1、Designation: D 6387 99 (Reapproved 2005)Standard Test Methods forComposition of Turpentine and Related Terpene Productsby Capillary Gas Chromatography1This standard is issued under the fixed designation D 6387; the number immediately following the designation indicates the year oforiginal adoption o
2、r, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon (e) indicates an editorial change since the last revision or reapproval.1. Scope1.1 These test methods describe the determination of theamounts of a-pinene, b-pi
3、nene, dipentene, terpene alcohols,and other terpene compounds in turpentine and related terpeneproducts using capillary gas chromatography. The two methodsfor determining the amount of the individual terpene com-pounds are the “internal standard” method, which yieldsabsolute values, and the “area pe
4、rcent” method, which yieldsrelative values.1.2 The values stated in SI units are to be regarded asstandard. No other units of measurement are included in thisstandard.1.3 This standard does not purport to address all of thesafety concerns, if any, associated with its use. It is theresponsibility of
5、the user of the standard to establish appro-priate safety and health practices and determine the applica-bility of regulatory limitations prior to use.NOTE 1Overall this test method gives excellent repeatability but onlymoderate reproducibility. This greater than normal differential is aconsequence
6、of the variety of gas chromatography (GC) columns andother variables used by participants. These variables, coupled with thecomplex composition of the test products, enabled some workers toseparate peaks that others reported as one peak; thus, this test methodgives excellent precision within a given
7、 laboratory on a given GC. Whenlaboratory to laboratory comparison have to be made, however, it isessential that the GC operating conditions be defined closely. Subcom-mittee D01.34 will be working on this problem prior to the next versionof this test method.2. Referenced Documents2.1 ASTM Standards
8、:2D13 Specification for Spirits of TurpentineD 801 Test Methods for Sampling and Testing DipenteneD 802 Test Methods for Sampling and Testing Pine OilD 804 Terminology Relating to Naval Stores, Including TallOil and Related ProductsD 3009 Test Method for Composition of Turpentine by GasChromatograph
9、y3E 691 Practice for Conducting an Interlaboratory Study toDetermine the Precision of a Test Method3. Terminology3.1 For definitions see Terminology D 804.4. Summary of Test Method4.1 A weighed mixture of the sample and internal standardis prepared, and an aliquot is injected into a temperatureprogr
10、ammable capillary gas chromatograph to obtain thechromatogram. The peak areas for the compounds to bedetermined and also for the internal standard are measured. Thepercentages of the compounds present are calculated from thepeak area of the compounds/internal standard, weight ofinternal standard/sam
11、ple, and the calibration factors. Alter-nately, the relative concentration of the compounds may becalculated using the area percent method. For hydrocarbons,the latter quantitation method usually is adequate to use sinceturpentine and related terpene products contain few nonelutingcompounds, and the
12、 individual response factors are of a similarvalue. A polar or nonpolar capillary column may be used forthe analysis, depending on the particular compounds requiringseparation and quantitation.NOTE 2Response factors should be employed if significant quantitiesof polar and nonpolar compounds are pres
13、ent in the sample.5. Significance and Use5.1 Earlier methods for characterizing turpentine and relatedterpene products were based on physical properties, such asthose in Specification D13 and Test Methods D 801 andD 802, and packed column gas chromatography for the majorconstituents (for example, a-
14、pinene, b-pinene) as in TestMethod D 3009. As terpene products became widely used aschemical raw material, the separation and quantitation ofcompounds present at lower concentrations in the productbecame more important. The capillary gas chromatographictechnique described in these test methods is a
15、rapid andconvenient means to perform these analyses.1These test methods are under the jurisdiction of ASTM Committee D01 onPaint and Related Coatings, Materials, and Applications and are the directresponsibility of Subcommittee D01.34 on Naval Stores.Current edition approved Dec. 1, 2005. Published
16、December 2005. Originallyapproved in 1999. Last previous edition approved in 1999 as D 6387 - 99.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Docum
17、ent Summary page onthe ASTM website.3Withdrawn.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.6. Apparatus6.1 Gas ChromatographA temperature programmable in-strument equipped with a flame ionization detector (FID) thatcan be operate
18、d at the conditions given in Section 8.6.2 ColumnEither a polar (polyethylene glycol) or non-polar (methylsilicone) capillary column, or both, may be useddepending on the polarity of the particular components needingseparation and quantitation. The recommended column dimen-sions are 30 m in length,
19、a 0.25-mm internal diameter, and a0.25 film thickness.Acolumn of differing dimensions may beused depending on the separations required.NOTE 3If the separation involves primarily polar compounds, thepolyethylene glycol column should be employed. When primarily nonpo-lar compounds are involved, a meth
20、yl silicone column should be selected.6.3 Analytical Balance, readable to 0.1 mg.6.4 Syringe,10L.7. Reagents7.1 Purity of ReagentsReagent grade chemicals shall beused in all tests. Unless otherwise indicated, it is intended thatall reagents shall conform to the specifications of the Commit-tee onAna
