1、Designation: D2804 02 (Reapproved 2012)Standard Test Method forPurity of Methyl Ethyl Ketone By Gas Chromatography1This standard is issued under the fixed designation D2804; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year
2、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.This standard has been approved for use by agencies of the Department of Defense.1. Scope*1.1 This test method covers the deter
3、mination of the purityof methyl ethyl ketone by gas chromatography. Impuritiesincluding water, acidity, and nonvolatile matter are measuredby appropriate ASTM procedures and the results are used tonormalize the chromatographic value.1.2 For purposes of determining conformance of an ob-served value o
4、r a calculated value using this test method torelevant specifications, test result(s) shall be rounded off “tothe nearest unit” in the last right-hand digit used in expressingthe specification limit, in accordance with the rounding-offmethod of Practice E29.1.3 The values stated in SI units are to b
5、e regarded asstandard. No other units of measurement are included in thisstandard.1.4 For hazard information and guidance, see the suppliersMaterial Safety Data Sheet.2. Referenced Documents2.1 ASTM Standards:2D1353 Test Method for Nonvolatile Matter in Volatile Sol-vents for Use in Paint, Varnish,
6、Lacquer, and RelatedProductsD1364 Test Method for Water in Volatile Solvents (KarlFischer Reagent Titration Method)D1613 Test Method for Acidity in Volatile Solvents andChemical Intermediates Used in Paint, Varnish, Lacquer,and Related ProductsD2593 Test Method for Butadiene Purity and HydrocarbonIm
7、purities by Gas ChromatographyD4626 Practice for Calculation of Gas ChromatographicResponse FactorsE29 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 and S
8、pe-cialty Chemicals (Withdrawn 2009)33. Summary of Test Method3.1 A representative specimen is introduced into a gas-chromatographic column. The methyl ethyl ketone is separatedfrom other impurities such as hydrocarbons, alcohols, acetone,di-sec-butyl ether, and ethyl acetate as the components aretr
9、ansported through the column by an inert carrier gas. Theseparated components are measured in the effluent by adetector and recorded as a chromatogram. The chromatogramis interpreted by applying component-attenuation and detector-response factors to the peak areas, and the relative concentra-tion is
10、 determined by relating individual peak response to thetotal peak response. Water, acidity, and nonvolatiles are mea-sured by the procedures listed in 3.2, and the results are usedto normalize the results obtained by gas chromatography.3.2 The appropriate ASTM test methods are:3.2.1 WaterTest Method
11、 D1364.3.2.2 AcidityTest Method D1613.3.2.3 Nonvolatile MatterTest Method D1353.4. Significance and Use4.1 This test method provides a measurement of commonlyfound impurities in commercially available methyl ethyl ke-tone. The measurement of these impurities and the resultsthereof can individually o
12、r when totaled and subtracted from100 (assay) be used for specification purposes.5. Apparatus5.1 ChromatographAny gas chromatograph having eithera thermal-conductivity or flame ionization detector providedthe system has sufficient sensitivity and stability to obtain for0.01 weight % of impurity a re
13、corder deflection of at least 2mm at a signal-to-noise ratio of at least 5 to 1. The specimen1This 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, a
14、nd Chemical Intermediates.Current edition approved July 1, 2012. Published September 2012. Originallyapproved in 1969. Last previous edition approved in 2007 as D2804 02 (2007).DOI: 10.1520/D2804-02R12.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Serv
15、ice at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.3The last approved version of this historical standard is referenced onwww.astm.org.*A Summary of Changes section appears at the end of this standardCopyright
16、ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States1size to be used in judging the sensitivity must be such that thecolumn is not overloaded.5.2 ColumnAny column capable of resolving methyl ethylketone from the impurities that may be present. Possi
17、bleimpurities are paraffins, acetone, methanol, ethanol, propanol,isopropanol, tert-butanol, sec-butanol, di-sec-butyl ether, andethyl acetate. The peaks should be resolved, quantitatively inproportion to concentration, within a practical elapsed time.Columns that meet the requirements of this test
18、method arelisted in Table 1. Other columns may be used, provided the userestablishes that a column gives the required separation and theprecision requirements of Section 13 are met.5.3 Specimen Introduction SystemAny specimen systemcapable of introducing a representative specimen into thecolumn may
