1、Designation: E1863 18Standard Test Method forAnalysis of Acrylonitrile by Gas Chromatography1This standard is issued under the fixed designation E1863; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of last revision. A nu
2、mber in parentheses indicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.1. Scope1.1 This test method covers the determination of the impu-rities in, and the purity of, acrylonitrile by flame ionizationdetector gas chromat
3、ography. It is applicable to acrylonitrile inthe range of 99 to 100 % purity.1.2 The values stated in SI units are to be regarded asstandard. The values given in parentheses are for informationonly.1.3 This standard does not purport to address all of thesafety concerns, if any, associated with its u
4、se. It is theresponsibility of the user of this standard to establish appro-priate safety, health, and environmental practices and deter-mine the applicability of regulatory limitations prior to use.Specific hazard statements are given in Sections 6 and 7.1.4 Review the current MSDS for detailed inf
5、ormationconcerning toxicity, first aid procedures, and safety precau-tions.1.5 This international standard was developed in accor-dance with internationally recognized principles on standard-ization established in the Decision on Principles for theDevelopment of International Standards, Guides and R
6、ecom-mendations issued by the World Trade Organization TechnicalBarriers to Trade (TBT) Committee.2. Referenced Documents2.1 ASTM Standards:2E180 Practice for Determining the Precision of ASTMMethods for Analysis and Testing of Industrial and Spe-cialty Chemicals (Withdrawn 2009)3E1178 Test Methods
7、for Analysis of Acrylonitrile (With-drawn 2016)33. Summary of Test Method3.1 In this test method, a representative sample of acrylo-nitrile is introduced in a gas chromatograph equipped with aflame ionization detector and a capillary column where specificimpurities are separated from the acrylonitri
8、le. The chromato-graphic area for each impurity is compared to the area of theinternal standard, toluene or other suitable known, added to thesample. From response factors of these impurities relative tothat of the internal standard and the amount of the standardadded, the concentration of the impur
9、ities are calculated. Otherimpurities, such as water, are obtained by use of Test MethodsE1178. The acrylonitrile content is obtained by subtracting thetotal amount of all impurities from 100.0.4. Significance and Use4.1 This test method is designed to obtain acrylonitrilepurity on the basis of impu
10、rities normally present in acryloni-trile and may be useful for final product inspection and processcontrol.4.2 This test method will measure the following impurities:acetone, acrolein, acetonitrile, and acetaldehyde. It also willallow calibration of other impurities including benzene,methacrylonitr
11、ile, oxazole, propionitrile, cis-crotononitrile,trans-crotononitrile, and others where specific impurity stan-dards are available.5. Apparatus5.1 Capillary Gas ChromatographAny gas chromato-graph equipped with a flame ionization detector and a splitinjection system for use with capillary columns tha
12、t can beoperated at the conditions given in Table 1.5.2 ColumnThe column, such as Supelcowax 10,4mustgive satisfactory resolution and proper peak shapes for thecomponents listed in Fig. 1.5.3 Recorder/IntegratorElectronic integration is recom-mended for this analysis.5.4 Syringe, 10 L capacity.1This
13、 test method is under the jurisdiction ofASTM Committee D20 on Plasticsand is the direct responsibility of Subcommittee D20.15 on Thermoplastic Materi-als.Current edition approved Oct. 1, 2018. Published October 2018. Originallyapproved in 1997. Last previous edition approved in 2007 as E1863 07, wh
