ASTM D6839-02(2007)

NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
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Designation:D6839 −02(Reapproved 2007)
Standard Test Method for
Hydrocarbon Types, Oxygenated Compounds and Benzene
in Spark Ignition Engine Fuels by Gas Chromatography
This standard is issued under the fixed designation D6839; 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 D4307 Practice for Preparation of Liquid Blends for Use as
Analytical Standards
1.1 This test method covers the quantitative determination
D4815 Test Method for Determination of MTBE, ETBE,
of saturates, olefins, aromatics and oxygenates in spark-
TAME, DIPE, tertiary-Amyl Alcohol and C to C Alco-
1 4
ignitionenginefuelsbymultidimensionalgaschromatography.
hols in Gasoline by Gas Chromatography
Each hydrocarbon type can be reported either by carbon
D5599 Test Method for Determination of Oxygenates in
number (see Note 1) or as a total.
Gasoline by Gas Chromatography and Oxygen Selective
NOTE 1—There can be an overlap between the C and C aromatics;
9 10
Flame Ionization Detection
however, the total is accurate. Isopropyl benzene is resolved from the C
aromatics and is included with the other C aromatics.
3. Terminology
1.2 This test method is applicable to spark-ignition engine
3.1 Definitions:
fuelwithtotalaromaticcontentupto50 %(V/V),totalolefinic
3.1.1 oxygenate, n—an oxygen-containing organic
content up to 30 % (V/V) and oxygen compounds up to 15 %
compound,whichmaybeusedasafuelorfuelsupplement,for
(V/V).
example, various alcohols and ethers.
1.3 This test method is not intended to determine individual
3.2 Definitions of Terms Specific to This Standard:
hydrocarbon components except benzene.
3.2.1 hydrogenation, n—the process of adding hydrogen to
1.4 Oxygenates as specified in Test Method D4815 have
olefin molecules as a result of a catalytic reaction.
been verified not to interfere with hydrocarbons. Within the
3.2.1.1 Discussion—Hydrogenation is accomplished when
round robin sample set, the following oxygenates have been
olefins in the sample contact platinum at a temperature of
tested: MTBE, ethanol, ETBE, and TAME. Other oxygenates
180°C in the presence of hydrogen. The olefins are converted
can be determined and quantified using Test Method D4815 or
intohydrogensaturatedcompoundsofthesamecarbonnumber
D5599.
and structure. Monoolefins and diolefins convert to paraffins
1.5 The values stated in SI units are to be regarded as
while cycloolefins and cyclodienes convert to cycloparaffins.
standard. No other units of measurement are included in this
3.2.2 trap, n—a device utilized to selectively retain specific
standard.
portions (individual or groups of hydrocarbons or oxygenates)
1.6 This standard does not purport to address all of the
of the test sample and to release the retained components by
safety concerns, if any, associated with its use. It is the
changing the trap temperature.
responsibility of the user of this standard to establish appro-
3.3 Acronyms:
priate safety and health practices and determine the applica-
3.3.1 ETBE—ethyl-tert-butylether
bility of regulatory limitations prior to use.
3.3.2 MTBE—methyl-tert-butylether
2. Referenced Documents
3.3.3 TAME—tert-amyl-methylether
2.1 ASTM Standards:
4. Summary of Test Method
4.1 A representative sample is introduced into a computer
This test method is under the jurisdiction of ASTM Committee D02 on
controlled gas chromatographic system consisting of switch-
Petroleum Products and Lubricants and is the direct responsibility of Subcommittee
D02.04.0L on Gas Chromatography Methods.
ing valves, columns, and an olefin hydrogenation catalyst, all
Current edition approved Nov. 1, 2007. Published January 2008. Originally
approved in 2002. Last previous edition approved in 2002 as D6839–02. DOI:
10.1520/D6839-02R07. The sole source of supply of theAC Reformulyzer known to the committee at
For referenced ASTM standards, visit the ASTM website, www.astm.org, or this time is AC Analytical Controls, Inc., 3494 Progress Dr., Bensalem, PA 19020.
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D6839−02 (2007)
FIG. 1Typical Instrument Configuration
operating at various temperatures. The valves are actuated at ever, a variety of spark-ignition engine fuels have been
predetermined times to direct portions of the sample to
analyzedwithoutsignificantperformancedeteriorationofthese
appropriate columns and traps. As the analysis proceeds, the traps.
columns separate these sample portions sequentially into
6.2 Commercial dyes used to distinguish between grades
groups of different hydrocarbon types that elute to a flame
and types of spark-ignition engine fuels have been found not to
ionization detector.
interfere with this test method.
