ASTM D5622-95(2005)

NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
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Designation:D5622–95 (Reapproved 2005)
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. 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 D4057 Practice for Manual Sampling of Petroleum and
Petroleum Products
1.1 These test methods cover the quantitative determination
D4815 Test 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-
pyrolysis. 1 4
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
Clean Air Act (1992)
methanol fuels.
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
3.1 Afuel specimen of 1 to 10 µLis injected by syringe into
oxygen-containing species is detected and quantitated. How-
a 950 to 1300°C high-temperature tube furnace that contains
ever, these test methods are similar in that the fuel is pyrolyzed
metallized carbon. Oxygen-containing compounds are pyro-
in a carbon-rich environment.
lyzed, and the oxygen is quantitatively converted into carbon
1.4 The values stated in SI units are to be regarded as
monoxide.
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
1.5 This standard does not purport to address all of the
downstream systems of reactors, scrubbers, separators, and
safety concerns, if any, associated with its use. It is the
detectors for the determination of the carbon monoxide con-
responsibility of the user of this standard to establish appro-
tent,henceoftheoxygenintheoriginalfuelsample.Theresult
priate safety and health practices and determine the applica-
is reported as mass % oxygen in the fuel.
bility of regulatory limitations prior to use.
4. Significance and Use
2. Referenced Documents
2 4.1 These test methods cover the determination of total
2.1 ASTM Standards:
oxygen in gasoline and methanol fuels, and they complement
D1298 Test Method for Density, Relative Density (Specific
Test Method D4815, which covers the determination of several
Gravity), or API Gravity of Crude Petroleum and Liquid
specific oxygen-containing compounds in gasoline.
Petroleum Products by Hydrometer Method
4.2 The presence of oxygen-containing compounds in gaso-
D4052 Test 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, 2005. Published June 2005. Originally
butyl ether, ethyl tertiary butyl ether, and ethanol into the
approved in 1994. Last previous edition approved in 2000 as D5622–95(2000).
gasoline. These test methods cover the quantitative determina-
DOI: 10.1520/D5622-95R05.
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 (2005)
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
5.5 The detector responses must be linear with respect to
carbon monoxide.
concentration, or nonlinear responses must be detectable and
,
4 8
5.1.1 Test Method A —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-
acidicgasesandwatervapor.Theproductsarethentransported
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.Athermal conductivity detector generates a response that
5.6.3 Absorber Tubes.
is proportional to the amount of carbon monoxide.
5,8
5.1.2 Test Method B —Nitrogen carrier gas transports the
6. Reagents
pyrolysis products through a scrubber to remove water vapor.
6.1 Purity of Reagents —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
6,8
5.1.3 Test Method C —Amixture 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 NISTSRM1837, whichcontainscertifiedconcentra-
(optional). The product gases are then homogenized in a
tions of methanol and t-butanol in reference fuel, can be used
mixing chamber, which maintains the reaction products at
to calibrate the instrument for the analysis of oxygenates in
absolute conditions of temperature, pressure, and volume. The
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.
7,8
5.1.4 Test Method D —Nitrogen carrier gas transports the 10
6.3 Quality Control Standard—NIST SRM 1838 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. 4 8
6.4.1 Test Method A:
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,
5.3 For instruments that measure carbon monoxide only, 6.4.1.6 Nickelized carbon, 20 % loading,
pyrolysis conditions must be established to quantitatively
6.4.1.7 Quartz chips, and
convert oxygen to carbon monoxide.
6.4.1.8 Quartz wool.
,
5 8
6.4.2 Test Method B:
6.4.2.1 Anhydrone (anhydrous magnesium perchlorate),
6.4.2.2 Carbon pyrolysis pellets, and
The sole source of supply of the apparatus (Carlo Erba Models 1106 and 1108)
6.4.2.3 Nitrogen carrier gas, 99.99 % pure.
known to the committee at this time is CE Elantech, Inc., 170 OberlinAve. N., Ste
,
6 8
5, Lakewood, NJ 08701. 6.4.3 Test Method C:
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.
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 Analar 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 (2005)
6.4.3.1 Anhydrone (an
...