1、Designation: E 1863 07Standard Test Method forAnalysis of Acrylonitrile by Gas Chromatography1This standard is issued under the fixed designation E 1863; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of last revision. A
2、number in parentheses indicates the year of last reapproval. Asuperscript epsilon (e) indicates an editorial change since the last revision or reapproval.1. Scope*1.1 This test method covers the determination of the impu-rities in, and the purity of, acrylonitrile by flame ionizationdetector gas chr
3、omatography. 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 i
4、ts use. It is theresponsibility of the user of this standard to establish appro-priate safety and health practices and determine the applica-bility of regulatory limitations prior to use. Specific hazardstatements are given in Sections 6 and 7.1.4 Review the current MSDS for detailed informationconc
5、erning toxicity, first aid procedures, and safety precau-tions.2. Referenced Documents2.1 ASTM Standards:2E 180 Practice for Determining the Precision of ASTMMethods for Analysis and Testing of Industrial and Spe-cialty ChemicalsE 1178 Test Methods for Analysis of Acrylonitrile3. Summary of Test Met
6、hod3.1 In this test method, a representative sample of acryloni-trile is introduced in a gas chromatograph equipped with aflame ionization detector and a capillary column where specificimpurities are separated from the acrylonitrile. The chromato-graphic area for each impurity is compared to the are
7、a 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 impurities are calculated. Otherimpurities, such as water, are obtained by
8、use of Test MethodsE 1178. 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 impurities normally present in acryloni-trile and may be useful for final
9、 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, meth-acrylonitrile, oxazole, propionitrile, cis-crotononitrile, trans-crotononitri
10、le, and others where specific impurity standards areavailable.5. Apparatus5.1 Capillary Gas ChromatographAny gas chromato-graph equipped with a flame ionization detector and a splitinjection system for use with capillary columns that can beoperated at the conditions given in Table 1.5.2 ColumnThe co
11、lumn, such as Supelcowax 10,3mustgive 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.6. Reagents and Materials6.1 Purity of ReagentsReagent grade chemicals sh
12、all beused in all tests. Unless otherwise indicated, it is intended thatall reagents conform to the specifications of the Committee onAnalytical Reagents of the American Chemical Society where1This test method is under the jurisdiction of ASTM Committee E15 onIndustrial and Specialty Chemicals and i
13、s the direct responsibility of SubcommitteeE15.02 on Product Standards.Current edition approved April 1, 2007. Published May 2007. Originallyapproved in 1997. Last previous edition approved in 2002 as E 1863 97 (2002).2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact AS
14、TM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.3A 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
15、columns fromother vendors may be used after shown to be suitable.1*A Summary of Changes section appears at the end of this standard.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.TABLE 1 Typical Instrument ParametersDetector: Flame i
16、onizationColumn:length: 60 minside diameter: 0.32 mmstationary phase: Supelcowax 10support: Fused silicafilm thickness, m: 1.0Temperature, 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 minI
17、nternal standard: TolueneSample size, L 2.0Split ratio 1:100Retention times, min (refer to Fig. 1 for typical chromatogram)Acetaldehyde 6Acetone 9Acrolein 10Benzene 18Methacrylonitrile 23Oxazole 29Propionitrile 29.5Toluene 30cis-Crotononitrile 38trans-Crotononitrile 49FIG. 1 Typical Chromatogram of
18、Acrylonitrile Calibration MixtureE1863072such specifications are available.4Other grades may be used,provided it is first ascertained 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
19、%.6.3 Hydrogen, high purity.6.4 Air, hydrogen free, high purity.6.5 Toluene, 99.0 % min purity or other internal standard,previously analyzed free of compounds coeluting with impu-rities in the sample.6.6 Acrylonitrile, highest purity available.NOTE 1High purity acrylonitrile can be obtained by frac
20、tional distil-lation.6.7 Acetone, at least 96 % pure.6.8 Acrolein, at least 96 % pure.6.9 Acetonitrile, at least 96 % pure.6.10 Acetaldehyde, 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
21、 and trans, at least 96 % pure,available only as a mixture.7. Hazards7.1 Acrylonitrile potentially is hazardous to human health ifnot properly handled. Acrylonitrile is a suspected humancarcinogen. Use acrylonitrile in a well-ventilated hood.7.2 Acrylonitrile can contribute to a toxic condition insy
22、stems of the human body, from inhalation, swallowing orcontact with the eyes or skin. Direct contact with acrylonitrilealso can cause skin burns.7.3 Acrylonitrile liquid and vapor are absorbed readily intoshoe leather and clothing and will penetrate most rubbers,barrier fabrics, or creams. Contact l
23、enses should not be worn inareas where eye contact with acrylonitrile could occur. Imper-meable protective clothing must be used. Consult the currentMSDS for recommended materials.8. Calibration and Standardization8.1 Prepare a synthetic mixture containing approximately99.4 mass % acrylonitrile and
24、the expected significant impu-rities at their expected concentrations. Weigh all components tothe nearest 0.1 mg. Fill a 100-mL volumetric 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
