ASTM D5501-94(1998)e1
(Test Method)Standard Test Method for Determination of Ethanol Content of Denatured Fuel Ethanol by Gas Chromatography
Standard Test Method for Determination of Ethanol Content of Denatured Fuel Ethanol by Gas Chromatography
SCOPE
1.1 This test method covers the determination of the ethanol content of denatured fuel ethanol by gas chromatography.
1.2 Ethanol is determined from 93 to 97 mass percent and methanol is determined from 0.1 to 0.6 mass percent. Equations used to convert these individual alcohols from mass percent to volume percent are provided.
1.3 This test method does identify and quantify methanol but does not purport to identify all individual components that make up the denaturant.
1.4 Water cannot be determined by this test method and shall be measured by a procedure such as Test Method D1364 and the result used to correct the chromatographic values.
1.5 This test method is inappropriate for impurities that boil at temperatures higher than 225°C or for impurities that cause poor or no response in a flame ionization detector, such as water.
1.6 The values stated in SI units are to be regarded as the standard. The values given in parentheses are provided for information purposes only.
1.7 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.
General Information
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Standards Content (Sample)
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An American National Standard
e1
Designation: D 5501 – 94 (Reapproved 1998)
Standard Test Method for
Determination of Ethanol Content of Denatured Fuel Ethanol
by Gas Chromatography
This standard is issued under the fixed designation D 5501; 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.
e NOTE—Editorial corrections were made to Section 2 and 12.3 in April 1998.
1. Scope Liquids by Digital Density Meter
D 4057 Practice for Manual Sampling of Petroleum and
1.1 This test method covers the determination of the ethanol
Petroleum Products
content of denatured fuel ethanol by gas chromatography.
D 4307 Practice for Preparation of Liquid Blends for Use as
1.2 Ethanol is determined from 93 to 97 mass % and
Analytical Standards
methanol is determined from 0.1 to 0.6 mass %. Equations
D 4626 Practice for Calculation of Gas Chromatographic
used to convert these individual alcohols from mass % to
Response Factors
volume % are provided.
D 4806 Specification for Denatured Fuel Ethanol for Blend-
1.3 This test method does identify and quantify methanol
ing with Gasolines for Use as Automotive Spark-Ignition
but does not purport to identify all individual components that
Engine Fuel
make up the denaturant.
E 355 Practice for Gas Chromatography Terms and Rela-
1.4 Water cannot be determined by this test method and
tionships
shall be measured by a procedure such as Test Method D 1364
E 594 Practice for Testing Flame Ionization Detectors Used
and the result used to correct the chromatographic values.
in Gas Chromatography
1.5 This test method is inappropriate for impurities that boil
E 1064 Test Method for Water in Organic Liquids by
at temperatures higher than 225°C or for impurities that cause
Coulometric Karl Fischer Titration
poor or no response in a flame ionization detector, such as
water.
3. Terminology
1.6 The values stated in SI units are to be regarded as the
3.1 Definitions—This test method makes reference to many
standard. The values given in parentheses are provided for
common gas chromatographic procedures, terms, and relation-
information purposes only.
ships. Detailed definitions can be found in Practices E 355 and
1.7 This standard does not purport to address all of the
E 594.
safety concerns, if any, associated with its use. It is the
responsibility of the user of this standard to establish appro-
4. Summary of Test Method
priate safety and health practices and determine the applica-
4.1 A representative aliquot of the fuel ethanol sample is
bility of regulatory limitations prior to use.
introduced into a gas chromatograph equipped with a methyl
silicone bonded phase fused silica capillary column. Helium
2. Referenced Documents
carrier gas transports the vaporized aliquot through the column
2.1 ASTM Standards:
where the components are separated by the chromatographic
D 1298 Test Method for Density, Relative Density (Specific
process. Components are sensed by a flame ionization detector
Gravity), or API Gravity of Crude Petroleum and Liquid
2 as they elute from the column. The detector signal is processed
Petroleum Products by Hydrometer Method
by an electronic data acquisition system. The ethanol and
D 1364 Test Method for Water in Volatile Solvents (Fischer
3 methanol components are identified by comparing their reten-
Reagent Titration Method)
tion times to the ones identified by analyzing standards under
D 4052 Test Method for Density and Relative Density of
identical conditions. The concentration of all components are
determined in mass percent area by normalization of the peak
areas.
This test method is under the jurisdiction of ASTM Committee D02 on
Petroleum Products and Lubricants and is the direct responsibility of Subcommittee
D02.04.0L on Gas Chromatography Methods.
Current edition approved Aug. 15, 1994. Published October 1994. Originally
published as D 5501–94. Last previous edition D 5501–94. Annual Book of ASTM Standards, Vol 05.02.
2 5
Annual Book of ASTM Standards, Vol 05.01. Annual Book of ASTM Standards, Vol 14.01.
