1、Designation: D 4291 04 (Reapproved 2009)Standard Test Method forTrace Ethylene Glycol in Used Engine Oil1This standard is issued under the fixed designation D 4291; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of last r
2、evision. 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
3、 to 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 app
4、lica-bility of regulatory limitations prior to use.For specific warningstatements, see Section 6.NOTE 1A qualitative determination of glycol-base antifreeze is pro-vided in Test Methods D 2982. Procedure A is sensitive to about 100 ppm.2. Referenced Documents2.1 ASTM Standards:2D 1193 Specification
5、for Reagent WaterD 2982 Test Methods for Detecting Glycol-Base Antifreezein Used Lubricating OilsD 4057 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 reproduci
6、blevolume 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. Significan
7、ce and Use4.1 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 engi
8、ne.5. Apparatus5.1 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
9、System, providing 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 tubepacke
10、d with 5 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 req
11、uired to 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 crimpe
12、d septum 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 wheresuch specifications a
13、re available.3Other grades may be used,1This test method is under the jurisdiction of ASTM Committee D02 onPetroleum Products and Lubricants and is the direct responsibility of SubcommitteeD02.04.0L on Gas Chromatography Methods.Current edition approved April 15, 2009. Published July 2009. Originall
14、yapproved in 1983. Last previous edition approved in 2004 as D 4291 04.2For 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 AST
15、M website.3Reagent Chemicals, American Chemical Society 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
16、Pharmacopeiaand National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,MD.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.provided it is first ascertained that the reagent is of sufficientlyhigh purity to permit it
17、s use without lessening the accuracy ofthe determination.6.2 Purity of WaterUnless otherwise indicated, referencesto water shall be understood to mean reagent water as definedby Type II of Specification D 1193.6.3 Air and Hydrogen(WarningThe air supply may befrom a cylinder under high pressure. Hydr
18、ogen is an extremelyflammable gas under pressure.)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, pre
19、pare dilutions of that solution.6.5 Carrier Gas, 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
20、inhaled, may produce nervecell damage.)6.8 Liquid 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
21、Column PreparationIf a packed column isused, prepare 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 Chrom
22、osorb T solid supportbecause of its static charge 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 res
23、inwhich will deform under pressure or severe vibration.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 c
24、olumn substrate.7.4 ChromatographPlace in service 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 g
25、lycol peak.8.2 Calculate a response factor for 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
26、 may be employed to obtain the responsefactor.9. Preparation of Sample9.1 Weigh approximately3gofsample, obtained as recom-mended in Practice D 4057, 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
27、n-hexane.9.2 Stopper and vigorously agitate the 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 3
28、0min.9.5 Remove an aliquot of the clear water layer from thecentrifuge tube with a Pasteur 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
29、the peaks at a sensitivity that allows themaximum peak size compatible with the method of measure-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, i
30、nject 5 L ofwater and allow to elute.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 Ove
31、n 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 In
32、itial 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 LD 4291 04 (2009)2NOTE 5Small amounts of ethylene glycol are retained by the chro-matographic column when
33、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 glycol in the original oilsample
34、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 9.1.12. Precision and Bias412.1 The
35、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 on identical testmaterial, would
36、 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 results, obtained by different op
37、erators, 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, mass ppm.NOTE 6The precision st
38、ated 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 chromatography; usedengine oil4Supp
39、orting 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 ChromatogramD 4291 04 (2009)3ASTM International takes no position respecting the validity of any patent
40、 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 is subject to revision at
41、 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 Headquarters. Your comment
42、s 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 b
43、y 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), or serviceastm.org (e-mail); or through the ASTM website(www.astm.org).D 4291 04 (2009)4
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