1、Designation: D4047 00 (Reapproved 2011)Designation: 149/93Standard Test Method forPhosphorus in Lubricating Oils and Additives by QuinolinePhosphomolybdate Method1This standard is issued under the fixed designation D4047; the number immediately following the designation indicates the year oforiginal
2、 adoption or, in the case of revision, the year 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 Defens
3、e.1. Scope1.1 This test method covers the determination of 0.005 to10.0 mass % phosphorus in unused lubricating oil and additiveconcentrates. There is no reason to doubt its applicability tofiltered, used lubricating oils, but no systematic study of thisapplication has been made.1.2 The test method
4、is applicable to samples containing anyof the phosphorus compounds in normal use.NOTE 1This test method extends the scope of the previous version ofIP 149 and replaces IP 148 and the previous version of IP 149 as a refereemethod.1.3 The values stated in SI units are to be regarded asstandard. No oth
5、er units of measurement are included in thisstandard.1.4 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 applica-bility o
6、f regulatory limitations prior to use. For specific hazardstatements, see 6.9.2. Referenced Documents2.1 ASTM Standards:2D1193 Specification for Reagent WaterD6299 Practice for Applying Statistical Quality Assuranceand Control Charting Techniques to Evaluate AnalyticalMeasurement System Performance2
7、.2 IP Standard:IP 148 Test Method for Phosphorous in Lubricating Oilsand Additives33. Summary of Test Method3.1 Additive concentrates are diluted with phosphorus-freewhite oil to produce a working blend.3.2 The sample is ignited with excess of zinc oxide wherebyphosphorus is converted to phosphate.
8、The residue is dissolvedin hydrochloric acid and any sulfide formed is oxidized withpotassium bromate. Phosphorus is then precipitated as quino-line phosphomolybdate and determined volumetrically byaddition of excess standard alkali and back titration withstandard acid.4. Significance and Use4.1 Kno
9、wledge of the phosphorus content, and thus thephosphorus-containing additives, in a lubricating oil or addi-tive can be used to predict performance characteristics.5. Apparatus5.1 Silica Crucibles, 40-mm internal diameter at the top and40 mm in height. The internal surface should be smooth andfree f
10、rom pitting.5.2 Muffle Furnace, capable of maintaining a temperature ofapproximately 700C, and fitted with ports to allow aircirculation.5.3 Beakers, 25-mL capacity.6. Reagents and Materials6.1 Purity of ReagentsReagent grade chemicals shall beused in all tests. Unless otherwise indicated, it is int
11、ended that1This test method is under the jurisdiction of ASTM Committee D02 onPetroleum Products and Lubricants and is the direct responsibility of SubcommitteeD02.03 on Elemental Analysis.Current edition approved May 1, 2011. Published May 2011. Originallyapproved in 1981. Last previous edition app
12、roved in 2005 as D4047 00 (2005).DOI: 10.1520/D4047-00R11.2For 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.3Av
13、ailable from Energy Institute, 61 New Cavendish St., London, WIG 7AR,U.K., http:/www.energyinst.org.uk.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.all reagents shall conform to the specifications of the Commit-tee on Analytical R
14、eagents of the American Chemical Society,where such specifications are available.4Other grades may beused, provided it is first ascertained that the reagent is ofsufficiently high purity to permit its use without lessening theaccuracy of the determination.6.2 Purity of WaterUnless otherwise indicate
15、d, referencesto water shall be understood to mean reagent water as definedby Type II or Type III of Specification D1193.6.3 Hydrochloric Acid, approximately 1 N reagent solution.6.4 Hydrochloric Acid (36 mass %)Concentrated hydro-chloric acid (HCl).6.5 Hydrochloride Acid, (0.1 N)Hydrochloric acid (H
16、Cl)accurately standardized.6.6 Mixed IndicatorMix 2 volumes of phenolphthaleinsolution with 3 volumes of thymol blue solution.6.7 Phenolphthalein Solution, (1 g/L in 95 % volumeethanol).6.8 Potassium Bromate (KBrO3), solid.6.9 Quinoline (WarningQuinoline has a high toxic acutesystemic rating.)Redist
17、illed synthetic or, if this is unobtain-able, quinoline freshly distilled from the technical product.Collect the colorless distillate in the boiling range from 232 to238C. Store the quinoline in an amber bottle in the dark.6.10 Quinoline Hydrochloride SolutionDissolve 20 mLofquinoline in 800 mL of h
18、ot water acidified with 25 mL ofconcentrated HCl; add a little paper pulp, cool, filter, and makeup to 1 L with water. This solution is stable for about 1 month.6.11 Sodium Hydroxide Solution (0.1 M)Sodium hydrox-ide (NaOH) accurately standardized.6.12 Sodium Molybdate SolutionDissolve 10 g of sodiu
