1、Designation: D4047 18Designation: 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 adoption or, in t
2、he 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 U.S. Department of Defense.1. Scope*1.
3、1 This test method covers the determination of 0.005 % to10.0 % by mass phosphorus in unused lubricating oil andadditive concentrates. There is no reason to doubt its applica-bility to filtered, used lubricating oils, but no systematic studyof this application has been made.1.2 The test method is ap
4、plicable 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 This test method is free from most interferences becausethe high insolub
5、ility of the quinoline phosphomolybdate pre-cipitate leads to constant composition and freedom from mostadsorbed or occluded impurities, especially from cations whichwould otherwise interfere in the subsequent titration of theprecipitate.1.4 Barium, calcium, magnesium, zinc, iron, aluminum,alkali sa
6、lts, citric acid and citrates, chromium up to 18 timesthe phosphorus content, and titanium up to 3.5 times do notinterfere with the test method.1.5 The values stated in SI units are to be regarded asstandard. No other units of measurement are included in thisstandard.1.6 This standard does not purpo
7、rt 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 practices and deter-mine the applicability of regulatory limitations prior to use.For specific hazard statements,
8、 see 6.9.1.7 This international standard was developed 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 TechnicalBa
9、rriers to Trade (TBT) Committee.2. Referenced Documents2.1 ASTM Standards:2D1193 Specification for Reagent WaterD4057 Practice for Manual Sampling of Petroleum andPetroleum ProductsD4177 Practice for Automatic Sampling of Petroleum andPetroleum ProductsD6299 Practice for Applying Statistical Quality
10、 Assuranceand Control Charting Techniques to Evaluate AnalyticalMeasurement System Performance2.2 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.
11、2 The sample is ignited with excess of zinc oxide wherebyphosphorus is converted to phosphate. 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 byadditio
12、n of excess standard alkali and back titration withstandard acid.1This test method is under the jurisdiction of ASTM Committee D02 onPetroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility ofSubcommittee D02.03 on Elemental Analysis.Current edition approved April 1, 2018. P
13、ublished April 2018. Originallyapproved in 1981. Last previous edition approved in 2013 as D4047 13. DOI:10.1520/D4047-18.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume information, ref
14、er to the standards Document Summary page onthe ASTM website.3Available from Energy Institute, 61 New Cavendish St., London, W1G 7AR,U.K., http:/www.energyinst.org.*A Summary of Changes section appears at the end of this standardCopyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West
15、Conshohocken, PA 19428-2959. United StatesThis international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for theDevelopment of International Standards, Guides and Recommendations issued by the World Trad
16、e Organization Technical Barriers to Trade (TBT) Committee.14. Significance and Use4.1 Knowledge 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 intern
17、al diameter at the top and40 mm in height. The internal surface should be smooth andfree from pitting.5.2 Muffle Furnace, capable of maintaining a temperature ofapproximately 700 C, and fitted with ports to allow aircirculation.5.3 Beakers, 25 mL capacity.5.4 Filtering Apparatus, a filter flask of c
18、apacity 500 mL,provided with a glass crucible adapter fitted in a rubber bungtogether with a rubber sleeve.5.5 Gooch Crucible, porcelain, 35 mm diameter at the top,or a filter funnel fitted with a porcelain filter disk of approxi-mately 20 mm diameter.5.6 Filter Pad, approximately 20 mm diameter.6.
