1、February 2012 Translation by DIN-Sprachendienst.English price group 8No 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).IC
2、S 75.160.20!$yx“1868594www.din.deDDIN EN 16135Automotive fuels Determination of manganese content in unleaded petrol Flame atomic absorption spectrometric method (FAAS)English translation of DIN EN 16135:2012-02Kraftstoffe fr Kraftfahrzeuge Bestimmung des Mangangehalts in unverbleitem Ottokraftstoff
3、 Flammenatomabsorptionsspektrometrisches Verfahren (FAAS)Englische bersetzung von DIN EN 16135:2012-02Carburants pour automobiles Dtermination de la teneur en manganse dans les essences sans plomb Mthode par spectromtrie dabsorption atomique de flamme (FAAS)Traduction anglaise de DIN EN 16135:2012-0
4、2www.beuth.deIn case of doubt, the German-language original shall be considered authoritative.Document comprises 12 pages02.12 DIN EN 16135:2012-02 2 A comma is used as the decimal marker. National foreword This standard has been prepared by Technical Committee CEN/TC 19 “Gaseous and liquid fuels, l
5、ubricants and related products of petroleum, synthetic and biological origin” (Secretariat: NEN, Netherlands). The responsible German body involved in its preparation was the Normenausschuss Materialprfung (Materials Testing Standards Committee), Working Committee NA 062-06-11 AA Atomspektrometrie o
6、f the Fachausschuss Minerall- und Brennstoffnormung. The DIN Standards corresponding to the International Standards referred to in this document are as follows: EN ISO 648 DIN EN ISO 648, DIN 12687 and DIN 12690 EN ISO 1042 DIN EN ISO 1042 EN ISO 3170 DIN EN ISO 3170 EN ISO 3171 DIN EN ISO 3171 EN I
7、SO 3675 DIN EN ISO 3675 EN ISO 4259 DIN EN ISO 4259 EN ISO 12185 DIN EN ISO 12185 National Annex NA (informative) Bibliography DIN 12687, Laboratory glassware One-mark pipettes, adjusted to contain DIN 12690, Laboratory glassware One-mark pipettes, class A and class B DIN EN ISO 648, Laboratory glas
8、sware Single-volume pipettes DIN EN ISO 1042, Laboratory glassware One-mark volumetric flasks DIN EN ISO 3170, Petroleum liquids Manual sampling DIN EN ISO 3171, Petroleum liquids Automatic pipeline sampling DIN EN ISO 3675, Crude petroleum and liquid petroleum products Laboratory determination of d
9、ensity Hydrometer method DIN EN ISO 4259, Petroleum products Determination and application of precision data in relation to methods of test DIN EN ISO 12185, Crude petroleum and petroleum products Determination of density Oscillating U-tube method EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN
10、 16135 December 2011 ICS 75.160.20 English Version Automotive fuels - Determination of manganese content in unleaded petrol - Flame atomic absorption spectrometric method (FAAS) Carburants pour automobiles - Dtermination de la teneur en manganse dans les essences sans plomb - Mthode par spectromtrie
11、 dabsorption atomique de flamme (FAAS)Kraftstoffe fr Kraftfahrzeuge - Bestimmung des Mangangehalts in unverbleitem Ottokraftstoff - Flammenatomabsorptionsspektrometrisches Verfahren (FAAS) This European Standard was approved by CEN on 29 October 2011. CEN members are bound to comply with the CEN/CEN
12、ELEC Internal Regulations which stipulate the conditions for giving this European Standard the status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such national standards may be obtained on application to the CEN-CENELEC Management Centre
13、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 responsibility of a CEN member into its own language and notified to the CEN-CENELEC Management Centre has the same status as the of
14、ficial versions. CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, S
15、lovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom. Management Centre: Avenue Marnix 17, B-1000 Brussels 2011 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 16135:2011: EEUROPEAN COMMITTEE FOR STANDARDIZATIONCOMIT EU
16、ROPEN DE NORMALISATIONEUROPISCHES KOMITEE FR NORMUNGEN 16135:2011 (E) 2 Contents Page Foreword 31 Scope 42 Normative references 43 Principle 44 Reagents .55 Apparatus .56 Sampling .67 Preparation of solutions .67.1 General 67.2 Preparation of the calibration and quality control solution 68 Calibrati
17、on 78.1 Preparation of instrument .78.2 Preparation of the calibration .78.3 Check of the calibration 79 Sample analysis .89.1 Sample solution preparation 89.2 Sample solution measurement .810 Calculation 811 Expression of results 912 Precision .912.1 General 912.2 Repeatability, r .912.3 Reproducib