19、mhydroxide (NaOH) and 18 g of ammonia-free molybdenumtrioxide in 200 mL of water and filter the solution.NOTE 2To avoid high blanks caused by silicate interference withalkaline reagents, including sodium molybdate solution, store in polythenecontainers.6.13 Thymol Blue Solution (1 g/L) in 95 % volum
20、e ethanol.6.14 Zinc Oxide (ZnO), finely divided.7. Blending Procedure7.1 Samples having a phosphorus content greater than 0.3mass % should be blended in white oil to give a phosphoruscontent in the range of 0.1 to 0.3 mass %.7.2 Calculate the mass of sample for a 10-g blend asfollows:A 5 2/P (1)wher
21、e:P = approximate percent phosphorus in the sample, andA = grams of sample required for a 10-g blend.7.3 Calculate the mass of white oil for a 10-g blend asfollows:B 5 10 2 A (2)where:B = mass of white oil, g.7.4 Weigh a quantity of sample A 6 0.01 g into a 25-mLbeaker.7.5 Weigh into the same beaker
22、 B g of white oil.7.6 Mix the sample and white oil thoroughly by stirring andwarming to approximately 50C.8. Procedure8.1 For additive concentrates, weigh into a crucible1gofthe homogenized blend prepared in 7.6.8.2 For lubricating oils, weigh into a crucible3gofsampleor smaller amount estimated to
23、contain not more than3gofphosphorus. The amount of sample to be taken is indicated inTable 1.8.3 Cover the sample with8gofzinc oxide and level thesurface. Apply heat from a Meker burner to the surface untilthe zinc oxide becomes red hot; then gently heat the cruciblefrom below with a small bunsen fl
24、ame so that the oil burns offvery gently. Finally, when no more vapor is evolved, ignitestrongly and transfer to a muffle furnace at 700C to burn offresidual carbon.8.4 Allow the crucible to cool and carefully transfer itscontents to a 600-mL beaker (Note 3), completing the transferwith a jet of wat
25、er from a wash bottle. Add about 50 mL ofwater to the contents of the beaker and rinse the crucible witha few millilitres of concentrated HCl. Add the acid rinsing tothe beaker and then sufficient concentrated HCl to bring thetotal volume of acid added to 23 mL.8.5 Heat the contents of the beaker un
26、til all the ZnO isdissolved, then boil until all hydrogen sulfide has been expelledfrom the solution (test with lead acetate paper). Allow to coolslightly, add 30 to 50 mg of KBrO3, and boil until all freebromine has been expelled from the solution (test with fluo-rescein paper).NOTE 3Glass apparatu
27、s should have good resistance to alkali. Do notuse scratched or etched beakers for the precipitation of quinolinephosphomolybdate.8.6 Dilute the liquid to a volume of about 150 mL withwater, add 30 mL of concentrated HCl and 30 mL of sodiummolybdate solution, rinsing the sides of the beaker with a l
28、ittlewater after each addition. Place the beaker on the hot plate andbring the liquid to the boil. Add a few drops of quinolinehydrochloride reagent from a coarse-tipped buret or pipet,swirling during the addition.4Reagent Chemicals, American Chemical Society Specifications, AmericanChemical Society
29、, Washington, DC. For suggestions on the testing of reagents notlisted by the American Chemical Society, see Analar Standards for LaboratoryChemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeiaand National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,MD.TAB
30、LE 1 Amount of SamplePhosphorus Content,mass %Approximate Massof Sample, gApproximate Volumeof 0.1 M NaOHsolution requiredP%m mL0.005 to 0.10 3 0.0050.0100.050.101.32.51325Above 0.10 to 0.30 0.100.200.3081725D4047 00 (2011)28.7 Bring to the boil again and add 2 mL of the reagentdropwise with swirlin
31、g. To the gently boiling liquid add thereagent in 2-mL increments until a total of 24 mL has beenadded, swirling during the addition. Stand the beaker on theedge of the hot plate or on a boiling water bath for 15 min forthe precipitate to settle. Cool to room temperature.8.8 Prepare a paper pulp pad
32、 (Note 4) in a funnel fitted witha porcelain filter disk and tamp down well. Decant the clearsupernatant liquid through the filter with applied suction andwash the precipitate twice by decantation with 20-mL portionsof 1 M HCl. Transfer the precipitate to the filter pad with coldwater and wash the b
33、eaker several times with volumes of 25 to30 mL of water to free the beaker from acid. Use these washesalso to wash the precipitate on the filter, allowing each portionof liquid to pass through before pouring on the next. Continueto wash until one portion of wash liquid fails to decolorize thesolutio
34、n when passed into a clean flask containing a few dropsof phenolphthalein solution and 1 drop of 0.1 N NaOHsolution. Six washes are usually sufficient.NOTE 4This can be made conveniently by placing an intact 20-mmdiameter accelerator disk in the funnel, moistening, and applying gentlesuction.8.9 Tra
