1、Designation: D4291 04 (Reapproved 2013)Standard Test Method forTrace Ethylene Glycol in Used Engine Oil1This standard is issued under the fixed designation D4291; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of last rev
2、ision. 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 ethyleneglycol as a contaminant in used engine oil. This test method isdesigned t
3、o quantitate ethylene glycol in the range from 5 to200 mass ppm.1.2 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-priate safety and health practices and determine the appli
4、ca-bility of regulatory limitations prior to use.FOR SPECIFIC WARNINGSTATEMENTS, SEE SECTION 6.NOTE 1A qualitative determination of glycol-base antifreeze isprovided in Test Methods D2982. Procedure A is sensitive to about 100ppm.2. Referenced Documents2.1 ASTM Standards:2D1193 Specification for Rea
5、gent WaterD2982 Test Methods for Detecting Glycol-Base Antifreezein Used Lubricating OilsD4057 Practice for Manual Sampling of Petroleum andPetroleum Products3. Summary of Test Method3.1 The sample of oil is extracted with water and theanalysis is performed on the water extract. A reproduciblevolume
6、 of the extract is injected into a gas chromatographusing on-column injection and the eluting compounds aredetected by a flame ionization detector. The ethylene glycolpeak area is determined and compared with areas obtainedfrom the injection of freshly prepared known standards.4. Significance and Us
7、e4.1 Leakage of aqueous engine coolant into the crank caseweakens the ability of the oil to lubricate. If ethylene glycol ispresent, it promotes varnish and deposit formation. This testmethod is designed for early detection to prevent coolant fromaccumulating and seriously damaging the engine.5. App
8、aratus5.1 Gas ChromatographAny gas chromatographequipped with the following:5.1.1 Flame Ionization Detector, capable of operating con-tinuously at a temperature equivalent to the maximum columntemperature employed, and connected to the column so as toavoid any cold spots.5.1.2 Sample Inlet System, p
9、roviding for on-column injec-tion and capable of operating continuously at a temperatureequivalent to the maximum column temperature employed.5.2 RecorderRecording potentiometer with a full-scaleresponse time of2sorless may be used.5.3 Columns1.2-m (4-ft) by 6.4-mm (14-in.) copper tubepacked with 5
10、mass % Carbowax 20-M liquid phase on 30/60mesh Chromosorb T solid support. As an alternative, a fusedsilica capillary column, 15 m long with a 0.53mm ID and2.0micron film thickness of a bonded polyethylene glycol canbe used.5.4 IntegratorManual, mechanical, or electronic integra-tion is required to
11、determine the peak area. However, bestprecision and automated operation can be achieved withelectronic integration.5.5 CentrifugeRCF 600 minimum and centrifuge tubeswith stoppers.5.6 SyringeA microsyringe, 10 L is needed for sampleintroduction.5.7 Pasteur Pipets.5.8 Vials, 2 mL, with crimped septum
12、caps.6. Reagents and Materials6.1 Purity of ReagentsReagent grade chemicals shall 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
13、 jurisdiction of ASTM Committee D02 onPetroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility ofSubcommittee D02.04.0L on Gas Chromatography Methods.Current edition approved Oct. 1, 2013. Published October 2013. Originallyapproved in 1983. Last previous edition approved in
14、2009 as D4291 04 (2009).DOI: 10.1520/D4291-04R13.2For 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.Copyright AS
15、TM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States1such specifications are available.3Other 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 det
16、ermination.6.2 Purity of WaterUnless otherwise indicated, referencesto water shall be understood to mean reagent water as definedby Type II of Specification D1193.6.3 Air and Hydrogen(WarningThe air supply may befrom a cylinder under high pressure. Hydrogen is an extremelyflammable gas under pressur
17、e.)6.4 Calibration MixturesA minimum of three mixtures ofwater and ethylene glycol are prepared to cover the range from5 to 200 mass ppm. Prepare one blend of approximately 2000mass ppm ethylene glycol in water to provide for accurateweighing; then, prepare dilutions of that solution.6.5 Carrier Gas
18、, helium or nitrogen may be used with theflame ionization detector. (WarningHelium and nitrogen arecompressed gases under high pressure.)6.6 Ethylene Glycol, 99 mass % pure.6.7 n-Hexane, 99 mol % pure. (Warningn-Hexane isextremely flammable, harmful if inhaled, may produce nervecell damage.)6.8 Liqu
19、id Phase and Solid Support, 5 mass % Carbowax20-M liquid phase on 30/60 mesh Chromosorb T solid support.6.9 Tubing, 6.4 mm (14 in.) in outside diameter, 1.2 m (4 ft)long of copper.6.10 Water, deionized or distilled.7. Preparation of Apparatus7.1 Packed Column PreparationIf a packed column isused, pr
20、epare it using the following steps:7.1.1 Prepare the packing, 5 mass % Carbowax 20-M liquidphase on 30/60 mesh Chromosorb T solid support, by anysatisfactory method used in the practice of gas chromatogra-phy.NOTE 2Care should be taken in handling Chromosorb T solid supportbecause of its static char
21、ge and softness. Chilling may be helpful inimproving its handling properties.7.1.2 Add the prepared packing to the copper tubing usingonly gentle tapping. Do not use vacuum or mechanical vibra-tion to pack the column. Chromosorb T solid support is a resinwhich will deform under pressure or severe vi