4.2 The mass concentration of each detected compound or
6.3 Commercial detergent additives utilized in spark-
hydrocarbon group is determined by the application of re-
ignition engine fuels have been found not to interfere with this
sponse factors to the areas of the detected peaks followed by
test method.
normalization to 100 %. For samples containing methanol or
other oxygenates that cannot be determined by this test
6.4 Dissolved water in spark-ignition engine fuels has been
method, the hydrocarbon results are normalized to 100 %
found not to interfere with this test method.
minus the value of the oxygenates as determined by another
test method such as Test Method D4815 or D5599.
7. Apparatus
4.3 The liquid volume concentration of each detected com-
7.1 The complete system that was used to obtain the
pound or hydrocarbon group is determined by application of
precision data shown in Section 14 is comprised of a computer
density factors to the calculated mass concentration of the
controlled gas chromatograph, automated sample injector, and
detected peaks followed by normalization to 100 %.
specific hardware modifications. These modifications include
columns, traps, a hydrogenator, and valves, which are de-
5. Significance and Use
scribed in 7.7, 7.8, and in Section 8. Fig. 1 illustrates a typical
5.1 A knowledge of spark-ignition engine fuel composition
instrument configuration (see Note 5). Other configurations,
is useful for regulatory compliance, process control, and
components, or conditions may be utilized provided they are
quality assurance.
capable of achieving the required component separations and
5.2 The quantitative determination of olefins and other
produce a precision that is equivalent to, or better than, that
hydrocarbon types in spark-ignition engine fuels is required to
shown in the precision tables.
comply with government regulations.
7.2 Gas Chromatograph, capable of temperature pro-
5.3 ThistestmethodisnotapplicabletoM85andE85fuels,
grammed operation at specified temperatures, equipped with a
which contain 85 % methanol and ethanol, respectively.
heated flash vaporization inlet that can be packed (packed
column inlet), a flame ionization detector, necessary flow
6. Interferences
controllers, and computer control.
6.1 Some types of sulfur-containing compounds are irre-
versibly adsorbed in the olefin trap reducing its capacity to 7.3 Sample Introduction System, automatic liquid sampler,
capable of injecting a 0.1 µL volume of liquid. The total
retain olefins. Sulfur containing compounds are also adsorbed
in the alcohol and ether-alcohol-aromatic (EAA) traps. How- injected sample shall be introduced to the chromatographic
D6839−02 (2007)
TABLE 1 Temperature Control Ranges of System Components
7.7 Valves, Column and Trap Switching—Automated, rotary
Typical Operating Maximum Maximum valves are recommended. The valves shall be intended for gas
Component Temperature Heating Cooling
chromatographic usage and meet the following requirements:
Range, °C Time, min Time, min
7.7.1 The valves must be capable of continuous operation at
Alcohol trap 60–280 2 5
operating temperatures that will prevent sample condensation.
Polar column 130 isothermal
Non-polar column 130 isothermal
7.7.2 The valves shall be constructed of materials that are
Olefin trap 120–280 1 5
nonreactive with the sample under analysis conditions. Stain-
Molsieve 13X column 90–430 Temperature
4 4
less steel, PFA, and Vespel are satisfactory.
programmed, ~10°/min
Porapak column 130–140 isothermal 7.7.3 Thevalvesshallhaveasmallinternalvolumebutoffer
Ether-alcohol-aromatic 70–280 1 5
little restriction to carrier gas flow under analysis conditions.
(EAA) trap
Hydrogenation catalyst 180 isothermal
7.8 Valves, Air—to control pressurized air for column and
Column switching 130 isothermal
trap cooling. Automated valves are recommended.
valves
NOTE 4—New valves, tubing, catalyst, columns, traps, and other
Sample lines 130 isothermal
materials that contact the sample or gasses may require conditioning prior
to operation in accordance with the manufacturer’s recommendations.
7.9 Gas Purifiers, to remove moisture and oxygen from
system thus excluding the use of split injections or carrier gas
helium, moisture and hydrocarbons from hydrogen, and mois-
purging of the inlet septum. An auto injector is recommended
ture and hydrocarbons from air.
but optional.
