ASTM D5399-09(2017)

Standard Test Method for Boiling Point Distribution of Hydrocarbon Solvents by Gas Chromatography

SIGNIFICANCE AND USE
5.1 The gas chromatographic determination of the boiling point distribution of hydrocarbon solvents can be used as an alternative to conventional distillation methods for control of solvents quality during manufacture, and specification testing.  
5.2 Boiling point distribution data can be used to monitor the presence of product contaminants and compositional variation during the manufacture of hydrocarbon solvents.  
5.3 Boiling point distribution data obtained by this test method are not equivalent to those obtained by Test Methods D86, D850, D1078, D2887, D2892, and D3710.
SCOPE
1.1 This test method covers the determination of the boiling point distribution of hydrocarbon solvents by capillary gas chromatography. This test method is limited to samples having a minimum initial boiling point of 37°C (99°F), a maximum final boiling point of 285°C (545°F), and a boiling range of 5 to 150°C (9 to 270°F) as measured by this test method.  
1.2 For purposes of determining conformance of an observed or calculated value using this test method to relevant specifications, test result(s) shall be rounded off “to the nearest unit” in the last right-hand digit used in expressing the specification limit, in accordance with the rounding-off method of Practice E29.  
1.3 The values stated in SI units are standard. The values given in parentheses are for information purposes only.  
1.4 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, health, and environmental practices and determine the applicability of regulatory limitations prior to use.  
1.5 This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.

General Information

• Status: Historical
• Publication Date: 30-Nov-2017
• ICS: 71.040.50 - Physicochemical methods of analysis
• Technical Committee: D01 - Paint and Related Coatings, Materials, and Applications
• Drafting Committee: D01.35 - Solvents, Plasticizers, and Chemical Intermediates

Standards Content (Sample)

NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Contact ASTM International (www.astm.org) for the latest information
Designation: D5399 − 09 (Reapproved 2017)
Standard Test Method for
Boiling Point Distribution of Hydrocarbon Solvents by Gas
Chromatography
This standard is issued under the fixed designation D5399; 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 D850 Test Method for Distillation of Industrial Aromatic
Hydrocarbons and Related Materials
1.1 This test method covers the determination of the boiling
D1078 Test Method for Distillation Range of Volatile Or-
point distribution of hydrocarbon solvents by capillary gas
ganic Liquids
chromatography. This test method is limited to samples having
D2887 Test Method for Boiling Range Distribution of Pe-
a minimum initial boiling point of 37°C (99°F), a maximum
troleum Fractions by Gas Chromatography
final boiling point of 285°C (545°F), and a boiling range of 5
D2892 Test Method for Distillation of Crude Petroleum
to 150°C (9 to 270°F) as measured by this test method.
(15-Theoretical Plate Column)
1.2 For purposes of determining conformance of an ob-
D3710 Test Method for Boiling Range Distribution of Gaso-
served or calculated value using this test method to relevant
line and Gasoline Fractions by Gas Chromatography
specifications, test result(s) shall be rounded off “to the nearest
(Withdrawn 2014)
unit” in the last right-hand digit used in expressing the
E29 Practice for Using Significant Digits in Test Data to
specification limit, in accordance with the rounding-off method
Determine Conformance with Specifications
of Practice E29.
E691 Practice for Conducting an Interlaboratory Study to
Determine the Precision of a Test Method
1.3 The values stated in SI units are standard. The values
given in parentheses are for information purposes only.
3. Terminology
1.4 This standard does not purport to address all of the
3.1 Definitions:
safety concerns, if any, associated with its use. It is the
3.1.1 initial boiling point (IBP), n—the point at which a
responsibility of the user of this standard to establish appro-
cumulative area count equal to 0.5 % of the total area under the
priate safety, health, and environmental practices and deter-
chromatogram is obtained.
mine the applicability of regulatory limitations prior to use.
1.5 This international standard was developed in accor-
3.1.2 final boiling point (FBP), n—the point at which a
dance with internationally recognized principles on standard-
cumulative area count equal to 99.5 % of the total area under
ization established in the Decision on Principles for the
the chromatogram is obtained.
Development of International Standards, Guides and Recom-
4. Summary of Test Method
mendations issued by the World Trade Organization Technical
Barriers to Trade (TBT) Committee.
4.1 The sample is introduced into a capillary gas chromato-
graphic column that separates hydrocarbons in the order of
2. Referenced Documents
increasing boiling point. The column temperature is raised at a
reproducible rate and the area under the chromatogram is
2.1 ASTM Standards:
recorded throughout the run. Boiling points are assigned from
D86 Test Method for Distillation of Petroleum Products and
a calibration curve obtained under the same conditions by
Liquid Fuels at Atmospheric Pressure
running a known mixture of hydrocarbons covering the boiling
range expected in the sample. From these data, the boiling
point distribution of the sample is obtained.
This test method is under the jurisdiction of ASTM Committee D01 on Paint
and Related Coatings, Materials, and Applications and is the direct responsibility of
5. Significance and Use
Subcommittee D01.35 on Solvents, Plasticizers, and Chemical Intermediates.
Current edition approved Dec. 1, 2017. Published December 2017. Originally
5.1 The gas chromatographic determination of the boiling
approved in 1993. Last previous edition approved in 2009 as D5399 – 09. DOI:
point distribution of hydrocarbon solvents can be used as an
10.1520/D5399-09R17.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM
Standards volume information, refer to the standard’s Document Summary page on The last approved version of this historical standard is referenced on
the ASTM website. www.astm.org.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D5399 − 09 (2017)
TABLE 1 Calibration Mixture
alternative to conventional distillation methods for control of
solvents quality during manufacture, and specification testing. Peak Number Compound Identification Normal Boiling Point, °C
1 n-Pentane 36.1
5.2 Boiling point distribution data can be used to monitor
2 2-Methyl Pentane 60.0
the presence of product contaminants and compositional varia-