18、ility, R 913 Test report 9Bibliography . 10DIN EN 16135:2012-02 EN 16135:2011 (E) 3 Foreword This document (EN 16135:2011) has been prepared by Technical Committee CEN/TC 19 “Gaseous and liquid fuels, lubricants and related products of petroleum, synthetic and biological origin”, the secretariat of
19、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, at the latest by June 2012, and conflicting national standards shall be withdrawn at the latest by June 2012. Attention is drawn to the possibi
20、lity 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 or all such patent rights. This document answers requirements originating from the amended Fuels Quality Directive 2. According to the CEN/CENELEC
21、 Internal Regulations, the national standards organizations of the following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania,
22、Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and the United Kingdom. DIN EN 16135:2012-02 EN 16135:2011 (E) 4 1 Scope This European Standard specifies a method based on flame atomic absorption spectrometry (FAAS) for the determinat
23、ion of manganese content present as methylcyclopentadienyl manganese tricarbonyl (MMT 1) in unleaded petrol from about 2 mg/l to about 8 mg/l. This test method is applicable to unleaded petrol containing up to 3,7 % (m/m) oxygen, including those with ethanol up to 10 % (V/V). NOTE 1 Manganese as MMT
24、 is added to petrol to increase antiknock properties. 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 associated with its use. It is the responsibility of the user of th
25、is European Standard to establish appropriate safety and health practices and to determine the applicability of regulatory limitations prior to use. NOTE 2 Solutions of MMT in unleaded petrol are unstable when exposed to light. Low and erratic results are expected if samples are exposed to light pri
26、or the analysis. NOTE 3 Manganese contents higher than 8 mg/l can be measured after preliminary dilution of the sample with a suitable solvent. However, the precision has not been established for such procedure. NOTE 4 Application to the determination of other manganese compounds in unleaded petrol
27、has not been tested. NOTE 5 For the purposes of this European Standard, the terms “% (m/m)” and “% (V/V)” are used to represent the mass fraction () and the volume fraction () of a material respectively. 2 Normative references The following referenced documents are indispensable for the application
28、of this document. For dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (including any amendments) applies. EN ISO 648, Laboratory glassware Single-volume pipettes (ISO 648:2008) EN ISO 1042, Laboratory glassware One-mark volumetr
29、ic flasks (ISO 1042:1998) EN ISO 3170, Petroleum liquids Manual sampling (ISO 3170:2004) EN ISO 3171, Petroleum liquids Automatic pipeline sampling (ISO 3171:1988) EN ISO 3675, Crude petroleum and liquid petroleum products Laboratory determination of density Hydrometer method (ISO 3675:1998) EN ISO
30、12185, Crude petroleum and petroleum products Determination of density Oscillating U-tube method (ISO 12185:1996) 3 Principle A portion of petrol sample is diluted with a hydrocarbon solvent. The solution is then aspirated into the air/acetylene flame of an atomic absorption spectrometer. The absorb
31、ance is measured at 279,5 nm. Manganese content is calculated by comparison with calibration solutions prepared from suitable manganese compounds. 1) MMT is a registered trademark of Ethyl Corporation. DIN EN 16135:2012-02 EN 16135:2011 (E) 5 4 Reagents Unless specified otherwise, only chemicals whi
32、ch are known to have a high degree of purity shall be used. 4.1 Kerosene, boiling range between 150 C and 250 C, analytical reagent grade. NOTE Other grades of kerosene with analyte concentration below the detection limit of the instrument and screened by performing a wavelength scan for analyte ele
33、ments may be used. 4.2 2,2,4-trimethylpentane (iso-octane), analytical reagent grade. 4.3 Xylene (mixture of isomers), analytical reagent grade. 4.4 Solvent, add 25 ml iso-octane (4.2) and 25 ml xylene (4.3) to a 50 ml glass bottle (5.1.3) and mix thoroughly. 4.5 Manganese standard solution, dissolv
34、ed in oil, c(Mn) = 1 000 mg/kg. NOTE 1 A multi-element standard solution may also be used instead of the single element standard solution. NOTE 2 Some element standard solutions are supplied with different element content on the market. These solutions may be used instead of the required solutions,
