1、Designation: D6387 99 (Reapproved 2014)1Standard 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
2、, in the case of revision, 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.1NOTENote 6 was corrected editorially in December 2014.1. Scope1.1 These test methods descr
3、ibe the determination of theamounts of -pinene, -pinene, 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” me
4、thod, which yieldsabsolute values, and the “area percent” 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, a
5、ssociated with its use. It is theresponsibility of 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. Thi
6、s greater than normal differential is aconsequence 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
7、test methodgives excellent precision within a given laboratory on a given GC. Whenlaboratory to laboratory comparison have to be made, however, it isessential that the GC operating conditions be defined closely.2. Referenced Documents2.1 ASTM Standards:2D13 Specification for Spirits of TurpentineD80
8、1 Test Methods for Sampling and Testing 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Chemicals, IncludingTall Oil and Related ProductsD3009 Test Method for Compostition of Turpentine by GasChromatography (Withdrawn 1999)3E691 Practice for Conducting
9、an Interlaboratory Study toDetermine 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 chromatogra
10、ph 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/sample, and the calibration factors.A
11、lternately, the relative concentration 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
12、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 present in the sample.5. Significance an
13、d Use5.1 Earlier methods for characterizing turpentine and relatedterpene products were 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 Method1Th
14、ese 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 Pine Chemicals and HydrocarbonResins.Current edition approved Dec. 1, 2014. Published January 2015. Originallyapprove
15、d in 1999. Last previous edition approved in 2010 as D6387 99 (2010).DOI: 10.1520/D6387-99R14E01.2For 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
16、ent 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 C700, West Conshohocken, PA 19428-2959. United States1D3009. As terpene products became widely used as chemicalraw mater
17、ial, the separation and 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 p
18、rogrammable in-strument equipped with a flame ionization detector (FID) thatcan be operated 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 n
19、eedingseparation and quantitation. 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
20、 glycol column should be 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,
21、 it is intended thatall 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 it
22、s use without lessening theaccuracy of the determination.7.2 -Pinene, purity 99+%.7.3 -Pinene, 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
23、 of Calibration Standard8.1 To a 2-dram 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 oflower split ratios.NOTE 4Other t
24、erpene 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 separations.Adjustments in opera
25、ting 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 Temperature 250CCarrier gas Heliu
26、mLinear gas velocity 19.520.5 cm/sSplit ratio 100:1 maxDetector FIDHydrogen 30 mL/minAir 400 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
27、individual relative responsefactors as follows:RRF15W1A13AISWIS(1)where:RRF1= Relative response 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 standa
28、rd; and,WIS= Weight of n-decane internal standard (WIS= weightn-decane used purity).NOTE 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
29、 and record the weight ofeach to 0.0001 g.11.2 Approximately 1 mL of hexane may be added to thevial to make the sample easier to handle and not overload thecolumn or detector.4Reagent Chemicals, American Chemical Society Specifications, AmericanChemical Society, Washington, DC. For suggestions on th
30、e 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 Convention, Inc. (USPC), Rockville,MD.D6387 99 (2014)1212. Analysis12.1 Inject 0
31、.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.FIG. 1 (a)GC/FID ChromatogramsFIG. 1 (b)GC/FID Chromatograms (continued)D6387 99 (2014)13NOTE 6See Fig. 1a through 1c for chromatograms of a typical pineoi
32、l, turpentine, and dipentene, respectively.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 response factor for terpene compound beingdetermined;WIS= weight
33、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 Bias15.1 Internal Standard MethodAn interlaboratory studyof the
34、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 within/between analysis of the date are given in ASTMResearch
35、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 about2.4 % Dipentene:15.1.2.1 Repeatability Limit95 % for -pi
36、nene = 0.4, for-pinene = 0.3, and for dipentene = 0.2.15.1.2.2 Reproducibility Limit95 % 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 for dipentene = 0.1.15.1.2.4 Reproducibility Standard Deviation% f
37、or-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 Limit95 % for terpinolene = 0.1,for -terpineol = 1.5 and for -terpineol = 0.1.15.1.3.2 Repr
38、oducibility Limit95 % 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 = 0.03.15.1.3.4 Reproducibility Standard Deviation% for terpi-nolene = 0.2, for -terpineol = 3.3 and f
39、or -terpineol = 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 Limit95 % for -pinene = 0.2, fordipentene = 0.8, and for terpinolene = 0.6.15.1.4.2 Reproducibility Limit95 % for -pinene = 3.3,for
40、dipentene = 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 = 0.9.5Supporting data have been filed at ASTM
41、 International Headquarters and maybe obtained by requesting Research Report RR:D01-1111. ContactASTM CustomerService at serviceastm.org.FIG. 1 (c)GC/FID Chromatograms (continued)D6387 99 (2014)1415.1.5 BiasSince there is no accepted reference material,method or laboratory suitable for determining t
42、he bias for theprocedure in this test method for measuring componentconcentration, 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 of Gas Chromatograph17.1 Set c
43、onditions 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 individual peaks, exclusive ofthe
44、 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:Terpene, % 5 A 3 100!/TA (3)where:A = peak area for terpene comp
45、ound being determined, andTA = sum of areas of all peaks, except solvent peak.21. Report21.1 Report the area percent of the individual terpenecompounds to the nearest 0.1 %.22. Precision and Bias22.1 Area Percent MethodAn interlaboratory study of thecapillary GC determination of various terpenes and
46、 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 precisio
47、n information given belowis based on three separate analyses of each individual sample.22.1.2 Precision for a Turpentine Material Containingabout 51.1 % -Pinene, about 28.8 % -Pinene, and about2.7 % Dipentene:22.1.2.1 Repeatability Limit95 % for -pinene = 0.3, for-pinene = 0.1 and for dipentene = 0.
48、1.22.1.2.2 Reproducibility Limit95 % for -pinene = 2.1,for -pinene = 0.5, and for dipentene = 0.2.22.1.2.3 Repeatability Standard Deviation% for -pinene= 0.1, for -pinene = 0.04, and for dipentene = 0.03.22.1.2.4 Reproducibility Standard Deviation% for-pinene = 0.7, for -pinene = 0.2, and for dipent
49、ene = 0.1.22.1.3 Precision for a Pine Oil Product Containing about2.9 % terpinolene, about 37.9 % -Terpineol, and about 1.7 %-Terpineol:22.1.3.1 Repeatability Limit95 % for terpinolene = 0.1,for -terpineol = 0.3, and for -terpineol = 0.02.22.1.3.2 Reproducibility Limit95 % for terpinolene = 0.6,for -terpineol = 3.8, and for -terpineol = 0.4.22.1.3.3 Repeatability Standard Deviation% for terpi-nolene = 0.02, for -terpineol = 0.1, and for -terpineol = 0.03.22.1.3.4 Reprodu
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