1、Designation: D 3329 03Standard Test Method forPurity of Methyl Isobutyl Ketone by Gas Chromatography1, 2This standard is issued under the fixed designation D 3329; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of last re
2、vision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon (e) indicates an editorial change since the last revision or reapproval.This standard has been approved for use by agencies of the Department of Defense.1. Scope*1.1 This test method covers the determination
3、of the purityof methyl isobutyl ketone (MIBK) by gas chromatography andin addition provides a means for measuring certain impuritiessuch as methyl isobutyl carbinol which are of interest. Impu-rities such as water and acidity are measured by other appro-priate ASTM procedures and the results are use
4、d to normalizethe chromatographic value.1.2 The values stated in SI units are to be regarded as thestandard. The values given in parentheses are for informationonly.1.3 The following applies to all specified limits in thisstandard; for purposes of determining conformance with thisstandard, an observ
5、ed value or a calculated value shall berounded off “to the nearest unit” in the last right-hand digitused in expressing the specification limit, in accordance withthe round-off method of Practice E 29.1.4 This standard does not purport to address all of thesafety concerns, if any, associated with it
6、s 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 specific hazard information and guidance, see thesuppliers Material Safety Data Sheet for the materials li
7、sted inthis test method.2. Referenced Documents2.1 ASTM Standards:2D 1364 Test Method for Water in Volatile Solvents (KarlFischer Reagent Titration Method)D 1613 Test Method for Acidity in Volatile Solvents andChemical Intermediates Used in Paint, Varnish, Lacquer,and Related ProductsD 2593 Test Met
8、hod for Butadiene Purity and HydrocarbonImpurities by Gas ChromatographyE 180 Practice for Determining the Precision of ASTMMethods for Analysis and Testing of Industrial and Spe-cialty ChemicalsE29 Practice for Using Significant Digits in Test Data toDetermine Conformance with SpecificationsE 260 P
9、ractice for Packed Column Gas Chromatography3. Summary of Test Method3.1 A representative specimen is introduced onto a gas-liquid partition column. Methyl isobutyl ketone is separatedfrom impurities such as acetone, 2-propanol, pentanone, mesi-tyl oxide, methyl isobutyl carbinol, and several uniden
10、tifiedcompounds as the components are transported through thecolumn by an inert carrier gas. The separated components aremeasured in the effluent by a detector and recorded as achromatogram. The chromatogram is interpreted by applyingcomponent attenuation and detector response factors to thepeak are
11、as, and the relative concentrations are determined byrelating the individual peak responses to the total peak re-sponse. Water and acidity are measured in accordance with TestMethods D 1364 and D 1613 and the results are used tonormalize the values obtained by gas chromatography.4. Significance and
12、Use4.1 This test method provides a measurement of commonlyfound impurities in commercially available methyl isobutylketone. The measurement of these impurities and the resultsthereof can individually or when totaled and subtracted from100 (assay) be used for specification acceptance.5. Apparatus5.1
13、ChromatographAny gas liquid chromatographic in-strument having either a thermal conductivity or flame ioniza-tion detector provided the system has sufficient sensitivity andstability to obtain for 0.01 % of impurity a recorder deflectionof at least 2 mm at a signal-to-noise ratio of at least 5 to 1.
