ASTM D5307-97(2002)e1

An American National Standard
e1
Designation: D 5307 – 97 (Reapproved 2002)
Standard Test Method for
Determination of Boiling Range Distribution of Crude
Petroleum by Gas Chromatography
This standard is issued under the fixed designation D 5307; 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—Warnings were moved from notes to section text editorially January 2003.
1. Scope 3.1.2 corrected area slice, n—an area slice corrected for
baseline drift, by subtraction of the exactly corresponding area
1.1 This test method covers the determination of the boiling
slice in a previously recorded blank (nonsample) analysis;
range distribution of water-free crude petroleum through
correction for signal offset may also be required.
538°C (1000°F). Material boiling above 538°C is reported as
3.1.3 cumulative corrected area, n—the accumulated sum
residue. This test method is applicable to whole crude samples,
of corrected area slices from the beginning of the analysis
that can be solubilized in a solvent to permit sampling by
through a given retention time, ignoring any nonsample area
means of a microsyringe.
(for example, solvent).
1.2 The values stated in SI units are to be regarded as the
3.1.4 initial boiling point (IBP), n—the temperature (corre-
standard. The values stated in inch-pound units are for infor-
sponding to the retention time) at which a cumulative corrected
mation only.
area count equal to 0.5 % of the theoretical total area is
1.3 This standard does not purport to address all of the
obtained.
safety concerns, if any, associated with its use. It is the
3.1.5 residue, RES n—the amount of sample boiling above
responsibility of the user of this standard to establish appro-
538°C (1000°F).
priate safety and health practices and determine the applica-
3.1.6 theoretical total area, T n—the area that would have
bility of regulatory limitations prior to use. Specific precau-
been obtained if the entire sample had been eluted from the
tionary statements are given in 7.2, 7.5, 7.6, 7.7, and 7.9.
column.
2. Referenced Documents
3.1.6.1 Discussion—This is determined in 12.3.
3.2 Abbreviations:Abbreviations:
2.1 ASTM Standards:
3.2.1 A common abbreviation of hydrocarbon compounds is
D 2892 Test Method for Distillation of Crude Petroleum
to designate the number of carbon atoms in the compound. A
(15-Theoretical Plate Column)
prefix is used to indicate the carbon chain form, while a
D 4057 Practice for Manual Sampling of Petroleum and
subscripted suffix denotes the number of carbon atoms (for
Petroleum Products
example, normal decane = n-C ; isotetradecane = i-C ).
10 14
3. Terminology
4. Summary of Test Method
3.1 Definitions of Terms Specific to This Standard:
4.1 The crude oil sample is diluted with carbon disulfide,
3.1.1 area slice, n—the area, resulting from the integration
and the resulting solution is injected into a gas chromato-
of the chromatographic detector signal, within a specified
graphic column that separates hydrocarbons in boiling point
retention time interval.
order. The column temperature is raised at a reproducible,
3.1.1.1 Discussion—In area slice mode (see 6.2.2), peak
linear rate, and the area under the chromatogram is recorded
detection parameters are bypassed and the detector signal
throughout the run. Boiling points are assigned to the time axis
integral is recorded as area slices of consecutive, fixed duration
by comparison to a calibration curve obtained under the same
time intervals.
chromatographic conditions by running a mixture of
n-paraffins of known boiling point through a temperature of
This test method is under the jurisdiction of ASTM Committee D02 on
538°C (1000°F). The amount of sample boiling above 538°C is
Petroleum Products and Lubricants and is the direct responsibility of Subcommittee
estimated by means of a second analysis of the crude oil to
D02.04.0H on Chromatographic Methods.
Current edition approved June 10, 1997. Published October 1997. Originally
which an internal standard has been added. From these data,
published as D 5307 – 92. Last previous edition D 5307 – 92.
the boiling range distribution of the water-free sample is
Annual Book of ASTM Standards, Vol 05.01.
3 calculated.
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.
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D 5307 – 97 (2002)
5. Significance and Use provided for programming the entire column, including the
point of sample introduction, up to the maximum column
5.1 The determination of the boiling range distribution is an
temperature employed.
essential requirement in crude oil assay. This information can
6.1.5 Flow Controller—The chromatograph must be
be used to estimate refinery yields and, along with other
equipped with a flow controller capable of maintaining carrier
information, to evaluate the economics of using one particular
gas flow constant to 6 1 % over the full operating temperature
crude as opposed to another.
range of the column. The inlet pressure of the carrier gas,
5.2 Results obtained by this test method are equivalent to
supplied to the chromatograph, must be sufficiently high to
those obtained from Test Method D 2892. (See Appendix X1.)
compensate for the increase of backpressure in the column as
5.3 This test method is faster than Test Method D 2892 and
the temperature is programmed upward. An inlet pressure of
can be used when only small volumes of samples are available.
