1、Designation: D4047 00 (Reapproved 2011)D4047 13Designation: 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 of
2、original 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 o
3、f Defense.1. Scope Scope*1.1 This test method covers the determination of 0.005 to 10.0 mass % phosphorus in unused lubricating oil and additiveconcentrates. There is no reason to doubt its applicability to filtered, used lubricating oils, but no systematic study of thisapplication has been made.1.2
4、 The test method is applicable to samples containing any of the phosphorus compounds in normal use.NOTE 1This test method extends the scope of the previous version of IP 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
5、 because the high insolubility of the quinoline phosphomolybdate precipitateleads to constant composition and freedom from most adsorbed or occluded impurities, especially from cations which wouldotherwise interfere in the subsequent titration of the precipitate.1.4 Barium, calcium, magnesium, zinc,
6、 iron, aluminum, alkali salts, citric acid and citrates, chromium up to 18 times thephosphorus content, and titanium up to 3.5 times do not interfere with the test method.1.5 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.1.6
7、 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibilityof the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatorylimitations prior to use. For specific hazard
8、 statements, see 6.9.2. Referenced Documents2.1 ASTM Standards:2D1193 Specification for Reagent WaterD6299 Practice for Applying Statistical Quality Assurance and Control Charting Techniques to Evaluate Analytical Measure-ment System Performance2.2 IP Standard:IP 148 Test Method for Phosphorous in L
9、ubricating Oils and Additives33. Summary of Test Method3.1 Additive concentrates are diluted with phosphorus-free white oil to produce a working blend.3.2 The sample is ignited with excess of zinc oxide whereby phosphorus is converted to phosphate. The residue is dissolvedin hydrochloric acid and an
10、y sulfide formed is oxidized with potassium bromate. Phosphorus is then precipitated as quinolinephosphomolybdate and determined volumetrically by addition of excess standard alkali and back titration with standard acid.1 This test method is under the jurisdiction of ASTM Committee D02 on Petroleum
11、Products and Lubricants and is the direct responsibility of Subcommittee D02.03 onElemental Analysis.Current edition approved May 1, 2011June 15, 2013. Published May 2011August 2013. Originally approved in 1981. Last previous edition approved in 20052011 asD4047 00 (2005).(2011). DOI: 10.1520/D4047-
12、00R11.10.1520/D4047-13.2 For referencedASTM standards, visit theASTM website, www.astm.org, or contactASTM Customer Service at serviceastm.org. For Annual Book of ASTM Standardsvolume information, refer to the standards Document Summary page on the ASTM website.3 Available from Energy Institute, 61
13、New Cavendish St., London, WIG 7AR, U.K., http:/www.energyinst.org.uk.This document is not an ASTM standard and is intended only to provide the user of an ASTM standard an indication of what changes have been made to the previous version. Becauseit may not be technically possible to adequately depic
14、t all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current versionof the standard as published by ASTM is to be considered the official document.*A Summary of Changes section appears at the end of this standardCopyright ASTM Internationa
15、l, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States14. Significance and Use4.1 Knowledge of the phosphorus content, and thus the phosphorus-containing additives, in a lubricating oil or additive can beused to predict performance characteristics.5. Apparatus5.1 Sili
16、ca Crucibles, 40-mm internal diameter at the top and 40 mm in height. The internal surface should be smooth and freefrom pitting.5.2 Muffle Furnace, capable of maintaining a temperature of approximately 700C, and fitted with ports to allow air circulation.5.3 Beakers, 25-mL capacity.5.4 Filtering Ap
17、paratus, a filter flask of capacity 500 mL, provided with a glass crucible adapter fitted in a rubber bung togetherwith 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 approximately20 mm diameter.5.6 Filter Pad, appr
18、oximately 20 mm diameter.6. Reagents and Materials6.1 Purity of ReagentsReagent grade chemicals shall be used in all tests. Unless otherwise indicated, it is intended that allreagents shall conform to the specifications of the Committee on Analytical Reagents of the American Chemical Society, wheres
