DIN EN 15837-2010 Ethanol as a blending component for petrol - Determination of phosphorus copper and sulfur content - Direct method by inductively coupled plasma optical emission .pdf

1、April 2010 Translation by DIN-Sprachendienst.English price group 9No 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 7

2、5.160.20!$aZs“1625580www.din.deDDIN EN 15837Ethanol as a blending component for petrol Determination of phosphorus, copper and sulfur content Direct method by inductively coupled plasma optical emissionspectrometry (ICP OES)English translation of DIN EN 15837:2010-04Ethanol zur Verwendung als Blendk

3、omponente in Ottokraftstoff Bestimmung des Gehalts an Phosphor, Kupfer und Schwefel Direktes Verfahren durch optische Emissionsspektrometrie mit induktiv gekoppeltemPlasma (ICP OES)Englische bersetzung von DIN EN 15837:2010-04Ethanol comme base de mlange lessence Dtermination de la teneur en phospho

4、re, en cuivre et en soufre Mthode directe par spectromtrie dmission atomique par plasma couplage inductif(ICP OES)Traduction anglaise de DIN EN 15837:2010-04www.beuth.deIn case of doubt, the German-language original shall be considered authoritative.Document comprises 13 pages04.10 DIN EN 15837:2010

5、-04 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, lubricants and related products of petroleum, synthetic and biological origin” (Secretariat: NEN, Netherlands). The responsible German body invol

6、ved in its preparation was the Normenausschuss Materialprfung (Materials Testing Standards Committee), Working Committee NA 062-06-81 AA Spiegelausschuss zu CEN/TC 19 Gasfrmige und flssige Kraft- und Brennstoffe, Schmierstoffe und verwandte Produkte mit minerallstmmiger, synthetischer oder biologisc

7、her Herkunft of the Fachausschuss Minerall- und Brennstoffnormung (FAM). The DIN Standard corresponding to the International Standard referred to in this document is as follows: EN ISO 3696 DIN ISO 3696 National Annex NA (informative) Bibliography DIN ISO 3696, Water for analytical laboratory use Sp

8、ecification and test methods EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 15837 December 2009 ICS 75.160.20 English Version Ethanol as a blending component for petrol - Determination of phosphorus, copper and sulfur content - Direct method by inductively coupled plasma optical emission spect

9、rometry (ICP OES) Ethanol comme base de mlange lessence - Dtermination de la teneur en phosphore, en cuivre et en soufre - Mthode directe par spectromtrie dmission atomique par plasma couplage inductif (ICP OES) Ethanol zur Verwendung als Blendkomponente in Ottokraftstoff - Bestimmung des Gehalts an

10、 Phosphor, Kupfer und Schwefel - Direktes Verfahren durch optische Emissionsspektrometrie mit induktiv gekoppeltem Plasma (ICP OES) This European Standard was approved by CEN on 7 November 2009. CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions

11、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 Management Centre or to any CEN member. This European Standard exists in three offi

12、cial 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 Management Centre has the same status as the official versions. CEN members are the national standards bodies of Austria

13、, Belgium, Bulgaria, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom. EUROPEAN COMMITT

14、EE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG Management Centre: Avenue Marnix 17, B-1000 Brussels 2009 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 15837:2009: EEN 15837:2009 (E) 2 Content

15、s Page Foreword 31 Scope 42 Normative references 43 Principle 44 Reagents .45 Apparatus .56 Sampling .67 Preparation of calibration solutions 68 Calibration 68.1 Preparation of the instrumentation 68.2 Execution of the calibration 68.3 Check of calibration 79 Sample analysis .710 Calculation 811 Exp

16、ression of results 812 Precision .812.1 General 812.2 Repeatability, r .812.3 Reproducibility, R 913 Test report 9Annex A (normative) Ethanol density 10Bibliography . 11DIN EN 15837:2010-04 EN 15837:2009 (E) 3 Foreword This document (EN 15837:2009) has been prepared by Technical Committee CEN/TC 19

17、“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, at the latest by

18、June 2010 and conflicting national standards shall be withdrawn at the latest by June 2010. 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 or all such patent ri

