NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.

Please contact ASTM International (www.astm.org) for the latest information.

An American National Standard
Designation: D 5307 – 97

Standard Test Method for

Determination of Boiling Range Distribution of Crude
Petroleum by Gas Chromatography1
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 (´) indicates an editorial change since the last revision or reapproval.

1. Scope slice in a previously recorded blank (nonsample) analysis;

1.1 This test method covers the determination of the boiling correction for signal offset may also be required.
range distribution of water-free crude petroleum through 3.1.3 cumulative corrected area, n—the accumulated sum
538°C (1000°F). Material boiling above 538°C is reported as of corrected area slices from the beginning of the analysis
residue. This test method is applicable to whole crude samples, through a given retention time, ignoring any nonsample area
that can be solubilized in a solvent to permit sampling by (for example, solvent).
means of a microsyringe. 3.1.4 initial boiling point (IBP), n—the temperature (corre-
1.2 The values stated in SI units are to be regarded as the sponding to the retention time) at which a cumulative corrected
standard. The values stated in inch-pound units are for infor- area count equal to 0.5 % of the theoretical total area is
mation only. obtained.
1.3 This standard does not purport to address all of the 3.1.5 residue, RES n—the amount of sample boiling above
safety concerns, if any, associated with its use. It is the 538°C (1000°F).

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responsibility of the user of this standard to establish appro- 3.1.6 theoretical total area, T n—the area that would have
priate safety and health practices and determine the applica- been obtained if the entire sample had been eluted from the
column.
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bility of regulatory limitations prior to use. Specific precau-
tionary statements are given in Note 1, Note 2, Note 3, Note 4, 3.1.6.1 Discussion—This is determined in 12.3.
and Note 5. 3.2 Abbreviations:Abbreviations:

2. Referenced Documents Document Preview 3.2.1 A common abbreviation of hydrocarbon compounds is

to designate the number of carbon atoms in the compound. A
2.1 ASTM Standards: prefix is used to indicate the carbon chain form, while a
D 2892 Test Method for Distillation of Crude Petroleum subscripted suffix denotes the number of carbon atoms (for
(15-Theoretical Plate Column) 2 ASTM D5307-97
example, normal decane = n-C10; isotetradecane = i-C14).
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D 4057 Practice for Manual Sampling of Petroleum and
4. Summary of Test Method
Petroleum Products3
4.1 The crude oil sample is diluted with carbon disulfide,
3. Terminology and the resulting solution is injected into a gas chromato-
3.1 Definitions of Terms Specific to This Standard: graphic column that separates hydrocarbons in boiling point
3.1.1 area slice, n—the area, resulting from the integration order. The column temperature is raised at a reproducible,
of the chromatographic detector signal, within a specified linear rate, and the area under the chromatogram is recorded
retention time interval. throughout the run. Boiling points are assigned to the time axis
3.1.1.1 Discussion—In area slice mode (see 6.2.2), peak by comparison to a calibration curve obtained under the same
detection parameters are bypassed and the detector signal chromatographic conditions by running a mixture of
integral is recorded as area slices of consecutive, fixed duration n-paraffins of known boiling point through a temperature of
time intervals. 538°C (1000°F). The amount of sample boiling above 538°C is
3.1.2 corrected area slice, n—an area slice corrected for estimated by means of a second analysis of the crude oil to
baseline drift, by subtraction of the exactly corresponding area which an internal standard has been added. From these data,
the boiling range distribution of the water-free sample is
1
calculated.
This test method is under the jurisdiction of ASTM Committee D02 on
Petroleum Products and Lubricants and is the direct responsibility of Subcommittee
D02.04.0H on Chromatographic Methods.
5. Significance and Use
Current edition approved June 10, 1997. Published October 1997. Originally 5.1 The determination of the boiling range distribution is an
published as D 5307 – 92. Last previous edition D 5307 – 92. essential requirement in crude oil assay. This information can
2
Annual Book of ASTM Standards, Vol 05.01.
3
Annual Book of ASTM Standards, Vol 05.02. be used to estimate refinery yields and, along with other

