ASTM D6387-99(2005)
(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
Earlier methods for characterizing turpentine and related terpene products were based on physical properties, such as those in Specification D 13 and Test Methods D 801 and D 802, and packed column gas chromatography for the major constituents (for example, α-pinene, β-pinene) as in Test Method D 3009. 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 alpha-pinene, α-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. Subcommittee D01.34 will be working on this problem prior to the next version of this test method.
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Standards Content (Sample)
NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
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Designation:D6387–99(Reapproved2005)
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 D802 Test Methods for Sampling and Testing Pine Oils
D804 Terminology Relating to Naval Stores, Including Tall
1.1 These test methods describe the determination of the
Oil and Related Products
amounts of a-pinene, b-pinene, dipentene, terpene alcohols,
D3009 Test Method for Composition of Turpentine by Gas
and other terpene compounds in turpentine and related terpene
Chromatography
productsusingcapillarygaschromatography.Thetwomethods
E691 Practice 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
NOTE 1—Overall this test method gives excellent repeatability but only
peak area of the compounds/internal standard, weight of
moderate reproducibility. This greater than normal differential is a
internal standard/sample, and the calibration factors. Alter-
consequence of the variety of gas chromatography (GC) columns and
nately, the relative concentration of the compounds may be
other variables used by participants. These variables, coupled with the
calculated using the area percent method. For hydrocarbons,
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. Subcom-
value. A polar or nonpolar capillary column may be used for
mittee D01.34 will be working on this problem prior to the next version
the analysis, depending on the particular compounds requiring
of this test method.
separation and quantitation.
2. Referenced Documents
NOTE 2—Response factors should be employed if significant quantities
of polar and nonpolar compounds are present in the sample.
2.1 ASTM Standards:
D13 Specification for Spirits of Turpentine
5. Significance and Use
D801 Test Methods for Sampling and Testing Dipentene
5.1 Earliermethodsforcharacterizingturpentineandrelated
terpene products were based on physical properties, such as
These test methods are under the jurisdiction of ASTM Committee D01 on
those in Specification D13 and Test Methods D801 and D802,
Paint and Related Coatings, Materials, and Applications and are the direct
andpackedcolumngaschromatographyforthemajorconstitu-
responsibility of Subcommittee D01.34 on Naval Stores.
ents (for example, a-pinene, b-pinene) as in Test Method
Current edition approved Dec. 1, 2005. Published December 2005. Originally
D3009. As terpene products became widely used as chemical
approved in 1999. Last previous edition approved in 1999 as D6387 - 99. DOI:
10.1520/D6387-99R05.
raw material, the separation and quantitation of compounds
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
Standards volume information, refer to the standard’s Document Summary page on Withdrawn. The last approved verison of this historical standard is referenced
the ASTM website. on www.astm.org.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
D6387–99 (2005)
present at lower concentrations in the product became more manufacturer’s instructions to optimize desired separations.
important. The capillary gas chromatographic technique de- Adjustments in operating temperature and flow rate may be
scribed in these test methods is a rapid and convenient means necessarytomaintainoptimumperformanceofthecolumndue
to perform these analyses. to aging.
Column Temperature (Oven Temperature)
6. Apparatus
Initial 50°C
6.1 Gas Chromatograph—Atemperature programmable in-
Hold 5 min
strument equipped with a flame ionization detector (FID) that
Ramp 4°C/min
Final 240°C
can be operated at the conditions given in Section 8.
Hold 10 min
6.2 Column—Either a polar (polyethylene glycol) or non-
Injection port temperature 250°C
polar (methylsilicone) capillary column, or both, may be used
Injection port liner Glass-split
Detector Temperature 250°C
dependingonthepolarityoftheparticularcomponentsneeding
Carrier gas Helium
separation and quantitation. The recommended column dimen-
Linear gas velocity 19.5–20.5 cm/s
sions are 30 m in length, a 0.25-mm internal diameter, and a
Split ratio 100:1 max
Detector FID
0.25µfilmthickness.Acolumnofdifferingdimensionsmaybe
Hydrogen 30 mL/min
used depending on the separations required.
Air 400 mL/min
Make up gas 30 mL/min
NOTE 3—If the separation involves primarily polar compounds, the
polyethylene glycol column should be employed. When primarily nonpo-
10. Calibration of Gas Chromatograph
lar compounds are involved, a methyl silicone column should be selected.
10.1 Inject 0.1 to 1.0 µL of the standard prepared in 8.1.
6.3 Analytical Balance, readable to 0.1 mg.
Record the retention time and the areas for each of the
6.4 Syringe,10µL.
components. Then, calculate the individual relative response
7. Reagents factors as follows:
7.1 Purity of Reagents—Reagent grade chemicals shall be
W A
1 IS
RRF 5 3 (1)
A W
used in all tests. Unless otherwise indicated, it is intended that
1 IS
all reagents shall conform to the specifications of the Commit-
where:
teeonAnalyticalReagentsoftheAmericanChemicalSociety ,
RRF = Relative response factor of individual terpene
where such specifications are available. Other grades may be
compound;
used, provided it is first ascertained that the reagent is of
W = Weight of individual terpene compound in stan-
sufficiently high purity to permit its use without lessening the
dard (W = weight used 3 purity);
accuracy of the determination.
A = Peak area of individual terpene compound;
7.2 a-Pinene, purity 99+%.
A = Peak area of n-decane internal standard; and,
IS
7.3 b-Pinene, purity 99+%
W = Weightofn-decaneinternalstandard(W =weight
IS IS
7.4 Other terpene compounds, suitable for use as reference
n-decane used 3 purity).
materials.
NOTE 5—For highest accuracy, the purity of this standard should be
7.5 n-Decane, purity 99+% (internal standard).
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
8.1 To a 2-dram vial, add similar milligram quantities of the
each to 0.0001 g.
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
the vial to dilute the standard for easier handling and the use of
column or detector.
lower split ratios.
12. Analysis
NOTE 4—Other terpene compounds may be added in an identical
manner to the pinenes.
12.1 Inject 0.1 to 1.0 µL of the test sample prepared in 11.1
to 11.2.
9. Gas Chromatograph Operating Conditions
9.1 The following temperatures are typical operating con-
13. Calculation
ditions only. The individual i
...
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