ASTM D6387-99(2014)e1
(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 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.
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´1
Designation: D6387 − 99 (Reapproved 2014)
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 6 was corrected editorially in December 2014.
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,
Current edition approved Dec. 1, 2014. Published January 2015. Originally
andpackedcolumngaschromatographyforthemajorconstitu-
approved in 1999. Last previous edition approved in 2010 as D6387–99(2010).
ents (for example, α-pinene, β-pinene) as in Test Method
DOI: 10.1520/D6387-99R14E01.
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 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
´1
D6387 − 99 (2014)
D3009. As terpene products became widely used as chemical swirl to mix.Approximately 1 mL of hexane may be added to
raw material, the separation and quantitation of compounds thevialtodilutethestandardforeasierhandlingandtheuseof
present at lower concentrations in the product became more lower split ratios.
important. The capillary gas chromatographic technique de-
NOTE 4—Other terpene compounds may be added in an identical
scribed in these test methods is a rapid and convenient means
manner to the pinenes.
to perform these analyses.
9. Gas Chromatograph Operating Conditions
6. Apparatus
9.1 The following temperatures are typical operating con-
6.1 Gas Chromatograph—Atemperature programmable in-
ditions only. The individual instrument should be set to
strument equipped with a flame ionization detector (FID) that
manufacturer’s instructions to optimize desired separations.
can be operated at the conditions given in Section 8.
Adjustments in operating temperature and flow rate may be
necessarytomaintainoptimumperformanceofthecolumndue
6.2 Column—Either a polar (polyethylene glycol) or non-
to aging.
polar (methylsilicone) capillary column, or both, may be used
Column Temperature (Oven Temperature)
dependingonthepolarityoftheparticularcomponentsneeding
separation and quantitation.The recommended column dimen-
Initial 50°C
sions are 30 m in length, a 0.25-mm internal diameter, and a
Hold 5 min
Ramp 4°C/min
0.25µfilmthickness.Acolumnofdifferingdimensionsmaybe
Final 240°C
used depending on the separations required.
Hold 10 min
Injection port temperature 250°C
NOTE 3—If the separation involves primarily polar compounds, the
Injection port liner Glass-split
polyethylene glycol column should be employed. When primarily nonpo-
Detector Temperature 250°C
larcompoundsareinvolved,amethylsiliconecolumnshouldbeselected.
Carrier gas Helium
Linear gas velocity 19.5–20.5 cm/s
6.3 Analytical Balance, readable to 0.1 mg.
Split ratio 100:1 max
Detector FID
6.4 Syringe, 10 µL.
Hydrogen 30 mL/min
Air 400 mL/min
7. Reagents
Make up gas 30 mL/min
7.1 Purity of Reagents—Reagent grade chemicals shall be
10. Calibration of Gas Chromatograph
used in all tests. Unless otherwise indicated, it is intended that
all reagents shall conform to the specifications of the Commit- 10.1 Inject 0.1 to 1.0 µL of the standard prepared in 8.1.
Record the retention time and the areas for each of the
teeonAnalyticalReagentsoftheAmericanChemicalSociety ,
where such specifications are available. Other grades may be components. Then, calculate the individual relative response
factors as follows:
used, provided it is first ascertained that the reagent is of
sufficiently high purity to permit its use without lessening the
W A
1 IS
RRF 5 3 (1)
accuracy of the determination. 1
A W
1 IS
7.2 α-Pinene, purity 99+%.
where:
7.3 β-Pinene, purity 99+%
RRF = Relative response factor of individual terpene com-
pound;
7.4 Other terpene compounds, suitable for use as reference
W = Weight of individual terpene compound in standard
materials. 1
(W = weight used × purity);
7.5 n-Decane, purity 99+% (internal standard).
A = Peak area of individual terpene compound;
A = Peak area of n-decane internal standard; and,
7.6 Hexane—capillary C grade or equivalent.
IS
W = Weight of n-decane internal standard (W = weight
IS IS
INTERNAL STANDARD METHOD
n-decane used × purity).
NOTE 5—For highest accuracy, the purity of this standard should be
8. Preparation of Calibration Standard
used to correct the weight terms.
8.1 Toa2-dramvial,addsimilarmilligramquantitiesofthe
11. Preparation of Test Sample
compounds to be quantitated plus n-decane. Cap the vial and
11.1 Accurately weigh ;50 mg of sample and ;15 mg of
n-decane directly into a 2-dram vial and record the weight of
Reagent Chemicals, American Chemical Society Specifications, American
each to 0.0001 g.
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
listed by the American Chemical Society, see Analar Standards for Laboratory
11.2 Approximately 1 mL of hexane
...
This document is not an ASTM standard and is intended only to provide the user of an ASTM standard an indication of what changes have been made to the previous version. Because
it may not be technically possible to adequately depict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current version
of the standard as published by ASTM is to be considered the official document.
´1 ´1
Designation: D6387 − 99 (Reapproved 2010) D6387 − 99 (Reapproved 2014)
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.
ε NOTE—Note 16 was corrected editorially in June 2010.December 2014.
1. 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.