21、lytical Reagents of theAmerican Chemical Society4,where such specifications are available. Other grades may beused, provided it is first ascertained that the reagent is ofsufficiently high purity to permit its use without lessening theaccuracy of the determination.7.2 a-Pinene, purity 99+%.7.3 b-Pin
22、ene, purity 99+%7.4 Other terpene compounds, suitable for use as referencematerials.7.5 n-Decane, purity 99+% (internal standard).7.6 Hexanecapillary C grade or equivalent.INTERNAL STANDARD METHOD8. Preparation of Calibration Standard8.1 To a 2-dram vial, add similar milligram quantities of thecompo
23、unds to be quantitated plus n-decane. Cap the vial andswirl to mix. Approximately 1 mL of hexane may be added tothe vial to dilute the standard for easier handling and the use oflower split ratios.NOTE 4Other terpene compounds may be added in an identicalmanner to the pinenes.9. Gas Chromatograph Op
24、erating Conditions9.1 The following temperatures are typical operating con-ditions only. The individual instrument should be set tomanufacturers instructions to optimize desired separations.Adjustments in operating temperature and flow rate may benecessary to maintain optimum performance of the colu
25、mn dueto aging.Column Temperature (Oven Temperature)Initial 50CHold 5 minRamp 4C/minFinal 240CHold 10 minInjection port temperature 250CInjection port liner Glass-splitDetector Temperature 250CCarrier gas HeliumLinear gas velocity 19.520.5 cm/sSplit ratio 100:1 maxDetector FIDHydrogen 30 mL/minAir 4
26、00 mL/minMake up gas 30 mL/min10. Calibration of Gas Chromatograph10.1 Inject 0.1 to 1.0 L of the standard prepared in 8.1.Record the retention time and the areas for each of thecomponents. Then, calculate the individual relative responsefactors as follows:RRF15W1A13AISWIS(1)where:RRF1= Relative res
27、ponse factor of individual terpenecompound;W1= Weight of individual terpene compound in stan-dard (W1= weight used 3 purity);A1= Peak area of individual terpene compound;AIS= Peak area of n-decane internal standard; and,WIS= Weight of n-decane internal standard (WIS= weightn-decane used 3 purity).NO
28、TE 5For highest accuracy, the purity of this standard should beused to correct the weight terms.11. Preparation of Test Sample11.1 Accurately weigh ;50 mg of sample and ;15 mg ofn-decane directly into a 2-dram vial and record the weight ofeach to 0.0001 g.11.2 Approximately 1 mL of hexane may be add
29、ed to thevial to make the sample easier to handle and not overload thecolumn or detector.12. Analysis12.1 Inject 0.1 to 1.0 L of the test sample prepared in 11.1to 11.2.13. Calculation13.1 Obtain the peak areas of all of the peaks needed fromthe chromatogram.NOTE 6See Fig. 1a through 1c for chromato
30、grams of a typicalturpentine, dipentene, and pine oil, respectively.13.2 Calculate the absolute value of each peak of interest, asfollows:4Reagent Chemicals, American Chemical Society Specifications, AmericanChemical Society, Washington, DC. For suggestions on the testing of reagents notlisted by th
31、e American Chemical Society, see Analar Standards for LaboratoryChemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeiaand National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,MD.D 6387 99 (2005)2Terpene Compound, % 5A13 RRF13 WISAIS3 Ws3 100 (2)where:A1= pe
32、ak area for terpene compound being determined;RRF1= relative response factor for terpene compoundbeing determined;WIS= weight of n-decane internal standard WIS= weightused 3 purity;AIS= peak area of n-decane internal standard; and,Ws= sample weight, g.14. Report14.1 Report the percentage of the indi
33、vidual terpene com-pound to the nearest 0.1 %.15. Precision and Bias15.1 Internal Standard MethodAn interlaboratory studyof the capillary GC determination of various terpenes andterpene alcohols in turpentine, dipentene, and pine oil was runin 1997 by seven laboratories using nonpolar columns. Thede
34、sign of the experiment was similar to that of Practice E 691,FIG. 1 (a)GC/FID ChromatogramsFIG. 1 (b)GC/FID Chromatograms (continued)D 6387 99 (2005)3and a within/between analysis of the date are given in ASTMResearch Report:D011111.515.1.1 Test Result The precision information given belowis based o
35、n three separate analyses of each individual sample.15.1.2 Precision for a Turpentine Material Containingabout 50.0 % a-Pinene, about 31.7 % b-Pinene, and about2.4 % Dipentene:15.1.2.1 Repeatability Limit, 95 % for a-pinene = 0.4, forb-pinene = 0.3, and for dipentene = 0.2.15.1.2.2 Reproducibility L
36、imit, 95 % for a-pinene = 3.5, forb-pinene = 5.4, and for dipentene = 0.7.15.1.2.3 Repeatability Standard Deviation, % for a-pinene= 0.1, for b-pinene = 0.1, and for dipentene = 0.1.15.1.2.4 Reproducibility Standard Deviation, % fora-pinene = 1.3, for b-pinene = 1.9, and for dipentene = 0.2.15.1.3 P
37、recision for a Pine Oil Product Containing about2.5 % Terpinolene, about 39.6 % a-Terpineol, and about 1.6 %g-Terpineol:15.1.3.1 Repeatability Limit, 95 % for terpinolene = 0.1, fora-terpineol = 1.5 and for g-terpineol = 0.1.15.1.3.2 Reproducibility Limit, 95 % for terpinolene = 0.5,for a-terpineol
38、= 9.2 and for g-terpineol = 1.1.15.1.3.3 Repeatability Standard Deviation, % for terpi-nolene = 0.03, for a-terpineol = 0.5 and for g-terpineol = 0.03.15.1.3.4 Reproducibility Standard Deviation, % for terpi-nolene = 0.2, for a-terpineol = 3.3 and for g-terpineol = 0.4.15.1.4 Precision for a Dipente
39、ne Product Containing about17.2 % a-Pinene, about 22.6 % Dipentene, and about 12.7 %Terpinolene:15.1.4.1 Repeatability Limit, 95 % for a-pinene = 0.2, fordipentene = 0.8, and for terpinolene = 0.6.15.1.4.2 Reproducibility Limit, 95 % for a-pinene = 3.3, fordipentene = 4.4, and for terpinolene = 2.7.