3 n-Hexane 68.9
4 2,4-Dimethyl Pentane 80.6
tion during the manufacture of hydrocarbon solvents.
5 n-Heptane 98.3
5.3 Boiling point distribution data obtained by this test
6 Toluene 110.6
7 n-Octane 125.6
method are not equivalent to those obtained by Test Methods
8 p-Xylene 138.3
D86, D850, D1078, D2887, D2892, and D3710.
9 n-Propyl Benzene 159.4
10 n-Decane 173.9
11 n-Butyl Benzene 183.3
6. Apparatus
12 n-Dodecane 216.1
6.1 Chromatograph—Any gas chromatograph that can
13 n-Tridecane 235.6
14 n-Tetradecane 253.9
handle capillary column and has the following characteristics:
15 n-Pentadecane 270.6
6.1.1 Detector—A flame ionization detector (FID) capable
16 n-Hexadecane 287.2
of continuous operation at a temperature equivalent to the
maximum column temperature employed.
6.1.2 Column Temperature Programmer—The chromato-
graph must be capable of reproducible linear temperature
component must have a retention time greater than any
programming over a range sufficient to establish a retention
component in the sample.
time of 1 min for n-pentane and to allow elution of entire
7.3 Carrier Gas, Helium (high purity)—Additional purifi-
sample within a reasonable time period.
cation is recommended by the use of molecular sieves or other
6.1.3 Sample Inlet System—The sample inlet system must
suitable agents to remove water, oxygen, and hydrocarbons.
be capable of operating continuously at a temperature up to the
7.3.1 Warning: Helium is a compressed gas under high
maximum column temperature employed, or provide on-
pressure.
column injection.
7.4 Detector Gases, Air, Hydrogen (high purity)—
NOTE 1—The use of cool, on-column injection using an automatic
Additional purification for air and hydrogen is recommended
injector or sampler has been shown to provide better precision relative to
by the use of molecular sieves, activated carbons, or other
manual injection.
suitable agents to remove water and organics.
6.1.4 Column—A 10 to 30 m by 0.53 mm inside diameter by
7.4.1 Warning: Air and hydrogen are compressed gases
3-µm bonded methyl silicone, fused silica, or equivalent
under high pressure. Hydrogen is an extremely flammable gas.
column that elutes components in order of boiling points, and
meets the resolution criteria specified in 8.2 must be used (see
8. Preparation of Apparatus
8.4).
8.1 Column Preparation—The column must be conditioned
6.1.5 Integrator—Means must be provided for determining
at the maximum operating temperature to reduce baseline shifts
the accumulated area under the chromatogram. This can be
due to bleeding of column substrate.
done by means of a computer or electronic integrator. A timing
device can be used to record the area at set time intervals. The
NOTE 2—The column can be conditioned using the following proce-
same basis for measuring time must be used to determine the dure:
(a) Disconnect the column from the detector,
retention times in the calibration, and the sample. The maxi-
(b) Purge the column at ambient temperature with carrier
mum signal measured must be within the linear range of the
gas for at least 30 min,
measuring system used.
(c) With carrier gas flowing through the column, raise the
6.1.6 Flow Controller—The chromatograph must be
column temperature to the maximum operating temperature
equipped with a constant-flow device capable of maintaining
and maintain the temperature at this level for 12 to 16 h,
the carrier gas at a constant flow rate throughout the tempera-
(d) Cool the column to ambient temperature,
ture program.
(e) Reconnect the column to the detector,
6.1.7 Sample Introduction—A microsyringe is required for
(f) Set the detector temperature to at least 5°C higher than
the introduction of the sample to the gas chromatograph (see
the maximum column temperature, and
Note 1).
(g) Program the column temperature up to the maximum
7. Reagents and Materials several times with normal carrier flow until a stable, flat
baseline is obtained.
7.1 Purity of Reagents—Reagent grade chemicals shall be
used in the preparation of the calibration mixture. 8.2 Column Resolution—To test column resolution, inject
the same volume of the calibration mixture as used during
7.2 Calibration Mixture—A synthetic blend of pure liquid
normal sample analysis and obtain the chromatogram by the
hydrocarbons of known boiling points. The components of the
procedure described in Section 9. Using the n-dodecane (C )
calibration mixture are listed in Table 1 and prepared by
and n-tridecane (C ) peaks, and Fig. 1, calculate the
mixing equivolume quantities of the components. At least one
resolution, R, as calculated from the equation:
component in the mixture must have a boiling point equal to or
lower than the initial boiling point of the sa
...