19、be used. Systems that have been used successfullyto introduce 1 to 10-L of methyl ethyl ketone specimensinclude microlitre syringes, micropipets, and liquid samplingvalves.5.4 RecorderAn electronic integrator or a recording po-tentiometer with a full-scale deflection of 5 mV or less,full-scale respo
20、nse time of 2 s or less, and sufficient sensitivityto meet the requirements of 5.1.6. 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 ionizationdetectors. The
21、minimum purity of any carrier should be 99.95mol %.6.1.1 WarningIf hydrogen is used, take special safetyprecaution to ensure that the system is free of leaks and that theeffluent is vented properly.6.2 Column Materials:6.2.1 Liquid PhaseThe materials successfully used incooperative work as liquid ph
22、ases are listed in Table 1 (seeNote 1).6.2.2 Solid SupportThe support for use in the packedcolumn is usually (PTFE)-fluorocarbon, crushed firebrick, ordiatomaceous earth. Table 1 lists conditions used successfullyin cooperative work (see Note 1).NOTE 1See research report for additional information,
23、available fromASTM International Headquarters. Request RR:D01-1107.6.2.3 Tubing MaterialCopper, stainless steel, nickel cop-per alloy, aluminum, and various plastic materials have beenfound to be satisfactory for column tubing. The material mustbe nonreactive with the substrate, sample, and carrier
24、gas.6.3 Standards for Calibration and Identification Standardsamples for all components present are needed for identifica-tion by retention time, and for calibration for quantitativemeasurements (Note 2).NOTE 2Mixtures of components may be used, provided there is nouncertainty as to the identity or
25、concentration of compounds involved.7. Preparation of Apparatus7.1 Column PreparationThe method used to prepare thecolumn is not critical provided that the finished columnproduces the required separation (Note 3). Partitioning liquids,supports, and loading levels used successfully in cooperativework
26、 are listed in Table 1. These may be obtained from mostchromatography supply houses.NOTE 3A suitable method for column preparation is described in TestMethod D2593.TABLE 1 Columns and Conditions Used Successfully in Cooperative WorkCase I Case II Case III Case IV Case V Case VIColumn:Liquid phasepac
27、kedpolyethyleneglycol 1500packedpolyethyleneglycol 400packedpolyethyleneglycol 300packedpolyethyleneglycol 200packedpolyethyleneglycol 1500capillarypolytrifluoro-propylsiloxaneLiquid phase, weight % 10 28 20 20 20 1.2 m filmSupport type TFE resin Pink, diato-maceous earthPink, diato-maceous earthWhi
28、te, diato-maceous earthPink, diato-maceous earthnoneSupport mesh size 40/60 30/60 40/60 60/80 60/80 .Length, ft (m) 12 (3.7) 18 (5.5) 10 (3.0) 10 (3.0) 20 (6.1) 32.8 (10.0)Outside diameter, in. (mm) 0.25 (6.4) 0.25 (6.4) 0.25 (6.4) 0.125 (3.2) 0.25 (6.4) 0.028 (0.72)Inside diameter, in. (mm) 0.21 (5
29、.3) 0.21 (5.3) 0.21 (5.3) 0.085 (2.2) 0.21 (5.3) 0.021 (0.53)Column temperature, C 100 80 75 70 100 30Carrier gas helium helium helium helium helium heliumCarrier flow rate, mL/min 60 80 35 60 50 3.7Typical retention time, minmethyl ethyl ketone6.9 17.0 11.0 5.8 16.5 8.8Relative retention time(methy
30、l ethyl ketone = 1.00):Propyl ether 0.19 0.14 . . . .Octenes 0.54 0.21 . 0.34 . 0.65sec-Butyl ether 0.78 0.45 . 0.47 1.21 .Acetone 0.61 0.54 0.64 0.67 0.67 0.60Ethyl acetate 0.81 . 0.82 0.78 0.85 0.78Methyl ethyl ketone 1.00 1.00 1.00 1.00 1.00 1.00tert-Butanol 1.00 1.12 1.27 1.71 1.03 0.39Methanol
31、1.10 . 1.36 1.71 1.09 0.27Isopropanol 1.20 1.32 . 2.03 2.12 0.34Ethanol 1.30 . 1.73 2.21 1.27 0.31sec-Butanol 2.12 2.26 2.73 3.50 1.94 0.53n-Propanol 2.35 . 3.27 3.97 . 0.43D2804 02 (2012)27.2 ChromatographInstall the column in the chromato-graph and establish the operating conditions required to gi
32、vethe desired separation. Relative component retention times,along with the typical retention time for methyl ethyl ketoneare listed in Table 1. Allow sufficient time for the instrument toreach equilibrium as indicated by a stable recorder baseline.8. Calibration and Standardization8.1 Identificatio
33、nSelect the conditions of column tem-perature and carrier-gas flow that will give the necessarycomponent resolution. Determine the retention time for eachcomponent by injecting small amounts of the compound eitherseparately or in mixtures.8.2 StandardizationThe area under the peak of the chro-matogr
34、am is considered a quantitative measure of the amountof the corresponding compound. The relative area is propor-tional to the concentrations if the detector responds equally toall of the sample components. Differences in detector responsemay be corrected by use of relative response factors obtainedb