19、Reagents and Materials6.1 Purity of ReagentsReagent grade chemicals shall beused in all tests. Unless otherwise indicated, it is intended thatall reagents shall conform to the specifications of the Commit-tee on Analytical Reagents of the American Chemical Society,where such specifications are avail
20、able.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 indicated, referencesto water shall be understood to mean reagent water as definedby
21、 Type II or Type III of Specification D1193.6.3 Hydrochloric Acid, approximately 1 N reagent solution.6.4 Hydrochloric Acid (36 % by mass)Concentrated hy-drochloric acid (HCl).6.5 Hydrochloride Acid, (0.1 N)Hydrochloric acid (HCl)accurately standardized.6.6 Mixed IndicatorMix 2 volumes of phenolphth
22、aleinsolution with 3 volumes of thymol blue solution.6.7 Phenolphthalein Solution, (1 g L in 95 % volume etha-nol).6.8 Potassium Bromate (KBrO3), solid.6.9 Quinoline (WarningQuinoline has a high toxic acutesystemic rating.)Redistilled synthetic or, if this isunobtainable, quinoline freshly distilled
23、 from the technicalproduct. Collect the colorless distillate in the boiling rangefrom 232 C to 238 C. Store the quinoline in an amber bottlein the dark.6.10 Quinoline Hydrochloride SolutionDissolve 20 mL ofquinoline in 800 mL of hot water acidified with 25 mL ofconcentrated HCl; add a little paper p
24、ulp, 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 sodiumhydroxide (NaOH) and 18 g of ammonia-free molybdenumtrioxide in 200 m
25、L 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 % volume ethanol.6.14 Zinc Oxide (ZnO), finely divided.6.15 Lead Acetate Test
26、 Paper.6.16 Fluorescein Test PaperPrepare by dipping a strip offilter paper into a 1 g L solution of fluorescein, sodium salt, in95 % by volume ethanol.6.17 White Oil, containing less than 0.005 % by massphosphorus.7. Blending Procedure7.1 Take samples in accordance with the instructions inPractices
27、 D4057 or D4177.7.2 Samples having a phosphorus content greater than 0.3 %by mass should be blended in white oil to give a phosphoruscontent in the range of 0.1 % to 0.3 % by mass.7.3 Calculate the mass of sample for a 10 g blend asfollows:A 5 2/P (1)where:P = approximate percent phosphorus in the s
28、ample, andA = grams of sample required for a 10 g blend.7.4 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.7.5 Weigh a quantity of sample A6 0.01 g into a 25 mLbeaker.7.6 Weigh into the same beaker B g of white oil.7.7 Mix the sample and white
29、 oil thoroughly by stirring andwarming to approximately 50 C.8. Procedure8.1 For additive concentrates, weigh into a crucible 1 g ofthe homogenized blend prepared in 7.7.4Reagent Chemicals, American Chemical Society Specifications, AmericanChemical Society, Washington, DC. For suggestions on the tes
30、ting 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.D4047 1828.2 For lubricating oils, weigh into a
31、 crucible 3 g of sampleor smaller amount estimated to contain not more than 3 g ofphosphorus. The amount of sample to be taken is indicated inTable 1.8.3 Cover the sample with 8 g of zinc oxide and level thesurface. Apply heat from a Meker burner to the surface untilthe zinc oxide becomes red hot; t
32、hen gently heat the cruciblefrom below with a small bunsen flame so that the oil burns offvery gently. Finally, when no more vapor is evolved, ignitestrongly and transfer to a muffle furnace at 700 C to burn offresidual carbon.8.4 Allow the crucible to cool and carefully transfer itscontents to a 60
33、0 mL beaker (Note 3), completing the transferwith a jet of water 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
34、 of acid added to 23 mL.8.5 Heat the contents of the beaker until 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 mg to 50 mg of KBrO3, and boil until all freebromine has been expelled from
35、 the solution (test with fluo-rescein paper).NOTE 3Glass apparatus 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 s
36、odiummolybdate solution, rinsing the sides of the beaker with a littlewater 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.8.7 Bring to the boil
37、 again and add 2 mL of the reagentdropwise with swirling. 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
38、. Cool to room temperature.8.8 Prepare a paper pulp pad (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 prec
39、ipitate to the filter pad with coldwater and wash the beaker several times with volumes of25 mL to 30 mL of water to free the beaker from acid. Usethese washes also to wash the precipitate on the filter, allowingeach portion of liquid to pass through before pouring on thenext. Continue to wash until
40、 one portion of wash liquid fails todecolorize the solution when passed into a clean flask contain-ing a few drops of phenolphthalein solution and 1 drop of 0.1 NNaOH solution. Six washes are usually sufficient.NOTE 4This can be made conveniently by placing an intact 20 mmdiameter accelerator disk i
41、n the funnel, moistening, and applying gentlesuction.8.9 Transfer 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 thefu
42、nnel, using CO2-free water. Remove any traces of precipitateadhering 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 and
43、the precipitate is thoroughly dispersed. Ensure that no lumpsremain 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
44、solution until the precipitatehas dissolved and add approximately 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
45、 and suddenly to paleyellow. Record the volume of 0.1 M HCl 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 fol
46、lows:Phosphorus, mass % (3)5V12 V2!2 5 2 V3!# 30.01191 3 A1B!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
47、, for blank, with 0.1 M HCl, mL.9.2 Unblended SamplesCalculate the phosphorus contentof unblended samples from the following equation:Phosphorus, mass % 5 (4) V12 V2! 2 5 2 V3!#30.01191WTABLE 1 Amount of SamplePhosphorus Content,% by massApproximate Massof Sample, gApproximate Volumeof 0.1 M NaOHsol
48、ution requiredP%m mL0.005 to 0.103 0.005 1.30.010 2.50.05 130.10 25Above 0.10 to 0.300.10 80.20 170.30 25D4047 183where: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, mL.10. Report10.1
49、 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 the 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
