1、Designation: D 3893 03Standard Test Method forPurity of Methyl Amyl Ketone and Methyl Isoamyl Ketone byGas Chromatography1This standard is issued under the fixed designation D 3893; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, t
2、he year of last revision. A 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 purityof methyl amyl ketone and methyl isoamyl ketone. I
3、n 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, me-thyl butyl carbinol, methyl amyl ketone, and diisobut
4、yl ketone.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 method to r
5、elevantspecifications, 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 E 29.1.4 This standard does not purport to address all of thesafety concerns, if any, associat
6、ed with its 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.1.5 For hazard information and guidance, see the suppliersMaterial Safety Data Sheet.2. Referenced Docum
7、ents2.1 ASTM Standards:D 1364 Test Method for Water in Volatile Solvents (KarlFischer Reagent Titration Method)2D 1613 Test Method for Acidity in Volatile Solvents andChemical Intermediates Used in Paint, Varnish, Lacquer,and Related Products2E 29 Practice for Using Significant Digits in Test Data t
8、oDetermine the Conformance with Specifications3E 180 Practice for Determining the Precision of ASTMMethods for Analysis and Testing of Industrial Chemicals43. Summary of Method3.1 A representative specimen is introduced onto a gas-liquid partition column. The separated components are mea-sured in th
9、e effluent by a detector and recorded as a chromato-gram. The chromatogram is interpreted by applying componentattenuation 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
10、 are measured by Test Methods D 1364 and D 1613,respectively, and the results are used to normalize the valuesobtained 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
11、 concentration of their various impurities,several of which are critical in the application of these solvents.5. Apparatus5.1 ChromatographAny gas-liquid chromatographic in-strument having either a thermal conductivity or flame ioniza-tion detector and sufficient sensitivity and stability to obtain
12、for0.01 % impurity in the specimen a recorder deflection of atleast 20 mm at a signal-to-noise ratio of at least 5 to 1. Arecording integrator or computer data processing 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 v
13、aporization 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 stainless steeltubing packed with 80 to 90-mesh acid-washed, base-washed,and silanized diatomaceous earth support coated with 10.0 %20 000
14、molecular weight polyethylene glycol and a 8.33 %1This test method is under the jurisdiction of ASTM Committee D01 on Paintand Related Coatings, Materials, and Applications and is the direct responsibility ofSubcommittee D01.35 on Solvents, Plasticizers, and Chemical Intermediates.Current edition ap
15、proved July 10, 2003. Published August 2003. Originallyapproved in 1980. Last previous edition approved in 1999 as D 3893 - 99.2Annual Book of ASTM Standards, Vol 06.04.3Annual Book of ASTM Standards, Vol 14.02.4Annual Book of ASTM Standards, Vol 15.05.1*A Summary of Changes section appears at the e
16、nd of this standard.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.phenyl methyl (50:50) silicone. A capillary column, capable ofthe required separation may also be used.5.3 Specimen Introduction SystemAny system capable ofintroducin
17、g 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 to meet the requirements of5.1.6. Reagents and Materia
18、ls6.1 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 99.95 mol %. An oxygen removal system isrecommended f
19、or 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 polyethyl-ene glycol and phenyl methyl (50:50) silicone.6.2.2 Solid Su
20、pportAcid-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 the tubing with methylene chloride, then water, and
21、finally 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 most cases, the pure compounds required forcalibratio
22、n 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 chloride and add to the solidsupport. Add additional meth
23、ylene 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 methyl silicone in about 40mL of methylene chloride
24、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 and 12 g of thepacking prepared in 7.2 to a small gl
25、ass 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 to bedetermined.8. Calibration and Standardization8.
