1、Designation: D6387 19Standard Test Methods forComposition of Turpentine and Related Terpene Productsby Capillary Gas Chromatography1This standard is issued under the fixed designation D6387; the number immediately following the designation indicates the year oforiginal adoption or, in the case of re
2、vision, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.1. Scope1.1 These test methods describe the determination of theamounts of -pinene, -pinene, dipentene, terpen
3、e 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 percent” method, which yi
4、eldsrelative 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 the user of the standar
5、d to establish appro-priate safety, health, and environmental practices and deter-mine the applicability of regulatory limitations prior to use.NOTE 1Overall this test method gives excellent repeatability but onlymoderate reproducibility. This greater than normal differential is aconsequence of the
6、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 labora
7、tory on a given GC. Whenlaboratory to laboratory comparison have to be made, however, it isessential that the GC operating conditions be defined closely.1.4 This international standard was developed in accor-dance with internationally recognized principles on standard-ization established in the Deci
8、sion on Principles for theDevelopment of International Standards, Guides and Recom-mendations issued by the World Trade Organization TechnicalBarriers to Trade (TBT) Committee.2. Referenced Documents2.1 ASTM Standards:2D13 Specification for Spirits of TurpentineD801 Test Methods for Sampling and Tes
9、ting DipenteneD802 Test Methods for Sampling and Testing Pine OilsD804 Terminology Relating to Pine Chemicals, IncludingTall Oil and Related ProductsD3009 Test Method for Compostition of Turpentine by GasChromatography (Withdrawn 1999)3E691 Practice for Conducting an Interlaboratory Study toDetermin
10、e the Precision of a Test Method3. Terminology3.1 For definitions see Terminology D804.4. Summary of Test Method4.1 A weighed mixture of the sample and internal standardis prepared, and an aliquot is injected into a temperatureprogrammable capillary gas chromatograph to obtain thechromatogram. The p
11、eak 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/sample, and the calibration factors.Alternately, the relative concentrat
12、ion of the compounds maybe calculated 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 individual response factors are of a similarvalue. A polar or nonpolar
13、 capillary column may be used forthe analysis, depending on the particular compounds requiringseparation and quantitation.1These test methods are under the jurisdiction of ASTM Committee D01 onPaint and Related Coatings, Materials, and Applications and are the directresponsibility of Subcommittee D0
14、1.34 on Pine Chemicals and HydrocarbonResins.Current edition approved Jan. 1, 2019. Published January 2019. Originallyapproved in 1999. Last previous edition approved in 2014 as D6387 99 (2014)1.DOI: 10.1520/D6387-19.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact AST
15、M Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.3The last approved version of this historical standard is referenced onwww.astm.org.Copyright ASTM International, 100 Barr Harbor Drive, PO Box
16、C700, West Conshohocken, PA 19428-2959. United StatesThis international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for theDevelopment of International Standards, Guides and Recommendations issued by the
17、 World Trade Organization Technical Barriers to Trade (TBT) Committee.1NOTE 2Response factors should be employed if significant quantitiesof polar and nonpolar compounds are present in the sample.5. Significance and Use5.1 Earlier methods for characterizing turpentine and relatedterpene products wer
18、e based on physical properties, such asthose in Specification D13 and Test Methods D801 and D802,and packed column gas chromatography for the major constitu-ents (for example, -pinene, -pinene) as in Test MethodD3009. As terpene products became widely used as chemicalraw material, the separation and
19、 quantitation of compoundspresent at lower concentrations in the product became moreimportant. The capillary gas chromatographic technique de-scribed in these test methods is a rapid and convenient meansto perform these analyses.6. Apparatus6.1 Gas ChromatographA temperature programmable in-strument
20、 equipped with a flame ionization detector (FID) thatcan be operated at the conditions given in Section 9.6.2 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 qu
21、antitation. The recommended column dimen-sions are 30 m in length, 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 b
22、e employed. When primarily nonpo-lar compounds are involved, a methyl silicone column should be selected.6.3 Analytical Balance, readable to 0.1 mg.6.4 Syringe, 10 L.7. Reagents7.1 Purity of ReagentsReagent grade chemicals shall beused in all tests. Unless otherwise indicated, it is intended thatall
23、 reagents shall conform to the specifications of the Commit-tee onAnalytical 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
24、 theaccuracy of the determination.7.2 -Pinene, purity 99+%.7.3 -Pinene, purity 99+%.7.4 n-Decane, purity 99+% (internal standard).7.5 n-Nonane, 99+% (alternate internal standard).7.6 Other terpene compounds, suitable for use as referencematerials.7.7 Hexanecapillary C grade or equivalent.INTERNAL ST
25、ANDARD METHOD8. Preparation of Calibration Standard8.1 To a suitable vial, add similar milligram quantities of thecompounds 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 oflow
26、er split ratios.NOTE 4Other terpene compounds may be added in an identicalmanner to the pinenes.9. Gas Chromatograph Operating Conditions9.1 The following temperatures are typical operating con-ditions only. The individual instrument should be set tomanufacturers instructions to optimize desired sep
