1、ICS 75.160.20Prfung von Ottokraftstoffen Bestimmung des Phosphor-gehaltes Teil 1: Wellenlngendispersive Rntgenfluoreszenz-Analyse (RFA)In keeping with current practice in standards published by the International Organization for Standardization(ISO), a comma has been used throughout as the decimal m
2、arker.Ref. No. DIN 51440-1 : 2003-02English price group 06 Sales No. 010604.04DEUTSCHE NORM February 2003 No part of this translation may be reproduced without the prior permission ofDIN Deutsches Institut fr Normung e.V., Berlin. Beuth Verlag GmbH, 10772 Berlin, Germany,has the exclusive right of s
3、ale for German Standards (DIN-Normen).Translation by DIN-Sprachendienst.In case of doubt, the German-language original should be consulted as the authoritative text.Determining the phosphorus content of petrolsby wavelength-dispersive X-ray fluorescencespectrometryContinued on pages 2 to 4.Supersede
4、s DIN 51440-1,October 1988 edition.51440-1ForewordThis standard has been prepared by Technical Committee Rntgenfluoreszenz-Analyse of the Fachaus-schuss Minerall- und Brennstoffnormung of the Normenausschuss Materialprfung (Materials TestingStandards Committee).AmendmentsThis standard differs from t
5、he October 1988 edition as follows:a) the scope has been extended to include petrols as in DIN EN 228;b) the apparatus clause has been brought into line with current technology;c) the standard has been editorially revised and references have been updated.Previous editionDIN 51440-1: 1988-10.1 ScopeT
6、his standard specifies a method of determining the phosphorus content of petrols as in DIN EN 228, inconcentrations from 10 mg/l to 100 mg/l.2 Normative referencesThis standard incorporates, by dated or undated reference, provisions from other publications. Thesenormative references are cited at the
7、 appropriate places in the text, and the titles of the publications arelisted below. For dated references, subsequent amendments to or revisions of any of these publicationsapply to this standard only when incorporated in it by amendment or revision. For undated references, thelatest edition of the
8、publication referred to applies.DIN 12691 Class AS fast delivery one-mark bulb pipettes, with a waiting time of 15 seconds, for labo-ratory useDIN 51418-1 X-ray emission and X-ray fluorescence analysis General concepts and basic principlesDIN 51418-2 X-ray emission and X-ray fluorescence analysis Te
9、rminology and principles of measure-ment, calibration and evaluationPage 2DIN 51440-1 : 2003-02DIN 51632-1 Regular white spirits Requirements and testingDIN 51632-2 Low-aromatics white spirit Requirements and testingDIN 51750-1 Sampling of petroleum products GeneralDIN 51750-2 Sampling of liquid pet
10、roleum productsDIN EN 228 Automotive fuels Unleaded petrols Requirements and test methodsDIN EN ISO 4259 Petroleum products Determination and application of precision data in relation to meth-ods of test (ISO 4259 : 1992 + Corr 1 : 1993)3 PrincipleA mixture of ten parts by volume of the sample to be
11、 analysed and one part by volume of zirconium referencesolution is exposed in a sample vessel to the primary radiation of an X-ray tube. The count rates of thephosphorus Kaand zirconium La1X-ray fluorescence radiation thus emitted and those of the backgroundradiation are measured, and used to calcul
12、ate the net count rate ratio. The phosphorus content of the sampleis determined from calibration graphs prepared on the basis of phosphorus reference solutions.The method is generally applicable to sample material of any composition, irrespective of the type of phospho-rus compounds detected and of
13、any other elements they contain.4 ApparatusIn addition to standard laboratory equipment, the following shall be used.4.1 Wavelength-dispersive X-ray spectrometer (cf. DIN 51418 series), capable of measuring the countrates of the phosphorus Kaand zirconium La1 X-ray fluorescence radiations and having
14、 the following param-eters.a) X-ray tube, meeting the following requirements:Anode: chromium, rhodium, or scandium.Voltage: at least 50 kV.Current: at least 50 mA.b) Collimator aperture: wide.c) Analyser crystal: germanium1).d) X-ray path: helium.e) Detector: flow-proportional counter, with pulse he
15、ight analyser.Other spectrometers may be used and the above parameters may be modified provided that regular compara-tive measurements demonstrate that the precision specified in this standard is achieved and interferences due,for example, to sulfur or calcium are taken into account.4.2 Polypropylen
