ASTM D6387-99

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Designation:D6387–99
Standard Test Methods for
Composition of Turpentine and Related Terpene Products
by Capillary Gas Chromatography
This standard is issued under the fixed designation D 6387; 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 (e) indicates an editorial change since the last revision or reapproval.
1. Scope E 691 Practice for Conducting an Interlaboratory Study to
Determine the Precision of a Test Method
1.1 These test methods describe the determination of the
amounts of a-pinene, b-pinene, dipentene, terpene alcohols,
3. Terminology
and other terpene compounds in turpentine and related terpene
3.1 For definitions see Terminology D 804.
productsusingcapillarygaschromatography.Thetwomethods
for determining the amount of the individual terpene com-
4. Summary of Test Method
pounds are the “internal standard” method, which yields
4.1 A weighed mixture of the sample and internal standard
absolute values, and the “area percent” method, which yields
is prepared, and an aliquot is injected into a temperature
relative values.
programmable capillary gas chromatograph to obtain the
1.2 This standard does not purport to address all of the
chromatogram. The peak areas for the compounds to be
safety concerns, if any, associated with its use. It is the
determinedandalsofortheinternalstandardaremeasured.The
responsibility of the user of the standard to establish appro-
percentages of the compounds present are calculated from the
priate safety and health practices and determine the applica-
peak area of the compounds/internal standard, weight of
bility of regulatory limitations prior to use.
internal standard/sample, and the calibration factors. Alter-
NOTE 1—Overall this test method gives excellent repeatability but only
nately, the relative concentration of the compounds may be
moderate reproducibility. This greater than normal differential is a
calculated using the area percent method. For hydrocarbons,
consequence of the variety of gas chromatography (GC) columns and
the latter quantitation method usually is adequate to use since
other variables used by participants. These variables, coupled with the
turpentine and related terpene products contain few noneluting
complex composition of the test products, enabled some workers to
compounds,andtheindividualresponsefactorsareofasimilar
separate peaks that others reported as one peak; thus, this test method
gives excellent precision within a given laboratory on a given GC. When value. A polar or nonpolar capillary column may be used for
laboratory to laboratory comparison have to be made, however, it is
the analysis, depending on the particular compounds requiring
essential that the GC operating conditions be defined closely. Subcom-
separation and quantitation.
mittee D01.34 will be working on this problem prior to the next version
of this test method. NOTE 2—Response factors should be employed if significant quantities
of polar and nonpolar compounds are present in the sample.
2. Referenced Documents
5. Significance and Use
2.1 ASTM Standards:
5.1 Earliermethodsforcharacterizingturpentineandrelated
D13 Specification for Spirits of Turpentine
terpene products were based on physical properties, such as
D 801 Test Methods for Sampling and Testing Dipentene
those in Specification D13 and Test Methods D 801 and
D 802 Test Methods for Sampling and Testing Pine Oil
D 802, and packed column gas chromatography for the major
D 804 TerminologyRelatingtoNavalStores,IncludingTall
constituents (for example, a-pinene, b-pinene) as in Test
Oil and Related Products
Method D 3009. As terpene products became widely used as
D 3009 Test Method for Composition of Turpentine by Gas
chemical raw material, the separation and quantitation of
Chromatography
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
These test methods are under the jurisdiction of ASTM Committee D-01 on
convenient means to perform these analyses.
Paint and Related Coatings, Materials, and Applications and are the direct
responsibility of Subcommittee D01.34 on Naval Stores.
Current edition approved April 10, 1999. Published June 1999.
2 3
Annual Book of ASTM Standards, Vol 06.03. Annual Book of ASTM Standards, Vol 14.02.
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D6387–99
6. Apparatus
Column Temperature (Oven Temperature)
6.1 Gas Chromatograph—Atemperature programmable in-
Initial 50°C
strument equipped with a flame ionization detector (FID) that
Hold 5 min
Ramp 4°C/min
can be operated at the conditions given in Section 8.
Final 240°C
6.2 Column—Either a polar (polyethylene glycol) or non-
Hold 10 min
polar (methylsilicone) capillary column, or both, may be used Injection port temperature 250°C
Injection port liner Glass-split
dependingonthepolarityoftheparticularcomponentsneeding
Detector Temperature 250°C
separation and quantitation. The recommended column dimen-
Carrier gas Helium
sions are 30 m in length, a 0.25-mm internal diameter, and a
Linear gas velocity 19.5–20.5 cm/s
Split ratio 100:1 max
0.25µfilmthickness.Acolumnofdifferingdimensionsmaybe
Detector FID
used depending on the separations required.
Hydrogen 30 mL/min
Air 400 mL/min
NOTE 3—If the separation involves primarily polar compounds, the
Make up gas 30 mL/min
polyethylene glycol column should be employed. When primarily nonpo-
lar compounds are involved, a methyl silicone column should be selected.
10. Calibration of Gas Chromatograph
6.3 Analytical Balance, readable to 0.1 mg.
10.1 Inject 0.1 to 1.0 µL of the standard prepared in 8.1.
6.4 Syringe,10µL.
Record the retention time and the areas for each of the
components. Then, calculate the individual relative response
7. Reagents
factors as follows:
7.1 Purity of Reagents—Reagent grade chemicals shall be
used in all tests. Unless otherwise indicated, it is intended that W A
1 IS
RRF 5 3 (1)
all reagents shall conform to the specifications of the Commit- A W
1 IS
teeonAnalyticalReagentsoftheAmericanChemicalSociety ,
where:
where such specifications are available. Other grades may be
RRF = Relative response factor of individual terpene
used, provided it is first ascertained that the reagent is of
compound;
sufficiently high purity to permit its use without lessening the
W = Weight of individual terpene compound in stan-
accuracy of the determination.
dard (W = weight used 3 purity);
7.2 a-Pinene, purity 99+%.
A = Peak area of individual terpene compound;
7.3 b-Pinene, purity 99+%
A = Peak area of n-decane internal standard; and,
IS
7.4 Other terpene compounds, suitable for use as reference
W = Weight of n-decane internal standard (W =
IS IS
materials.
weight n-decane used 3 purity).
7.5 n-Decane, purity 99+% (internal standard).
7.6 Hexane—capillary C grade or equivalent. NOTE 5—For highest accuracy, the purity of this standard should be
used to correct the weight terms.
INTERNAL STANDARD METHOD
11. Preparation of Test Sample
8. Preparation of Calibration Standard
11.1 Accurately weigh ;50 mg of sample and ;15 mg of
8.1 To a 2-dram vial, add similar milligram quantities of the
n-decane directly into a 2-dram vial and record the weight of
compounds to be quantitated plus n-decane. Cap the vial and
each to 0.0001 g.
swirl to mix. Approximately 1 mL of hexane may be added to
11.2 Approximately 1 mL of hexane may be added to the
the vial to dilute the standard for easier handling and the use of
vial to make the sample easier to handle and not overload the
lower split ratios.
column or detector.
NOTE 4—Other terpene compounds may be added in an identical
manner to the pinenes.
12. Analysis
9. Gas Chromatograph Operating Conditions
12.1 Inject 0.1 to 1.0 µL of the test sample prepared in 11.1
9.1 The following temperatures are typical operating con-
to 11.2.
ditions only. The individual instrument should be set to
manufacturer’s instructions to optimize desired separations.
13. Calculation
Adjustments in operating temperature and flow rate may be
13.1 Obtain the peak areas of all of the peaks needed from
necessarytomaintainoptimumperformanceofthecolumndue
the chromatogram.
to aging.
NOTE 6—See Fig. 1a through 1c for chromatograms of a typica
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