ASTM D3893-03(2017) Standard Test Method for Purity of Methyl Amyl Ketone and Methyl Isoamyl Ketone by Gas Chromatography.pdf

1、Designation: D3893 03 (Reapproved 2017)Standard Test Method forPurity of Methyl Amyl Ketone and Methyl Isoamyl Ketone byGas Chromatography1This standard is issued under the fixed designation D3893; the number immediately following the designation indicates the year oforiginal adoption or, in the cas

2、e 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.1. Scope1.1 This test method covers the determination of the purityof methyl amyl ketone and methyl iso

3、amyl ketone. In addition,the method determines total ketones and various impuritieswhich may include acetone, isopropyl alcohol, methyl propylketone, methyl isobutyl ketone, methyl butyl ketone, methylisobutyl carbinol, mesityl oxide, methyl isoamyl ketone,methyl butyl carbinol, methyl amyl ketone,

4、and diisobutylketone.1.2 Water and acid cannot be determined by this testmethod. They must be determined by other appropriate ASTMprocedures, and the results used to normalize the chromato-graphic data.1.3 For purposes of determining conformance of an ob-served or a calculated value using this test

5、method to relevantspecifications, test result(s) shall be rounded “off to the nearestunit” in the last right-hand digit used in expressing thespecification limit, in accordance with the rounding-off methodof Practice E29.1.4 The values stated in SI units are to be regarded asstandard. No other units

6、 of measurement are included in thisstandard.1.5 For hazard information and guidance, see the suppliersSafety Data Sheet.1.6 This standard does not purport to address all of thesafety concerns, if any, associated with its use. It is theresponsibility of the user of this standard to establish appro-p

7、riate safety, health, and environmental practices and deter-mine the applicability of regulatory limitations prior to use.1.7 This international standard was developed in accor-dance with internationally recognized principles on standard-ization established in the Decision on Principles for theDevel

8、opment of International Standards, Guides and Recom-mendations issued by the World Trade Organization TechnicalBarriers to Trade (TBT) Committee.2. Referenced Documents2.1 ASTM Standards:2D1364 Test Method for Water in Volatile Solvents (KarlFischer Reagent Titration Method)D1613 Test Method for Aci

9、dity in Volatile Solvents andChemical Intermediates Used in Paint, Varnish, Lacquer,and Related ProductsE29 Practice for Using Significant Digits in Test Data toDetermine Conformance with SpecificationsE180 Practice for Determining the Precision of ASTMMethods for Analysis and Testing of Industrial

10、and Spe-cialty Chemicals (Withdrawn 2009)33. Summary of Method3.1 A representative specimen is introduced onto a gas-liquid partition column. The separated components are mea-sured in the effluent by a detector and recorded as a chromato-gram. The chromatogram is interpreted by applying componentatt

11、enuation and detector response factors to the peak areas andrelative concentrations are determined by relating the indi-vidual peak responses to the total peak response. Water andacidity are measured by Test Methods D1364 and D1613,respectively, and the results are used to normalize the valuesobtain

12、ed by gas chromatography.4. Significance and Use4.1 This procedure is designed to determine the purity of thetwo ketones, methyl isoamyl ketone and methyl amyl ketone,and to obtain the concentration of their various impurities,several of which are critical in the application of these solvents.5. App

13、aratus5.1 ChromatographAny gas-liquid chromatographic in-strument having either a thermal conductivity or flame ioniza-tion detector and sufficient sensitivity and stability to obtain for0.01 % impurity in the specimen a recorder deflection of at1This test method is under the jurisdiction of ASTM Co

14、mmittee D01 on Paintand Related Coatings, Materials, and Applications and is the direct responsibility ofSubcommittee D01.35 on Solvents, Plasticizers, and Chemical Intermediates.Current edition approved Dec. 1, 2017. Published December 2017. Originallyapproved in 1980. Last previous edition approve

15、d in 2009 as D3893 09. DOI:10.1520/D3893-03R17.2For 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 page onthe ASTM website.3The last appr

16、oved 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 StatesThis international standard was developed in accordance with internationally recognized principles on standardization

17、 established in the Decision on Principles for theDevelopment of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.1least 20 mm at a signal-to-noise ratio of at least 5 to 1. Arecording integrator or computer data p