22、bration.7.2 Column InstallationThe column must be attached tothe injection port in such a way as to allow on-columninjection.7.3 Column ConditioningThe column must be condi-tioned at the operating temperature to reduce baseline shift dueto bleeding of column substrate.7.4 ChromatographPlace in servi
23、ce in accordance withmanufacturers instructions. Typical operating conditions areshown in Table 1.8. Calibration8.1 Analyze each of the calibration mixtures following theprocedure in Section 10, injecting exactly 5 L and record thearea of the ethylene glycol peak.8.2 Calculate a response factor for
24、each calibration mixtureas follows:F 5 C/A (1)where:F = response factor for ethylene glycol,C = concentration in mass ppm of ethylene glycol in water,andA = peak area for ethylene glycol.8.3 Calculate an average response factor.NOTE 3A calibration curve may be employed to obtain the responsefactor.9
25、. Preparation of Sample9.1 Weigh approximately3gofsample, obtained as recom-mended in Practice D4057, to the nearest 0.1 mg into thestoppered centrifuge tube. Add approximately3gofwater,weighed to the nearest 0.1 mg, to the centrifuge tube. Add 5mL of n-hexane.9.2 Stopper and vigorously agitate the
26、centrifuge tube forapproximately 5 min.9.3 Centrifuge the tube for 30 min.9.4 If there is no clear water layer, remove and discard theupper oil layer, taking care not to remove any of the wateremulsion. Add another 5 mL of n-hexane and centrifuge for 30min.3Reagent Chemicals, American Chemical Socie
27、ty Specifications, AmericanChemical Society, Washington, DC. For Suggestions on the testing of reagents notlisted by the American Chemical Society, see Annual Standards for LaboratoryChemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeiaand National Formulary, U.S. Pharmacopeia
28、l Convention, Inc. (USPC), Rockville,MD.TABLE 1 Typical Operating ConditionsPacked ColumnColumn: 1.2 m (4 ft) by 6.4 mm (14 in.) OD copperPacking: 5 mass % Carbowax 20-M liquid phase on 30/60 mesh ChromosorbT solid supportDetector: FIDDetector Temperature: 200CInjection Port Temperature: 150CColumn
29、Oven Temperature: 130CCarrier Gas Flow: 60 mL/minSample Size: 5 LCapillary ColumnColumn: 15 m by 0.53mm fused silica capillary with 2 m of bondedpolyethylene glycol stationary phaseDetector: FIDDetector Temperature: 300CInjection Port Temperature: 250CColumn Oven Initial Temperature: 150CColumn Oven
30、 Initial Hold Time: 0 minColumn Oven Temperature Program Rate: 10C/minColumn Oven Program Final Temperature: 200CColumn Oven Program Final Hold Time: 5 minCarrier Gas Flow: 22 mL/minSample Size: 1 LD4291 04 (2013)29.5 Remove an aliquot of the clear water layer from thecentrifuge tube with a Pasteur
31、pipet and place in a 2-mL vial.Crimp a cap on the vial.10. Procedure10.1 Set the operating conditions of the chromatograph asdescribed in 7.4. Inject exactly 5 L of water extract directly onthe column. Record the peaks at a sensitivity that allows themaximum peak size compatible with the method of m
32、easure-ment.NOTE 4A typical chromatogram obtained with packed columns isshown in Fig. 1. A typical chromatogram obtained with capillary columnsis shown in Fig. 2.10.2 After each sample analysis is completed, inject 5 L ofwater and allow to elute.NOTE 5Small amounts of ethylene glycol are retained by
33、 thechromatographic column when higher concentrations of the glycol areinjected. Therefore, when analyzing for very low concentrations ofethylene glycol, make repeated injections of water until no peak is foundat the ethylene glycol retention time.11. Calculations11.1 The concentration of ethylene g
34、lycol in the original oilsample is calculated as follows:Ethylene glycol, mass ppm 5 F 3 A 3 WW/WS(2)where:F = response factor for ethylene glycol as calculated in8.3,A = peak area for ethylene glycol,WW= weight of the water as determined in 9.1, andWS= weight of the oil sample as determined in 9.1.
35、12. Precision and Bias412.1 The precision of this test method as obtained bystatistical examination of interlaboratory test results is asfollows:12.1.1 RepeatabilityThe difference between successivetest results obtained by the same operator with the sameapparatus under constant operating conditions
36、on identical testmaterial, would in the long run, in the normal and correctoperation of test method, exceed the following values only inone case in twenty.Repeatability, n 5 0.212X (3)where:X = ethylene glycol content, mass ppm.12.1.2 ReproducibilityThe difference between two singleand independent r
37、esults, obtained by different operators, work-ing in different laboratories on identical test material, would inthe long run, in the normal and correct operation of the testmethod, exceed the following values only in one case intwenty.Reproducibility, R 5 0.528X (4)where:X = ethylene glycol content,
38、 mass ppm.NOTE 6The precision stated in this test method was determined usingpacked columns.12.2 BiasBias cannot be determined because there is noacceptable reference material suitable for determining the biasfor the procedure in this test method.13. Keywords13.1 antifreeze; ethylene glycol; gas chr
39、omatography; usedengine oil4Supporting data have been filed at ASTM International Headquarters and maybe obtained by requesting Research Report RR:D02-1167.FIG. 1 Typical Packed Column ChromatogramFIG. 2 Typical Capillary Column ChromatogramD4291 04 (2013)3ASTM International takes no position respec
40、ting 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 rights, are entirely their own responsibility.This sta
41、ndard 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 Internati
42、onal 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
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