19、ghts. According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, I

20、taly, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom. DIN EN 15837:2010-04 EN 15837:2009 (E) 4 1 Scope This European Standard specifies an inductively coupled plasma optical emission spectrometry

21、 (ICP OES) method for the direct determination of elements content in ethanol, namely phosphorus in the range (0,13 to 1,90) mg/kg, copper in the range (0,050 to 0,300) mg/kg, and sulfur in the range (2,0 to 15,0) mg/kg. WARNING The use of this method may involve hazardous equipment, materials and o

22、perations. This method does not purport to address to all of the safety problems associated with its use, but it is the responsibility of the user to search and establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. NOTE For the purp

23、oses of this document, the terms “% (m/m)” and “% (V/V)“ are used to represent respectively the mass fraction (w) and volume fraction (). 2 Normative references The following referenced documents are indispensable for the application of this document. For dated references, only the edition cited app

24、lies. For undated references, the latest edition of the referenced document (including any amendments) applies. EN ISO 3170, Petroleum liquids Manual sampling (ISO 3170:2004) EN ISO 3675, Crude petroleum and liquid petroleum products Laboratory determination of density Hydrometer method (ISO 3675:19

25、98) EN ISO 3696, Water for analytical laboratory use Specification and test methods (ISO 3696:1987) EN ISO 12185, Crude petroleum and petroleum products Determination of density Oscillating U-tube method (ISO 12185:1996) 3 Principle A portion of a sample is directly injected into the spray-chamber o

26、f an inductively coupled plasma emission spectrometer. The element content is determined by comparing the emission of the element in the test portion with the emission of the calibration solutions at the same wavelength. The calibration solutions are prepared from suitable compounds dissolved in eth

27、anol. 4 Reagents Use only reagents of recognized analytical grade, unless otherwise specified. 4.1 Phosphorus standard solution, ready-made commercially available phosphorus aqueous standard solution, 1 000 mg/l. 4.2 Copper standard solution, ready-made commercially available copper aqueous standard

28、 solution, 1 000 mg/l. 4.3 Sulfur standard solution, which shall be either 4.3.1 or 4.3.2. 4.3.1 Sulfur standard solution, ready-made commercially available sulfur aqueous standard solution, 1 000 mg/l, or DIN EN 15837:2010-04 EN 15837:2009 (E) 5 4.3.2 Tetrabutylammonium hydrogen -sulfate (CH3CH2CH2

29、CH2)4N(HSO4), (MW 339,53 g/mol). If tetrabutylammonium hydrogen sulfate is used, weigh 264,5 mg in a 25 ml volumetric flask (5.3). Bring to the mark with ethanol (4.5) and homogenise. The actual concentration of sulfur shall be calculated, as 1 000 mg/l only represents a target concentration. NOTE I

30、f a ready-made sulfur aqueous standard solution is employed, the solubility in ethanol of the sulfur compound should be checked. For instance, ammonium sulphate, used in most commercially available solutions, is insoluble in ethanol. 4.4 Water, for analytical laboratory use, conforming to grade 3 of

31、 EN ISO 3696. 4.5 Ethanol, 99 % minimum purity. 4.6 Argon, regulated compressed gas of 99,996 % minimum purity for the ICP spectrometer. 5 Apparatus 5.1 Inductively coupled plasma optical emission spectrometer, capable of monitoring one of the following wavelengths of each element, according to Tabl

32、e 1. NOTE 1 Wavelengths are expressed as vacuum lines or as air lines (in brackets) according to the expression of the different manufacturers of ICP spectrometers. NOTE 2 The copper line at 213,598 nm can interfere with the phosphorus line at 213,618 nm, but the low concentration range of copper do

33、es not show appreciable interference in phosphorus measurements. A cooled spray-chamber set at 2 C may be used, provided that the temperature is controlled ( 1 C), if the plasma is not stable with ethanol. Table 1 ICP-OES wavelength capability Element Wavelength nm Phosphorus 177,499 (177,434) (213,

34、618) 178,287 (178,222) Copper 324,754 327,395 Sulfur 180,731(180,669) 182,034 (181,972) 182,624 (182,562) 5.2 Balance, capable of weighing to the nearest 0,1 mg. 5.3 Glassware, 25 ml, 50 ml and 100 ml volumetric flasks. In order to avoid contamination due to phosphates contained in the detergents us

35、ed for glassware cleaning, wash the flasks at least twice with an approximate 5 mol/l solution of nitric acid. Rinse with water (4.4) and dry. 5.4 Graduated pipettes or variable volume automatic pipettes, fitted with disposable polypropylene tips. 5.5 Ultrasonic bath, able to contain 100 ml flasks.