18、rocessing system mayalso be used.5.1.1 The injection port of the chromatograph must have avolume of at least 1.2 mL to provide for proper vaporization ofthe specimen. The use of a smaller injection port or on-columninjection causes peak broadening and tailing.5.2 ColumnFour and one half m of 3.2-mm

19、stainless steeltubing packed with 80 to 90-mesh acid-washed, base-washed,and silanized diatomaceous earth support coated with 10.0 %20 000 molecular weight polyethylene glycol and a 8.33 %phenyl methyl (50:50) silicone. A capillary column, capable ofthe required separation may also be used.5.3 Speci

20、men Introduction SystemAny system capable ofintroducing a representative specimen onto the column. Micro-liter syringes have been used successfully.5.4 RecorderA recording potentiometer with a full-scaledeflection of 1 mV, full-scale response time of1sorless, andsufficient sensitivity and stability

21、to meet the requirements of5.1.6. Reagents and Materials6.1 Carrier Gas, appropriate to the type of detector used.Helium or hydrogen may be employed with thermal conduc-tivity detectors and nitrogen, helium, or argon with flameionization detectors. The minimum purity of the carrier gasused should be

22、 99.95 mol %. An oxygen removal system isrecommended for the carrier gas.6.1.1 WarningIf hydrogen is used, take special safetyprecautions to ensure that the system is free of leaks and thatthe effluent is vented properly.6.2 Column Materials:6.2.1 Liquid Phase20 000 molecular weight polyethyleneglyc

23、ol and phenyl methyl (50:50) silicone.6.2.2 Solid SupportAcid-washed, base-washed, and si-lanized diatomaceous earth, 80 to 90 mesh.6.2.3 SolventsMethylene chloride, reagent grade.6.2.4 Tubing MaterialThe stainless steel tubing must beof uniform internal diameter and must be clean. Wash theinside of

24、 the tubing with methylene chloride, then water, andfinally methyl alcohol and blow dry with nitrogen.6.3 Standards for Calibration and IdentificationStandardsamples of all components are needed for establishing identi-fication by retention time and for calibration for quantitativemeasurements. In m

25、ost cases, the pure compounds required forcalibration cannot be purchased and must be purified bydistillation before use.7. Preparation of Column7.1 Place 50 g of the solid support, 80 to 90 mesh, in a largeevaporating dish. Dissolve 12.5 g of the polyethylene glycol inabout 40 mL of methylene chlor

26、ide and add to the solidsupport. Add additional methylene chloride to wet and coverthe solid support. Evaporate the methylene chloride in a fumehood with gentle stirring and under a gentle stream of nitrogen.7.2 Place 50 g of the solid support in a large evaporatingdish. Dissolve 10 g of the phenyl

27、methyl silicone in about 40mL of methylene chloride and add to the solid support. Addadditional methylene chloride to wet and cover the solidsupport. Evaporate the methylene chloride in a fume hood withgentle stirring and under a gentle stream of nitrogen.7.3 Add 12 g of the packing prepared in 7.1

28、and 12 g of thepacking prepared in 7.2 to a small glass bottle or beaker andmix well. The mixture is used as the column packing material.7.4 Column PreparationThe method used to pack thecolumn is not critical provided that the finished columnproduces the required separation of all of the components

29、to bedetermined.8. Calibration and Standardization8.1 ChromatographInstall the column in the chromato-graph and adjust the operating parameters as directed in Table1. Allow sufficient time for the instrument to reach equilibriumas indicated by a stable recorder baseline.8.2 Determine the retention t

30、ime of each component byinjecting small amounts either separately or in known mix-tures. The components should elute close to the typicalretention times given in Table 1 and the chromatograms shouldclosely approximate those shown in Fig. 1 and Fig. 2.8.3 The area under each peak of the chromatogram

31、isconsidered a quantitative measure of the corresponding com-pound. The relative area is proportional to concentration if thedetector responds equally to all the sample components. Theresponse to different components is generally significantlydifferent for both flame ionization and thermal conductiv

32、itydetectors. This difference in detector response may be cor-rected by use of relative response factors obtained by injectingand measuring the response of pure components or knownblends. For accurate determination of the impurities, prepareand analyze a known blend containing the impurities inconce

33、ntrations that approximate the maximum specificationlimit. Calculate the response factors relative to unity for themajor ketone.TABLE 1 Instrument Conditions and Retention TimesTemperature,C:Column, isothermal 100Injection port 170Detector block 210Carrier gas HeliumFlow rate, mL/min 25MethylAmylKet

