ASTM D5399-09(2023)

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 °C to 150 °C (9 °F 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: Published
• Publication Date: 30-Jun-2023
• 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

Relations

• Refers: ASTM D86-23a - Standard Test Method for Distillation of Petroleum Products and Liquid Fuels at Atmospheric Pressure
• Effective Date: 01-Dec-2023
• Refers: ASTM D86-23ae1 - Standard Test Method for Distillation of Petroleum Products and Liquid Fuels at Atmospheric Pressure
• Effective Date: 01-Dec-2023
• Refers: ASTM D2892-23 - Standard Test Method for Distillation of Crude Petroleum (15-Theoretical Plate Column)
• Effective Date: 01-Nov-2023
• Refers: ASTM D2887-23 - Standard Test Method for Boiling Range Distribution of Petroleum Fractions by Gas Chromatography
• Effective Date: 01-Jul-2023
• Refers: ASTM D2892-20 - Standard Test Method for Distillation of Crude Petroleum (15-Theoretical Plate Column)
• Effective Date: 01-Jun-2020
• Refers: ASTM D2887-19 - Standard Test Method for Boiling Range Distribution of Petroleum Fractions by Gas Chromatography
• Effective Date: 01-Jul-2019
• Refers: ASTM D2892-18 - Standard Test Method for Distillation of Crude Petroleum (15-Theoretical Plate Column)
• Effective Date: 01-Apr-2018
• Refers: ASTM D2892-17 - Standard Test Method for Distillation of Crude Petroleum (15-Theoretical Plate Column)
• Effective Date: 01-May-2017
• Refers: ASTM D2892-16 - Standard Test Method for Distillation of Crude Petroleum (15-Theoretical Plate Column)
• Effective Date: 01-Dec-2016
• Refers: ASTM D86-16 - Standard Test Method for Distillation of Petroleum Products and Liquid Fuels at Atmospheric Pressure
• Effective Date: 01-Jul-2016
• Refers: ASTM D2887-15 - Standard Test Method for Boiling Range Distribution of Petroleum Fractions by Gas Chromatography
• Effective Date: 01-Jul-2015
• Refers: ASTM D2892-15 - Standard Test Method for Distillation of Crude Petroleum (15-Theoretical Plate Column)
• Effective Date: 01-Apr-2015
• Refers: ASTM E691-13 - Standard Practice for Conducting an Interlaboratory Study to Determine the Precision of a Test Method
• Effective Date: 01-May-2013
• Refers: ASTM D2887-13 - Standard Test Method for Boiling Range Distribution of Petroleum Fractions by Gas Chromatography
• Effective Date: 01-May-2013
• Refers: ASTM D2892-13 - Standard Test Method for Distillation of Crude Petroleum (15-Theoretical Plate Column)
• Effective Date: 01-May-2013

Overview

ASTM D5399-09(2023) sets out the standard test method for determining the boiling point distribution of hydrocarbon solvents using capillary gas chromatography. Developed by ASTM International, this method offers an alternative to traditional distillation-based approaches for quality control and specification testing of hydrocarbon solvents. The standard applies to samples with an initial boiling point of at least 37 °C (99 °F), a final boiling point up to 285 °C (545 °F), and a boiling range of 5 °C to 150 °C as evaluated by this technique.

Adhering to globally recognized principles on standardization, ASTM D5399 plays a critical role in chemical, petrochemical, and industrial applications where knowledge of boiling range is vital for product consistency, regulatory compliance, and process optimization.

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Key Topics

• Boiling Point Distribution by Gas Chromatography:
  The method involves injecting the hydrocarbon solvent sample into a gas chromatograph equipped with a capillary column and a flame ionization detector (FID). Compounds are separated based on increasing boiling points, and a calibration curve is used to assign boiling point values.

• Quality Control and Specification Testing:
  Boiling point distribution data generated by this method are instrumental for controlling solvent quality during manufacturing and for verifying conformance to product specifications.

• Detection of Contaminants and Composition Monitoring:
  Gas chromatographic analysis enables early detection of contaminants and helps monitor compositional consistency throughout production.

• Results Reporting:
  The standard specifies reporting temperatures at 1% intervals from initial boiling point (IBP, at 0.5% total area) to final boiling point (FBP, at 99.5% total area), offering precise data for in-depth analysis.

• Precision and Reproducibility:
  ASTM D5399 outlines procedures to assure repeatability and reproducibility, including requirements for calibration, sample preparation, and regular instrument performance checks.