This document is not an ASTM standard and is intended only to provide the user of an ASTM standard an indication of what changes have been made to the previous version. Because
it may not be technically possible to adequately depict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current version
of the standard as published by ASTM is to be considered the official document.
Designation: D5399 − 09 D5399 − 09 (Reapproved 2017)
Standard Test Method for
Boiling Point Distribution of Hydrocarbon Solvents by Gas
Chromatography
This standard is issued under the fixed designation D5399; 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*Scope
1.1 This test method covers the determination of the boiling point distribution of hydrocarbon solvents by capillary gas
chromatography. This test method is limited to samples having a minimum initial boiling point of 37°C (99°F), a maximum final
boiling point of 285°C (545°F), and a boiling range of 5 to 150°C (9 to 270°F) as measured by this test method.
1.2 For purposes of determining conformance of an observed or calculated value using this test method to relevant
specifications, test result(s) shall be rounded off “to the nearest unit” in the last right-hand digit used in expressing the specification
limit, in accordance with the rounding-off method of Practice E29.
1.3 The values stated in SI units are standard. The values given in parentheses are for information purposes only.
1.4 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 safety, health, and healthenvironmental practices and determine the
applicability of regulatory limitations prior to use.
1.5 This international standard was developed in accordance with internationally recognized principles on standardization
established in the Decision on Principles for the Development of International Standards, Guides and Recommendations issued
by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
2. Referenced Documents
2.1 ASTM Standards:
D86 Test Method for Distillation of Petroleum Products and Liquid Fuels at Atmospheric Pressure
D850 Test Method for Distillation of Industrial Aromatic Hydrocarbons and Related Materials
D1078 Test Method for Distillation Range of Volatile Organic Liquids
D2887 Test Method for Boiling Range Distribution of Petroleum Fractions by Gas Chromatography
D2892 Test Method for Distillation of Crude Petroleum (15-Theoretical Plate Column)
D3710 Test Method for Boiling Range Distribution of Gasoline and Gasoline Fractions by Gas Chromatography (Withdrawn
2014)
E29 Practice for Using Significant Digits in Test Data to Determine Conformance with Specifications
E691 Practice for Conducting an Interlaboratory Study to Determine the Precision of a Test Method
3. Terminology
3.1 Definitions:
3.1.1 initial boiling point (IBP), n—the point at which a cumulative area count equal to 0.5 % of the total area under the
chromatogram is obtained.
3.1.2 final boiling point (FBP), n—the point at which a cumulative area count equal to 99.5 % of the total area under the
chromatogram is obtained.
This test method is under the jurisdiction of ASTM Committee D01 on Paint and Related Coatings, Materials, and Applications and is the direct responsibility of
Subcommittee D01.35 on Solvents, Plasticizers, and Chemical Intermediates.
Current edition approved Dec. 1, 2009Dec. 1, 2017. Published December 2009December 2017. Originally approved in 1993. Last previous edition approved in 2009 as
D5399 – 04 (2009).D5399 – 09. DOI: 10.1520/D5399-09.10.1520/D5399-09R17.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM Standards
volume information, refer to the standard’s Document Summary page on the ASTM website.
The last approved version of this historical standard is referenced on www.astm.org.
*A Summary of Changes section appears at the end of this standard
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D5399 − 09 (2017)
4. Summary of Test Method
4.1 The sample is introduced into a capillary gas chromatographic column that separates hydrocarbons in the order of increasing
boiling point. The column temperature is raised at a reproducible rate and the area under the chromatogram is recorded throughout
the run. Boiling points are assigned from a calibration curve obtained under the same conditions by running a known mixture of
hydrocarbons covering the boiling range expected in the sample. From these data, the boiling point distribution of the sample is
obtained.
5. Significance and Use
5.1 The gas chromatographic determination of the boiling point distribution of hydrocarbon solvents can be used as an
alternative to conventional distillation methods for control of solvents quality during manufacture, and specification testing.
5.2 Boiling point distribution data can be used to monitor the presence of product contaminants and compositional variation
during the manufacture of hydrocarbon solvents.
5.3 Boiling point distribution data obtained by this test method are not equivalent to those obtained by Test Methods D86, D850,
D1078, D2887, D2892, and D3710.
6. Apparatus
6.1 Chromatograph—Any gas chromatograph that can handle capillary column and has the following characteristics:
6.1.1 Detector—A flame ionization detector (FID) capable of continuous operation at a temperature equivalent to the maximum
column temperature employed.
6.1.2 Column Temperature Programmer—The chromatograph must be capable of reproducible linear temperature programming
over a range sufficient to establish a retention time of 1 min for n-pentane and to allow elution of entire sample within a reasonable
time period.
6.1.3 Sample Inlet System—The sample inlet system must be capable of operating continuously at a temperature up to the
maximum column temperature employed, or provide on-column injection.
NOTE 1—The use of cool, on-column injection using an automatic injector or sampler has been shown to provide better precision relative to manual
injection.
6.1.4 Column—A 10 to 30 m by 0.53 mm inside diameter by 3-μm bonded methyl silicone, fused silica, or equivalent column
that elutes components in order of boiling points, and meets the resolution criteria specified in 8.2 must be used (see 8.4).
6.1.5 Integrator—Means must be provided for determining the accumulated area under the chromatogram. This can be done by
means of a computer or electronic integrator. A timing device can be used to record the area at set time intervals. The same basis
for measuring time must be used to determine the retention times in the calibration, and the sample. The maximum signal measured
must be within the linear range of the measuring system used.
6.1.6 Flow Controller—The chromatograph must be equipped with a constant-flow device capable of maintaining the carrier gas
at a constant flow rate throughout the temperature program.
6.1.7 Sample Introduction—A microsyringe is required for the introduction of the sample to the gas chromatograph (see Note
1).
7. Reagents and Materials
7.1 Purity of Reagents—Reagent grade chemicals shall be used in the preparation of the calibration mixture.
7.2 Calibration Mixture—A synthetic blend of pure liquid hydrocarbons of known boiling points. The components of the
calibration mixture are listed in Table 1 and prepared by mixing equivolume quantities of the components. At least one component
in the mixture must have a boiling point equal to or lower than the initial boiling point of the sample, and one component must
have a retention time greater than any component in the sample.
7.3 Carrier Gas, heliumHelium (high purity)—Additional purification is recommended by the use of molecular sieves or other
suitable agents to remove water, oxygen, and hydrocarbons.
7.3.1 Warning: Helium is a compressed gas under high pressure.
7.4 Detector Gases, air, hydrogenAir, Hydrogen (high purity)—Additional purification for air and hydrogen is recommended by
the use of molecular sieves, activated carbons, or other suitable agents to remove water and organics.
7.4.1 Warning: Air and hydrogen are compressed gases under high pressure. Hydrogen is an extremely flammable gas.
8. Preparation of Apparatus
8.1 Column Preparation—The column must be conditioned at the maximum operating temperature to reduce baseline shifts due
to bleeding of column substrate.
NOTE 2—The column can be conditioned using the following procedure:
(a) Disconnect the column from the detector,
D5399 − 09 (2017)
TABLE 1 Calibration Mixture
Peak Number Compound Identification Normal Boiling Point, °C
1 n-Pentane 36.1
2 2-Methyl Pentane 60.0
3 n-Hexane 68.9
4 2,4-Dimethyl Pentane 80.6
5 n-Heptane 98.3
6 Toluene 110.6
7 n-Octane 125.6
8 p-Xylene 138.3
9 n-Propyl Benzene 159.4
10 n-Decane 173.9
11 n-Butyl Benzene 183.3
12 n-Dodecane 216.1
13 n-Tridecane 235.6
14 n-Tetradecane 253.9
15 n-Pentadecane 270.6
16 n-Hexadecane 287.2
(b) Purge the column at ambient temperature with carrier gas for at least 30 min,
(c) With carrier gas flowing through the column, raise the column temperature to the maximum operating temperature and
maintain the temperature at this level for 12 to 16 h,
(d) Cool the column to ambient temperature,
(e) Reconnect the column to the detector,
(f) Set the detector temperature to at least 5°C higher than the maximum column temperature, and
(g) Program the column temperature up to the maximum several times with normal carrier flow until a stable, flat baseline is
obtained.
8.2 Column Resolution—To test column resolution, inject the same volume of the calibration mixture as used during normal
sample analysis and obtain the chromatogram by the procedure described
...