DIN EN 16136-2015 Automotive fuels - Determination of manganese and iron content in unleaded petrol - Inductively coupled plasma optical emission spectrometry (ICP OES) method Germ.pdf

1、April 2015 Translation by DIN-Sprachendienst.English price group 10No part of this translation may be reproduced without prior permission ofDIN Deutsches Institut fr Normung e. V., Berlin. Beuth Verlag GmbH, 10772 Berlin, Germany,has the exclusive right of sale for German Standards (DIN-Normen).ICS

2、75.160.20!%B3V“2311651www.din.deDDIN EN 16136Automotive fuels Determination of manganese and iron content in unleaded petrol Inductively coupled plasma optical emission spectrometry (ICP OES)method;English version EN 16136:2015,English translation of DIN EN 16136:2015-04Kraftstoffe fr Kraftfahrzeuge

3、 Bestimmung des Gehaltes an Mangan und Eisen in unverbleitem Ottokraftstoff Optische Emissionsspektrometrie mit induktiv gekoppeltem Plasma (ICP OES);Englische Fassung EN 16136:2015,Englische bersetzung von DIN EN 16136:2015-04Carburants pour automobiles Dtermination des teneurs en fer et en mangans

4、e dans les essences sans plomb Mthode spectromtrique optique par plasma couplage inductif (ICP OES);Version anglaise EN 16136:2015,Traduction anglaise de DIN EN 16136:2015-04SupersedesDIN EN 16136:2012-02www.beuth.deIn case of doubt, the German-language original shall be considered authoritative.Doc

5、ument comprises 15 pages 03.15 DIN EN 16136:2015-04 2 A comma is used as the decimal marker. National foreword This document (EN 16136:2015) has been prepared by Technical Committee CEN/TC 19 “Gaseous and liquid fuels, lubricants and related products of petroleum, synthetic and biological origin” (S

6、ecretariat: NEN, Netherlands). The responsible German body involved in its preparation was the DIN-Normenausschuss Materialprfung (DIN Standards Committee Materials Testing), Working Committee NA 062-06-11 AA Atomspektrometrie of the Fachausschuss Minerall- und Brennstoffnormung. Amendments This sta

7、ndard differs from DIN EN 16136:2012-02 as follows: a) the manganese content has been lowered to about 0,5 mg/l to 7,5 mg/l; b) the determination of iron content, which can be added to petrol as ferrocene has been included. Previous editions DIN EN 16136: 2012-02 EUROPEAN STANDARD NORME EUROPENNE EU

8、ROPISCHE NORM EN 16136 February 2015 ICS 71.080.60; 75.160.20 Supersedes EN 16136:2011English Version Automotive fuels - Determination of manganese and iron content in unleaded petrol - Inductively coupled plasma optical emission spectrometry (ICP OES) method Carburants pour automobiles - Dterminati

9、on des teneurs en fer et en manganse dans les essences sans plomb - Mthode spectromtrique optique par plasma couplage inductif (ICP OES) Kraftstoffe fr Kraftfahrzeuge - Bestimmung des Gehaltes an Mangan und Eisen in unverbleitem Ottokraftstoff - Optische Emissionsspektrometrie mit induktiv gekoppelt

10、em Plasma (ICP OES) This European Standard was approved by CEN on 12 December 2014. CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this European Standard the status of a national standard without any alteration. Up-to-date lists an

11、d bibliographical references concerning such national standards may be obtained on application to the CEN-CENELEC Management Centre or to any CEN member. This European Standard exists in three official versions (English, French, German). A version in any other language made by translation under the

12、responsibility of a CEN member into its own language and notified to the CEN-CENELEC Management Centre has the same status as the official versions. CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugosla

13、v Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE

14、 NORMALISATION EUROPISCHES KOMITEE FR NORMUNG CEN-CENELEC Management Centre: Avenue Marnix 17, B-1000 Brussels 2015 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 16136:2015 EEN 16136:2015 (E) 2 Contents Page Foreword 3 1 Scope 4

15、2 Normative references 4 3 Principle 4 4 Reagents .4 5 Apparatus .5 6 Sampling .6 7 Preparation of solutions .6 7.1 General 6 7.2 Preparation of the internal standard solution .7 7.3 Preparation of the manganese intermediate solution7 7.4 Preparation of the iron intermediate solution .7 7.5 Preparat

16、ion of the calibration solutions 7 7.6 Preparation of quality control solution7 8 Calibration 8 8.1 General 8 8.2 Calibration of the ICP OES spectrometer 8 8.3 Procedure A 8 8.4 Procedure B 9 8.5 Check of calibration 9 9 Sample analysis 10 9.1 Sample solution preparation . 10 9.2 Sample solution mea

