ASTM D6387-99(2010)e1

Standard Test Methods for Composition of Turpentine and Related Terpene Products by Capillary Gas Chromatography

SIGNIFICANCE AND USE
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 . 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 and health 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.

General Information

• Status: Historical
• Publication Date: 31-May-2010
• Technical Committee: D01 - Paint and Related Coatings, Materials, and Applications
• Drafting Committee: D01.34 - Pine Chemicals and Hydrocarbon Resins

Relations

• Replaces: ASTM D6387-99(2005) - Standard Test Methods for Composition of Turpentine and Related Terpene Products by Capillary Gas Chromatography
• Effective Date: 01-Jun-2010
• Replaced By: ASTM D6387-99(2014)e1 - Standard Test Methods for Composition of Turpentine and Related Terpene Products by Capillary Gas Chromatography
• Effective Date: 01-Dec-2014
• Referred By: ASTM D801-02(2022) - Standard Test Methods for Sampling and Testing Dipentene
• Effective Date: 01-Jun-2010
• Referred By: ASTM D233-13(2022) - Standard Test Methods of Sampling and Testing Turpentine
• Effective Date: 01-Jun-2010
• Referred By: ASTM D802-02(2022) - Standard Test Methods for Sampling and Testing Pine Oils
• Effective Date: 01-Jun-2010

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
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Designation: D6387 − 99(Reapproved 2010)
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.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
ε NOTE—Note 1 was corrected editorially in June 2010.
1. Scope D802Test Methods for Sampling and Testing Pine Oils
D804Terminology Relating to Pine Chemicals, Including
1.1 These test methods describe the determination of the
Tall Oil and Related Products
amounts of α-pinene, β-pinene, dipentene, terpene alcohols,
D3009Test Method for Compostition of Turpentine by Gas
and other terpene compounds in turpentine and related terpene
Chromatography (Withdrawn 1999)
productsusingcapillarygaschromatography.Thetwomethods
E691Practice for Conducting an Interlaboratory Study to
for determining the amount of the individual terpene com-
Determine the Precision of a Test Method
pounds are the “internal standard” method, which yields
absolute values, and the “area percent” method, which yields
3. Terminology
relative values.
3.1 For definitions see Terminology D804.
1.2 The values stated in SI units are to be regarded as
standard. No other units of measurement are included in this
4. Summary of Test Method
standard.
4.1 A weighed mixture of the sample and internal standard
1.3 This standard does not purport to address all of the
is prepared, and an aliquot is injected into a temperature
safety concerns, if any, associated with its use. It is the
programmable capillary gas chromatograph to obtain the
responsibility of the user of the standard to establish appro-
chromatogram. The peak areas for the compounds to be
priate safety and health practices and determine the applica-
determinedandalsofortheinternalstandardaremeasured.The
bility of regulatory limitations prior to use.
percentages of the compounds present are calculated from the
peak area of the compounds/internal standard, weight of
NOTE 1—Overall this test method gives excellent repeatability but only
moderate reproducibility. This greater than normal differential is a
internal standard/sample, and the calibration factors.
consequence of the variety of gas chromatography (GC) columns and
Alternately, the relative concentration of the compounds may
other variables used by participants. These variables, coupled with the
becalculatedusingtheareapercentmethod.Forhydrocarbons,
complex composition of the test products, enabled some workers to
the latter quantitation method usually is adequate to use since
separate peaks that others reported as one peak; thus, this test method
gives excellent precision within a given laboratory on a given GC. When turpentine and related terpene products contain few noneluting
laboratory to laboratory comparison have to be made, however, it is
compounds,andtheindividualresponsefactorsareofasimilar
essential that the GC operating conditions be defined closely.
value. A polar or nonpolar capillary column may be used for
the analysis, depending on the particular compounds requiring
2. Referenced Documents
separation and quantitation.
2.1 ASTM Standards:
NOTE 2—Response factors should be employed if significant quantities
D13Specification for Spirits of Turpentine
of polar and nonpolar compounds are present in the sample.
D801Test Methods for Sampling and Testing Dipentene
5. Significance and Use
These test methods are under the jurisdiction of ASTM Committee D01 on
5.1 Earliermethodsforcharacterizingturpentineandrelated
Paint and Related Coatings, Materials, and Applications and are the direct
terpene products were based on physical properties, such as
responsibility of Subcommittee D01.34 on Pine Chemicals and Hydrocarbon
Resins. those in Specification D13 and Test Methods D801 and D802,
CurrenteditionapprovedJune1,2010.PublishedJuly2010.Originallyapproved
andpackedcolumngaschromatographyforthemajorconstitu-
in 1999. Last previous edition approved in 2005 as D6387–99(2005). DOI:
ents (for example, α-pinene, β-pinene) as in Test Method
10.1520/D6387-99R10E01.
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
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D6387 − 99 (2010)
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
necessarytomaintainoptimumperformanceofthecolumndue
6.1 Gas Chromatograph—Atemperature 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 8.
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
dependingonthepolarityoftheparticularcomponentsneeding
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
0.25µfilmthickness.Acolumnofdifferingdimensionsmaybe
Carrier gas Helium
used depending on the separations required.
Linear gas velocity 19.5–20.5 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
larcompoundsareinvolved,amethylsiliconecolumnshouldbeselected.
Air 400 mL/min
Make up gas 30 mL/min
6.3 Analytical Balance, readable to 0.1 mg.
6.4 Syringe, 10 µL. 10. Calibration of Gas Chromatograph
10.1 Inject 0.1 to 1.0 µL of the standard prepared in 8.1.
7. Reagents
Record the retention time and the areas for each of the
7.1 Purity of Reagents—Reagent grade chemicals shall be components. Then, calculate the individual relative response
used in all tests. Unless otherwise indicated, it is intended that factors as follows:
all reagents shall conform to the specifications of the Commit-
W A
1 IS
RRF 5 3 (1)
teeonAnalyticalReagentsoftheAmericanChemicalSociety ,
A W
1 IS
where such specifications are available. Other grades may be
where:
used, provided it is first ascertained that the reagent is of
sufficiently high purity to permit its use without lessening the RRF = relative response factor of individual terpene com-
accuracy of the determination. pound;
W = Weight of individual terpene compound in standard
7.2 α-Pinene, purity 99+%.
(W = weight used × purity);
7.3 β-Pinene, purity 99+%
A = Peak area of individual terpene compound;
A = Peak area of n-decane internal standard; and,
7.4 Other terpene compounds, suitable for use as reference IS
W = Weight of n-decane internal standard (W = weight
IS IS
materials.
n-decane used × purity).
7.5 n-Decane, purity 99+% (internal standard).
NOTE 5—For highest accuracy, the purity of this standard should be
used to correct the weight terms.
7.6 Hexane—capillary C grade or equivalent.
11. Preparation of Test Sample
INTERNAL STANDARD METHOD
11.1 Accurately weigh ;50 mg of sample and ;15 mg of
8. Preparation of Calibration Standard n-decane directly into a 2-dram vial and record the weight of
each to 0.0001 g.
8.1 Toa2-dramvial,addsimilarmilligramquantitiesofthe
compounds to be quantitated plus n-decane. Cap the vial and
11.2 Approximately 1 mL of hexane may be added to the
swirl to mix.Approximately 1 mL of hexane may be added to
vial to make the sample easier to handle and not overload the
thevialtodilutethestandardforeasierhandlingandtheuseof
column or detector.
lower split ratios.
12. Analysis
12.1 Inject 0.1 to 1.0 µLof the test sample prepared in 11.1
to 11.2.
Reagent Chemicals, American Chemical Society Specifications, Ame
...