36、DIN EN 15837:2010-04 EN 15837:2009 (E) 6 6 Sampling Unless otherwise specified, obtain samples in accordance with the procedures given in EN ISO 3170 and/or in accordance with the requirements of national standards or regulations for the sampling of the product under test. High density polyethylene

37、containers (HDPE) shall be used. The containers shall be carefully cleaned and rinsed with water (4.4) to avoid contamination, and then dried. Thoroughly mix the samples in their containers immediately prior to withdrawal of the test portions. 7 Preparation of calibration solutions Dilute the standa

38、rd solution (4.1 to 4.3) with ethanol (4.5) in five 100 ml volumetric flasks to obtain calibration solutions having the element concentrations as specified in Table 2. Table 2 Concentrations for calibration solutions Solution Phosphorus mg/l Copper mg/l Sulfur mg/l 1 (blank) 0 0 0 2 0,1 0,05 1,0 3 0

39、,5 0,10 5,04 1,0 0,20 10,0 5 1,5 0,40 20,0The solutions shall be freshly prepared for each series of analyses. 8 Calibration 8.1 Preparation of the instrumentation Since instrumentations stemming from diverse manufacturers have different configurations and settings, it is difficult to specify an exa

40、ct procedure. Follow the manufacturers instructions for setting up the instrument with organic solutions. The choice of the instrumental parameters shall be determined so as to obtain the best signal/background ratio for all elements. The analytical lines recommended in Table 1 shall be used. A back

41、ground correction shall be performed using wavelengths close to each analytical line, but not affected by other lines. It is important to ensure that analytical lines and background wavelengths used in calibration also match exactly the ones used in the check of calibration (8.3) and samples analysi

42、s (9). 8.2 Execution of the calibration Conduct the aspiration of the calibration solutions 1 to 5 (see Table 2). Read out the intensity of the analytical lines and the corresponding background wavelengths chosen for copper, phosphorus and sulfur of each solution. DIN EN 15837:2010-04 EN 15837:2009

43、(E) 7 Calculate the net intensities of the analytical lines by subtracting the intensities of the corresponding background wavelengths. Some instruments are equipped with software which allows the automatic correction for the background. Carry out three measurements (x) for each solution. Calculate

44、the arithmetical mean of the three measurements, x . Calculate the relative standard deviation (RSD) in percent of each mean according to: ()xnxxRSD1)(1002=(1) where n is the number of measurements (i.e. n = 3). The RSD of calibration solutions 2 to 5 (Table 2) for all elements shall be lower than 5

45、 %. If this is not the case, refer to manufacturers instructions for better instrumental parameters. Construct the calibration curve of each element from these means using linear regression, by plotting the emission intensity values versus the concentrations of the element. The regression coefficien

46、t of the linear regression shall be at least 0,995. If not, the procedure should be corrected in case of errors and, if necessary, the calibration procedure should be repeated from Clause 7 onward. 8.3 Check of calibration A Quality Control (QC) sample shall be freshly prepared for each series of an

47、alyses. The concentration of the QC sample is set in accordance with the specification level to be checked. The QC sample shall be prepared from certified reference materials or other sources of certified stock solutions in order to verify sensitivity and accuracy of the calibration curve. The QC sa

48、mple concentration shall be measured after the calibration has been established. If the QC check differs from the reference values for copper, phosphorus or sulfur by more than R/1,41 (reproducibility divided by 1,41), verify that the concentration is correct by preparing a new QC sample. If the new

49、 QC sample differs from the given values, a new calibration shall be established. The values obtained with the QC sample shall be measured with a RSD (8.2) lower than 5 %. 9 Sample analysis Shake vigorously the sample container and homogenise using the ultrasonic bath (5.5) for 1 minute prior to withdrawal of the test portions. Conduct the aspiration of the sample solution. Carry out three measurements in the same way as for the calib