7.4 Gas Flow and Pressure Controllers, with adequate
8. Reagents and Materials
precision to provide reproducible flow and pressure of helium
8.1 Air, compressed, <10 mg/kg each of total hydrocarbons
tothe chromatographicsystem,hydrogenforthehydrogenator,
and H O. (Warning—Compressed gas under high pressure
and hydrogen and air for the flame ionization detector. Control
that supports combustion.)
of air flow for cooling specific system components and for
8.2 Helium, 99.999 % pure, <0.1 mg/kg H O. (Warning—
automated valve operation is also required. 2
Compressed gas under high pressure.)
7.5 Electronic Data Acquisition System, shall meet or ex-
8.3 Hydrogen, 99.999 % pure, <0.1 mg/kg H O.
ceed the following specifications (see Note 2): 2
(Warning—Extremely flammable gas under high pressure.)
7.5.1 Capacity for 150 peaks for each analysis.
7.5.2 Normalized area percent calculation with response
8.4 Columns, Traps, and Hydrogenation Catalyst (System
factors.
Components)—This test method requires the use of four
7.5.2.1 Area summation of peaks that are split or of groups
columns, two traps, and a hydrogenation catalyst (see Note 3).
of components that elute at specific retention times.
Each system component is independently temperature con-
7.5.3 Noise and spike rejection capability.
trolled as described in 7.6 and Table 1. Refer to Fig. 1 for the
7.5.4 Sampling rate for fast (<0.5 s) peaks (>20 Hz to give
location of the components in the system (see Note 5). The
10 points across peak).
following list of components contains guidelines that are to be
7.5.5 Peak width detection for narrow and broad peaks.
used to judge suitability. The guidelines describe temperatures
7.5.6 Perpendicular drop and tangent skimming, as re-
and times as used in the current system. Alternatives can be
quired.
used provided that the separation as described is obtained and
the separation characteristics of the entire system are not
NOTE 2—Standard supplied software is typically satisfactory.
limited.
7.6 Temperature Controllers of System Components —The
NOTE5—Fig.1showsanadditionaltrap,Molsieve5A,androtaryvalve
independent temperature control of numerous columns and
V4 that are not required for this test method. They are included in Fig. 1
traps,thehydrogenationcatalyst,columnswitchingvalves,and
because they were present in the instrumentation used to generate the
sample lines is required. All of the system components that
precision data. They can be used for more detailed analyses outside the
contact the sample shall be heated to a temperature that will
scope of this test method, where an iso-normal paraffin, iso-normal olefin
prevent condensation of any sample component. Table 1 lists determination is desired. There is no statistical data included in this test
method relating to their use.
the system components and operating temperatures (see Note
3).Someofthecomponentsrequireisothermaloperation,some
8.4.1 Alcohol Trap—Within a temperature range from 140
require rapid heating and cooling, while one requires repro-
to 160°C, this trap must elute benzene, toluene, all paraffins,
ducible temperature programming. The indicated temperatures
olefins, naphthenes, and ethers within the first 2 min after
aretypical;however,thecontrolsystemsutilizedshallhavethe
sample injection while retaining C + aromatics, all alcohols,
capability of operating at temperatures 620°C of those indi-
and any other sample components.
cated to accommodate specific systems. Temperature control
8.4.1.1 At a temperature of 280°C, all retained components
may be by any means that will meet the requirements listed in
from 8.4.1 shall elute within 2 min of when the trap is
Table 1.
backflushed.
NOTE 3—The system components and temperatures listed in Table 1
8.4.2 Polar Column—At a temperature of 130°C, this col-
and Section 8 are specific to the analyzer used to obtain the precision data
umn must retain all aromatic components in the sample longer
showninSection14.Othercolumnsandtrapsthatcanadequatelyperform
the required separations are also satisfactory but may require different
temperatures. PFA and Vespel are trademarks of E. I. DuPont de Nemours and Co.
D6839−02 (2007)
TABLE 2 System Validation Test Mixture
than the time required to elute all non-aromatic components
boiling below 185°C, within the first 5 min after sample Approximate
Component Concentration Warning
injection.
Mass, %
8.4.2.1 The column shall elute benzene, toluene, and all
A
Cyclopentane 1.1
non-aromatic components with a boiling point below 215°C A
Pentane 1.1
A
Cyclohexane 2.1
within 10 min of the introduction of these compounds into the
A
2,3-Dimethylbutane 2.1
column.
A
Hexane 2.1
A
8.4.2.2 This column shall elute all retained aromatic com-
1-Hexene 1.5
A
ponents from 8.4.2 within 10 min of when this column is Methylcyclohexane 4.0
A
4-Methyl-1-hexene 1.6
backflushed.
B
Heptane 3.5
8.4.3 Non-Polar Column—At a
...