it impractical to specify all
of the required operating conditions. 9.5.2 Recalibrate the instrument with the appropriate cali-
8.2 The carrier gas can be scrubbed to remove traces of bration standard after each set of ten samples.
oxygen and oxygen-containing compounds.
10. Calculation and Report
9. Calibration and Standardization 10.1 Calculate the mass % oxygen for the QC standard and
9.1 Calibration for Test Methods A, B, and C, Oxygenates in samples as follows:
Gasoline: R3K
9.1.1 Use a syringe to introduce 1 to 10 µL, or 1 to 10 mg, Mass % Oxygen 5 M3 r (2)
of the blank. The amount of specimen must be precisely
known. Measure the response. Repeat the introduction and where:
measurement until stable readings are observed. R = blank corrected instrument response,
9.1.2 In similar fashion, introduce 1 to 10 µL, or 1 to 10 mg, K = K-factor, refer to Eq 1, assume unity for Test Method
of SRM 183710 and measure the response. Repeat two times D,
with the same quantity of the SRM. If the blank corrected M = mass of sample, mg,
responses do not agree within 2 % relative, take corrective = volume (µL) 3 density (g/mL), and
action and repeat the calibration. r = recovery, refer to 9.4.3, assume unity for Test Meth-
ods A, B, and C.
9.1.3 Calculate the K-factor as follows:
10.2 For instruments with computer data systems, the cal-
Cstd 3 Mstd
K5 Ravg (1) culation of the K-factor (Eq 1) and the calculation of mass %
oxygen (Eq 2) can be automatic with a digital readout
where: provided.
C std = mass % oxygen in the SRM, 10.3 Report mass % oxygen to the nearest 0.01 %.
Mstd = mass of the SRM, mg,

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 D 5622 – 95 (2005)
11. Precision and Bias 11 Mass % Oxygen Range Repeatability, Mass % Oxygen
1.0 to 5.0 % 0.06 %
11.1 Precision—The precision of these test methods was 40 to 50 % 0.81 %
determined by statistical analysis of interlaboratory test results.
Twelve laboratories analyzed in duplicate eight different 11.1.2 Reproducibility—The difference between two single
samples, providing a total of thirteen data sets. One laboratory and independent results, obtained by different operators work-
used two different test methods. The breakdown on data sets by ing in different laboratories on identical test materials, would in
test method is: Test Method A, three; Test Method B, two; Test the long run, in the normal and correct operation of the test
Method C, three; Test Method D, five. The statistical analysis method, exceed the following values in only one case in
was performed on the set of 13 data sets because the reductive twenty.
pyrolysis technique is common to all four test methods. Mass % Oxygen Range Reproducibility, Mass % Oxygen
1.0 to 5.0 % 0.26 %
Separate statistics were not determined for individual test 40 to 50 % 0.81 %
methods. The sample set included anhydrous methanol and
gasoline stocks that were spiked with one or more of the 11.2 Bias—Bias was determined from interlaboratory re-
following: isobutanol, n-butanol, sec-butanol, tert-butanol, di- sults obtained on NIST SRM 1838,10 which contains ethanol.
isopropyl ether, ethanol, ethyl tert-butyl ether, methanol, me- The null hypothesis that was tested was that the true difference
thyl tert-butyl ether, n-propanol, isopropanol, tert-amyl methyl between the grand average result and the NIST certified value
ether. is zero. The result of the hypothesis testing was that if the true
11.1.1 Repeatability—The difference between two test re- difference was zero, the determined difference would occur by
sults, obtained by the same operator with the same apparatus chance approximately 50 % of the time. Hence, the null
under constant operating conditions on identical test materials hypothesis of no difference or no bias is accepted.
would, in the long run, in the normal and correct operation of 12. Keywords
the test method, exceed the following values in only one case
in twenty. 12.1 carbon dioxide; carbon monoxide; di-isopropyl ether;
ethanol; ethyl tert-butyl ether; isobutanol; isopropanol; metha-
nol; methyl tert-butyl ether; n-butanol; n-propanol; oxygen;
11
Supporting data have been filed at ASTM International Headquarters and may reductive pyrolysis; sec-butanol; tert-butanol; tert-amyl methyl
be obtained by requesting Research Report RR:D02-1338. ether

APPENDIX

(Nonmandatory Information)

X1. EFFECT OF WATER IN GASOLINE CONTAINING OXYGENATES

X1.1 The Clean Air Act (1992) requirement for oxygenates tert-butyl ether, sec-butanol, n-butanol, methanol, di-isopropyl
in gasoline implicitly excludes water-borne oxygen from the ether, n-propanol. A few millilitres of each water-spiked
specification for total oxygen. Experimental evidence indicates gasoline were treated with 200 mg of potassium carbonate
that for typical oxygenated gasolines, the maximum amount of prior to analysis. The results obtained on the treated, spiked
soluble water is approximately 0.1 mass %. This corresponds samples did not differ from the results obtained on the neat
to 0.09 mass % oxygen which is very close to the repeatability gasolines by more than 0.02 mass % oxygen, which is within
of these test methods. When oxygen from dissolved water must the repeatability of these test methods.
be excluded from the analysis, the gasoline can be pretreated
with potassium carbonate or Molecular Sieve 3A prior to X1.3 The literature13 describes an alternative technique for
analysis by these test methods. removing water from gasoline, namely, treatment of the
gasoline with Molecular Sieve 3A. In an experiment similar to
X1.2 According to the patent literature,12 gasoline can be that described in X1.2, water-spiked, oxygenated gasolines
treated with potassium carbonate to remove dissolved water. were pretreated with Sieve 3A prior to analysis by Test Method
Test Method B was used to analyze five different gasolines that B. The results obtained on the sieve treated, spiked samples did
were spiked with 0.1 mass % water. These gasolines contained not differ from the results obtained on the neat gasolines by
one or more of the following oxygenates at concentrations more than the repeatability of these test methods.
typical of gasolines: tert-amyl methyl ether, ethanol, ethyl
13
Burfield, D. R., and Smithers, R. H., “Desiccant Efficiency in Solvent and
Reagent Drying,” Journal of Organic Chemistry, Vol 48, No. 14, 1983, pp.
12
U.S. Patent No. 4 539 013, Sept. 3, 1985. 2420–2422.

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 D 5622 – 95 (2005)

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