1、November 2007DEUTSCHE NORM English price group 9No part of this standard 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 75.160.20!$J3*“1391607
2、www.din.deDDIN EN 15484Ethanol as a blending component for petrol Determination of inorganic chloride Potentiometric methodEnglish version of DIN EN 15484:2007-11Ethanol zur Verwendung als Blendkomponente in Ottokraftstoff Bestimmung des Gehalts an anorganischen Chloriden aus dem Eindampfrckstand Po
3、tentiometrisches VerfahrenEnglische Fassung DIN EN 15484:2007-11www.beuth.deDocument comprises 14 pagesDIN EN 15484:2007-11 2 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 biol
4、ogical origin” (Secretariat: NEN, Netherlands). The responsible German body involved in its preparation was the Normenausschuss Materialprfung (Materials Testing Standards Committee), Technical Committee NA 062-06-81 AA Gasfrmige und flssige Kraft- und Brennstoffe, Schmierstoffe und verwandte Produk
5、te mit minerallstmmiger, synthetischer oder biologischer Herkunft of the Fachausschuss Minerall- und Brennstoffnormung (FAM). EUROPEAN STANDARDNORME EUROPENNEEUROPISCHE NORMEN 15484August 2007ICS 71.080.60English VersionEthanol as a blending component for petrol - Determination ofinorganic chloride
6、- Potentiometric methodchlorure minral - Mthode potentiomtriqueEthanol zur Verwendung als Blendkomponente inOttokraftstoff - Bestimmung des Gehalts an anorganischenChloriden aus dem Eindampfrckstand -Potentiometrisches VerfahrenThis European Standard was approved by CEN on 30 June 2007.CEN members a
7、re bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this EuropeanStandard the status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such nationalstandards may be obtained on application to t
8、he CEN 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 translationunder the responsibility of a CEN member into its own language and notified to the CEN Management Centre has the same s
9、tatus as theofficial versions.CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Cyprus, Czech Republic, Denmark, Estonia, Finland,France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal,Romania,
10、 Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom.EUROPEAN COMMITTEE FOR STANDARDIZATIONCOMIT EUROPEN DE NORMALISATIONEUROPISCHES KOMITEE FR NORMUNGManagement Centre: rue de Stassart, 36 B-1050 Brussels 2007 CEN All rights of exploitation in any form and by any means reservedworldwi
11、de for CEN national Members.Ref. No. EN 15484:2007: Ethanol comme base de mlange lessence - Dosage duEN 15484:2007 (E) 2 Contents Page Foreword3 1 Scope 4 2 Normative references 4 3 Principle4 4 Reagents and materials 4 5 Apparatus .5 6 Samples and sampling5 7 Calibration 6 7.1 Preparation of the bl
12、ank test solution .6 7.2 Preparation of a 5,00 ml standard solution.6 7.3 Titration.6 7.4 Standardisation of 10,00 ml potassium chloride solution.7 7.5 Calculation of concentration of silver nitrate solution 7 7.6 Calculation of value of blank test.7 8 Sample analysis.7 8.1 Preparation of the dry re
13、sidue7 8.2 Preparation of the sample solution7 8.3 Titration.8 9 Calculation8 10 Expression of results 8 11 Precision.8 11.1 Repeatability, r .8 11.2 Reproducibility, R 8 12 Test report 9 Annex A (informative) Measurement example .10 Annex B (informative) Interferences11 B.1 Introduction11 B.2 Other
14、 halogens.11 B.3 Oxidizing agents 11 B.4 Ammonium and iron (III) salts 11 B.5 Cyanides, thiocyanates and sulphides .11 Bibliography 12 EN 15484:2007 (E) 3 Foreword This document (EN 15484:2007) has been prepared by Technical Committee CEN/TC 19 “Gaseous and liquid fuels, lubricants and related produ
15、ts 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 February 2008, and conflicting national standards shall
16、be withdrawn at the latest by February 2008. The method described in this document is based on ISO 6227 1 and a method from a European Regulation on wine 2. According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following countries are bound to implement this
17、European Standard: Austria, 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
18、 Kingdom. EN 15484:2007 (E) 4 1 Scope This standard specifies a potentiometric method for the determination of inorganic chloride content in ethanol from 4 mg/l to 30 mg/l. The chloride content is determined in aqueous solution after dissolution of the evaporation residue of the ethanol sample. WARN
19、ING Use of this standard may involve hazardous materials, operations and equipment. This standard does not purport to address all of the safety problems associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and to determin