17、surement 10 10 Calculation . 10 11 Expression of results . 11 12 Precision 11 12.1 General . 11 12.2 Repeatability, r 11 12.3 Reproducibility, R . 11 13 Test report . 11 Bibliography . 13 DIN EN 16136:2015-04 EN16136:2015(E)3 Foreword This document (EN 16136:2015) has been prepared by Technical Comm

18、ittee CEN/TC 19 “Gaseous and liquid fuels, lubricants and related products of petroleum, synthetic and biological origin”, the secretariat of which is held by NEN. This European Standard shall be given the status of a national standard, either by publication of an identical text or by endorsement, a

19、t the latest by August 2015, and conflicting national standards shall be withdrawn at the latest by August 2015. Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights. CEN and/or CENELEC shall not be held responsible for identifying any

20、or all such patent rights. This document supersedes EN 16136:2011. The major updates are the lowering of the manganese content to allow a specification setting of 2 mg/l of manganese in line with the FQD requirement per 2014-01-01, and the introduction in the scope of determination of iron content,

21、which can be added into petrol as ferrocene. This document answers requirements originating from the amended Fuels Quality Directive (FQD, 2). According to the CEN-CENELEC Internal Regulations, the national standards organizations of the following countries are bound to implement this European Stand

22、ard: Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spa

23、in, Sweden, Switzerland, Turkey and the United Kingdom. DINEN 16136:2015-04EN 16136:2015 (E) 4 1 Scope This European Standard specifies a method based on inductively coupled plasma optical emission spectrometry (ICP OES) for the determination of manganese content from about 0,5 mg/l to about 7,5 mg/

24、l and of iron content from about 1,4 mg/l to about 6,0 mg/l in unleaded petrol containing up to 3,7 % (m/m) oxygen. WARNING The use of this European Standard may involve hazardous materials, operations and equipment. This European Standard does not purport to address all of the safety problems assoc

25、iated with its use. It is the responsibility of the user of this European Standard to establish appropriate safety and health practices and to determine the applicability of regulatory limitations prior to use. NOTE 1 Manganese as MMT and iron as ferrocene are added to petrol to increase anti-knock

26、properties. NOTE 2 Solutions of MMT in petrol are unstable when exposed to light. Low and erratic results are expected if petrol samples are exposed to light prior the analysis. Iron and manganese contents higher than 6,0 mg/l and 7,5 mg/l respectively may be measured after preliminary dilution of t

27、he sample with a suitable solvent. However, the precision has not been established for such a procedure. Further work regarding automotive ethanol (E85) fuel is on-going in CEN. NOTE 3 For the purposes of this European Standard, the terms “% (m/m)” and “% (V/V)” are used to represent the mass fracti

28、on () and the volume fraction () of a material respectively. 2 Normative references The following documents, in whole or in part, are normatively referenced in this document and are indispensable for its application. For dated references, only the edition cited applies. For undated references, the l

29、atest edition of the referenced document (including any amendments) applies. EN ISO 1042, Laboratory glassware One-mark volumetric flasks (ISO 1042) EN ISO 3170, Petroleum liquids Manual sampling (ISO 3170) EN ISO 3171, Petroleum liquids Automatic pipeline sampling (ISO 3171) EN ISO 3675, Crude petr

30、oleum and liquid petroleum products Laboratory determination of density Hydrometer method (ISO 3675) EN ISO 12185, Crude petroleum and petroleum products Determination of density Oscillating U-tube method (ISO 12185) 3 Principle A petrol sample is diluted with a hydrocarbon solvent. The solution is

31、introduced directly into the plasma of an ICP OES spectrometer. Iron and manganese contents are calculated by comparison with calibration solutions prepared from suitable iron and manganese compounds. An internal standard is employed to correct viscosity and vapour pressure effects. 4 Reagents Unles

32、s specified otherwise, only chemicals which are known to have a high degree of purity shall be used. Some ready-made commercial multi-element Standard solutions may be used instead of the single element Standard solution (4.4 and 4.5). DIN EN 16136:2015-04 EN 16136:2015 (E) 5 IMPORTANT In the case o

33、f using several mono-element Standard solutions, attention shall be paid to ensure that they are free of other analyte elements. 4.1 Kerosene, boiling range between 150 C and 250 C, analytical reagent grade. Other grades of kerosene with analyte concentrations below the detection limit of the instru

34、ment for the elements under investigation may be used. In this case, perform a wavelength scan for analyte elements to check spectral interferences. 4.2 Heptane, analytical reagent grade. 4.3 Solvent, add 25 ml heptane (4.2) to a 500 ml HDPE bottle (5.1.2) and fill to 500 ml with kerosene (4.1). 4.4