16、e film, 6,3 mm thick, phosphorus-free, used for lining the sample beaker.4.3 Balance, with 0,1 mg scale intervals.4.4 One-mark bulb pipettes, of capacities 2 ml and 20 ml (e.g. DIN 12691 VPAS 2 and DIN 12691 VPAS 20 pipettes).4.5 Conical flask, of capacity 50 ml, with conical socket.5 ReagentsThe fo
17、llowing reagents shall be used.5.1 White spirit, as in DIN 51632-1 or DIN 51632-2.5.2 Tri-n-butyl phosphate, C12H27O4P, or any other oil-soluble phosphorus compound of known phospho-rus content.5.3 Zirconium solution, containing zirconium octoate or any other oil-soluble zirconium compound.5.4 2-eth
18、ylhexanoic acid, phosphorus-free, for stabilizing the zirconium solution, if necessary.1) Using a germanium crystal completely suppresses the (often troublesome) second-order Ca-Kbradiation.Page 3DIN 51440-1 : 2003-025.5 100 mg/l phosphorus stock solution, prepared by dissolving the requisite amount
19、 of tri-n-butyl phos-phate or any other oil-soluble phosphorus compound in white spirit.5.6 10 g/l zirconium octoate solution, prepared by dissolving the requisite amount of zirconium octoate inwhite spirit.6 SamplingAs in DIN 51750-1 and DIN 51750-2.7 Plotting the phosphorus calibration graph7.1 Ze
20、ro member compensation solutionUse white spirit as specified in clause 5 as zero member compensation solution.7.2 Checking the polypropylene filmRecord the X-ray spectrum with the zero member compensation solution using the polypropylene film in the0,603 nm to 0,625 nm spectral range. If any phospho
21、rus peak that is visible exceeds the noise by a factor oftwo or more, discard the film. Repeat this check every time the batch of film is replaced.7.3 Reference solutionsDilute the phosphorus stock solution with white spirit to obtain solutions with phosphorus contents of100 mg/l, 50 mg/l, 30 mg/l,
22、20 mg/l, 10 mg/l and 5 mg/l.7.4 Calibration solutionsAdd one part by volume (e.g. 2 ml) of zirconium solution to ten parts by volume (e.g. 20 ml) of each phosphorusreference solution and mix thoroughly in 50 ml conical flasks sealed with a ground glass stopper to preventevaporation losses.7.5 Measur
23、ement of count ratesTransfer the calibration solutions to sample vessels having loosely fitting lids and expose them consecutivelyto the primary radiation of the X-ray tube. Measure the count rates of the P-Kafluorescence radiation at0,615 5 nm, IP, the Zr-La1fluorescence radiation at 0,607 nm, IZr,
24、 and the background radiation at 0,622 nm,IU. Adjust the equipment so that the Zr-La1line count is at least 40 000 throughout the period of measurement.Calculate the net count rate ratio, R0, for every calibration solution, using the following equation:IP IUR0=IZr IU7.6 Calibration graphsPlot the co
25、unt rate ratio of the individual calibration solutions as a function of the phosphorus concentration.Check the calibration graphs obtained at least every six months.NOTE: Many modern spectrometers are equipped with a computer that stores calibration graphs and outputsthe required contents directly.8
26、 Procedure8.1 Add one part by volume (e.g. 2 ml) of zirconium solution to ten parts by volume (e.g. 20 ml) of the samplematerial to be analysed, mix thoroughly and determine the net count rate ratio for each mixture, R0, as specifiedin subclause 7.5.8.2 Determine the phosphorus concentration of the
27、sample, b(P), in mg/l, as a function of R0, determined asin subclause 7.5, from the calibrationgraph.9 Expression of resultRefer to this standard and report the phosphorus concentration in mg/l, to the nearest 1 mg/l.Page 4DIN 51440-1 : 2003-0210 Precision(cf. DIN EN ISO 4259)The specifications belo
28、w apply only to petrols containing 10 mg/l to 100 mg/l of phosphorus.Repeatability limit(same operator, same equipment)If two results are obtained under repeatability conditions, both results shall be considered acceptable and inconformity with this standard if they differ by no more than 3 mg/l.Rep
29、roducibility limit(different operators, different equipment)If two laboratories each obtain a result under reproducibility conditions, both results shall be considered asacceptable and in conformity with this standard if they differ by no more than 5 mg/l.Other relevant standardsDIN 12700-3 Burettes
30、 fitted with offset burette stopcock with tail, for laboratory useDIN 51363-2 Determining the phosphorus content of lubricating oils and additives by X-ray fluorescenceanalysisDIN 51769-6 Determination of total lead content of petrol with a lead content exceeding 25 mg/l by wave-length-dispersive X-ray spectrometry (XRS)DIN 51769-11 Determination of total lead content of petrol with a lead content of 4 mg/l to 25 mg/l by wave-length-dispersive X-ray spectrometry (XRS)