550 kPa gage (80 psig) has been found satisfactory with the
Also, this test method gives results up to 538°C while Test
columns described in Table 1.
Method D 2892 is limited to 400°C.
6.2 Data Retrieval System:
6. Apparatus
6.2.1 Recorder—A 0–1 mV range recording potentiometer
6.1 Gas Chromatograph—Any gas chromatograph may be or equivalent, with a full-scale response time of2sor less may
be used for graphic presentation of the FID signal.
used that has the capabilities described below and meets the
performance requirements in Section 10.
6.2.2 Integrator—Electronic integrator or computer-based
6.1.1 Detector—This test method is limited to the use of the
chromatography data system must be used for detector signal
flame ionization detector (FID). The detector must be capable
integration and accumulation. The integrator/computer system
of operating continuously at a temperature equal to or greater
must have normal chromatographic software for measuring
than the maximum column temperature employed, and it must
retention time and areas of eluting peaks (peak detection
be connected to the column so as to avoid cold spots.
mode). In addition, the system must be capable of converting
6.1.2 Column Temperature Programmer—The chromato-
the continuously integrated detector signal into area slices
graph must be capable of reproducible, linear programmed
representing contiguous fixed duration time intervals (area
temperature operation over a range sufficient to establish a
slice mode). The recommended time interval is 1 s. No time
retention time of at least 1 min for the IBP and to elute
interval shall be greater than 12 s. The system must be capable
compounds with boiling points of 538°C (1000°F) before the
of subtracting the area slice of a blank run from the corre-
end of the temperature ramp.
sponding area slice of a sample run. Alternatively, the baseline
6.1.3 Cryogenic Column Oven—If the IBP of the crude oil
chromatogram can be subtracted from the sample chromato-
is below 90°C (194°F), an initial column temperature below
gram and the net resulting chromatogram can be processed in
ambient will be required. This necessitates a cryogenic cooling
the slice mode. A computer program that performs the slice
option on the gas chromatograph. Typical initial column
calculation as a post-run calculation is also used.
temperatures are listed in Table 1.
6.3 Column—Any gas chromatographic column that pro-
6.1.4 Sample Inlet System—Either of the following two
vides separation in order of boiling points and meets the
types of sample inlet systems may be used.
performance requirements of Section 10 can be used. Columns
6.1.4.1 Flash Vaporization—A vaporizing sample inlet sys-
and conditions, which have been used successfully, are shown
tem must be capable of operating continuously at a temperature
in Table 1.
equivalent to the maximum column temperature employed.
6.4 Microsyringe—A 5 or 10 μL syringe is used for sample
The sample inlet system also must be connected to the
introduction. The use of an automated liquid sampling device
chromatographic column so as to avoid any cold spots.
is highly recommended.
6.1.4.2 On-Column—Capable of introducing a liquid
sample directly onto the head of the column. Means must be
7. Reagents and Materials
7.1 Purity of Reagents—Reagent-grade chemicals shall be
TABLE 1 Typical Operating Conditions
used in all tests. Unless otherwise indicated, it is intended that
12 3
all reagents conform to the specifications of the Committee on
Analytical Reagents of the American Chemical Society where
Column length, mm (in.) 457 (18) 610 (24) 457 (18)
1 1 1 4
Column diameter, mm (in.) 3.17 ( ⁄8) 3.17 ( ⁄8) 3.17 ( ⁄8)
such specifications are available. Other grades may be used,
Liquid phase 10 % UCW-982 3 % OV-1 10 % SE-30
provided it is first ascertained that the reagent is of sufficiently
Chromosorb Chromosorb Chromosorb
Support material high purity to permit its use without lessening the accuracy of
A A A
P -AW W -HP P -AW
the determination.
Column temperature initial −30 −30 −40
value,° C
Column temperature final 380 350 360
value,° C
Programming rate, °C/min 10 10 10
Reagent Chemicals, American Chemical Society Specifications, American
Carrier gas type N He N
2 2
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
Carrier gas flow, mL/min 25 20 28
listed by the American Chemical Society, see Analar Standards for Laboratory
Detector temperature, °C 400 380 400
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
Injection port temperature, °C 380 375 400
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
A
See Footnote 5. MD.