14、ich waswithdrawn January 2016 and reinstated in October 2018. DOI: 10.1520/E1863-18.2For 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 Document Summary p
15、age onthe ASTM website.3The last approved version of this historical standard is referenced onwww.astm.org.4A Supelcowax 10 fused silica capillary column (60 m by 0.32 mm ID by 1 mfilm thickness), has been found to be suitable, but similar polar wax columns fromother vendors may be used after shown
16、to be suitable.Copyright ASTM International, 100 Barr Harbor Drive, PO Box 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 theDevel
17、opment of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.16. Reagents and Materials6.1 Purity of ReagentsReagent grade chemicals shall beused in all tests. Unless otherwise indicated, it is intended thatall reage
18、nts conform to the specifications of the Committee onAnalytical Reagents of the American Chemical Society whereTABLE 1 Typical Instrument ParametersDetector: Flame ionizationColumn:length: 60 minside diameter: 0.32 mmstationary phase: Supelcowax 10support: Fused silicafilm thickness, m: 1.0Temperatu
19、re, Cinjector: 225detector: 350oven: 50 initial, hold 25 min, rate 10/min, 90 final, hold 20 minCarrier Gas: HeliumFlow: 20 cm/sTotal chromatograph run time: 54 minInternal standard: TolueneSample size, L 2.0Split ratio 1:100Retention times, min (refer to Fig. 1 for typical chromatogram)Acetaldehyde
20、 6Acetone 9Acrolein 10Benzene 18Methacrylonitrile 23Oxazole 29Propionitrile 29.5Toluene 30cis-Crotononitrile 38trans-Crotononitrile 49FIG. 1 Typical Chromatogram of Acrylonitrile Calibration MixtureE1863 182such specifications are available.5Other grades may be used,provided it is first ascertained
21、that the reagent is of sufficientlyhigh purity to permit its use without lessening the accuracy ofthe determination.6.2 Carrier Gas, helium minimum purity 99.995 mol %.6.3 Hydrogen, high purity.6.4 Air, hydrogen free, high purity.6.5 Toluene, 99.0 % min purity or other internal standard,previously a
22、nalyzed free of compounds coeluting with impu-rities in the sample.6.6 Acrylonitrile, highest purity available.NOTE 1High purity acrylonitrile can be obtained by fractionaldistillation.6.7 Acetone, at least 96 % pure.6.8 Acrolein, at least 96 % pure.6.9 Acetonitrile, at least 96 % pure.6.10 Acetalde
23、hyde, at least 96 % pure.6.11 Benzene, at least 96 % pure.6.12 Methacrylonitrile, at least 96 % pure.6.13 Propionitrile, at least 96 % pure.6.14 Crotononitrile, cis and trans, at least 96 % pure,available only as a mixture.7. Hazards7.1 Acrylonitrile potentially is hazardous to human health ifnot pr
24、operly handled. Acrylonitrile is a suspected humancarcinogen. Use acrylonitrile in a well-ventilated hood.7.2 Acrylonitrile can contribute to a toxic condition insystems of the human body, from inhalation, swallowing orcontact with the eyes or skin. Direct contact with acrylonitrilealso can cause sk
25、in burns.7.3 Acrylonitrile liquid and vapor are absorbed readily intoshoe leather and clothing and will penetrate most rubbers,barrier fabrics, or creams. Contact lenses should not be worn inareas where eye contact with acrylonitrile could occur. Imper-meable protective clothing must be used. Consul
26、t the currentMSDS for recommended materials.8. Calibration and Standardization8.1 Prepare a synthetic mixture containing approximately99.4 mass % acrylonitrile and the expected significant impu-rities at their expected concentrations. Weigh all components tothe nearest 0.1 mg. Fill a 100-mL volumetr
27、ic flask about threefourths full of the synthetic mixture. With a microsyringe add10 L of toluene. Mix well. Add synthetic mixture to the markand again mix well. If toluene is used as the internal standard,using a density of 0.867 for toluene and 0.806 for acrylonitrile,this solution will contain 0.
