ASTM D3710-95(2004)
(Test Method)Standard Test Method for Boiling Range Distribution of Gasoline and Gasoline Fractions by Gas Chromatography
Standard Test Method for Boiling Range Distribution of Gasoline and Gasoline Fractions by Gas Chromatography
SIGNIFICANCE AND USE
The determination of the boiling range distribution of gasoline by GC distillation provides an insight into the composition of the components from which the gasoline has been blended. This insight also provides essential data necessary to calculate the vapor pressure of gasoline, which has been traditionally determined by Test Method D 323. In addition, the Test Method D 86 distillation curve can be predicted using GCD data. See Annex A1.
The GCD method facilitates online controls at the refinery, and its results offer improved means of describing several car performance parameters. These parameters include: (1) car-starting index, (2) vapor-lock index or vapor-liquid ratio, and (3) warm-up index. The car-starting and vapor-lock indexes have been found to be mostly affected by the front end of the Test Method D 86 distillation curve (up to about 200°F (93°C)). The warm-up index is affected by the middle and to a lesser extent by the back end of the Test Method D 86 curve, that is, the temperatures corresponding to the 50 to 90 % off range. Since the boiling range distribution provides fundamental information on composition, an improved expression for the above performance parameters may be worked out, even when the boiling range distribution curve is not smooth. Currently, car performance cannot be assessed accurately under such conditions.
SCOPE
1.1 This test method covers the determination of the boiling range distribution of gasoline and gasoline components. This test method is applicable to petroleum products and fractions with a final boiling point of 500°F (260°C) or lower as measured by this test method.
1.2 This test method is designed to measure the entire boiling range of gasoline and gasoline components with either high or low Reid vapor pressure and is commonly referred to as gas chromatography (GC) distillation (GCD).
1.3 This test method has not been validated for gasolines containing oxygenated compounds (for example, alcohols or ethers).
1.4 The values stated in inch-pound 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. For specific hazard statements, see Notes 9, 10, 11, and 15.
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An American National Standard
Designation:D3710–95 (Reapproved 2004)
Standard Test Method for
Boiling Range Distribution of Gasoline and Gasoline
Fractions by Gas Chromatography
This standard is issued under the fixed designation D3710; 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 (e) indicates an editorial change since the last revision or reapproval.
1. Scope 3. Terminology
1.1 Thistestmethodcoversthedeterminationoftheboiling 3.1 Definitions:
range distribution of gasoline and gasoline components. This 3.1.1 final boiling point (FBP)—the point at which a cumu-
test method is applicable to petroleum products and fractions lative volume count equal to 99.5% of the total volume count
with a final boiling point of 500°F (260°C) or lower as under the chromatogram is obtained.
measured by this test method. 3.1.2 initial boiling point (IBP)—the point at which a
1.2 This test method is designed to measure the entire cumulative volume count equal to 0.5% of the total volume
boiling range of gasoline and gasoline components with either count under the chromatogram is obtained.
high or low Reid vapor pressure and is commonly referred to 3.1.3 relative molar response—the measured area of a
as gas chromatography (GC) distillation (GCD). compound divided by the moles present in the synthetic
1.3 This test method has not been validated for gasolines mixture relative to an arbitrarily chosen component.
containing oxygenated compounds (for example, alcohols or 3.1.4 response factor—a constant of proportionality that
ethers). converts area to liquid volume.
1.4 The values stated in inch-pound units are to be regarded 3.1.5 system noise—the difference between the maximum
as the standard. The values given in parentheses are for and minimum area readings per second for the first 20 area
information only. readings in the blank run.
1.5 This standard does not purport to address all of the 3.1.6 volume count—the product of the area under a peak
safety concerns, if any, associated with its use. It is the and a response factor.
responsibility of the user of this standard to establish appro-
4. Summary of Test Method
priate safety and health practices and determine the applica-
bility of regulatory limitations prior to use. For specific hazard 4.1 The sample is introduced into a gas chromatographic
column which separates hydrocarbons in boiling point order.
statements, see Note 9 and 7.2.
