ASTM D5622-95(2011)
(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
SIGNIFICANCE AND USE
These test methods cover the determination of total oxygen in gasoline and methanol fuels, and they complement Test Method D4815, which covers the determination of several specific oxygen-containing compounds in gasoline.
The presence of oxygen-containing compounds in gasoline can promote more complete combustion, which reduces carbon monoxide emissions. The Clean Air Act (1992) requires that gasoline sold within certain, specified geographical areas contain a minimum percent of oxygen by mass (presently 2.7 mass %) during certain portions of the year. The requirement can be met by blending compounds such as methyl tertiary butyl ether, ethyl tertiary butyl ether, and ethanol into the gasoline. These test methods cover the quantitative determination of total oxygen which is the regulated parameter.
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 standard. No other units of measurement are included in this standard.
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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Designation: D5622 − 95(Reapproved 2011)
Standard Test Methods for
Determination of Total Oxygen in Gasoline and Methanol
Fuels by Reductive Pyrolysis
This standard is issued under the fixed designation D5622; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope D4057Practice for Manual Sampling of Petroleum and
Petroleum Products
1.1 These test methods cover the quantitative determination
D4815Test Method for Determination of MTBE, ETBE,
of total oxygen in gasoline and methanol fuels by reductive
TAME, DIPE, tertiary-Amyl Alcohol and C to C Alco-
1 4
pyrolysis.
hols in Gasoline by Gas Chromatography
1.2 Precision data are provided for 1.0 to 5.0 mass%
2.2 Other Standards:
oxygen in gasoline and for 40 to 50 mass% oxygen in 3
Clean Air Act (1992)
methanol fuels.
3. Summary of Test Method
1.3 Several types of instruments can be satisfactory for
these test methods. Instruments can differ in the way that the 3.1 Afuelspecimenof1to10µLisinjectedbysyringeinto
oxygen-containing species is detected and quantitated. a 950 to 1300°C high-temperature tube furnace that contains
However, these test methods are similar in that the fuel is metallized carbon. Oxygen-containing compounds are
pyrolyzed in a carbon-rich environment. pyrolyzed, and the oxygen is quantitatively converted into
carbon monoxide.
1.4 The values stated in SI units are to be regarded as
standard. No other units of measurement are included in this 3.2 A carrier gas, such as nitrogen, helium, or a helium/
standard. hydrogen mixture, sweeps the pyrolysis gases into any of four
downstream systems of reactors, scrubbers, separators, and
1.5 This standard does not purport to address all of the
detectors for the determination of the carbon monoxide
safety concerns, if any, associated with its use. It is the
content, hence of the oxygen in the original fuel sample. The
responsibility of the user of this standard to establish appro-
result is reported as mass % oxygen in the fuel.
priate safety and health practices and determine the applica-
bility of regulatory limitations prior to use.
4. Significance and Use
2. Referenced Documents
4.1 These test methods cover the determination of total
oxygen in gasoline and methanol fuels, and they complement
2.1 ASTM Standards:
TestMethodD4815,whichcoversthedeterminationofseveral
D1298Test Method for Density, Relative Density (Specific
specific oxygen-containing compounds in gasoline.
Gravity), or API Gravity of Crude Petroleum and Liquid
Petroleum Products by Hydrometer Method
4.2 Thepresenceofoxygen-containingcompoundsingaso-
D4052Test Method for Density, Relative Density, and API
line can promote more complete combustion, which reduces
Gravity of Liquids by Digital Density Meter
carbonmonoxideemissions.TheCleanAirAct(1992)requires
that gasoline sold within certain, specified geographical areas
contain a minimum percent of oxygen by mass (presently 2.7
These test methods are under the jurisdiction of Committee D02 on Petroleum
Products and Lubricants and are the direct responsibility of Subcommittee D02.03 mass %) during certain portions of the year. The requirement
on Elemental Analysis.
can be met by blending compounds such as methyl tertiary
Current edition approved May 1, 2011. Published August 2011. Originally
butyl ether, ethyl tertiary butyl ether, and ethanol into the
approved in 1994. Last previous edition approved in 2005 as D5622–95(2005).
gasoline.These test methods cover the quantitative determina-
DOI: 10.1520/D5622-95R11.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
tion of total oxygen which is the regulated parameter.
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
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
D5622 − 95 (2011)
5. Apparatus 5.4 A system of scrubbers and separators must be estab-
4,5,6,7,8 lished to effectively remove pyrolysis products that interfere
5.1 Oxygen Elemental Analyzer —Avariety of instru-
with the detection of carbon monoxide or carbon dioxide, or
mentation can be satisfactory. However, the instrument must
both.
reductively pyrolize the specimen and convert oxygen to
carbon monoxide. 5.5 The detector responses must be linear with respect to
4,8
5.1.1 Test Method A —Helium carrier gas transports the concentration, or nonlinear responses must be detectable and
pyrolysis products through a combination scrubber to remove accurately related to concentration.
acidicgasesandwatervapor.Theproductsarethentransported
5.6 Selected items are available from the instrument manu-
to a molecular sieve gas chromatographic column where the
facturer.
carbon monoxide is separated from the other pyrolysis prod-
5.6.1 Pyrolysis tubes,
ucts.Athermal conductivity detector generates a response that
5.6.2 Scrubber tubes, and
is proportional to the amount of carbon monoxide.