19、uch specifications are available.4 Other grades may be used, provided it is first ascertained that the reagent is of sufficiently highpurity to permit its use without lessening the accuracy of the determination.6.2 Purity of WaterUnless otherwise indicated, references to water shall be understood to
20、 mean reagent water as defined byType II or Type III of Specification D1193.6.3 Hydrochloric Acid, approximately 1 N reagent solution.6.4 Hydrochloric Acid (36 mass %)Concentrated hydrochloric acid (HCl).6.5 Hydrochloride Acid, (0.1N)Hydrochloric acid (HCl) accurately standardized.6.6 Mixed Indicato
21、rMix 2 volumes of phenolphthalein solution with 3 volumes of thymol blue solution.6.7 Phenolphthalein Solution, (1 g/L in 95 % volume ethanol).6.8 Potassium Bromate (KBrO3), solid.6.9 Quinoline (WarningQuinoline has a high toxic acute systemic rating.)Redistilled synthetic or, if this is unobtainabl
22、e,quinoline freshly distilled from the technical product. Collect the colorless distillate in the boiling range from 232 to 238C. Storethe quinoline in an amber bottle in the dark.6.10 Quinoline Hydrochloride SolutionDissolve 20 mL of quinoline in 800 mL of hot water acidified with 25 mL ofconcentra
23、ted HCl; add a little paper pulp, cool, filter, and make up to 1 L with water. This solution is stable for about 1 month.6.11 Sodium Hydroxide Solution (0.1 M)Sodium hydroxide (NaOH) accurately standardized.6.12 Sodium Molybdate SolutionDissolve 10 g of sodium hydroxide (NaOH) and 18 g of ammonia-fr
24、ee molybdenum trioxidein 200 mL of water and filter the solution.NOTE 2To avoid high blanks caused by silicate interference with alkaline 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
25、 divided.6.15 Lead Acetate Test Paper.6.16 Fluorescein Test PaperPrepare by dipping a strip of filter paper into a 1 g/L solution of fluorescein, sodium salt, in 95vol % ethanol.6.17 White Oil, containing less than 0.005 mass % phosphorus.4 Reagent Chemicals, American Chemical Society Specifications
26、, American Chemical Society, Washington, DC. For suggestions on the testing of reagents not listed bythe American Chemical Society, see Analar Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia and NationalFormulary, U.S. Pharmacopeial Convention, I
27、nc. (USPC), Rockville, MD.D4047 1327. Blending Procedure7.1 Samples having a phosphorus content greater than 0.3 mass % should be blended in white oil to give a phosphorus contentin the range of 0.1 to 0.3 mass %.7.2 Calculate the mass of sample for a 10-g blend as follows:A 52/P (1)where:P = approx
28、imate 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 as follows:B 5102A (2)where:B = mass of white oil, g.7.4 Weigh a quantity of sample A6 0.01 g into a 25-mL beaker.7.5 Weigh into the same beaker B g of white
29、oil.7.6 Mix the sample and white oil thoroughly by stirring and warming to approximately 50C.8. Procedure8.1 For additive concentrates, weigh into a crucible 1 g of the homogenized blend prepared in 7.6.8.2 For lubricating oils, weigh into a crucible 3 g of sample or smaller amount estimated to cont
30、ain not more than 3 g ofphosphorus. The amount of sample to be taken is indicated in Table 1.8.3 Cover the sample with 8 g of zinc oxide and level the surface. Apply heat from a Meker burner to the surface until the zincoxide becomes red hot; then gently heat the crucible from below with a small bun
31、sen flame so that the oil burns off very gently.Finally, when no more vapor is evolved, ignite strongly and transfer to a muffle furnace at 700C to burn off residual carbon.8.4 Allow the crucible to cool and carefully transfer its contents to a 600-mL beaker (Note 3), completing the transfer with aj
32、et of water from a wash bottle.Add about 50 mLof water to the contents of the beaker and rinse the crucible with a few millilitresof concentrated HCl.Add the acid rinsing to the beaker and then sufficient concentrated HCl to bring the total volume of acid addedto 23 mL.8.5 Heat the contents of the b
33、eaker until all the ZnO is dissolved, then boil until all hydrogen sulfide has been expelled fromthe solution (test with lead acetate paper). Allow to cool slightly, add 30 to 50 mg of KBrO3, and boil until all free bromine hasbeen expelled from the solution (test with fluorescein paper).NOTE 3Glass
34、 apparatus should have good resistance to alkali. Do not use scratched or etched beakers for the precipitation of quinolinephosphomolybdate.8.6 Dilute the liquid to a volume of about 150 mL with water, add 30 mL of concentrated HCl and 30 mL of sodium molybdatesolution, rinsing the sides of the beak