35、y injecting and measuring the response to pure (99 weight %minimum) compounds or known blends. It is permissible touse the established response factors shown in Table 2 instead ofstandardization.8.3 In using literature values, area response from thermal-conductivity detectors is corrected by multipl
36、ying each com-ponent area by the respective weight factor above.NOTE 4It must be recognized that the use of published responsefactors serves only as a rough estimate, due to differences in equipmentgeometry, condition, and types of detectors. It is preferable for eachanalyst to determine actual resp
37、onse factors on his own instrument. Referto Practice D4626 for calculation of gas chromatographic response factor.NOTE 5When thermal-conductivity detectors are used for the analysisof high-purity methyl ethyl ketone, the difference between area percent iswithin the precision of the method.9. Procedu
38、re9.1 Using a suitable method selected from 5.3, introducesufficient representative liquid specimen into the chromato-graph to ensure a minimum of 10 % recorder deflection for a0.1 % concentration of impurity at the most sensitive-operatingsetting of the instrument.9.2 Using the same conditions as f
39、or component identifica-tion and standardization, record the peaks of all compounds atattenuation settings that provide maximum peak heights.10. Calculation10.1 Measure the area of all peaks (Note 6) and multiply bythe appropriate attenuation factor to express the peak areas ona common basis. If a f
40、lame ionization detector was used, applythe appropriate detector-response factors to correct for thedifference in response to the components. Calculate the weightpercent composition by dividing the individual correctedcomponent areas by the total corrected area. Make correctionsto account for the wa
41、ter, acidity, and nonvolatile matter asdetermined by the ASTM procedures given in 3.1.NOTE 6Peak areas may be determined by any method that meets theprecision limits given in Section 12. Methods found to be acceptableinclude planimetering, integration, and triangulation (multiplying the peakheight b
42、y the width at the half-height).10.2 Calculate weight percent as follows:Methyl ethyl ketone, weight% 5 A/B! 3 100 2 C! (1)where:A = corrected peak response,B = sum of corrected peak responses, andC = sum of water, acidity, and nonvolatile impurities.11. Report11.1 Report the following information:
43、weight percent ofmethyl ethyl ketone and any impurities of interest to the nearest0.01 %.12. Precision and Bias12.1 PrecisionThe precision statements are based upon aninterlaboratory study in which one operator in six differentlaboratories analyzed in duplicate on two days two specimensof methyl eth
44、yl ketone from different manufacturers. Theresults were analyzed in accordance with Practice E180, andthe within-laboratory standard deviation was found to be0.007 % absolute with 12 degrees of freedom and the between-laboratories standard deviation 0.033 % absolute with fivedegrees of freedom. Base
45、d on these standard deviations thefollowing criteria should be used for judging the acceptabilityat the 95 % confidence level, of results obtained on methylethyl ketone having a purity of 99 to 100 %:12.1.1 RepeatabilityTwo results each the mean of tworuns obtained by a single analyst on different d
46、ays should beconsidered suspect if they differ by more than 0.02 % absolute.12.1.2 ReproducibilityTwo results each the mean of tworuns obtained by analysts in different laboratories should beconsidered suspect if they differ by more than 0.12 % absolute.12.2 BiasBias can not been determined for this
47、 testmethod because there is no accepted reference material.13. Keywords13.1 GC; methyl ethyl ketone; purity by gaschromatographyTABLE 2 Thermal Conductivity DetectorA, BThermalMoleResponseWeightFactorMethyl ethyl ketone 98 0.74Di-n-butyl ether 160 0.81Di-isopropyl ether 130 0.79Ethyl acetate 111 0.
48、79sec-Butanol 97 0.76tert-Butanol 96 0.77Acetone 86 0.68Isopropanol 85 0.71Propanol 83 0.72Ethanol 72 0.64Methanol 55 0.58AThe data on the thermal conductivity response are based on data presented byMessner, A. E. et al, Analytical Chemistry, Vol 31, 1959, pp. 230233, and Dietz,W. A., Journal of Gas
49、 Chromatography, Vol 5, No. 2, February 1967, pp 6871(see Note 4 of this test method).BFor reference, hydrogen flame response data on all compounds except theethers are presented in the above paper by W. A. Dietz.D2804 02 (2012)3SUMMARY OF CHANGESCommittee D01.35 has identified the location of selected changes to this standard since the last issue(D2804 - 98) that may impact the use of this standard.(1) Added Practice E29 to the Scope section. (2) Added Practice E29 to the Referenced Documents section.ASTM International takes no position respectin