20、e the applicability of regulatory limitations prior to use. NOTE For the purposes of this document, the terms “% (m/m)” and “% (V/V)” are used to represent respectively the mass fraction and the volume fraction. 2 Normative references The following referenced documents are indispensable for the appl
21、ication 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 3170, Petroleum liquids Manual sampling (ISO 3170:2004) EN ISO 3696, Water for analytical laboratory use Sp
22、ecification and test methods (ISO 3696:1987) 3 Principle A weighed test portion of ethanol sample is evaporated on a water bath. The dry residue is dissolved in deionised water. Inorganic chloride content is determined by potentiometric titration either manually or using automated equipment. 4 Reage
23、nts and materials All reagents shall be of analytical reagent grade or of higher purity. 4.1 Acetone. 4.2 Nitric acid, approximately 1,40 g/ml, about 68 % (m/m) solution. 4.3 Potassium nitrate, solution saturated at room temperature. 4.4 Silver nitrate solution 1, c (AgNO3) = 0,1 mol/l approximately
24、. Dissolve 8,5 g of silver nitrate in a 500 ml one-mark volumetric flask, dilute to the mark and mix. Store in a dark glass bottle. 4.5 Silver nitrate solution 2, c (AgNO3) = 0,004 mol/l approximately. Prepare the solution at the time of use from silver nitrate solution 1 (4.4), diluting when requir
25、ed in a one-mark volumetric flask. 4.6 Potassium chloride standard reference solution 1, c (KCl) = 0,100 mol/l. Weigh 3,727 6 g of potassium chloride to the nearest 0,000 1 g. Potassium chloride was previously dried for 1 h at about 130 C and cooled in a dessicator. Dissolve in a little water and tr
26、ansfer the solution quantitatively into a 500 ml one-mark volumetric flask. Dilute to the mark and mix. This solution shall not be kept for more than one month. EN 15484:2007 (E) 5 4.7 Potassium chloride standard reference solution 2, c (KCl) = 0,004 mol/l. Prepare the solution at the time of use fr
27、om the standard reference potassium chloride solution 1 (4.6), diluting when required in a one-mark volumetric flask. 4.8 Water, for analytical laboratory use, conforming to grade 3 of EN ISO 3696. 5 Apparatus 5.1 Evaporating dish, capacity 100 ml to 250 ml. 5.2 Water bath 5.3 Drying oven, thermosta
28、tically controlled at (105 2) C. 5.4 Dessicator, containing freshly activated silica gel (or equivalent desiccant) with moisture a content indicator. 5.5 Analytical balance, capable of weighing to the nearest 0,1 mg. 5.6 Pipette, volumetric, class A, capable of delivering 25 ml. 5.7 Potentiometric t
29、itration apparatus, comprising: 5.7.1 Potentiometer, sensitivity at least 2 mV, covering the range 500 mV to +500 mV. 5.7.2 Reference electrodes. 5.7.2.1 Calomel electrode, fitted with a reservoir filled with saturated potassium chloride solution, or 5.7.2.2 Double junction silver/silver chloride el
30、ectrode. The outer electrolyte must be saturated potassium nitrate solution (4.3), the inner electrolyte may be potassium chloride 3 mol/l or saturated potassium nitrate (4.3). 5.7.3 Bridge, containing saturated potassium nitrate solution (4.3), to be connected to the calomel electrode (5.7.2.1) and
31、 fitted with porous diaphragms at the ends. 5.7.4 Measuring electrodes, being either 5.7.4.1 Silver electrode, or 5.7.4.2 Chloride or silver ion-selective electrode. 5.8 One-mark flasks, 25 ml volume. 5.9 Magnetic stirrer, with a polytetrafluorethylene (PFTE)-coated rod. 5.10 Burettes, with fine poi
32、nt tip, graduated in 0,02 ml or 0,01 ml divisions. 6 Samples and sampling Unless otherwise specified, laboratory samples shall be obtained by the procedures described in EN ISO 3170. High density polyethylene containers shall be used. The containers should be carefully cleaned and rinsed with pure w
33、ater before use to avoid contamination. Samples should be analysed as soon as possible after removal from bulk supplies, to prevent loss of chloride. EN 15484:2007 (E) 6 Thoroughly mix samples in their containers immediately prior to drawing test portions. 7 Calibration 7.1 Preparation of the blank
34、test solution At the same time as the determination, carry out a blank test, using 25 ml of water (4.8). 7.2 Preparation of a 5,00 ml standard solution 7.2.1 Place the blank test solution in a beaker of suitable capacity. Add, using one of the burettes (5.10), 5,00 ml of the potassium chloride solut
35、ion (4.7). 7.2.2 Add a quantity of the acetone (4.1) to obtain a ratio of acetone to aqueous solution preferably equal to 80/10 (V/V) but, in any case, not lower than 50/50 (V/V). 7.3 Titration Introduce into the beaker a magnetic stirrer rod (5.9), place the beaker on the stirrer and set it in moti