35、er with a little water after each addition. Place the beaker on the hot plate and bring the liquidto the boil. Add a few drops of quinoline hydrochloride reagent from a coarse-tipped buret or pipet, swirling during the addition.8.7 Bring to the boil again and add 2 mL of the reagent dropwise with sw
36、irling. To the gently boiling liquid add the reagentin 2-mL increments until a total of 24 mL has been added, swirling during the addition. Stand the beaker on the edge of the hotplate or on a boiling water bath for 15 min for the precipitate to settle. Cool to room temperature.8.8 Prepare a paper p
37、ulp pad (Note 4) in a funnel fitted with a porcelain filter disk and tamp down well. Decant the clearsupernatant liquid through the filter with applied suction and wash the precipitate twice by decantation with 20-mL portions of 1TABLE 1 Amount of SamplePhosphorus Content,mass %Approximate Massof Sa
38、mple, gApproximate Volumeof 0.1 M NaOHsolution 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 133M HCl. Transfer the precipitate to the filter pad with cold water and wash the beaker several times with volumes of 25 to 30 mLof water to free t
39、he beaker from acid. Use these washes also to wash the precipitate on the filter, allowing each portion of liquidto pass through before pouring on the next. Continue to wash until one portion of wash liquid fails to decolorize the solution whenpassed into a clean flask containing a few drops of phen
40、olphthalein solution and 1 drop of 0.1 N NaOH solution. Six washes areusually sufficient.NOTE 4This can be made conveniently by placing an intact 20-mm diameter accelerator disk in the funnel, moistening, and applying gentle suction.8.9 Transfer the precipitate, pad, and disk to the 500-mL conical f
41、lask. This can be done conveniently with a glass rod havinga drawn-out pointed end. Insert the funnel in the flask and wash into it any portions of the precipitate remaining in the funnel, usingCO2-free water. Remove any traces of precipitate adhering to the funnel by wiping with a slip of moist fil
42、ter-paper; add this to thecontents of the flask. Add CO2-free water until the volume of liquid in the flask is about 120 mL.8.10 Shake the flask until the pulp pad is disintegrated and the precipitate is thoroughly dispersed. Ensure that no lumps remainotherwise difficulty may be encountered in diss
43、olving them in the NaOH solution.8.11 From a buret slowly add 0.1 M NaOH solution shaking the flask vigorously to ensure complete solution of the precipitate.Continue to add 0.1 M NaOH solution until the precipitate has dissolved and add approximately 5 mL in excess. Use Table 1 toestimate the volum
44、e of alkali required. Record the volume of 0.1 M NaOH solution added (V1). Add about six drops of mixedindicator and titrate with 0.1 M HCl until the color changes from violet through gray and suddenly to pale yellow. Record thevolume of 0.1 M HCl used (V2).8.12 Make a blank determination omitting t
45、he sample. In the final titration add 5.0 mL of 0.1 M NaOH solution and titrate with0.1 M HCl (V3).9. Calculation9.1 Blended SamplesCalculate the phosphorus content of blended samples as follows:Phosphorus,mass % (3)5V12V 2!252V3!#30.011913A1B!W 3Awhere:A = mass of original sample in 10 g blend, gB
46、= 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,V 2 = back titration with 0.1 M HCl, mL,V3 = back titration, for blank, with 0.1 M HCl, mL.9.2 Unblended SamplesCalculate the phosphorus content of unblended samples from th
47、e following equation:Phosphorus,mass %5 (4)V12V2!252V 3!#30.01191Wwhere: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, mL.10. Report10.1 Report result to three significant figures a
48、s the Phosphorus Content, Test Method D4047 and IP 148.11. Quality Control11.1 Confirm the performance of the test procedure by analyzing a quality control sample which is stable and representative ofthe sample of interest.11.1.1 When the quality control/quality assurance protocols are already estab
49、lished in the testing facility, these may be used toconfirm the reliability of the test result.11.1.2 When there is no quality control/quality assurance protocol established in the testing facility, Appendix X1 can be usedto perform this function.D4047 13412. Precision and Bias12.1 The precision of this method as obtained by statistical examination of interlaboratory results5 is as follows:12.1.1 RepeatabilityThe difference between successive test results obtained by the same operator with the same apparatusunder constant operating conditions on id