14、 Thespecimen size used in judging the sensitivity must be such thatthe column is not overloaded, which would result in peak1This test method is under the jurisdiction of ASTM Committee D01 on Paintand Related Coatings, Materials, and Applications and is the direct responsibility ofSubcommittee D01.3
15、5 on Solvents, Plasticizers, and Chemical Intermediates.Current edition approved Dec.1, 2003. Published December 2003. Originallyapproved in 1974. Last previous edition approved in 1999 as D 3329 99.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service
16、 at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.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 19428-2
17、959, United States.broadening, loss of resolution, shifting retention times andformation of leading peaks.5.2 ColumnAny column capable of resolving methylisobutyl ketone from the impurities that may be present.Possible impurities are hydrocarbons, acetone, 2-propanol,2-pentanone, 3-pentanone, mesity
18、l oxide, mesityl oxide iso-mer, and methyl isobutyl carbinol. Columns that meet thisrequirement are described in Table 1. Other columns, includingcapillary columns, may be used, provided the user establishesthat a column gives the required separation and the peak shapesare satisfactory for measureme
19、nt so that the precision require-ments of Section 12 are met.5.3 Specimen Introduction SystemAny system capable ofintroducing a representative specimen onto the column. Mi-crolitre syringes have been used successfully.5.4 RecorderA recording potentiometer with a full-scaledeflection of 5 mV or less,
20、 full-scale response time of2sorless, and sufficient sensitivity and stability to meet the require-ments of 5.1.6. Reagents and Materials6.1 Carrier GasCarrier gas appropriate to the type ofdetector used. Helium or hydrogen may be employed withthermal conductivity detectors and nitrogen, helium, or
21、argonwith flame ionization detectors. The minimum purity of thecarrier gas used should be 99.95 mol %. (WarningIf hydro-gen is used, take special safety precautions to ensure that thesystem is free from leaks and that the effluent is ventedproperly.)6.2 Column Materials:6.2.1 Liquid PhaseThe materia
22、ls successfully used incooperative test work are listed in Table 1. (See Note 1.)NOTE 1Suppliers of liquid phases and supports can be found inResearch Report RR:D01-1042, available from ASTM InternationalHeadquarters.6.2.2 Solid SupportThe materials and their mesh sizessuccessfully used in cooperati
23、ve work are shown in Table 1.(See Note 1.)6.2.3 Tubing MaterialCopper, stainless steel, and alumi-num have been found satisfactory for column tubing. Thetubing must be nonreactive with the substrate, sample, andcarrier gas and be of uniform internal diameter.6.3 Standards for Calibration and Identif
24、icationStandardsamples of all components present are needed for identificationby retention time and for calibration for quantitative measure-ments.7. Preparation of Apparatus7.1 Column PreparationThe method used to prepare thecolumn is not critical provided that the finished columnproduces the requi
25、red separation (Note 2). Partitioning liquids,supports, and loading levels used successfully in cooperativework are listed in Table 1.NOTE 2A suitable method for column preparation is described in TestMethod D 2593. Additional useful information may be found in PracticeE 260.7.1.1 Prepacked columns
26、conforming to requirements listedin Table 1 and in 5.2 and 6.2 may be obtained from anyreputable chromatography supply company.7.2 ChromatographInstall the column in the chromato-graph and establish the operating conditions required to givethe desired separation. Allow sufficient time for the instru
27、mentto reach equilibrium as indicated by a stable recorder baseline.Control the detector temperature so that it is constant to within1C without thermostat cycling that causes an uneven baseline.Adjust the carrier-gas flow rate to a constant value.TABLE 1 Columns and Conditions Used Successfully in C
28、ooperative Work (See Note 1)Case I Case II Case III Case IV Case V Case VIColumn:Liquid phase polyethylene glycol,MW 1450polyethylene glycol,MW 540ethylene oxide/propylene oxidecopolymerpolyethylene glycol,MW 20Mpolyethylene glycol,MW 3350polyethylene glycolLiquid phase, weight % 15 20 20 25 25 1.2
29、m filmSupport diatomaceous earth,acid washeddiatomaceous earth diatomaceous earth,acid washeddiatomaceous earth diatomaceous earth capillarySupport mesh size 60 to 80 60 to 80 45 to 60 60 to 80 60 to 80 N/ALength, m (ft) 6.1 (20) 5.5 (18) 6.1 (20) 3.0 (10) 3.7 (12) 10 (33)Diameter, mm (in.) 3.2 (18)
30、 6.4 (14) 6.4 (14) 3.2 (18) 6.4 (14) 0.53 (0.021)Temperature, C 90 100 160 75 to 200programmed at4/min145 40 to 180 at5/minCarrier gas: helium helium helium helium helium heliumFlow rate, mL/min 30 50 60 20 80 5Typical retention time, min:Methyl isobutyl ketone 9.3 27.2 8.1 11.2 7.7 1.84Relative ret
31、ention time,MIBK = 1.00:Acetone 0.42 0.39 0.52 0.42 0.39 0.362-propanol 0.66 0.57 0.65 0.56 0.592- and 3-pentanone 0.85 0.82 0.78 . . 0.79Methyl isobutyl ketone 1.00 1.00 1.00 1.00 1.00 1.00a-Mesityl oxide 1.45 1.41 1.27 . . .b-Mesityl oxide 1.89 1.85 1.63 1.24 1.52 .Methyl isobutyl carbinol 2.11 2.