35、but an initial mass to mass dilution has to be done. 4.6 Manganese intermediate solution, c(Mn) = 20 mg/kg. Weigh 0,50 g 0,01 g of manganese standard solution (4.5) into a 50 ml bottle (5.1.3). Add kerosene (4.1) to 25,00 g 0,01 g. Each mass shall be weighed to the nearest 0,1 mg. In case manganese
36、standard solutions (4.5) with different manganese content are used, the mass of standard solution shall be adjusted accordingly to achieve 20 mg/kg manganese content. 4.7 Air, oil free, under pressure in a steel cylinder, or compressed air. 4.8 Acetylene, 99,0 % min., under pressure in a steel cylin
37、der. 5 Apparatus 5.1 Laboratory equipment 5.1.1 General All glassware shall be cleaned carefully before use. 5.1.2 Glassware, usual laboratory glassware, together with the following: 5.1.2.1 Beakers, 50 ml. 5.1.2.2 Volumetric flasks, 20 ml, according to EN ISO 1042, with taper sleeve and plug. 5.1.3
38、 Bottles, 50 ml, with screw caps, high-density polyethylene (HDPE). 5.1.4 Two-mark pipette, capacity 5 ml, conforming to class A of EN ISO 648, with suction ball, or alternatively graduated pipettes or variable volume automatic pipettes, fitted with disposable polypropylene tips. CAUTION Attention s
39、hall be paid during the use of pipettes in the presence of volatile solvents or petrol samples. DIN EN 16135:2012-02 EN 16135:2011 (E) 6 5.2 Analytical balance, capable of weighing to the nearest 0,1 mg. 5.3 Flame atomic absorption spectrometer, equipped with manganese hollow cathode lamp or lamp em
40、itting specific radiation of manganese, fitted with a burner head for acetylene and air flame, and suitable for use with organic solutions. 6 Sampling IMPORTANT The laboratory shall receive a sample which is truly representative and was not damaged or altered during transport or storage. Unless othe
41、rwise specified in the commodity specification, samples shall be taken as described in EN ISO 3170 or EN ISO 3171 and/or in accordance with the requirements of national regulations for the sampling of the product under test. The samples shall be filled into clean containers. 7 Preparation of solutio
42、ns 7.1 General In order to avoid inhomogeneity, all calibration solutions shall be shaken vigorously before use. It is strongly advised to use freshly prepared calibration solutions. 7.2 Preparation of the calibration and quality control solution The calibration solutions and the Quality Control (QC
43、) solution shall be prepared as indicated in Table 1. The mass of the manganese intermediate solution (4.6) shall be weighed to the nearest 0,1 mg in a 20 ml volumetric flask (5.1.2.2). For each calibration solution, add 5,0 ml of the solvent (4.4) and fill with kerosene (4.1) to the mark. Calibrati
44、on solutions shall be homogenized by shaking. Table 1 Concentration of manganese in calibration and quality control solutions Calibration solutions Manganese intermediate solutiong Manganese concentration mg/l blank 0,0 0,001 0,2 0,2 2 0,5 0,53 1,0 1,0 4 1,5 1,55 2,0 2,0 QC 1,0 1,0DIN EN 16135:2012-
45、02 EN 16135:2011 (E) 7 8 Calibration 8.1 Preparation of instrument 8.1.1 Switch on the atomic absorption spectrometer (5.3) following the manufacturer instruction. Allow the spectrometer and the lamp to obtain stability and adjust the instrumental conditions for manganese analysis. Set the wavelengt
46、h at 279,5 nm as described by the manufacturer. 8.1.2 Install the burner-head for acetylene-air and ignite the flame. 8.1.3 Adjust the flow rates of air (4.7) and acetylene (4.8) to obtain an oxidising flame, which should be fuel lean and light blue in colour. Aspirate the kerosene (4.1) and adjust
47、the flow rate of kerosene to keep the flame lean and blue. NOTE A reduced flow rate of kerosene (4.1) is employed to avoid the formation of carbon residues that can affect the stability of the flame. 8.2 Preparation of the calibration 8.2.1 Set the absorbance to zero while aspirating the kerosene (4
48、.1). 8.2.2 Aspirate calibration solution 3 and adjust the burner position to get the maximum absorbance. 8.2.3 Set the absorbance to zero while aspirating the blank (7.2). Aspirate calibration solutions 1 to 5 (7.2) to check for linearity. 8.2.4 Aspirate calibration solutions 1 to 5 (7.2) and record the absorbance values. For each calibration solution perform three absorbance measurements with an integration time from 3 s to 5 s and ca