35、 Manganese Standard solution, commercially available in oil, c(Mn) = 100 mg/kg. 4.5 Iron Standard solution, commercially available in oil, c(Fe) = 100 mg/kg. Some commercial element Standard solutions are furnished with higher content on the market. Those solutions may be used instead of the require

36、d solutions, but an initial mass to mass dilution has to be done according to recommendations given in 7.4. 4.6 Element Standard solution, of one of the elements cobalt, scandium, yttrium, etc. commercially available in oil (analyte free), for example with 1 000 mg/kg per element, available as singl

37、e element standards. NOTE The internal Standard solutions are commonly available as single element standards with various element contents. 4.7 Argon, with a purity of 99,995 % (V/V). Small amounts of oxygen (purity 99,995 % (V/V) may be added, for instance in accordance with the operating instructi

38、ons of the equipment manufacturer, to the argon gas stream using a metering valve (30 ml/min to 100 ml/min) to prevent carbon deposits in the area of the plasma torch. 5 Apparatus 5.1 Laboratory equipment: All glassware shall be cleaned carefully before use. 5.1.1 Glassware, usual laboratory glasswa

39、re, together with the following: 5.1.1.1 Beakers, 50 ml. 5.1.1.2 Volumetric flasks, 20 ml, 50 ml and 500 ml according to EN ISO 1042, with taper sleeve and plug. 5.1.2 Bottles, 50 ml and 500 ml, with screw caps, high-density polyethylene (HDPE). 5.1.3 Graduated pipettes or variable volume automatic

40、pipettes, fitted with disposable polypropylene tips capable to measure up to the nearest 0,01 ml. CAUTION Attention shall be paid with air displacement pipettes in the presence of volatile solvents or petrol samples. 5.2 Analytical balance, capable of weighing to the nearest 0,1 mg. DINEN 16136:2015

41、-04EN 16136:2015 (E) 6 5.3 ICP OES spectrometer: ICP OES spectrometer equipped for the analysis of organic liquids, with a high-frequency generator and a nebulizer suitable for organic solvents. The use of a feed pump for sample introduction into the nebulizer is required. Both setup and operation o

42、f the ICP OES spectrometer shall be done in accordance with operating instructions of the manufacturer. A cooled spray chamber may be used, provided that the temperature is controlled 1 C. Table 1 gives the recommended wavelengths. As the magnitude of the background signal highly depends on spectral

43、 structures caused by the samples nature, only net intensities are to be recorded. Table 1 Recommended wavelengths Element Wavelength nm Manganese 257,610 259,372 260,569 279,482 279,827 293,931 Iron 234,350 238,204 240,488 259,940 261,187 Cobalt 238,892 Scandium 361,383 Yttrium 224,306 360,073 371,

44、029 6 Sampling IMPORTANT The laboratory shall receive a sample which is truly representative and was not damaged or altered during transport or storage. Unless otherwise specified in the commodity specification, samples shall be taken as described in EN ISO 3170 or EN ISO 3171 and/or in accordance w

45、ith the requirements of national regulations for the sampling of the product under test. The samples shall be stored in clean, opaque containers. 7 Preparation of solutions 7.1 General In order to avoid inhomogeneity, iron and manganese standard solutions (4.4 and 4.5) shall be shaken vigorously bef

46、ore use. It is strongly advised to use freshly prepared calibration solutions. DIN EN 16136:2015-04 EN16136:2015(E)7 7.2 Preparation of the internal standard solution Weigh 2,00 g of cobalt, scandium or yttrium stock solution (4.6) with a precision of 0,01 g in a 50 ml volumetric flask (5.1.1.2) Fil

47、l up to 50 ml with kerosene (4.1). This prepared solution shall be homogenized by vigorous shaking. The same standard batch shall be used for all samples and calibration standards. 7.3 Preparation of the manganese intermediate solution Weigh 1,50 g 0,01 g of manganese standard solution (4.4) into a

48、50 ml HDPE bottle (5.1.2). Add solvent (4.3) to 15,00 g 0,01 g. In case manganese standard solutions (4.4) with different manganese content are used, the mass of standard solution shall be adjusted accordingly to achieve 10 mg/kg manganese content. 7.4 Preparation of the iron intermediate solution Weigh 1,50 g 0,01 g of iron standard solution (4.5) into a 50 ml HDPE bottle (5.1.2). Add solvent (4.3) to 15,00 g 0,01 g. In case iron standard solutions (4.5) with different iron content are used,