Conditionsareselectedsoastomeasureisopentaneandlighter
2. Referenced Documents
saturates discretely. Normal pentane and heavier compounds
2.1 ASTM Standards: are not completely resolved but are measured as pseudo
D86 Test Method for Distillation of Petroleum Products at components of narrow boiling range. The column temperature
Atmospheric Pressure is raised at a reproducible rate and the area under the
D323 Test Method for Vapor Pressure of Petroleum Prod- chromatogram is recorded throughout the run. Boiling tem-
ucts (Reid Method) peraturesareassignedtothetimeaxisfromacalibrationcurve,
D1265 Practice for Sampling Liquefied Petroleum (LP) obtained under the same conditions by running a known
Gases (Manual Method) mixture of hydrocarbons covering the boiling range expected
D4057 Practice for Manual Sampling of Petroleum and inthesample.Fromthesedatatheboilingrangedistributionof
Petroleum Products the sample is obtained.
5. Significance and Use
This test method is under the jurisdiction of ASTM Committee D02 on
5.1 The determination of the boiling range distribution of
Petroleum Products and Lubricants and is the direct responsibility of Subcommittee
gasoline by GC distillation provides an insight into the
D02.04 on Chromatographic Distribution Methods.
Current edition approved Nov. 1, 2004. Published November 2004. Originally
composition of the components from which the gasoline has
e1
approved in 1978. Last previous edition approved in 1999 as D3710–99 .
been blended. This insight also provides essential data neces-
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
sarytocalculatethevaporpressureofgasoline,whichhasbeen
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 traditionallydeterminedbyTestMethodD323.Inaddition,the
the ASTM website.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
D3710–95 (2004)
higher temperatures only serves to shorten the useful life of the detector,
Test Method D86 distillation curve can be predicted using
and generally contributes to higher noise levels and greater drift.
GCD data. See Annex A1.
5.2 The GCD method facilitates online controls at the
6.1.2 Column Temperature Programmer—The chromato-
refinery, and its results offer improved means of describing
graph must be capable of program temperature operation over
severalcarperformanceparameters.Theseparametersinclude:
arangesufficienttoestablisharetentiontimeofatleast15sfor
(1) car-starting index, (2) vapor-lock index or vapor-liquid
propane and of allowing elution of the entire sample within a
ratio, and (3) warm-up index. The car-starting and vapor-lock
reasonable time period. Subambient capability may be re-
indexeshavebeenfoundtobemostlyaffectedbythefrontend
quired.Theprogrammingratemustbesufficientlyreproducible
of the Test MethodD86 distillation curve (up to about 200°F
to meet the requirements of 8.7.
(93°C)).The warm-up index is affected by the middle and to a
NOTE 3—If the column is operated at subambient temperature, exces-
lesser extent by the back end of the Test MethodD86 curve,
sively low initial column temperature must be avoided, to ensure that the
that is, the temperatures corresponding to the 50 to 90% off
stationary phase remains liquid. The initial temperature of the column
range. Since the boiling range distribution provides fundamen-
should be only low enough to obtain a calibration curve meeting the
talinformationoncomposition,animprovedexpressionforthe
specifications of this test method.
above performance parameters may be worked out, even when
6.1.3 Sample Inlet System—The sample inlet system must
the boiling range distribution curve is not smooth. Currently,
be capable of operating continuously at a temperature equiva-
car performance cannot be assessed accurately under such
lenttothemaximumcolumntemperatureemployed,orprovide
conditions.
on-column injection with some means of programming the
entirecolumn,includingpointofsampleintroductionuptothe
6. Apparatus
maximum temperature required.The sample inlet system must
6.1 Chromatograph—Any gas chromatograph may be used
beconnectedtothechromatographiccolumnsoastoavoidany
that meets the performance requirements in Section 8. Place in
cold spots.