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Applications

• Hydrocarbon Solvent Manufacturing:
  Ensures consistent product quality by providing reliable boiling point distribution profiles, essential for meeting manufacturing targets and client requirements.

• Specification and Compliance Testing:
  Used widely in laboratory environments for certifying that hydrocarbon solvents adhere to industry standards and customer specifications.

• Quality Assurance in Supply Chains:
  Helps suppliers and buyers maintain product consistency, minimize risks of contamination, and streamline acceptance testing.

• Research and Product Development:
  Facilitates in-depth analysis required in R&D settings to optimize formulations and evaluate new solvent compositions.

• Environmental and Safety Monitoring:
  Enables the detection of off-specification material early in the production process, supporting compliance with environmental and occupational health regulations.

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Related Standards

• ASTM D86 – Distillation of Petroleum Products and Liquid Fuels at Atmospheric Pressure
• ASTM D850 – Distillation of Industrial Aromatic Hydrocarbons and Related Materials
• ASTM D1078 – Distillation Range of Volatile Organic Liquids
• ASTM D2887 – Boiling Range Distribution of Petroleum Fractions by Gas Chromatography
• ASTM D2892 – Distillation of Crude Petroleum (15-Theoretical Plate Column)
• ASTM D3710 – Boiling Range Distribution of Gasoline and Gasoline Fractions by Gas Chromatography (withdrawn)
• ASTM E29 – Practice for Using Significant Digits in Test Data to Determine Conformance with Specifications
• ASTM E691 – Practice for Conducting an Interlaboratory Study to Determine the Precision of a Test Method

These related standards address various distillation and compositional analysis techniques, supporting a comprehensive approach to solvent and fuel testing.

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By adopting ASTM D5399-09(2023), laboratories and manufacturers gain a robust, reproducible, and internationally recognized procedure for analyzing the boiling point distribution of hydrocarbon solvents, supporting effective quality management and regulatory compliance in the chemical and petroleum industries.

Standards Content (Sample)

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.
Designation: D5399 − 09 (Reapproved 2023)
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
D2892 Test Method for Distillation of Crude Petroleum
5 °C to 150 °C (9 °F to 270 °F) as measured by this test
(15-Theoretical Plate Column)
method.
D3710 Test Method for Boiling Range Distribution of Gaso-
1.2 For purposes of determining conformance of an ob-
line and Gasoline Fractions by Gas Chromatography
served or calculated value using this test method to relevant 3
(Withdrawn 2014)
specifications, test result(s) shall be rounded off “to the nearest
E29 Practice for Using Significant Digits in Test Data to
unit” in the last right-hand digit used in expressing the
Determine Conformance with Specifications
specification limit, in accordance with the rounding-off method
E691 Practice for Conducting an Interlaboratory Study to
of Practice E29.
Determine the Precision of a Test Method
1.3 The values stated in SI units are standard. The values
3. Terminology
given in parentheses are for information purposes only.
3.1 Definitions:
1.4 This standard does not purport to address all of the
3.1.1 initial boiling point (IBP), n—the point at which a
safety concerns, if any, associated with its use. It is the
cumulative area count equal to 0.5 % of the total area under the
responsibility of the user of this standard to establish appro-
chromatogram is obtained.
priate safety, health, and environmental practices and deter-
mine the applicability of regulatory limitations prior to use.
3.1.2 final boiling point (FBP), n—the point at which a
1.5 This international standard was developed in accor-
cumulative area count equal to 99.5 % of the total area under
dance with internationally recognized principles on standard-
the chromatogram is obtained.
ization established in the Decision on Principles for the
4. Summary of Test Method
Development of International Standards, Guides and Recom-
mendations issued by the World Trade Organization Technical
4.1 The sample is introduced into a capillary gas chromato-
Barriers to Trade (TBT) Committee.
graphic column that separates hydrocarbons in the order of
increasing boiling point. The column temperature is raised at a
2. Referenced Documents
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 July 1, 2023. Published August 2023. Originally
5.1 The gas chromatographic determination of the boiling
approved in 1993. Last previous edition approved in 2017 as D5399 – 09 (2017).
point distribution of hydrocarbon solvents can be used as an
DOI: 10.1520/D5399-09R23.
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 (2023)
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 m to 30 m by 0.53 mm inside diameter
7.4.1 Warning: Air and hydrogen are compressed gases
by 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 h 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
...