1、Designation: D 4291 04An American National StandardStandard 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 yea
2、r 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 ethyleneglycol as a contaminant in used engine oil. This test meth
3、od isdesigned to quantitate ethylene glycol in the range from 5 to200 mass ppm.1.2 The values stated in SI units are to be regarded as thestandard. The values given in parentheses are for informationonly.1.3 This standard does not purport to address all of thesafety concerns, if any, associated with
4、 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.For specific warningstatements, see Section 6.NOTE 1A qualitative determination of glycol-base antifreeze is pr
5、o-vided in Test Methods D 2982. ProcedureAis sensitive to about 100 ppm.2. Referenced Documents2.1 ASTM Standards:2D 1193 Specification for Reagent WaterD 2982 Test Methods for Detecting Glycol-Base Antifreezein Used Lubricating OilsD 4057 Practice for Manual Sampling of Petroleum andPetroleum Produ
6、cts3. Summary of Test Method3.1 The sample of oil is extracted with water and theanalysis is performed on the water extract. A reproduciblevolume of the extract is injected into a gas chromatographusing on-column injection and the eluting compounds aredetected by a flame ionization detector. The eth
7、ylene glycolpeak area is determined and compared with areas obtainedfrom the injection of freshly prepared known standards.4. Significance 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 an
8、d deposit formation. This testmethod is designed for early detection to prevent coolant fromaccumulating and seriously damaging the engine.5. Apparatus5.1 Gas ChromatographAny gas chromatographequipped with the following:5.1.1 Flame Ionization Detector, capable of operating con-tinuously at a temper
9、ature equivalent to the maximum columntemperature employed, and connected to the column so as toavoid any cold spots.5.1.2 Sample Inlet System, providing for on-column injec-tion and capable of operating continuously at a temperatureequivalent to the maximum column temperature employed.5.2 RecorderR
10、ecording 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 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 an
11、d2.0micron film thickness of a bonded polyethylene glycol canbe used.5.4 IntegratorManual, mechanical, or electronic integra-tion is required to determine the peak area. However, bestprecision and automated operation can be achieved withelectronic integration.5.5 CentrifugeRCF 600 minimum and centri
12、fuge tubeswith stoppers.5.6 SyringeA microsyringe, 10 L is needed for sampleintroduction.5.7 Pasteur Pipets.5.8 Vials, 2 mL, with crimped septum caps.1This test method is under the jurisdiction of ASTM Committee D02 onPetroleum Products and Lubricants and is the direct responsibility of Subcommittee
13、D02.04 on Hydrocarbon Analysis.Current edition approved Nov. 1, 2004. Published November 2004. Originallyapproved in 1983. Last previous edition approved in 1998 as D 429193(1998).2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org
14、. 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 19428-2959, United States.
15、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 are available.3
16、Other 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 determination.6.2 Purity of WaterUnless otherwise indicated, referencesto water shall be understood to mean reagent water as definedby Type
17、II of Specification D 1193.6.3 Air and Hydrogen(WarningThe air supply may befrom a cylinder under high pressure. Hydrogen 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
18、. 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, helium or nitrogen may be used with theflame ionization detector. (WarningHelium and nitrogen arecompressed gases under high pressure.
19、)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 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 o
20、utside 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, 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 suppor
21、t, 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 charge and softness. Chilling may be helpful inimproving its handling properties.7.1.2 Add the prepared packing to the copper tubing usingon
22、ly 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 vibration.7.2 Column InstallationThe column must be attached tothe injection port in such a way as to allow on-columninjection.7.3 Column
23、ConditioningThe column must be condi-tioned at the operating temperature to reduce baseline shift dueto bleeding of column substrate.7.4 ChromatographPlace in service in accordance withmanufacturers instructions. Typical operating conditions areshown in Table 1.8. Calibration8.1 Analyze each of the
24、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 each calibration mixtureas follows:F 5 C/A (1)where:F = response factor for ethylene glycol,C = concentration in mass ppm of ethylene gl
25、ycol 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. Preparation of Sample9.1 Weigh approximately3gofsample, obtained as recom-mended in Practice D 4057, to the nearest 0.1 mg into thesto
26、ppered 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 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 theu
27、pper 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 Society Specifications, AmericanChemical Society, Washington, DC. For suggestions on the testing of reagents notlisted by the American Chemi
28、cal Society, see Annual Standards for LaboratoryChemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeiaand National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,MD.TABLE 1 Typical Operating ConditionsPacked ColumnColumn: 1.2 m (4 ft) by 6.4 mm (14 in.) OD cop
29、perPacking: 5 mass % Carbowax 20-M liquid phase on 30/60 mesh ChromosorbT solid supportDetector: FIDDetector Temperature: 200CInjection Port Temperature: 150CColumn Oven Temperature: 130CCarrier Gas Flow: 60 mL/minSample Size: 5 LCapillary ColumnColumn: 15 m by 0.53mm fused silica capillary with 2 m
30、 of bondedpolyethylene glycol stationary phaseDetector: FIDDetector Temperature: 300CInjection Port Temperature: 250CColumn Oven Initial Temperature: 150CColumn Oven Initial Hold Time: 0 minColumn Oven Temperature Program Rate: 10C/minColumn Oven Program Final Temperature: 200CColumn Oven Program Fi
31、nal Hold Time: 5 minCarrier Gas Flow: 22 mL/minSample Size: 1 LD42910429.5 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.
32、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 measure-ment.NOTE 4A typical chromatogram obtained with packed columns isshown in Fig. 1. A typical chromatogram obtained with capillary columns
33、is 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 the chro-matographic column when higher concentrations of the glycol areinjected. Therefore, when analyzing for very low concentrations ofethy
34、lene 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 is calculated as follows:Ethylene glycol, mass ppm 5 F 3 A 3 WW/WS(2)where:F = response factor for ethylene g
35、lycol 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 precision of this test method as obtained bystatistical examination of interlaboratory test results is asfoll
36、ows:12.1.1 RepeatabilityThe difference between successivetest results obtained by the same operator with the sameapparatus under constant operating conditions on identical testmaterial, would in the long run, in the normal and correctoperation of test method, exceed the following values only inone c
37、ase 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 operators, work-ing in different laboratories on identical test material, would inthe long run, in the normal a
38、nd 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 stated in this test method was determined usingpacked columns.12.2 BiasBias cannot be determined because there
39、is noacceptable reference material suitable for determining the biasfor the procedure in this test method.13. Keywords13.1 antifreeze; ethylene glycol; gas chromatography; usedengine oil4Supporting data have been filed at ASTM International Headquarters and maybe obtained by requesting Research Repo
40、rt RR:D02-1167.FIG. 1 Typical Packed Column ChromatogramFIG. 2 Typical Capillary Column ChromatogramD4291043SUMMARY OF CHANGESSubcommittee D02.04 has identified the location of selected changes to this standard since the last issue(D 429193(1998) that may impact the use of this standard.(1) Revised
41、5.3 to allow the use of a capillary column.(2) Revised 7.1.(3) Revised Table 1.(4) Revised Note 4.(5) Revised the caption under Fig. 1.(6) Added Fig. 2.(7) Added Note 6.ASTM International takes no position respecting the validity of any patent rights asserted in connection with any item mentionedin
42、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 any time by the responsible technical committee and must
43、 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 comments will receive careful consideration at a meeting of ther
44、esponsible 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 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), or serviceastm.org (e-mail); or through the ASTM website(www.astm.org).D4291044