28、011 mass % toluene.8.2 Inject an appropriate amount of sample into the chro-matograph and obtain a chromatogram. Approximate retentiontimes are given in Table 1. A typical chromatograph is shownin Fig. 1.8.3 Measure the areas of all peaks, except the acrylonitrilepeak, including the toluene (interna
29、l standard) peak.8.4 Calculate the response factor for each impurity relativeto the internal standard as follows:Ri 5As 3 Fs 3 WiAi 3 Fi 3 Ws(1)where:Ri = response factor relative to the internal standard,As = area of internal standard peak,Ai = area of impurity peak,Fi = attenuation factor for impu
30、rity peak,Fs = attenuation factor for internal standard peak,Ws = internal standard in synthetic standard, mass %, and,Wi = impurity in synthetic standard, mass %.9. Procedure9.1 Establish stable instrument operation at the prescribedor selected operating conditions. Reference should be made tothe i
31、nstructions provided by the manufacturer of the chromato-graph.9.2 Fill a 100-mLvolumetric flask about three fourths full ofsample. Mix well. With a microsyringe, add 10 L of theinternal standard. Add sample to mark and again mix well. Iftoluene is used as the internal standard, using a density of 0
32、.867for toluene and 0.806 for acrylonitrile, this solution will 0.011mass % toluene.9.3 Inject an appropriate amount of sample into the chro-matograph and obtain the chromatogram.10. Calculation10.1 Measure the areas of all peaks, including the internalstandard, except the acrylonitrile peak.10.2 Ca
33、lculate the mass percent of the individual impurities,I, as follows:I 5Ai 3 Ri 3 Fi 3 WsAs 3 Fs(2)where:Ai = area of impurity peak,As = area of internal standard peak,Ri = response factor for impurity, relative to the internalstandard,Ws = concentration of internal standard, mass %,Fi = attenuation
34、factor for impurity, and,Fs = attenuation factor for internal standard.For unknown impurities or for known impurities for whichno response factor has been determined, a response factor (Ri)of 1.00 may be used.NOTE 2If an electronic integrator is used, Fs and Fi are usually 1.00.5Reagent Chemicals, A
35、merican Chemical Society Specifications , 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 Formu
36、lary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,MD.E1863 18310.3 Calculate the acrylonitrile content by subtracting thesum of all impurities from 100.00. Acrylonitrile mass% = 100.00 sum of all impurities, whether measured by gaschromatography or by Test Methods E1178.11. Report11.1 Repo
37、rt the concentration of each impurity to thenearest 1 mg/kg (ppm). Report any unidentified impurity orany identified impurity for which a response factor has notbeen determined to the nearest 1 ppm (internal standardequivalent).11.2 Report the sum of all impurities as total impurities tothe nearest
38、0.01 % and the acrylonitrile assay (by difference) tothe nearest 0.01 %.12. Precision and Bias12.1 The following criteria should be used for judging theacceptability of results for impurities (see Note 3):12.1.1 Repeatability (Single Analyst)The coefficient ofvariation for a single determination has
39、 been estimated to be5.8 % relative at 128 df. The 95 % limit for the differencebetween two such runs is 16 % relative.12.1.2 Laboratory Precision (Within-Laboratory, Between-Days Variability)The coefficient of variation of results (eachthe average of duplicates), obtained by the same analyst ondiff
40、erent days, has been estimated to be 4.2 % relative at 64 df.The 95 % limit for the difference between two such averages is12 % relative.12.1.3 Reproducibility (Multilaboratory)The coefficientof variation of results, each the average of duplicates, obtainedby analysts in different laboratories, has
41、been estimated to be9.4 % relative at 5 df. The 95 % limit for the differencebetween two such averages is 26 % relative.NOTE 3The above precision estimates are based on an interlaboratorystudy of analyses performed in 1988 on two samples of acrylonitrilecontaining approximately 18 and 82 mg/kg aceto
42、ne, 164 and 443 mg/kgacetonitrile, 10 and 74 mg/kg benzene, 134 mg/kg cis-crotononitrile, 68mg/kg trans-crotononitrile, 81 and 198 mg/kg methacrylonitrile, and 60and 194 mg/kg propionitrile. The precision for other impurities should bedetermined as needed. One analyst in each of six laboratories per
43、formedduplicate determinations and repeated one day later, for a total of 48determinations for each impurity. Practice E180 was used in developingthese precision estimates.612.2 BiasThe bias of this test method has not beendetermined because of the lack of acceptable reference mate-rial.13. Keywords
44、13.1 acrylonitrile; capillary; gas chromatography; impuri-ties; internal standardASTM International takes no position respecting the validity of any patent rights asserted in connection with any item mentionedin this standard. Users of this standard are expressly advised that determination of the va
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