35、nsfer the precipitate, pad, and disk to the 500-mLconical flask. This can be done conveniently with a glass rodhaving a drawn-out pointed end. Insert the funnel in the flaskand wash into it any portions of the precipitate remaining in thefunnel, using CO2-free water. Remove any traces of precipitate
36、adhering to the funnel by wiping with a slip of moistfilter-paper; add this to the contents of the flask. Add CO2-freewater until the volume of liquid in the flask is about 120 mL.8.10 Shake the flask until the pulp pad is disintegrated andthe precipitate is thoroughly dispersed. Ensure that no lump
37、sremain otherwise difficulty may be encountered in dissolvingthem in the NaOH solution.8.11 From a buret slowly add 0.1 M NaOH solution shakingthe flask vigorously to ensure complete solution of the precipi-tate. Continue to add 0.1 M NaOH solution until the precipitatehas dissolved and add approxim
38、ately 5 mL in excess. UseTable 1 to estimate the volume of alkali required. Record thevolume of 0.1 M NaOH solution added (V1). Add about sixdrops of mixed indicator and titrate with 0.1 M HCl until thecolor changes from violet through gray and suddenly to paleyellow. Record the volume of 0.1 M HCl
39、used (V2).8.12 Make a blank determination omitting the sample. Inthe final titration add 5.0 mL of 0.1 M NaOH solution andtitrate with 0.1 M HCl (V3).9. Calculation9.1 Blended SamplesCalculate the phosphorus content ofblended samples as follows:Phosphorus, mass % (3)5V12 V2! 2 5 2 V3!# 3 0.01191 3 A
40、 1 B!W 3 Awhere:A = mass of original sample in 10 g blend, gB = mass of white oil in 10-g blend, g,W = mass of blend taken for determination, g,V1= volume of 0.1 M NaOH solution added, mL,V2= back titration with 0.1 M HCl, mL,V3= back titration, for blank, with 0.1 M HCl, mL.9.2 Unblended SamplesCal
41、culate the phosphorus contentof unblended samples from the following equation:Phosphorus, mass % 5 (4)V12 V2! 2 5 2 V3!# 3 0.01191Wwhere:W = weight of sample taken, g,V1= volume of 0.1 M NaOH solution added, mL,V2= back titration with 0.1 M HCl, mL, andV3= back titration, for blank, with 0.1 M HCl,
42、mL.10. Report10.1 Report result to three significant figures as the Phos-phorus Content, Test Method D4047 and IP 148.11. Quality Control11.1 Confirm the performance of the test procedure byanalyzing a quality control sample which is stable and repre-sentative of the sample of interest.11.1.1 When t
43、he quality control/quality assurance protocolsare already established in the testing facility, these may be usedto confirm the reliability of the test result.11.1.2 When there is no quality control/quality assuranceprotocol established in the testing facility, Appendix X1 can beused to perform this
44、function.12. Precision and Bias12.1 The precision of this method as obtained by statisticalexamination of interlaboratory results5is as follows:12.1.1 RepeatabilityThe difference between successivetest results obtained by the same operator with the sameapparatus under constant operating conditions o
45、n identical testmaterial would, in the long run, in the normal and correctoperation of the test method, exceed the following values inonly one case in twenty, where x = average of the two testresults.Level of result (x) 0.005 0.079% 0.08 10%Repeatability 0.032 (x + 0.04) 0.0318x0.99212.1.2 Reproduci
46、bilityThe 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 following values in only one case intwenty, where x =
47、average of the two test results.Level of result (x) 0.005 0.079% 0.08 10%Reproducibility 0.074 (x + 0.04) 0.118x0.99212.2 Precision is given in Table 2 for typical values of x.These precision values have been obtained by statisticalexamination of interlaboratory results and are published for thefirs
48、t time in 1979.5A research report is not available.D4047 00 (2011)312.3 BiasThe bias of this test method cannot be deter-mined since an appropriate standard reference material con-taining a known level of phosphorus in liquid petroleumhydrocarbon is not available.13. Keywords13.1 additives; lubricat
49、ing oils; phosphomolybdate; phos-phorousAPPENDIX(Nonmandatory Information)X1. QUALITY CONTROLX1.1 Confirm the performance of the instrument or the testprocedure by analyzing a quality control (QC) sample.X1.2 Prior to monitoring the measurement process, the userof the method needs to determine the average value and controllimits of the QC sample (see Practice D6299 and ASTM MNL7).6X1.3 Record the QC results and analyze by control chartsor other statistically equivalent techniques to ascertain thestatistical control status of the total testing
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