serviceinaccordancewithmanufacturer’sinstructions.Typical
6.1.4 FlowControllers—Chromatographsmustbeequipped
operating conditions are shown in Table 1.
with constant-flow controllers capable of holding carrier gas
6.1.1 Detector—Either a thermal conductivity or a flame
flow constant to 61% over the full operating temperature
ionization detector may be used. Detector stability must be
range.
such that the sensitivity and baseline drift requirements as
6.2 Sample Introduction—Sample introduction may be ei-
definedinSection8aremet.Thedetectoralsomustbecapable
ther by means of a constant-volume liquid sample valve or by
of operating continuously at a temperature equivalent to the
injection with a microsyringe through a septum. If the sample
maximum column temperature employed, and it must be
is injected manually, cool the syringe to 0 to 4°C (32 to 40°F)
connected to the column so as to avoid any cold spots.
before taking the sample from the sample vial.
NOTE 1—Caremustbetakenthatthesamplesizechosendoesnotallow
some peaks to exceed the linear range of the detector. This is especially NOTE 4—Automatic liquid-sampling devices or other sampling means,
critical with the flame ionization detector. With thermal conductivity suchassealedseptum-cappedvials,maybeused,providednolossoflight
detectors, sample sizes of the order of 1 to 5 µLgenerally are satisfactory. ends occurs. The system must be operated at a temperature sufficiently
With flame ionization detectors, the sample size should not exceed 1 µL. high to vaporize completely hydrocarbons with an atmospheric boiling
NOTE 2—Itisnotdesirabletooperatethedetectorattemperaturesmuch pointof500°F(260°C),andthesamplingsystemmustbeconnectedtothe
higher than the maximum column temperature employed. Operation at chromatographic column so as to avoid any cold spots.
TABLE 1 Gas Chromatography Column and Conditions
Column:
Liquid phase, material UCW-982 Supelco 2100 UCW-98 OV-101 UCW-98
weight % 10 20 10 10 10
Solid support, material Chromosorb P Chromosorb W Chromosorb G Chromosorb P Supelcoport
mesh size 80/100 80/100 60/80 60/80 80/100
Length, m (ft) 0.5 (1.5) 1.5 (5) 0.9 (3) 1.2 (4) 1.5 (5)
Outside diameter, mm (in.) 6.4 (1/4) 3.2 (1/5) 6.4 (1/4) 3.2 (1/8) 3.2 (1/8)
Temperatures:
Initial column temperature, °C −30 40 −20 0 0
Final column temperature, °C 250 250 200 250 230
Detector temperature, °C 250 250 345 250 250
Injection zone temperature, °C 250 300 345 250 230
Operating Variables:
Program rate, °C/min 10.6 16 10 15 16
Carrier gas He He He He He
flow rate, cm /min 50 30 60 29 30
Sample size, µL 3 2 3 2 1
Detector voltage (or mA) 150 mA 160 mA 135 mA . 175 mA
Instrument:
Detector type TC TC TC TC TC
Sampling system automatic syringe syringe syringe valve valve
Area measurement method integrating A/D integrating A/D integrating A/D time slice time slice
Time slices per second 2 1/2 5 5 1/2
D3710–95 (2004)
6.3 Recorder—A recording potentiometer or equivalent 6.5 Integrator—Means must be provided for determining
with a full-scale response time of2sor less may be used. the accumulated area under the chromatogram. This can be
6.4 Column—Any column and conditions may be used, done by means of a computer, or automatic operation can be
provided, under the conditions of the test method, separations achievedwithelectronicintegration.Atimingdeviceisusedto
are in order of boiling points and the column meets the record the accumulated area at set time intervals. The same
performance requirements in Section 8. See Table 1 for basis for measuring time must be used to determine retention
columnsandconditionsthathavebeenusedsuccessfully.Since times in the calibration, the blank, and the sample. If an
astablebaselineisanessentialrequirementofthistestmethod, electronic integrator is used, the maximum area measurement
provisions must be made to compensate for column bleed. must be within the linear range of the integrator.