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1
NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Please contact ASTM International (www.astm.org) for the latest information.
D 5307 – 97
information, to evaluate the economics of using one particular 6.1.5 Flow Controller—The chromatograph must be
crude as opposed to another. equipped with a flow controller capable of maintaining carrier
5.2 Results obtained by this test method are equivalent to gas flow constant to 6 1 % over the full operating temperature
those obtained from Test Method D 2892D 2892. (See Appen- range of the column. The inlet pressure of the carrier gas,
dix X1.) supplied to the chromatograph, must be sufficiently high to
5.3 This test method is faster than Test Method compensate for the increase of backpressure in the column as
D 2892D 2892 and can be used when only small volumes of the temperature is programmed upward. An inlet pressure of
samples are available. Also, this test method gives results up to550 kPa gage (80 psig) has been found satisfactory with the
538°C while Test Method D 2892D 2892 is limited to 400°C. columns described in Table 1.
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 of 2 s or less may
used that has the capabilities described below and meets the be used for graphic presentation of the FID signal.
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
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6.1.3 Cryogenic Column Oven—If the IBP of the crude oil
is below 90°C (194°F), an initial column temperature below
chromatogram can be substracted from the sample chromato-
gram and the net resulting chromatogram can be processed in

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ambient will be required. This necessitates a cryogenic cooling
option on the gas chromatograph. Typical initial column
the slice mode. A computer program that performs the slice
calculation as a post-run calculation is also used.
6.3 Column—Any gas chromatographic column that pro-
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temperatures are listed in Table 1.
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
in Table 1.
ASTM D5307-97
tem must be capable of operating continuously at a temperature
equivalent to the maximum column temperature employed. 6.4 Microsyringe—A 5 or 10 µL syringe is used for sample
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introduction. The use of an automated liquid sampling device
The sample inlet system also must be connected to the
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
provided for programming the entire column, including the 7.1 Purity of Reagents—Reagent-grade chemicals shall be
point of sample introduction, up to the maximum column used in all tests. Unless otherwise indicated, it is intended that
temperature employed. all reagents conform to the specifications of the Committee on
Analytical Reagents of the American Chemical Society where
such specifications are available.4 Other grades may be used,
TABLE 1 Typical Operating Conditions provided it is first ascertained that the reagent is of sufficiently
1 2 3 high purity to permit its use without lessening the accuracy of
Column length, mm (in.) 457 (18) 610 (24) 457 (18) the determination.
Column diameter, mm (in.) 3.17 (1⁄8) 3.17 (1⁄8) 3.17 (1⁄8) 7.2 Air—Zero grade (hydrocarbon free) for use with the
Liquid phase 10 % UCW-982 3 % OV-1 10 % SE-30
FID. (Warning—See Note 1.)
Chromosorb Chromosorb Chromosorb
Support material
PA-AW WA-HP PA-AW NOTE 1—Warning: Air is a compressed gas under high pressure and
Column temperature initial −30 −30 −40 supports combustion.
value,° C
Column temperature final 380 350 360
value,° C
Programming rate, °C/min 10 10 10 4
Reagent Chemicals, American Chemical Society Specifications, American
Carrier gas type N2 He N2 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.