2. Referenced Documents
2.1 ASTM Standards:
D13 Specification for Spirits of Turpentine
D801 Test Methods for Sampling and Testing Dipentene
D802 Test Methods for Sampling and Testing Pine Oils
D804 Terminology Relating to Pine Chemicals, Including Tall Oil and Related Products
D3009 Test Method for Compostition of Turpentine by Gas Chromatography (Withdrawn 1999)
E691 Practice for Conducting an Interlaboratory Study to Determine the Precision of a Test Method
3. Terminology
3.1 For definitions see Terminology D804.
4. Summary of Test Method
4.1 A weighed mixture of the sample and internal standard is prepared, and an aliquot is injected into a temperature
programmable capillary gas chromatograph to obtain the chromatogram. The peak areas for the compounds to be determined and
also for the internal standard are measured. The percentages of the compounds present are calculated from the peak area of the
compounds/internal standard, weight of internal standard/sample, and the calibration factors. Alternately, the relative concentration
of the compounds may be calculated using the area percent method. For hydrocarbons, the latter quantitation method usually is
adequate to use since turpentine and related terpene products contain few noneluting compounds, and the individual response
These test methods are under the jurisdiction of ASTM Committee D01 on Paint and Related Coatings, Materials, and Applications and are the direct responsibility of
Subcommittee D01.34 on Pine Chemicals and Hydrocarbon Resins.
Current edition approved June 1, 2010Dec. 1, 2014. Published July 2010January 2015. Originally approved in 1999. Last previous edition approved in 20052010 as
D6387 - 99 (2005).D6387– 99 (2010). DOI: 10.1520/D6387-99R10E01.10.1520/D6387-99R14E01.
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’sstandard’s Document Summary page on the ASTM website.
The last approved version of this historical standard is referenced on www.astm.org.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
´1
D6387 − 99 (2014)
factors are of a similar value. A polar or nonpolar capillary column may be used for the analysis, depending on the particular
compounds requiring separation and quantitation.
NOTE 2—Response factors should be employed if significant quantities of polar and nonpolar compounds are present in the sample.
5. 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.
6. Apparatus
6.1 Gas Chromatograph—A temperature programmable instrument equipped with a flame ionization detector (FID) that can be
operated at the conditions given in Section 8.
6.2 Column—Either a polar (polyethylene glycol) or nonpolar (methylsilicone) capillary column, or both, may be used
depending on the polarity of the particular components needing separation and quantitation. The recommended column dimensions
are 30 m in length, a 0.25-mm internal diameter, and a 0.25 μ film thickness. A column of differing dimensions may be used
depending on the separations required.
NOTE 3—If the separation involves primarily polar compounds, the polyethylene glycol column should be employed. When primarily nonpolar
compounds are involved, a methyl silicone column should be selected.
6.3 Analytical Balance, readable to 0.1 mg.
6.4 Syringe, 10 μL.
7. Reagents
7.1 Purity of Reagents—Reagent grade chemicals shall be used in all tests. Unless otherwise indicated, it is intended that all
reagents shall conform to the specifications of the Committee on Analytical Reagents of the American Chemical Society , where
such specifications are available. Other grades may be used, provided it is first ascertained that the reagent is of sufficiently high
purity to permit its use without lessening the accuracy of the determination.
7.2 α-Pinene, purity 99+%.
7.3 β-Pinene, purity 99+%
7.4 Other terpene compounds, suitable for use as reference materials.
7.5 n-Decane, purity 99+% (internal standard).
7.6 Hexane—capillary C grade or equivalent.
INTERNAL STANDARD METHOD
8. Preparation of Calibration Standard
8.1 To a 2-dram vial, add similar milligram quantities of the compounds to be quantitated plus n-decane. Cap the vial and swirl
to mix. Approximately 1 mL of hexane may be added to the vial to dilute the standard for easier handling and the use of lower
split ratios.
NOTE 4—Other terpene compounds may be added in an identical manner to the pinenes.
9. Gas Chromatograph Operating Conditions
9.1 The following temperatures are typical operating conditions only. The individual instrument should be set to manufacturer’s
instructions to optimize desired separations. Adjustments in operating temperature and flow rate may be necessary to maintain
optimum performance of the column due to aging.
Column Temperature (Oven Temperature)
Initial 50°C
Hold 5 min
Ramp 4°C/min
Final 240°C
Reagent Chemicals, American Chemical Society Specifications, American Chemical Society, Washington, DC. For suggestions on the testing of reagents not listed by
the American Chemical Society, see Analar Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia and National
Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, MD.
´1
D6387 − 99 (2014)
Hold 10 min
Injection port temperature 250°C
Injection port liner Glass-split
Detector Temperature 250°C
Carrier gas Helium
Linear gas velocity 19.5–20.5 cm/s
Split ratio 100:1 max
Detector FID
Hydrogen 30 mL/min
Air 400 mL/min
Make up gas 30 mL/min
10. Calibration of Gas Chromatograph
10.1 Inject 0.1 to 1.0 μL of the standard prepared in 8.1. Record the retention time and the areas for each of the components.
Then, calculate the individual relative response factors as follows:
W A
1 IS
RRF 5 3 (1)
A W
1 IS
where:
RRF = Relative response factor of individual terpene compound;
W = Weight of individual terpene compound in standard (W = weight used × purity);
1 1
A = Peak area of individual terpene compound;
A = Peak area of n-decane internal standard; and,
IS
W = Weight of n-decane internal standard (W = weight n-decane used × purity).
IS IS
where:
RRF = Relative response factor of individual terpene compound;
W = Weight of individual terpene compound in standard (W = weight used × purity);
1 1
A = Peak area of individual terpene compound;
A = Peak area of n-decane internal standard; and,
IS
W = Weight of n-decane internal standard (W = weight n-decane used × purity).
IS IS
NOTE 5—For highest accuracy, the purity of this standard should be used to correct
...
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