32、07 1.48 1.42 1.95 2.24D33290328. Calibration and Standardization8.1 IdentificationSelect the conditions of column tem-perature and carrier gas flow that will give the necessaryresolution of the components. Determine the retention time ofeach component by injecting small amounts either separatelyor i
33、n known mixtures. Relative component retention timesalong with the typical retention time for methyl isobutyl ketoneare given in Table 1.8.2 StandardizationThe area under each peak of thechromatogram is considered a quantitative measure of thecorresponding compound. The relative area is proportional
34、 toconcentration if the detector responds equally to all the samplecomponents. When flame ionization detectors are used theresponse to different components is generally significantlydifferent. Differences in detector response may be corrected byuse of relative response factors obtained by injecting
35、andmeasuring the response to pure (99 weight % minimum)components or known blends. When thermal conductivitydetectors are used for the analysis of high-purity methylisobutyl ketone, the difference between area percent andweight percent is within the precision of the test method.NOTE 3Much data on th
36、ermal conductivity and flame ionizationdetector responses may be found in the literature. Useful information isgiven by Messner, et al3and by Dietz.49. Procedure9.1 Introduce a representative specimen into the chromato-graph using a microlitre syringe. Use sufficient specimen toensure a minimum of 1
37、0 % recorder deflection for a 0.1 %concentration of impurity at the most sensitive setting of theinstrument.9.2 Using the same conditions as for component identifica-tion and standardization, record the peaks of all components atattenuation settings that provide maximum peak heights.10. Calculation1
38、0.1 Measure the area of all peaks (Note 4) and multiplyeach area by the appropriate attenuation factor to express thepeak areas on a common basis. If a flame ionization detectorwas used, apply the appropriate detector response factors tocorrect for the difference in response to the components.Calcul
39、ate the weight percent composition by dividing theindividual corrected component areas by the total correctedarea. Make corrections to account for water and acidity presentas determined in accordance with Test Methods D 1364 andD 1613.NOTE 4Peak areas may be determined by any method that meets thepr
40、ecision limits given in Section 12. Methods found to be acceptable areplanimetering and integration.10.2 Calculate the weight percent W of each component asfollows:W 5 A/B! 3 100 2 C! (1)where:A = corrected peak response,B = sum of corrected peak responses, andC = sum of water and acidity.11. Report
41、11.1 Report the following information: weight percent ofmethyl isobutyl ketone and any impurities of interest to thenearest 0.01 % absolute. Duplicate runs for major componentsthat agree within 0.05 % absolute are acceptable for averaging(95 % confidence level).12. Precision and Bias512.1 PrecisionT
42、he precision statements are based upon aninterlaboratory study in which one operator in six differentlaboratories analyzed two samples of methyl isobutyl ketone induplicate on two days. One sample represented commercialmaterial having a purity of 99.8 % and containing 0.03 %methyl isobutyl carbinol
43、and the other was prepared by adding0.28 % of methyl isobutyl carbinol to the first sample. Theresults were analyzed in accordance with Practice E 180.Because one laboratory failed to report trace impurities, theirresults were omitted from the calculation of the precisionstatements. The within-labor
44、atory standard deviation andbetween-laboratory standard deviation were found to be asfollows:WithinLaboratoryBetweenLaboratoryMethyl isobutyl ketone 0.014 0.078Methyl isobutyl carbinol 0.011 0.044Degrees of freedom 10 4Based upon these standard deviations, the following criteriashould be used for ju
45、dging the acceptability of results at the95 % confidence level for methyl isobutyl ketone having apurity of 99 to 100 % and containing from 0.0 to 0.5 % of theimpurity methyl isobutyl carbinol.12.1.1 RepeatabilityTwo results, each the mean of dupli-cates, obtained by the same operator on different d
46、ays shouldbe considered suspect if they differ by more than 0.05 %absolute for methyl isobutyl ketone or 0.03 % absolute formethyl isobutyl carbinol.12.1.2 ReproducibilityTwo results, each the mean of du-plicates, obtained by operators in different laboratories shouldbe considered suspect if they di
47、ffer by more than 0.30 %absolute for methyl isobutyl ketone or 0.17 % absolute formethyl isobutyl carbinol.12.2 BiasBias can not be determined for this test methodbecause there is no available material having an acceptedreference value.13. Keywords13.1 gas chromatography; ketone; methyl isobutyl ket
48、one;MIBK; purity; solvent3Messner, A. E., et al, Analytical Chemistry, Vol 31, 1959, pp. 230233.4Dietz, W.A., Journal of Gas Chromatography, Vol 5, No. 2, February 1967, pp.6871.5Supporting data are available from ASTM International Headquarters. RequestRR:D01-1042.D3329033SUMMARY OF CHANGESCommitte
49、e D01 has identified the location of selected changes to this standard since the last issue(D 3329 99) that may impact the use of this standard.(1) Added Practice E29on significant digits to the Scope. (2) Added Practice E29to the Referenced Documents 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 validity of any such patent rights, and the riskof infringement of such ri
