ASTM D6387-19(2023)
(Test Method)Standard Test Methods for Composition of Turpentine and Related Terpene Products by Capillary Gas Chromatography
Standard Test Methods for Composition of Turpentine and Related Terpene Products by Capillary Gas Chromatography
SIGNIFICANCE AND USE
5.1 Earlier methods for characterizing turpentine and related terpene products were based on physical properties, such as those in Specification D13 and Test Methods D801 and D802, and packed column gas chromatography for the major constituents (for example, α-pinene, β-pinene) as in Test Method D3009. As terpene products became widely used as chemical raw material, the separation and quantitation of compounds present at lower concentrations in the product became more important. The capillary gas chromatographic technique described in these test methods is a rapid and convenient means to perform these analyses.
SCOPE
1.1 These test methods describe the determination of the amounts of α-pinene, β-pinene, dipentene, terpene alcohols, and other terpene compounds in turpentine and related terpene products using capillary gas chromatography. The two methods for determining the amount of the individual terpene compounds are the “internal standard” method, which yields absolute values, and the “area percent” method, which yields relative values.
1.2 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.3 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 the standard to establish appropriate safety, health, and environmental practices and determine the applicability of regulatory limitations prior to use.
Note 1: Overall this test method gives excellent repeatability but only moderate reproducibility. This greater than normal differential is a consequence of the variety of gas chromatography (GC) columns and other variables used by participants. These variables, coupled with the complex composition of the test products, enabled some workers to separate peaks that others reported as one peak; thus, this test method gives excellent precision within a given laboratory on a given GC. When laboratory to laboratory comparison have to be made, however, it is essential that the GC operating conditions be defined closely.
1.4 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
Relations
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: D6387 − 19 (Reapproved 2023)
Standard Test Methods for
Composition of Turpentine and Related Terpene Products
by Capillary Gas Chromatography
This standard is issued under the fixed designation D6387; 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 2. Referenced Documents
1.1 These test methods describe the determination of the 2.1 ASTM Standards:
amounts of α-pinene, β-pinene, dipentene, terpene alcohols, D13 Specification for Spirits of Turpentine
and other terpene compounds in turpentine and related terpene D801 Test Methods for Sampling and Testing Dipentene
products using capillary gas chromatography. The two methods D802 Test Methods for Sampling and Testing Pine Oils
for determining the amount of the individual terpene com- D804 Terminology Relating to Pine Chemicals, Including
pounds are the “internal standard” method, which yields Tall Oil and Related Products
absolute values, and the “area percent” method, which yields D3009 Test Method for Compostition of Turpentine by Gas
relative values. Chromatography (Withdrawn 1999)
E691 Practice for Conducting an Interlaboratory Study to
1.2 The values stated in SI units are to be regarded as
Determine the Precision of a Test Method
standard. No other units of measurement are included in this
standard.
3. Terminology
1.3 This standard does not purport to address all of the
3.1 For definitions see Terminology D804.
safety concerns, if any, associated with its use. It is the
responsibility of the user of the standard to establish appro-
4. Summary of Test Method
priate safety, health, and environmental practices and deter-
mine the applicability of regulatory limitations prior to use. 4.1 A weighed mixture of the sample and internal standard
is prepared, and an aliquot is injected into a temperature
NOTE 1—Overall this test method gives excellent repeatability but only
programmable capillary gas chromatograph to obtain the
moderate reproducibility. This greater than normal differential is a
chromatogram. The peak areas for the compounds to be
consequence of the variety of gas chromatography (GC) columns and
other variables used by participants. These variables, coupled with the
determined and also for the internal standard are measured. The
complex composition of the test products, enabled some workers to
percentages of the compounds present are calculated from the
separate peaks that others reported as one peak; thus, this test method
peak area of the compounds/internal standard, weight of
gives excellent precision within a given laboratory on a given GC. When
internal standard/sample, and the calibration factors.
laboratory to laboratory comparison have to be made, however, it is
essential that the GC operating conditions be defined closely. Alternately, the relative concentration of the compounds may
be calculated using the area percent method. For hydrocarbons,
1.4 This international standard was developed in accor-
the latter quantitation method usually is adequate to use since
dance with internationally recognized principles on standard-
turpentine and related terpene products contain few noneluting
ization established in the Decision on Principles for the
compounds, and the individual response factors are of a similar
Development of International Standards, Guides and Recom-
value. A polar or nonpolar capillary column may be used for
mendations issued by the World Trade Organization Technical
the analysis, depending on the particular compounds requiring
Barriers to Trade (TBT) Committee.
separation and quantitation.