26、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 time of each component byinjecting small amounts eith
27、er 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 isconsidered a quantitative measure of the correspon
28、ding 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 conductivitydetectors. This difference in detector response m
29、ay 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 inconcentrations that approximate the maximum specification
30、limit. Calculate the response factors relative to unity for themajor ketone.9. 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 themost sensitive setting of the inst
31、rument.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 heights.TABLE 1 Instrument Condi
32、tions and Retention TimesTemperature, C:Column, isothermal 100Injection port 170Detector block 210Carrier gas HeliumFlow rate, mL/min 25MethylAmylKetoneMethylIsoamylKetoneRelative retention times,major component = 1.00Air 0.04 0.05Acetone 0.14 0.18Isopropyl alcohol 0.18 0.23Methyl propyl ketone 0.31
33、 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 1.00Methyl butyl carbinol 0.82 1.02Methyl amyl ketone 1.00 1.16Diisobutyl ketone 1.04 1.25D389303210. Calculation10.1 Measure the area of all peaks (N
34、ote 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 composition by divid-ing the individual corrected component areas
35、 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 results determine peak areasby electronic integration.10.2
36、 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.10.3 Calculate the total ketones concentration by summingthe weight percent of all ketones dete
37、cted.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 that agree within 0.15 %absolute are acceptable for averaging (95 % confidence level).FIG. 1 Typical Chromatogram of Methyl A
38、myl KetoneD3893033Duplicate runs for the impurities that agree within 0.03 %absolute are acceptable for averaging.12. Precision and Bias512.1 PrecisionThe precision statements are based upon aninterlaboratory study in which one operator in five laboratoriesanalyzed in duplicate on two different days
39、 one sample of eachof the following ketones of the average composition shown inTable 2. The results were analyzed in accordance with PracticeE 180. The within-laboratory and between-laboratories stan-dard deviations were found to be as shown in Table 3. Basedupon these standard deviations, the follo
40、wing criteria should beused for judging the acceptability of results at the 95 %confidence level.12.1.1 RepeatabilityTwo results, each the mean of dupli-cates, obtained by the same operator on different days shouldbe considered suspect if they differ by more than as shown inTable 4.5Supporting data
41、are available from ASTM International Headquarters. RequestRR:D01 1043.FIG. 2 Typical Chromatogram of Methyl Isoamyl KetoneTABLE 2 Average Compositions of Samples Used inPrecision DeterminationMethylIsoamylKetone(MIAK)MethylAmylKetone(MAK)Total ketones 99.66 99.76MIAK 99.0 .MAK . 99.11Isopropyl alco
42、hol (IPA) 0.06 0.06Mesityl oxide (MO) 0.12 .Methyl isoamyl carbinol (MIAC) 0.11 .Methyl isobutyl carbinol (MIBC) . 0.04D389303412.1.2 ReproducibilityTwo results, each the mean of du-plicates, obtained by operators in different laboratories shouldbe considered suspect if they differ by more than as s
43、hown inTable 4.12.2 BiasBias cannot be determined for this test methodbecause there is no available material having an acceptedreference value.13. Keywords13.1 gas chromatography; methyl amyl ketone (MAK);methyl isoamyl ketone (MIAK); purity; solventsSUMMARY OF CHANGESCommittee D01 has identified th
44、e location of selected changes to this standard since the last date of issue(D 3893 - 99) that may impact the use of this standard.(1) Added reference to Practice E 29 in 1.3 of the Scopesection.(2) Added Practice E 29 to list of Referenced Documents.ASTM International takes no position respecting t
45、he 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 validity of any such patent rights, and the riskof infringement of such rights, are entirely their own responsibility.This standard
46、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 comments are invited either for revision of this standard or for additional standardsand should be addressed to ASTM International H
47、eadquarters. 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
48、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 copies) of this standard may be obtained by contacting ASTM at the aboveaddress or at 610-832-9585 (phone), 610-832-9555 (fax), o
49、r serviceastm.org (e-mail); or through the ASTM website(www.astm.org).TABLE 3 Standard DeviationWithinLaboratoryBetweenLaboratoriesMethyl Isoamyl Ketone:Total ketones 0.047 (10)A0.160 (4)MIAK 0.047 (8) 0.250 (3)IPA 0.004 (8) 0.012 (3)MO 0.010 (6) 0.010 (2)MIAC 0.010 (6) 0.020 (3)Methyl Amyl Ketone:Total ketones 0.015 (10)A0.158 (4)MAK 0.070 (8) 0.190 (3)IPA 0.007 (8) 0.010 (3)MIBC 0.003 (6) 0.013 (2)ADegrees of freedom are shown in parentheses.TABLE 4 PrecisionRepeatability,% absoluteReproducibility,% absoluteMethyl Isoamyl Ketone:Total ketones 0.15 0.62MIAK 0.1