40、15.1.4.3 Repeatability Standard Deviation, % for a-pinene= 0.07, for dipentene = 0.3 and for terpinolene = 0.2.15.1.4.4 Reproducibility Standard Deviation, % fora-pinene = 1.2, for dipentene = 1.6 and for terpinolene = 0.9.15.1.5 BiasSince there is no accepted reference material,method or laboratory
41、 suitable for determining the bias for theprocedure in this test method for measuring component con-centration, no statement on bias is being made.AREA PERCENT METHOD16. Preparation of Retention Time Standard16.1 Prepare similar to 8.1 except that only approximateweights need to be used.17. Set-Up o
42、f Gas Chromatograph17.1 Set conditions as described in 9.1.18. Preparation of Test Sample18.1 Preparation described in 11.1 and 11.2 except that aninternal standard is not added.19. Analysis19.1 Inject 0.1 to 1.0 L of the test sample prepared in 18.1.20. Calculation20.1 Sum the areas of all the indi
43、vidual peaks, exclusive ofthe solvent peak, to obtain the total peak area.NOTE 7See Fig. 1a, 1b, or 1c for chromatograms of a typicalturpentine, dipentene, and pine oil, respectively.20.2 Calculate the relative percent of each terpene com-pound present, as follows:5Supporting data is available from
44、ASTM International Headquarters. RequestRR:D 011111.FIG. 1 (c)GC/FID Chromatograms (continued)D 6387 99 (2005)4Terpene, % 5A 3 100!/ TA (3)where:A = peak area for terpene compound being determined,andTA = sum of areas of all peaks, except solvent peak.21. Report21.1 Report the area percent of the in
45、dividual terpenecompounds to the nearest 0.1 %.22. Precision and Bias22.1 Area Percent MethodAn interlaboratory study of thecapillary GC determination of various terpenes and terpenealcohols in turpentine, dipentene, and pine oil was run in 1997by seven laboratories using nonpolar columns. The desig
46、n ofthe experiment was similar to that of Practice E 691, and awithin/between analysis of the date are given in ASTMResearch Report RR:D011111.522.1.1 Test Result The precision information given belowis based on three separate analyses of each individual sample.22.1.2 Precision for a Turpentine Mate
47、rial Containingabout 51.1 % a-Pinene, about 28.8 % b-Pinene, and about2.7 % Dipentene:22.1.2.1 Repeatability Limit, 95 % for a-pinene = 0.3, forb-pinene = 0.1 and for dipentene = 0.1.22.1.2.2 Reproducibility Limit, 95 % for a-pinene = 2.1, forb-pinene = 0.5, and for dipentene = 0.2.22.1.2.3 Repeatab
48、ility Standard Deviation, % for a-pinene= 0.1, for b-pinene = 0.04, and for dipentene = 0.03.22.1.2.4 Reproducibility Standard Deviation, % fora-pinene = 0.7, for b-pinene = 0.2, and for dipentene = 0.1.22.1.3 Precision for a Pine Oil Product Containing about2.9 % terpinolene, about 37.9 % a-Terpine
49、ol, and about 1.7 %g-Terpineol:22.1.3.1 Repeatability Limit, 95 % for terpinolene = 0.1, fora-terpineol = 0.3, and for g-terpineol = 0.02.22.1.3.2 Reproducibility Limit, 95 % for terpinolene = 0.6,for a-terpineol = 3.8, and for g-terpineol = 0.4.22.1.3.3 Repeatability Standard Deviation, % for terpi-nolene = 0.02, for a-terpineol = 0.1, and for g-terpineol = 0.03.22.1.3.4 Reproducibility Standard Deviation, % for terpi-nolene = 0.2, for a-terpineol = 3.3 and for g-terpineol = 0.01.22.1.4 Precision for a Dipenetene Product Containingabout 17.6 % a-Pi
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