These test methods are under the jurisdiction of ASTM Committee D01 on
Paint and Related Coatings, Materials, and Applications and are the direct For referenced ASTM standards, visit the ASTM website, www.astm.org, or
responsibility of Subcommittee D01.34 on Pine Chemicals and Hydrocarbon contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
Resins. Standards volume information, refer to the standard’s Document Summary page on
Current edition approved Oct. 1, 2023. Published October 2023. Originally the ASTM website.
approved in 1999. Last previous edition approved in 2019 as D6387 – 19. DOI: The last approved version of this historical standard is referenced on
10.1520/D6387-19R23. www.astm.org.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D6387 − 19 (2023)
NOTE 2—Response factors should be employed if significant quantities
INTERNAL STANDARD METHOD
of polar and nonpolar compounds are present in the sample.
8. Preparation of Calibration Standard
5. Significance and Use
8.1 To a suitable vial, add similar milligram quantities of the
5.1 Earlier methods for characterizing turpentine and related
compounds to be quantitated plus n-decane. Cap the vial and
terpene products were based on physical properties, such as
swirl to mix. Approximately 1 mL of hexane may be added to
those in Specification D13 and Test Methods D801 and D802,
the vial to dilute the standard for easier handling and the use of
and packed column gas chromatography for the major constitu-
lower split ratios.
ents (for example, α-pinene, β-pinene) as in Test Method
NOTE 4—Other terpene compounds may be added in an identical
D3009. As terpene products became widely used as chemical
manner to the pinenes.
raw material, the separation and quantitation of compounds
present at lower concentrations in the product became more
9. Gas Chromatograph Operating Conditions
important. The capillary gas chromatographic technique de-
9.1 The following temperatures are typical operating con-
scribed in these test methods is a rapid and convenient means
ditions only. The individual instrument should be set to
to perform these analyses.
manufacturer’s instructions to optimize desired separations.
Adjustments in operating temperature and flow rate may be
6. Apparatus
necessary to maintain optimum performance of the column due
6.1 Gas Chromatograph—A temperature programmable in-
to aging.
strument equipped with a flame ionization detector (FID) that
Column Temperature (Oven Temperature)
can be operated at the conditions given in Section 9.
Initial 50 °C
6.2 Column—Either a polar (polyethylene glycol) or non-
Hold 5 min
polar (methylsilicone) capillary column, or both, may be used
Ramp 4 °C ⁄min
Final 240 °C
depending on the polarity of the particular components needing
Hold 10 min
separation and quantitation. The recommended column dimen-
Injection port temperature 250 °C
sions are 30 m in length, a 0.25 mm internal diameter, and a
Injection port liner Glass-split
Detector Temperature 250 °C
0.25 μ film thickness. A column of differing dimensions may be
Carrier gas Helium (or Hydrogen)
used depending on the separations required.
Linear gas velocity 19.5 cm ⁄s to 20.5 cm ⁄s
Split ratio 100:1 max
NOTE 3—If the separation involves primarily polar compounds, the
Detector FID
polyethylene glycol column should be employed. When primarily nonpo-
Hydrogen 30 mL/min
lar compounds are involved, a methyl silicone column should be selected.
Air 400 mL/min
Make up gas 30 mL/min
6.3 Analytical Balance, readable to 0.1 mg.
NOTE 5—Hydrogen is an alternate choice as a carrier gas with greater
6.4 Syringe, 10 μL.
separation efficiency; however, the use of hydrogen may require additional
safety considerations.
7. Reagents
10. Calibration of Gas Chromatograph
7.1 Purity of Reagents—Reagent grade chemicals shall be
used in all tests. Unless otherwise indicated, it is intended that
10.1 Inject 0.1 μL to 1.0 μL of the standard prepared in 8.1.
all reagents shall conform to the specifications of the Commit-
Record the retention time and the areas for each of the
tee on Analytical Reagents of the American Chemical Society ,
components. Then, calculate the individual relative response
where such specifications are available. Other grades may be
factors as follows:
used, provided it is first ascertained that the reagent is of
W A
1 IS
sufficiently high purity to permit its use without lessening the
RRF 5 × (1)
A W
1 IS
accuracy of the determination.
where:
7.2 α-Pinene, purity 99+%.
RRF = relative response factor of individual terpene com-
7.3 β-Pinene, purity 99+%.
pound;
7.4 n-Decane, purity 99+% (internal standard).
W = Weight of individual terpene compound in standard
(W = weight used × purity);
7.5 n-Nonane, 99+% (alternate internal standard).
A = Peak area of individual terpene compound;
7.6 Other terpene compounds, suitable for use as reference
A = Peak area of n-decane internal standard; and,
IS
materials.
W = Weight of n-decane internal standard (W = weight
IS IS
n-decane used × purity).
7.7 Hexane—capillary C grade or equivalent.
NOTE 6—For highest accuracy, the purity of this standard should be
used to correct the weight terms.
ACS Reagent Chemicals, Specifications and Procedures for Reagents and
11. Preparation of Test Sample
Standard-Grade Reference Materials, American Chemical Society, Washington,
DC. For suggestions on the testing of reagents not listed by th
...
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