1、Designation: D4291 04 (Reapproved 2017)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 from5 mass ppm to 200 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, health, and environmental practice
4、s and deter-mine the applicability of regulatory limitations prior to use.For specific warning statements, see Section 6.NOTE 1A qualitative determination of glycol-base antifreeze isprovided in Test Methods D2982. Procedure A is sensitive to about100 ppm.1.3 This international standard was develope
5、d in accor-dance with internationally recognized principles on standard-ization established in the Decision on Principles for theDevelopment of International Standards, Guides and Recom-mendations issued by the World Trade Organization TechnicalBarriers to Trade (TBT) Committee.2. Referenced Documen
6、ts2.1 ASTM Standards:2D1193 Specification for Reagent 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 per
7、formed 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 ethylene glycolpeak area is determined and compared with areas obtainedfrom the injection of freshl
8、y 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 and deposit formation. This testmethod is designed for early detection to prevent coolant fromaccu
9、mulating 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 temperature equivalent to the maximum columntemperature employed, and connected to the column so as to
10、avoid 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 RecorderRecording potentiometer with a full-scaleresponse time of 2 s or less may be used.5.3 Columns1.2
11、m by 6.4 mm (4 ft by14 in.) copper tubepacked with 5 % by mass Carbowax 20-M liquid phase on30/60 mesh Chromosorb T solid support. As an alternative, afused silica capillary column, 15 m long with a 0.53 mm IDand 2.0 micron film thickness of a bonded polyethylene glycolcan be used.5.4 IntegratorManu
12、al, 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 centrifuge tubeswith stoppers.5.6 SyringeA microsyringe, 10 L is needed for sampleintroductio
13、n.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, Liquid Fuels, and Lubricants and is the direct responsibility ofSubcommittee D02.04.0L on Gas Chromatography Methods.Current edition approved Oct. 1,
14、 2017. Published November 2017. Originallyapproved in 1983. Last previous edition approved in 2013 as D4291 04 (2013).DOI: 10.1520/D4291-04R17.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards vo
15、lume information, refer to the standards Document Summary page onthe ASTM website.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United StatesThis international standard was developed in accordance with internationally recognized principles on sta
16、ndardization established in the Decision on Principles for theDevelopment of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.16. Reagents and Materials6.1 Purity of ReagentsReagent grade chemicals shall beused in
17、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.3Other grades may be used,provided it is first ascertained that the reagent is of suffic
18、ientlyhigh 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 II of Specification D1193.6.3 Air and Hydrogen(WarningThe air supply may befrom a cylin
19、der 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 mass ppm to 200 mass ppm. Prepare one blend of approxi-mately 2000 mass ppm ethylene glycol in water to
20、 provide foraccurate weighing; 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.)6.6 Ethylene Glycol, 99 % by mass pure.6.7 n-Hexane, 99 mol % pure. (Warning
21、n-Hexane isextremely flammable, harmful if inhaled, may produce nervecell damage.)6.8 Liquid Phase and Solid Support, 5 % by 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 di
22、stilled.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 % by mass Carbowax 20-Mliquid phase on 30/60 mesh Chromosorb T solid support, byany satisfactory method used in the practice of gas chromatog-r
23、aphy.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 usingonly gentle tapping. Do not use vacuum or mechanical vibra-tion to pac
24、k 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 ConditioningThe column must be condi-tioned at the operating tempera
25、ture 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 calibration mixtures following theprocedure in Section 10, injecting
26、 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 glycol in water,andA = peak area for ethylene glycol.8.3 Calculate an
27、average response factor.NOTE 3A calibration curve may be employed to obtain the responsefactor.9. Preparation of Sample9.1 Weigh approximately 3 g of sample, obtained as recom-mended in Practice D4057, to the nearest 0.1 mg into thestoppered centrifuge tube. Add approximately 3 g of water,weighed to
28、 the nearest 0.1 mg, to the centrifuge tube. Add5mLofn-hexane.9.2 Stopper and vigorously agitate the centrifuge tube forapproximately 5 min.3Reagent Chemicals, American Chemical Society Specifications, AmericanChemical Society, Washington, DC. For Suggestions on the testing of reagents notlisted by
29、the American Chemical 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
30、mm (14 in.) OD copperPacking: 5 % by mass Carbowax 20-M liquid phase on 30/60 meshChromosorb T solid supportDetector: FIDDetector Temperature: 200 CInjection Port Temperature: 150 CColumn Oven Temperature: 130 CCarrier Gas Flow: 60 mL minSample Size: 5 LCapillary ColumnColumn: 15 m by 0.53 mm fused
31、silica capillary with 2 m of bondedpolyethylene glycol stationary phaseDetector: FIDDetector Temperature: 300 CInjection Port Temperature: 250 CColumn Oven Initial Temperature: 150 CColumn Oven Initial Hold Time: 0 minColumn Oven Temperature Program Rate: 10 C minColumn Oven Program Final Temperatur
32、e: 200 CColumn Oven Program Final Hold Time: 5 minCarrier Gas Flow: 22 mL minSample Size: 1 LD4291 04 (2017)29.3 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-hexan
33、e and centrifuge for30 min.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
34、 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 columnsis shown in Fig. 2.10.2 After each sample an
35、alysis is completed, inject 5 L ofwater and allow to elute.NOTE 5Small amounts of ethylene glycol are retained by thechromatographic column when higher concentrations of the glycol areinjected. Therefore, when analyzing for very low concentrations ofethylene glycol, make repeated injections of water
36、 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 glycol as calculated in8.3,A = peak area for et
37、hylene glycol,WW= mass of the water as determined in 9.1, andWS= mass 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 asfollows:12.1.1 RepeatabilityThe difference between suc
38、cessivetest 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 case in twenty.Repeatability, n 5 0.212X (3)where:X
39、 = 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 and correct operation of the testmethod, exceed the
40、 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 is noacceptable reference material suitable for de
41、termining 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 Report RR:D02-1167.FIG. 1 Typical Packed Column Chroma
42、togramFIG. 2 Typical Capillary Column ChromatogramD4291 04 (2017)3ASTM 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 s
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46、s 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). Permission rights to photocopy the standard may also be secured from the Copyright Clearance Center, 222Rosewood Drive, Danvers, MA 01923, Tel: (978) 646-2600; http:/ 04 (2017)4