25、 toluene is used as the internal standard,using a density of 0.867 for toluene and 0.806 for acrylonitrile,this solution will contain 0.011 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
26、typical chromatograph is shownin Fig. 1.8.3 Measure the areas of all peaks, except the acrylonitrilepeak, including the toluene (internal 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
27、factor relative to the internal standard,As = area of internal standard peak,Ai = area of impurity peak,Fi = attenuation factor for impurity peak,Fs = attenuation factor for internal standard peak,Ws = internal standard in synthetic standard, mass %, and,Wi = impurity in synthetic standard, mass %.9
28、. Procedure9.1 Establish stable instrument operation at the prescribedor selected operating conditions. Reference should be made tothe instructions 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, a
29、dd 10 L of theinternal standard. Add sample to mark and again mix well. Iftoluene is used as the internal standard, using a density of 0.867for 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 th
30、e chromatogram.10. Calculation10.1 Measure the areas of all peaks, including the internalstandard, except the acrylonitrile peak.10.2 Calculate 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 pe
31、ak,Ri = response factor for impurity, relative to the internalstandard,Ws = concentration of internal standard, mass %,Fi = attenuation factor for impurity, and,Fs = attenuation factor for internal standard.For unknown impurities or for known impurities for whichno response factor has been determine
32、d, a response factor (Ri)of 1.00 may be used.NOTE 2If an electronic integrator is used, Fs and Fi are usually 1.00.10.3 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 o
33、r by Test Methods E 1178.11. Report11.1 Report the concentration of each impurity to thenearest 1 mg/kg (ppm). Report any unidentified impurity or4Reagent Chemicals, American Chemical Society Specifications , AmericanChemical Society, Washington, DC. For suggestions on the testing of reagents notlis
34、ted 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.E1863073any identified impurity for which a response factor has notbee
35、n determined to the nearest 1 ppm (internal standardequivalent).11.2 Report the sum of all impurities as total impurities tothe nearest 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 theacceptabilit
36、y of results for impurities (see Note 3):12.1.1 Repeatability (Single Analyst)The coefficient ofvariation for a single determination has 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-Laborator
37、y, Between-Days Variability)The coefficient of variation of results (eachthe average of duplicates), obtained by the same analyst ondifferent 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 (Mul
38、tilaboratory)The coefficientof variation of results, each the average of duplicates, obtainedby analysts in different laboratories, has 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 base
39、d on an interlaboratorystudy of analyses performed in 1988 on two samples of acrylonitrilecontaining approximately 18 and 82 mg/kg acetone, 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 60an
40、d 194 mg/kg propionitrile. The precision for other impurities should bedetermined as needed. One analyst in each of six laboratories performedduplicate determinations and repeated one day later, for a total of 48determinations for each impurity. Practice E 180 was used in developingthese precision e
41、stimates.512.2 BiasThe bias of this test method has not beendetermined because of the lack of acceptable reference mate-rial.13. Keywords13.1 acrylonitrile; capillary; gas chromatography; impuri-ties; internal standardSUMMARY OF CHANGESCommittee E15.02 has identified the location of selected changes
42、 to this standard since the last issue(E 1863 - 97 (2002) that may impact the use of this standard.(1) Updated units of measure to comply with the InternationalSystem of Units (SI).(2) Added numbered paragraph in Scope stating that the SIunits are to be considered standard.(3) Deleted (Formerly call
43、ed Repeatability) from the title of12.1.2.(4) Added Summary of Changes section.ASTM 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 vali
44、dity of any such patent rights, and the riskof infringement of such rights, are entirely their own responsibility.This standard is subject to revision at any time by the responsible technical committee and must be reviewed every five years andif not revised, either reapproved or withdrawn. Your comm
45、ents are invited either for revision of this standard or for additional standardsand should be addressed to ASTM International Headquarters. Your comments will receive careful consideration at a meeting of theresponsible technical committee, which you may attend. If you feel that your comments have
46、not received a fair hearing you shouldmake your views known to the ASTM Committee on Standards, at the address shown below.This standard is copyrighted by ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959,United States. Individual reprints (single or multiple c
47、opies) of this standard may be obtained by contacting ASTM at the aboveaddress or at 610-832-9585 (phone), 610-832-9555 (fax), or serviceastm.org (e-mail); or through the ASTM website(www.astm.org).5Supporting data are available from ASTM International Headquarters as aresearch report. Request RR: E15 - 1059.E1863074
