ASTM D5622-95(2000)
(Test Method)Standard Test Methods for Determination of Total Oxygen in Gasoline and Methanol Fuels by Reductive Pyrolysis
Standard Test Methods for Determination of Total Oxygen in Gasoline and Methanol Fuels by Reductive Pyrolysis
SCOPE
1.1 These test methods cover the quantitative determination of total oxygen in gasoline and methanol fuels by reductive pyrolysis.
1.2 Precision data are provided for 1.0 to 5.0 mass% oxygen in gasoline and for 40 to 50 mass% oxygen in methanol fuels.
1.3 Several types of instruments can be satisfactory for these test methods. Instruments can differ in the way that the oxygen-containing species is detected and quantitated. However, these test methods are similar in that the fuel is pyrolyzed in a carbon-rich environment.
1.4 The values stated in SI units are to be regarded as the standard. The values given in parentheses are for information only.
1.5 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.
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Standards Content (Sample)
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An American National Standard
Designation:D5622–95 (Reapproved 2000)
Standard Test Methods for
Determination of Total Oxygen in Gasoline and Methanol
Fuels by Reductive Pyrolysis
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 3. Summary of Test Method
1.1 These test methods cover the quantitative determination 3.1 Afuel specimen of 1 to 10 µLis injected by syringe into
of total oxygen in gasoline and methanol fuels by reductive a 950 to 1300°C high-temperature tube furnace that contains
pyrolysis. metallized carbon. Oxygen-containing compounds are pyro-
1.2 Precision data are provided for 1.0 to 5.0 mass % lyzed, and the oxygen is quantitatively converted into carbon
oxygen in gasoline and for 40 to 50 mass % oxygen in monoxide.
methanol fuels. 3.2 A carrier gas, such as nitrogen, helium, or a helium/
1.3 Several types of instruments can be satisfactory for hydrogen mixture, sweeps the pyrolysis gases into any of four
these test methods. Instruments can differ in the way that the downstream systems of reactors, scrubbers, separators, and
oxygen-containing species is detected and quantitated. How- detectors for the determination of the carbon monoxide con-
ever, these test methods are similar in that the fuel is pyrolyzed tent,henceoftheoxygenintheoriginalfuelsample.Theresult
in a carbon-rich environment. is reported as mass % oxygen in the fuel.
1.4 The values stated in SI units are to be regarded as the
4. Significance and Use
standard. The values given in parentheses are for information
4.1 These test methods cover the determination of total
only.
1.5 This standard does not purport to address all of the oxygen in gasoline and methanol fuels, and they complement
Test Method D 4815, which covers the determination of
safety concerns, if any, associated with its use. It is the
responsibility of the user of this standard to establish appro- several specific oxygen-containing compounds in gasoline.
4.2 The presence of oxygen-containing compounds in gaso-
priate safety and health practices and determine the applica-
bility of regulatory limitations prior to use. line can promote more complete combustion, which reduces
carbonmonoxideemissions.TheCleanAirAct(1992)requires
2. Referenced Documents
that gasoline sold within certain, specified geographical areas
2.1 ASTM Standards: contain a minimum percent of oxygen by mass (presently 2.7
D 1298 Test Method for Density, Relative Density (Specific mass %) during certain portions of the year. The requirement
Gravity), or API Gravity of Crude Petroleum and Liquid can be met by blending compounds such as methyl tertiary
Petroleum Products by Hydrometer Method butyl ether, ethyl tertiary butyl ether, and ethanol into the
D 4052 Test Method for Density and Relative Density of gasoline. These test methods cover the quantitative determina-
Liquids by Digital Density Meter tion of total oxygen which is the regulated parameter.
D 4057 Practice for Manual Sampling of Petroleum and
3 5. Apparatus
Petroleum Products
, , ,
5 6 7 8
5.1 Oxygen Elemental Analyzer —A variety of instru-
D 4815 Test Method for Determination of MTBE, ETBE,
TAME, DIPE, tertiary-Amyl Alcohol and C to C Alco- mentation can be satisfactory. However, the instrument must
1 4
reductively pyrolize the specimen and convert oxygen to
hols in Gasoline by Gas Chromatography
2.2 Other Standard: carbon monoxide.
Clean Air Act (1992)
Carlo Erba Models 1106 and 1108 have been found satisfactory for these
analyses. They are available from CE Elantech, Inc., 170 Oberlin Ave. N., Ste 5,
These test methods are under the jurisdiction of Committee D02 on Petroleum Lakewood, NJ 08701.
Products and Lubricants and are the direct responsibility of Subcommittee D02.03 LecoModelRO-478hasbeenfoundsatisfactoryforthisanalysis.Itisavailable
on Elemental Analysis. from Leco Corp., 3000 Lakeview Ave., St. Joseph, MI 49085.
Current edition approved Aug. 15, 1995. Published October 1995. Originally Perkin-Elmer Series 2400 has been found satisfactory for this analysis. It is
published as D 5622 – 94. Last previous edition D 5622 – 94. available from Perkin-Elmer Corp., 761 Main Ave., Norwalk, CT 06859.