5.6.3 Absorber Tubes.
5,8
5.1.2 Test Method B —Nitrogen carrier gas transports the
pyrolysis products through a scrubber to remove water vapor.
6. Reagents
The pyrolysis products then flow through tandem infrared
6.1 Purity of Reagents —Reagent grade chemicals shall be
detectors that measure carbon monoxide and carbon dioxide,
used in all tests. Unless otherwise indicated, it is intended that
respectively.
all reagents conform to the specifications of the Committee on
6,8
5.1.3 Test Method C —Amixture of helium and hydrogen
Analytical Reagents of theAmerican Chemical Society where
(95:5%), helium, or argon transports the pyrolysis products
such specifications are available. Other grades may be used,
throughtworeactorsinseries.Thefirstreactorcontainsheated
provided it is first ascertained that the reagent is of sufficiently
copper which removes sulfur-containing products. The second
high purity to permit its use without lessening the accuracy of
reactor contains a scrubber which removes acidic gases and a
the determination.
reactant which oxidizes carbon monoxide to carbon dioxide
6.2 Calibration Standards:
(optional). The product gases are then homogenized in a
6.2.1 NISTSRM1837, whichcontainscertifiedconcentra-
mixing chamber, which maintains the reaction products at
tions of methanol and t-butanol in reference fuel, can be used
absolute conditions of temperature, pressure, and volume. The
to calibrate the instrument for the analysis of oxygenates in
mixing chamber is subsequently depressurized through a
gasoline.
column that separates carbon monoxide (or carbon dioxide, if
6.2.2 Anhydrous methanol, 99.8% minimum assay, can be
operating in the oxidation mode) from interfering compounds.
used to calibrate the instrument for the analysis of methanol
A thermal conductivity detector measures a response propor-
fuels.
tional to the amount of carbon monoxide or carbon dioxide.
7,8
6.2.3 Isooctane, or other hydrocarbons, can be used as the
5.1.4 Test Method D —Nitrogen carrier gas transports the
blank provided the purity is satisfactory.
pyrolysis products through scrubbers to remove acidic gases
and water vapor. A reactor containing cupric oxide at 325°C
6.3 Quality Control Standard—NIST SRM 1838 can be
oxidizesthecarbonmonoxidetocarbondioxide,whichinturn
used to check the accuracy of the calibration.
is transported into a coulometric carbon dioxide detector.
6.4 The instrument manufacturers require additional re-
Coulometrically generated base titrates the acid formed by
agents.
reacting carbon dioxide with monoethanolamine.
4,8
6.4.1 Test Method A:
5.2 Atechnique must be established to make a quantitative
6.4.1.1 Anhydrone (anhydrous magnesium perchlorate),
introduction of the test specimen into the analyzer. Specimen
6.4.1.2 Ascarite II (sodium hydroxide on silica),
vials and transfer labware must be clean and dry.
6.4.1.3 Helium carrier gas, 99.995% pure,
6.4.1.4 Molecular sieve, 5Å, 60 to 80 mesh,
5.3 For instruments that measure carbon monoxide only,
6.4.1.5 Nickel wool,
pyrolysis conditions must be established to quantitatively
6.4.1.6 Nickelized carbon, 20% loading,
convert oxygen to carbon monoxide.
6.4.1.7 Quartz chips, and
6.4.1.8 Quartz wool.
5,8
The sole source of supply of the apparatus (Thermo Scientific formerly known 6.4.2 Test Method B:
as Carlo Erba Models 1108, 1110, now FLASH 1112 and FLASH 2000) known to
6.4.2.1 Anhydrone (anhydrous magnesium perchlorate),
the committee at this time is CE Elantech, Inc., 170 Oberlin Ave. N., Ste 5,
6.4.2.2 Carbon pyrolysis pellets, and
Lakewood, NJ 08701.
5 6.4.2.3 Nitrogen carrier gas, 99.99% pure.
Thesolesourceofsupplyoftheapparatus(LecoModelRO-478)knowntothe
committee at this time is Leco Corp., 3000 Lakeview Ave., St. Joseph, MI 49085.
The sole source of supply of the apparatus (Perkin-Elmer Series 2400) known
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
Thesolesourceofsupplyoftheapparatus(UIC,Inc./CoulometricsModel5012 listed by the American Chemical Society, see Annual Standards for Laboratory
CO 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,
If you are aware of alternative suppliers, please provide this information to MD.
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, which you may attend. burg, MD 20899.
D5622 − 95 (2011)
6,8
6.4.3 Test Method C:
R = average of the blank correcte
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