2
NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Please contact ASTM International (www.astm.org) for the latest information.
D 5307 – 97
7.3 Calcium Chloride, Anhydrous (CaCl2). 9. Preparation of Apparatus
7.4 Calibration Mixture—A mixture of n-paraffins dis- 9.1 Column Preparation—Any satisfactory method used in
solved in carbon disulfide (Warning—see Note 2) covering the the practice of the art, that will produce a column meeting the
boiling range of the sample through 538°C (1000°F). At least requirements of Section 10, may be used.
one compound in the mixture must have a boiling point equal 9.2 Column Conditioning—The column must be condi-
to or lower than the IBP of the sample. Methane, ethane, tioned at the maximum operating temperature to reduce base-
propane, or butane can be added to the calibration mixture, if line shifts due to bleeding of the column substrate. The column
necessary, by injecting about 1 mL of the pure gaseous can be conditioned rapidly and effectively using the following
compound into a septum-capped, sealed vial containing the rest procedure:
of the calibration mixture, using a gas syringe. If n-paraffin
9.2.1 Connect the column to the inlet system but leave the
peaks can be unambiguously identified in the sample chro-
detector end free.
matogram, their retention times can be used for calibration.
9.2.2 Purge the column at ambient temperature with carrier
7.5 Carbon Disulfide (CS2)—Carbon disulfide (99 % mini-
gas.
mum purity) is used as a viscosity reducing solvent because it
9.2.3 Turn off the carrier gas and allow the column to
is miscible with crude oils and has only a slight response with
depressurize completely.
the FID. (Warning—See Note 2.)
9.2.4 Seal off the open end of the column with an appropri-
NOTE 2—Warning: Carbon disulfide is extremely volatile, flammable, ate fitting.
and toxic.
9.2.5 Raise the column to the maximum operating tempera-
7.6 Carrier Gas—Nitrogen or helium of high purity that has ture and hold at this temperature 4 to 6 h, with no flow through
been dried over molecular sieves or similar suitable drying the column.
agents. (Warning—See Note 3.) 9.2.6 Cool the column to ambient temperature.
NOTE 3—Warning: Helium and nitrogen are compressed gases under 9.2.7 Remove the cap from the column and connect the
high pressure. column to the detector. Re-establish carrier flow.
7.7 Column Resolution Test Mixture—A mixture of 1 % 9.2.8 Program the column temperature to the maximum

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each of n-C16 and n-C18 paraffin in a suitable solvent, such as
n-octane, for use in testing the column resolution. (Warning—
several
9.3 An
times with normal carrier gas flow rate.
alternate method of column conditioning, that has

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See Note 4.) been found effective with columns with an initial loading of
5 % liquid phase, consists of purging the column (disconnected
NOTE 4—Warning: n-Octane is flammable and harmful if inhaled. from the detector) with normal carrier gas flow rate for 12 to 16
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7.8 Detector Response Test Mixture—An accurately
weighed mixture of approximately equal masses of at least six
h, while holding the column at the maximum operating
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
ASTM D5307-97 accordance with the manufacturer’s instructions. Typical oper-
of CS2(or sufficient CS2 to ensure a stable solution at room ating conditions are shown in Table 1.
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temperature). 9.4.1 Excessively low initial column temperature must be
7.9 Hydrogen—Hydrogen of high quality (hydrocarbon avoided to ensure that the column phase functions as gas-liquid
free) is used as fuel gas for the FID. (Warning—See Note 5.) chromatographic column. Consult the stationary phase manu-
NOTE 5—Warning: Hydrogen is an extremely flammable gas under facturer’s literature for minimum operating temperature. The
high pressure. initial temperature of the column should be only low enough to
obtain a calibration curve meeting the specifications under
7.10 Internal Standard—A mixture of approximately equal
6.1.3.
amounts of four n-paraffins, n-C14 through n-C17. Concentra-
9.4.2 Silica from combustion of column material deposits
tions of the individual components need not be known but must
on the FID parts. This deposit must be removed regularly, by
be within the linear range of the detector/electronics system
brushing, because it changes response characteristics of the
used.
detector.
7.11 Liquid Phase—A nonreactive, nonpolar liquid or gum
of low volatility. Silicone gum rubbers are typically used. In 9.4.3 Silica deposits also can plug the end of the flame jet.
general, liquid phase loadings of 3 to 10 % have been found This problem can be alleviated greatly by utilizing a flame jet
most satisfactory. with an inside diameter of at least 0.76 mm (0.030 in.)
7.12 Solid Support—A diatomaceous earth or equivalent
nonreactive particulate material. Typical particle size ranges 10. System Performance
are 60/80 or 80/100 mesh. 10.1 Resolution—Analyze an aliquot of the column resolu-
tion test mixture (see 7.7) utilizing identical conditions as used
8. Sampling in the analysis of samples. The resolution of n-C16 and
8.1 Obtain samples for analysis by this test method in n-C18n-paraffin peaks must be between three and ten when
accordance with instructions given in Practice D 4057D 4057. calculated in accordance with the following equation (refer to
8.1.1 Ensure that samples are received in sealed containers Fig. 1):
and show no evidence of leakage. R 5 [2~t2 2 t1!#/[1.699~Y2 1 Y1!# (1)