ASTM D3710-95(1999)e1
(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
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
e1
Designation:D3710–95 (Reapproved 1999)
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.
e NOTE—Warning statements were made part of the text in November 1999.
1. Scope 3. Terminology
1.1 This test method covers the determination of the boiling 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 D-2 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
D02.04.0H on Chromatographic Methods.
composition of the components from which the gasoline has
Current edition approved Sept. 10, 1995. Published November 1995. Originally
published as D3710–78. Last previous edition D3710–93.
been blended. This insight also provides essential data neces-
Annual Book of ASTM Standards, Vol 05.01.
sarytocalculatethevaporpressureofgasoline,whichhasbeen
Annual Book of ASTM Standards, Vol 05.02.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
D3710
detectors, sample sizes of the order of 1 to 5 µLgenerally are satisfactory.
traditionallydeterminedbyTestMethodD323.Inaddition,the
With flame ionization detectors, the sample size should not exceed 1 µL.
Test Method D86 distillation curve can be predicted using
NOTE 2—Itisnotdesirabletooperatethedetectorattemperaturesmuch
GCD data. See Annex A1.
higher than the maximum column temperature employed. Operation at
5.2 The GCD method facilitates on-line controls at the
higher temperatures only serves to shorten the useful life of the detector,
refinery, and its results offer improved means of describing
and generally contributes to higher noise levels and greater drift.
severalcarperformanceparameters.Theseparametersinclude:
6.1.2 Column Temperature Programmer—The chromato-
(1) car-starting index, (2) vapor-lock index or vapor-liquid
graph must be capable of program temperature operation over
ratio, and (3) warm-up index. The car-starting and vapor-lock
arangesufficienttoestablisharetentiontimeofatleast15sfor
indexes have been found to be mostly affected by the front end
propane and of allowing elution of the entire sample within a
of the Test Method D86 distillation curve (up to about 200°F
reasonable time period. Subambient capability may be re-
(93°C)). The warm-up index is affected by the middle and to a
quired.Theprogrammingratemustbesufficientlyreproducible
lesser extent by the back end of the Test Method D86 curve,
to meet the requirements of 8.7.
that is, the temperatures corresponding to the 50 to 90% off
range. Since the boiling range distribution provides fundamen-
NOTE 3—If the column is operated at subambient temperature, exces-
talinformationoncomposition,animprovedexpressionforthe
sively low initial column temperature must be avoided, to ensure that the
above performance parameters may be worked out, even when
stationary phase remains liquid. The initial temperature of the column
the boiling range distribution curve is not smooth. Currently, should be only low enough to obtain a calibration curve meeting the
specifications of this test method.
car performance cannot be assessed accurately under such
conditions.
6.1.3 Sample Inlet System—The sample inlet system must
be capable of operating continuously at a temperature equiva-
6. Apparatus
lenttothemaximumcolumntemperatureemployed,orprovide
6.1 Chromatograph—Any gas chromatograph may be used
on-column injection with some means of programming the
that meets the performance requirements in Section 8. Place in
entirecolumn,includingpointofsampleintroductionuptothe
serviceinaccordancewithmanufacturer’sinstructions.Typical
maximum temperature required.The sample inlet system must
operating conditions are shown in Table 1.
beconnectedtothechromatographiccolumnsoastoavoidany
6.1.1 Detector—Either a thermal conductivity or a flame
cold spots.
ionization detector may be used. Detector stability must be
6.1.4 FlowControllers—Chromatographsmustbeequipped
such that the sensitivity and baseline drift requirements as
with constant-flow controllers capable of holding carrier gas
definedinSection8aremet.Thedetectoralsomustbecapable
flow constant to 61% over the full operating temperature
of operating continuously at a temperature equivalent to the
range.
maximum column temperature employed, and it must be
6.2 Sample Introduction—Sample introduction may be ei-
connected to the column so as to avoid any cold spots.
ther by means of a constant-volume liquid sample valve or by
injection with a microsyringe through a septum. If the sample
NOTE 1—Caremustbetakenthatthesamplesizechosendoesnotallow
is injected manually, cool the syringe to 0 to 4°C (32 to 40°F)
some peaks to exceed the linear range of the detector. This is especially
critical with the flame ionization detector. With thermal conductivity before taking the sample from the sample vial.
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, −30 40 −20 0 0
°C
Final column temperature, 250 250 200 250 230
°C
Detector temperature, °C 250 250 345 250 250
Injection zone temperature, 250 300 345 250 230
°C
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
NOTE 4—Automatic liquid-sampling devices or other sampling means, (6) Program the column temperature up to the maximum several times
suchassealedseptum-cappedvials,maybeused,providednolossoflight with normal carrier gas flow. The column then should be ready for use.
ends occurs. The system must be operated at a temperature sufficiently NOTE 6—An alternative method of column conditioning, which has
high to vaporize completely hydrocarbons with an atmospheric boiling been found effective for columns with an initial loading of 10% liquid
pointof500°F(260°C),andthesamplingsystemmustbeconnectedtothe phase, consists of purging the column with carrier gas at the normal flow
chromatographic column so as to avoid any cold spots. rate while holding the column at maximum operating temperature for 12
to 16 h.
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
the requirements of Section 8, may be used. The column must
7. Reagents and Materials
be conditioned at the maximum operating temperature to
7.1 CalibrationMixture—Asyntheticmixtureofpureliquid
reduce baseline shifts due to bleeding of column substrate.
hydrocarbons of known boiling point covering the boiling
NOTE 5—The column can be conditioned very rapidly and effectively
range of the sample. At least one compound in the mixture
by the following procedure:
must have a boiling point equal to or lower than the initial
(1) Disconnect column from detector.
boiling point of the sample, and one compound must have a
(2) Purge the column thoroughly at ambient temperature with carrier
retention time greater than any component in the sample. The
gas.
concentration of all compounds heavier than n-butane must be
(3) Turn off the carrier gas and allow the column to depressurize
known within 0.1%. The synthetic composition shown in
completely.
(4) Raise the column temperature to the maximum operating tempera-
Table 1 should be used for gasoline analysis. Compounds
ture and hold at this temperature for at least 1 h with no flow through the
necessary for evaluation of system performance are noted in
column.
Table 2.
(5) Cool the column to at least 100°C before turning on carrier gas
again. NOTE 7—If the sample contains significant quantities of compounds
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 1956.
B
Necessary if sample contains isopentane and lighter compounds.
C
Necessary for system evaluation.
D
Replace 2-methylhexane (2-MeC ) or benzene if the sample contains more than 5 % benzene.
D3710
that can be identified on the chromatogram, these peaks may be used as
internal boiling point calibrations.
NOTE 8—Two calibration mixtures can be used for convenience. One
that contains known concentrations of isopentane and heavier compounds
can be used for determining response factors, sensitivity, and concentra-
tion repeatability. The other would contain a
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