3 6
Annual Book of ASTM Standards, Vol 06.04. Annual Book of ASTM Standards, Vol 15.05.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
D 5501
5. Significance and Use 6.4 Electronic Data Acquisition System— Any data acqui-
sition and integration device used for quantification of these
5.1 Fuel ethanol is required to be denatured with gasoline in
analyses must meet or exceed these minimum requirements:
accordance with Specification D 4806. State and federal laws
6.4.1 Capacity for at least 80 peaks/analysis,
specify the concentration of ethanol in gasoline blends. The
6.4.2 Normalized area percent calculation with response
determination of the amount of denaturant is important to
factors,
ensure the blended fuel complies with federal and state laws.
6.4.3 Identification of individual components based on re-
This test method provides a method of determining the
tention time,
percentage of ethanol (purity) of the fuel ethanol that is
6.4.4 Noise and spike rejection capability,
blended into gasoline.
6.4.5 Sampling rate for fast (<1 s) peaks,
6. Apparatus
6.4.6 Positive and negative sloping baseline correction,
6.4.7 Peak detection sensitivity compensation for narrow
6.1 Gas Chromatograph, capable of operating at the condi-
and broad peaks, and
tions listed in Table 1. A heated flash vaporizing injector
6.4.8 Non-resolved peaks separated by perpendicular drop
injector designed to provide a linear sample split injection (for
or tangential skimming as needed.
example, 200:1) is required for proper sample introduction.
Carrier gas controls shall be of adequate precision to provide
7. Reagents and Materials
reproducible column flows and split ratios in order to maintain
7.1 Purity of Reagents—Reagent grade chemicals shall be
analytical integrity. Pressure control devices and gauges shall
used in all tests. Unless otherwise indicated, it is intended that
be designed to attain the linear velocity required in the column
all reagents conform to the specifications of the Committee on
used. A hydrogen flame ionization detector with associated gas
Analytical Reagents of the American Chemical Society where
controls and electronics, designed for optimum response with
such specifications are available.
open tabular columns, is required.
7.2 Carrier Gas, helium, with a minimum purity of 99.95
6.2 Sample Introduction—Manual or automatic liquid sy-
mol %. Oxygen removal systems and gas purifiers should be
ringe sample injection to the splitting injector is employed.
used.
Devices capable of 0.1 to 0.5 μL injections are suitable. It
should be noted that inadequate splitter design, poor injection
NOTE 1—Warning: Helium, compressed gas under high pressure.
technique, and overloading the column can result in poor
7.3 Detector Gases, hydrogen, air, and nitrogen. The mini-
resolution. Avoid overloading, particularly of the ethanol peak,
mum purity of the gases used should be 99.95 % for the
and eliminate this condition during analysis.
hydrogen and nitrogen. The air should be hydrocarbon-free
6.3 Column—This test method utilizes a fused silica open
grade. Gas purifiers are recommended for the detector gases.
tubular column with non-polar methyl silicone bonded (cross-
linked) phase internal coating. Any column with equivalent or
NOTE 2—Warning: Hydrogen, extremely flammable gas under high
better chromatographic efficiency and selectivity to those pressure.
NOTE 3—Warning: Air and nitrogen, compressed gases under high
described in 6.3.1 can be used.
pressure.
6.3.1 Open tubular column with a non-polar methyl silicone
7.4 Standards for Calibration and Identification—
bonded (cross-linked) phase internal coating, either 150 m by
0.25 mm with a 1.0 μm film thickness, or 100 m by 0.25 mm Standards of all components to be analyzed are required for
establishing identification by retention time as well as calibra-
with a 0.5 film thickness is required.
tion for quantitative measurements. These materials shall be of
TABLE 1 Typical Operating Conditions
known purity and free of the other components to be analyzed.
Column Temperature Program 7.4.1 Ethanol (Warning—See Note 4, Note 5).
Column length 100 m 150 m
NOTE 4—Two grades of ethanol are available. Only absolute ethanol
Initial temperature 15°C 60°C
99.5 minimum percent meets the requirements of this test method.
Initial hold time 12 min 15 min
Program rate 30°C/min 30°C/min
7.4.2 Methanol (Warning—See Note 5).
Final temperature 250°C 250°C
7.4.3 Heptane (Warning—See Note 5).
Final hold time 19 min 23 min
Injector NOTE 5—Warning: These materials are flammable and may be harmful
or fatal, if ingested or inhaled.
Temperature 300°C
Split ratio 200:1
8. Sampling
Sample size 0.1 to 0.5 μL
Detector
8.1 Denatured ethanol can be sampled into an open con-
tainer since a vapor pressure of less than 21 kPa (3 psi) is
Type Flame ionization
Temperature 300°C
Fuel g
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