36、on. Introduce in the solution the measuring electrode (5.7.4) and the reference electrode (5.7.2). If, however, a calomel electrode (5.7.2.1) is used, introduce one end of the bridge (5.7.3) instead of the reference electrode and immerse the other end in a beaker of water containing the calomel elec
37、trode. Connect the electrodes to the potentiometer (5.7.1) and record the initial value of the potential, after having checked the zero setting of the instruments. Execute the titration by adding silver nitrate solution (4.5) in successive increments of 0,1 ml each. After each addition, wait for the
38、 potential to reach the steady value. In the first two columns of a table, note the successive volumes added and the corresponding potentials. In a third column, note the successive increments (1E) of the potential E. In a fourth column, note the differences (2E), positive or negative, between the s
39、uccessive increments (1E) of the potential E. The end of the titration corresponds to the addition of the 0,1 ml (V1) of the silver nitrate solution, which gives the maximum value of 1E. The exact volume (Veq), in ml, of silver nitrate solution (4.5) corresponding to the end of the reaction is given
40、 by the equation (for better comprehension see the example in Annex A): +=BbVVV10eq(1) where V0is the volume, in ml, of the silver nitrate solution (4.5) which gives the maximum increment of 1E; V1is the volume, in millilitres, of the silver nitrate solution (4.5); b is the first negative increment
41、of 2E; B is the sum of the absolute values of the last positive increment of 2E and the first negative increment of 2E. EN 15484:2007 (E) 7 7.4 Standardisation of 10,00 ml potassium chloride solution. Repeat the operations specified in Error! Reference source not found. and 7.3, this time using 10,0
42、0 ml instead of 5,00 ml, of potassium chloride solution (4.7). 7.5 Calculation of concentration of silver nitrate solution The concentration of the silver nitrate solution, c(AgNO3), expressed as moles of AgNO3 per litre, is given by the equation: ()()()3235KClAgNOVVcc=(2) where c(KCl) is the concen
43、tration, in mol/l, of potassium chloride solution (4.7); V2is the value, in ml, of Veqcorresponding to the titration of 10 ml of potassium chloride solution (4.7), in the presence of blank test solution; V3is the value, in ml, of Veqcorresponding to the titration of 5 ml of potassium chloride soluti
44、on (4.7), in the presence of blank test solution; 5 being the difference, in ml, between the two volumes of potassium chloride solution (4.7). 7.6 Calculation of value of blank test The value of the reagent blank test, V4, is given, in ml, by the equation: 2342 VVV = (3) where V2 and V3are as define
45、d in 7.5. 8 Sample analysis IMPORTANT One should always be aware of interferences originating from specific elements in the sample. Some known interferences are indicated in Annex B. 8.1 Preparation of the dry residue Add 25 ml (VE) of test portion to the evaporating dish (5.1). Place the dish with
46、sample on the boiling water bath (5.2) and allow to dry. Place the dish in the oven (5.3) at 105 C for 30 min and then transfer the dish to a desiccator (5.4). Allow the dish to cool for 30 min. Add 10 ml of water (4.8), to the evaporating dish and heat gently until complete dissolution of the dry r
47、esidue. Transfer the solution to a 25 ml one-mark flask. Repeat the treatment with 10 ml water. Add water to the mark. 8.2 Preparation of the sample solution Transfer the sample solution (8.1) in to a suitable beaker. Further proceed as specified in Error! Reference source not found2. If the chlorid
48、e ion content is very low, proceed from 8.1 using a larger volume of test portion (VE). EN 15484:2007 (E) 8 8.3 Titration Titrate the sample solution obtained in 8.2 with silver nitrate solution (4.5), following the procedure specified in 7.3. The volume of silver nitrate solution Veq, obtained from
49、 the equation (1), is designated V5. 9 Calculation The content C, in mg/l, of inorganic chloride in the test ethanol sample, is given by the equation ()E45V000 135,45VVC=a(4) where V5is the volume, in ml, of silver nitrate solution (8.3); V4is the value, in ml, of the blank test on the reagents (7.6); a is the actual concentration, in mol/l, of the silver nitrate solution used for standardisation (7.5); VE is the volume in ml, of the test portion; 35,45 is the atomic mass of chlorine in g/mol. 10 Expression of results T