2 8
Annual Book of ASTM Standards, Vol 05.01. UIC, Inc./Coulometrics Model 5012 CO coulometer and Model 5220
Annual Book of ASTM Standards, Vol 05.02. autosampler-furnace have been found satisfactory for this analysis. They are
Federal Register, Vol 57, No. 24, Feb. 5, 1992, p. 4408. available from UIC Inc., Box 863, Joliet, IL 60434.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
D5622–95 (2000)
5.1.1 Test Method A —Helium carrier gas transports the 6. Reagents
pyrolysis products through a combination scrubber to remove
6.1 Purity of Reagents —Reagent grade chemicals shall be
acidicgasesandwatervapor.Theproductsarethentransported
used in all tests. Unless otherwise indicated, it is intended that
to a molecular sieve gas chromatographic column where the
all reagents conform to the specifications of the Committee on
carbon monoxide is separated from the other pyrolysis prod-
Analytical Reagents of the American Chemical Society where
ucts.Athermal conductivity detector generates a response that
such specifications are available. Other grades may be used,
is proportional to the amount of carbon monoxide.
provided it is first ascertained that the reagent is of sufficiently
5.1.2 Test Method B —Nitrogen carrier gas transports the high purity to permit its use without lessening the accuracy of
the determination.
pyrolysis products through a scrubber to remove water vapor.
The pyrolysis products then flow through tandem infrared 6.2 Calibration Standards:
6.2.1 NIST SRM 1837 , which contains certified concen-
detectors that measure carbon monoxide and carbon dioxide,
trations of methanol and t-butanol in reference fuel, can be
respectively.
7 used to calibrate the instrument for the analysis of oxygenates
5.1.3 Test Method C —A mixture of helium and hydrogen
in gasoline.
(95:5 %), helium, or argon transports the pyrolysis products
6.2.2 Anhydrous methanol, 99.8 % minimum assay, can be
through two reactors in series.The first reactor contains heated
used to calibrate the instrument for the analysis of methanol
copper which removes sulfur-containing products. The second
fuels.
reactor contains a scrubber which removes acidic gases and a
6.2.3 Iso—octane,orotherhydrocarbons,canbeusedasthe
reactant which oxidizes carbon monoxide to carbon dioxide
blank provided the purity is satisfactory.
(optional). The product gases are then homogenized in a
6.3 Quality Control Standard—NIST SRM 1838 can be
mixing chamber, which maintains the reaction products at
used to check the accuracy of the calibration.
absolute conditions of temperature, pressure, and volume. The
6.4 The instrument manufacturers require additional re-
mixing chamber is subsequently depressurized through a
agents.
column that separates carbon monoxide (or carbon dioxide, if
6.4.1 Test Method A:
operating in the oxidation mode) from interfering compounds.
6.4.1.1 Anhydrone (anhydrous magnesium perchlorate),
A thermal conductivity detector measures a response propor-
6.4.1.2 Ascarite II (sodium hydroxide on silica),
tional to the amount of carbon monoxide or carbon dioxide.
6.4.1.3 Helium carrier gas, 99.995 % pure,
5.1.4 Test Method D —Nitrogen carrier gas transports the
6.4.1.4 Molecular sieve, 5Å, 60 to 80 mesh,
pyrolysis products through scrubbers to remove acidic gases
6.4.1.5 Nickel wool,
and water vapor. A reactor containing cupric oxide at 325°C
6.4.1.6 Nickelized carbon, 20 % loading,
oxidizes the carbon monoxide to carbon dioxide, which in turn
6.4.1.7 Quartz chips, and
is transported into a coulometric carbon dioxide detector.
6.4.1.8 Quartz wool.
Coulometrically generated base titrates the acid formed by
6.4.2 Test Method B:
reacting carbon dioxide with monoethanolamine.
6.4.2.1 Anhydrone (anhydrous magnesium perchlorate),
5.2 A technique must be established to make a quantitative 6.4.2.2 Carbon pyrolysis pellets, and
introduction of the test specimen into the analyzer. Specimen 6.4.2.3 Nitrogen carrier gas, 99.99 % pure.
6.4.3 Test Method C:
vials and transfer labware must be clean and dry.
6.4.3.1 Anhydrone (anhydrous magnesium perchlorate),
5.3 For instruments that measure carbon monoxide only,
6.4.3.2 Ascarite II (sodium hydroxide on silica),
pyrolysis conditions must be established to quantitatively
6.4.3.3 Carrier gas, either helium (95 %)/hydrogen (5 %),
convert oxygen to carbon monoxide.
mixture, 99.99 % pure; helium, 99.995 % pure; or argon,
5.4 A system of scrubbers and separators must be estab-
99.98 % pure,
lished to effectively remove pyrolysis products that interfere
6.4.3.4 Copper plus, wire form, and
with the detection of carbon monoxide or carbon dioxide, or
6.4.3.5 Platinized carbon.
both.
6.4.4 Test Method D: :
5.5 The detector responses must be linear with respect to
concentration, or nonlinear responses must be detectable and
accurately related to concentration. 9
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
5.6 Selected items are available from the instrument manu-
listed by the American Chemical Society, see Analar Standards for Laboratory
facturer.
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
5.6.1 Pyrolysis Tubes, and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
MD.
5.6.2 Scrubber Tubes, and
Available from the National Institute of Standards and Technology, Gaithers-
5.6.3 Absorber Tubes. burg, MD 2089
...
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