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D 5307 – 97 (2002)
7.2 Air—Zero grade (hydrocarbon free) for use with the 9. Preparation of Apparatus
FID. (Warning—Air is a compressed gas under high pressure
9.1 Column Preparation—Any satisfactory method used in
and supports combustion.)
the practice of the art, that will produce a column meeting the
7.3 Calcium Chloride, Anhydrous (CaCl ). requirements of Section 10, may be used.
9.2 Column Conditioning—The column must be condi-
7.4 Calibration Mixture—A mixture of n-paraffins dis-
tioned at the maximum operating temperature to reduce base-
solved in carbon disulfide (Warning—see 7.5) covering the
line shifts due to bleeding of the column substrate. The column
boiling range of the sample through 538°C (1000°F). At least
can be conditioned rapidly and effectively using the following
one compound in the mixture must have a boiling point equal
procedure:
to or lower than the IBP of the sample. Methane, ethane,
9.2.1 Connect the column to the inlet system but leave the
propane, or butane can be added to the calibration mixture, if
detector end free.
necessary, by injecting about 1 mL of the pure gaseous
9.2.2 Purge the column at ambient temperature with carrier
compound into a septum-capped, sealed vial containing the rest
gas.
of the calibration mixture, using a gas syringe. If n-paraffin
9.2.3 Turn off the carrier gas and allow the column to
peaks can be unambiguously identified in the sample chro-
depressurize completely.
matogram, their retention times can be used for calibration.
9.2.4 Seal off the open end of the column with an appropri-
7.5 Carbon Disulfide (CS )—Carbon disulfide (99 % mini-
ate fitting.
mum purity) is used as a viscosity reducing solvent because it
9.2.5 Raise the column to the maximum operating tempera-
is miscible with crude oils and has only a slight response with
ture and hold at this temperature 4 to 6 h, with no flow through
the FID. (Warning—Carbon disulfide is extremely volatile,
the column.
flammable, and toxic.)
9.2.6 Cool the column to ambient temperature.
7.6 Carrier Gas—Nitrogen or helium of high purity that has
9.2.7 Remove the cap from the column and connect the
been dried over molecular sieves or similar suitable drying
column to the detector. Re-establish carrier flow.
agents. (Warning—Helium and nitrogen are compressed gases
9.2.8 Program the column temperature to the maximum
under high pressure.)
several times with normal carrier gas flow rate.
7.7 Column Resolution Test Mixture—A mixture of 1 %
9.3 An alternate method of column conditioning, that has
each of n-C and n-C paraffin in a suitable solvent, such as
16 18
been found effective with columns with an initial loading of
n-octane, for use in testing the column resolution. (Warning—
5 % liquid phase, consists of purging the column (disconnected
n-Octane is flammable and harmful if inhaled.)
from the detector) with normal carrier gas flow rate for 12 to 16
7.8 Detector Response Test Mixture—An accurately h, while holding the column at the maximum operating
weighed mixture of approximately equal masses of at least six
temperature.
n-paraffins covering the carbon number range from 10 to 44.
9.4 Chromatograph—Place the chromatograph in service in
Dissolve one part of this mixture with approximately five parts accordance with the manufacturer’s instructions. Typical oper-
of CS (or sufficient CS to ensure a stable solution at room ating conditions are shown in Table 1.
2 2
temperature).
9.4.1 Excessively low initial column temperature must be
avoided to ensure that the column phase functions as gas-liquid
7.9 Hydrogen—Hydrogen of high quality (hydrocarbon
chromatographic column. Consult the stationary phase manu-
free) is used as fuel gas for the FID. (Warning—Hydrogen is
facturer’s literature for minimum operating temperature. The
an extremely flammable gas under high pressure.)
initial temperature of the column should be only low enough to
7.10 Internal Standard—A mixture of approximately equal
obtain a calibration curve meeting the specifications under
amounts of four n-paraffins, n-C through n-C . Concentra-
14 17
6.1.3.
tions of the individual components need not be known but must
9.4.2 Silica from combustion of column material deposits
be within the linear range of the detector/electronics system
on the FID parts. This deposit must be removed regularly, by
used.
brushing, because it changes response characteristics of the
7.11 Liquid Phase—A nonreactive, nonpolar liquid or gum
detector.
of
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