Traditionally this is done by using matching dual columns and 6.6 Sample Containers—Pressure cylinders or vials with
detectors.Atbest,thisprocedureisonlymarginallysuccessful. septums should be provided for the calibration mixture and
An even more satisfactory procedure is to record the area samples to avoid loss of light ends.
profileofthecolumnbleedduringablankrun,andsubtractthis 6.7 System—Any satisfactory combination of the above
profile from subsequent sample runs, as outlined in 11.1. components that will meet the performance requirements of
6.4.1 Column Preparation—Any satisfactory method, used Section 8.
in the practice of the art, that will produce a column meeting
7. Reagents and Materials
the requirements of Section 8, may be used. The column must
7.1 CalibrationMixture—Asyntheticmixtureofpureliquid
be conditioned at the maximum operating temperature to
hydrocarbons of known boiling point covering the boiling
reduce baseline shifts due to bleeding of column substrate.
range of the sample. At least one compound in the mixture
NOTE 5—The column can be conditioned very rapidly and effectively
must have a boiling point equal to or lower than the initial
by the following procedure:
boiling point of the sample, and one compound must have a
(1) Disconnect column from detector.
retention time greater than any component in the sample. The
(2) Purge the column thoroughly at ambient temperature with carrier
concentration of all compounds heavier than n-butane must be
gas.
(3) Turn off the carrier gas and allow the column to depressurize known within 0.1%. The synthetic composition shown in
completely.
Table 1 should be used for gasoline analysis. Compounds
(4) Raise the column temperature to the maximum operating tempera-
necessary for evaluation of system performance are noted in
ture and hold at this temperature for at least 1 h with no flow through the
Table 2.
column.
(5) Cool the column to at least 100°C before turning on carrier gas NOTE 7—If the sample contains significant quantities of compounds
again. that can be identified on the chromatogram, these peaks may be used as
(6) Program the column temperature up to the maximum several times internal boiling point calibrations.
with normal carrier gas flow. The column then should be ready for use. NOTE 8—Two calibration mixtures can be used for convenience. One
NOTE 6—An alternative method of column conditioning, which has that contains known concentrations of isopentane and heavier compounds
been found effective for columns with an initial loading of 10% liquid can be used for determining response factors, sensitivity, and concentra-
phase, consists of purging the column with carrier gas at the normal flow tion repeatability. The other would contain a complete boiling range of
rate while holding the column at maximum operating temperature for 12 compounds including propane, butane, and isobutane, whose concentra-
to 16 h. tions are known only approximately. It would be used for measuring
TABLE 2 Calibration Mixture
Typical Thermal
A
Relative Density, Approximate
Peak Number Compound Identification NBP, °F Conductivity
60/60°F Volume, %
Response Factors
B
1 nC −44 0.5077 1 1.15
B
2 isoC 11 0.5631 3 1.14
B
3 nC 31 0.5844 10 1.07
B
4 isoC 82 0.6248 9 1.08
5 nC 97 0.6312 7 1.03
6 2-MeC 140 0.6579 5 1.03
C
7 nC 156 0.6640 5 1.01
D
8 2,4-DiMeC 177 0.6772 5 1.07
9 nC 209 0.6882 9 1.00
C
10 Toluene 231 0.8719 10 0.89
11 nC 258 0.7068 5 0.98
C
12 p-Xylene 281 0.8657 12 0.90
C
13 n-Propylbenzene 319 0.8666 4 0.94
14 nC 345 0.7341 3 0.99
C
15 n-Butylbenzene 362 0.8646 3 0.93
C
16 nC 421 0.7526 3 1.00
C
17 nC 456 0.7601 2 1.02
18 nC 486 0.7667 2 1.04
19 nC 519 0.7721 2 1.05
A
“Selected Values of Properties of Hydrocarbons and Related Compounds,” American Petroleum Institute Project 44, Table 23-2, April 195
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