27、arations.Adjustments in operating temperature and flow rate may benecessary to maintain optimum performance of the column dueto aging.Column Temperature (Oven Temperature)Initial 50CHold 5 minRamp 4C/minFinal 240CHold 10 minInjection port temperature 250CInjection port liner Glass-splitDetector Temp
28、erature 250CCarrier gas Helium (or Hydrogen)Linear gas velocity 19.520.5 cm/sSplit ratio 100:1 maxDetector FIDHydrogen 30 mL/minAir 400 mL/minMake up gas 30 mL/minNOTE 5Hydrogen is an alternate choice as a carrier gas with greaterseparation efficiency; however, the use of hydrogen may require additi
29、onalsafety considerations.10. 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 respons
30、e factor of individual terpene com-pound;W1= Weight of individual terpene compound in standard(W1= weight used 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 purity).NOTE 6For
31、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 suitable vial and record the weight ofeach to 0.0001 g.4Reagent Chemicals, American Chemical Society Spec
32、ifications, AmericanChemical Society, Washington, DC. For suggestions on the testing of reagents notlisted by the American Chemical Society, see Analar Standards for LaboratoryChemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeiaand National Formulary, U.S. Pharmacopeial Conve
33、ntion, Inc. (USPC), Rockville,MD.D6387 19211.2 Approximately 1 mL of hexane may be added 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
34、all of the peaks needed fromthe chromatogram.NOTE 7See Fig. 1a through 1c for chromatograms of a typicalturpentine, dipentene, and pine oil, respectively. These chromatogramsfrom the 1997 round robin show that nonane was used as the internalstandard. While decane is also suitable for use on the pola
35、r column,nonane is the preferred standard for the non-polar column because of itsshorter retention time.13.2 Calculate the absolute value of each peak of interest, asfollows:Terpene Compound, % 5A13 RRF13 WISAIS3 Ws3100 (2)where:A1= peak area for terpene compound being determined;RRF1= relative resp
36、onse factor for terpene compound beingdetermined;WIS= weight of n-decane internal standard WIS= weightused purity;AIS= peak area of n-decane internal standard; and,Ws= sample weight, g.14. Report14.1 Report the percentage of the individual terpene com-pound to the nearest 0.1 %.15. Precision and Bia
37、s15.1 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. Thedesign of the experiment was similar to that of Practice E691,and a w
38、ithin/between analysis of the date are given in ASTMResearch Report: RR:D01-1111.515.1.1 Test ResultThe precision information given belowis based on three separate analyses of each individual sample.15.1.2 Precision for a Turpentine Material Containingabout 50.0 % -Pinene, about 31.7 % -Pinene, and
39、about2.4 % Dipentene:15.1.2.1 Repeatability Limit, 95 % for -pinene = 0.4, for-pinene = 0.3, and for dipentene = 0.2.15.1.2.2 Reproducibility Limit, 95 % for -pinene = 3.5, for-pinene = 5.4, and for dipentene = 0.7.15.1.2.3 Repeatability Standard Deviation, % for -pinene= 0.1, for -pinene = 0.1, and
40、 for dipentene = 0.1.15.1.2.4 Reproducibility Standard Deviation, % for-pinene = 1.3, for -pinene = 1.9, and for dipentene = 0.2.15.1.3 Precision for a Pine Oil Product Containing about2.5 % Terpinolene, about 39.6 % -Terpineol, and about 1.6 %-Terpineol:15.1.3.1 Repeatability Limit, 95 % for terpin
41、olene = 0.1, for-terpineol = 1.5 and for -terpineol = 0.1.15.1.3.2 Reproducibility Limit, 95 % for terpinolene = 0.5,for -terpineol = 9.2 and for -terpineol = 1.1.15.1.3.3 Repeatability Standard Deviation, % for terpi-nolene = 0.03, for -terpineol = 0.5 and for -terpineol = 0.03.5Supporting data hav
42、e been filed at ASTM International Headquarters and maybe obtained by requesting Research Report RR:D01-1111. ContactASTM CustomerService at serviceastm.org.FIG. 1 (a)GC/FID ChromatogramsD6387 19315.1.3.4 Reproducibility Standard Deviation, % for terpi-nolene = 0.2, for -terpineol = 3.3 and for -ter
43、pineol = 0.4.15.1.4 Precision for a Dipentene Product Containing about17.2 % -Pinene, about 22.6 % Dipentene, and about 12.7 %Terpinolene:15.1.4.1 Repeatability Limit, 95 % for -pinene = 0.2, fordipentene = 0.8, and for terpinolene = 0.6.15.1.4.2 Reproducibility Limit, 95 % for -pinene = 3.3, fordip
44、entene = 4.4, and for terpinolene = 2.7.15.1.4.3 Repeatability Standard Deviation, % for -pinene= 0.07, for dipentene = 0.3 and for terpinolene = 0.2.15.1.4.4 Reproducibility Standard Deviation, % for-pinene = 1.2, for dipentene = 1.6 and for terpinolene = 0.9.FIG. 1 (b)GC/FID Chromatograms (continu
45、ed)FIG. 1 (c)GC/FID Chromatograms (continued)D6387 19415.1.5 BiasSince there is no accepted reference material,method or laboratory suitable for determining the bias for theprocedure in this test method for measuring componentconcentration, no statement on bias is being made.AREA PERCENT METHOD16. P
46、reparation of Retention Time Standard16.1 Prepare similar to 8.1 except that only approximateweights need to be used.17. Set-Up of 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
47、 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 individual peaks, exclusive ofthe solvent peak, to obtain the total peak area.NOTE 8See Fig. 1a, 1b, or 1c for chromatograms of a typicalturpentine, dipentene, and pine oil, r
48、espectively.20.2 Calculate the relative percent of each terpene com-pound present, as follows:Terpene, % 5 A 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 individual terpene
49、compounds 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 design ofthe experiment was similar to that of Practice E691, and awithin/between analysis of the date are given in ASTMResearch Report RR:D01-1111.522.1.1 Test ResultThe precision information given belowis based on three separate analy