34、oneMethylIsoamylKetoneRelative retention times,major component = 1.00Air 0.04 0.05Acetone 0.14 0.18Isopropyl alcohol 0.18 0.23Methyl propyl ketone 0.31 0.38Methyl isobutyl ketone 0.35 0.45Methyl butyl ketone 0.51 0.64Methyl isobutyl carbinol 0.61 0.77Mesityl oxide 0.65 0.83Methyl isoamyl ketone 0.73

35、 1.00Methyl butyl carbinol 0.82 1.02Methyl amyl ketone 1.00 1.16Diisobutyl ketone 1.04 1.25D3893 03 (2017)29. Procedure9.1 Introduce a representative specimen into the chromato-graph using sufficient material to ensure a minimum 10 %recorder deflection for a 0.1 % concentration of impurity at themos

36、t sensitive setting of the instrument.NOTE 1The best separation of the impurities has been obtained withspecimen sizes of 1 or 2 L.9.2 Using the same conditions as for component identifica-tion and standardization, record the peaks of all components atattenuation settings that provide optimum peak h

37、eights.10. Calculation10.1 Measure the area of all peaks (Note 2) and multiplyeach area by the appropriate attenuation factor to express thepeak areas on a common basis. Apply the appropriate detectorresponse to each component to obtain the corrected peakresponse. Calculate the weight percent compos

38、ition by divid-ing the individual corrected component areas by the totalcorrected area. Make corrections to account for water andacidity present as determined by the ASTM methods given in2.1.NOTE 2Peak areas may be determined by any method that meets theprecision limits given in Section 12. For best

39、 results determine peak areasby electronic integration.10.2 Calculate the weight percent of each component asfollows:Weight% 5AB3 100 2 C! (1)where:A = corrected peak response,B = sum of corrected peak responses, andC = sum of water and acidity in weight percent.FIG. 1 Typical Chromatogram of Methyl

40、 Amyl KetoneD3893 03 (2017)310.3 Calculate the total ketones concentration by summingthe weight percent of all ketones detected.11. Report11.1 Report the total ketone content, purity, and quantity ofthe various impurities to the nearest 0.01 %. Duplicate runs forthe total ketone and purity values th

41、at agree within 0.15 %absolute are acceptable for averaging (95 % confidence level).Duplicate runs for the impurities that agree within 0.03 %absolute are acceptable for averaging.12. Precision and Bias412.1 PrecisionThe precision statements are based upon aninterlaboratory study in which one operat

42、or in five laboratoriesanalyzed in duplicate on two different days one sample of eachof the following ketones of the average composition shown inTable 2. The results were analyzed in accordance with PracticeE180. The within-laboratory and between-laboratories stan-dard deviations were found to be as

43、 shown in Table 3. Based4Supporting data have been filed at ASTM International Headquarters and maybe obtained by requesting Research Report RR:D01-1043. ContactASTM CustomerService at serviceastm.org.FIG. 2 Typical Chromatogram of Methyl Isoamyl KetoneTABLE 2 Average Compositions of Samples Used in

44、Precision DeterminationMethylIsoamylKetone(MIAK)MethylAmylKetone(MAK)Total ketones 99.66 99.76MIAK 99.0 .MAK . 99.11Isopropyl alcohol (IPA) 0.06 0.06Mesityl oxide (MO) 0.12 .Methyl isoamyl carbinol (MIAC) 0.11 .Methyl isobutyl carbinol (MIBC) . 0.04D3893 03 (2017)4upon these standard deviations, the

45、 following criteria should beused for judging the acceptability of results at the 95 %confidence level.12.1.1 RepeatabilityTwo results, each the mean ofduplicates, obtained by the same operator on different daysshould be considered suspect if they differ by more than asshown in Table 4.12.1.2 Reprod

46、ucibilityTwo results, each the mean ofduplicates, obtained by operators in different laboratoriesshould be considered suspect if they differ by more than asshown in Table 4.12.2 BiasBias cannot be determined for this test methodbecause there is no available material having an acceptedreference value

47、.13. Keywords13.1 gas chromatography; methyl amyl ketone (MAK);methyl isoamyl ketone (MIAK); purity; solventsASTM 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

48、that determination of the validity 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 reap

49、proved or withdrawn. Your comments 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 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 B