BS EN 15492:2012 BS 2000-563:2011 BSI Standards Publication Ethanol as a blending component for petrol — Determination of inorganic chloride and sulfate content — Ion chromatographic method BS EN 15492:2012 BRITISH STANDARD National foreword This British Standard is the UK implementation of EN 15492:2012 It supersedes BS EN 15492:2008, which is withdrawn The UK participation in its preparation was entrusted to Technical Committee PTI/13, Petroleum Testing and Terminology A list of organizations represented on this committee can be obtained on request to its secretary Energy Institute, under the brand of IP, publishes and sells all Parts of BS 2000, and all BS EN petroleum test methods that would be Part of BS 2000, both in its annual publication “Standard methods for analysis and testing of petroleum and related products and British Standard 2000 Parts” and individually Further information is available from: Energy Institute, 61 New Cavendish Street, London W1G 7AR Tel: 020 7467 7100 Fax: 020 7255 1472 This publication does not purport to include all the necessary provisions of a contract Users are responsible for its correct application © The British Standards Institution 2012 ISBN 978 580 70535 ICS 71.080.60; 75.160.20 Compliance with a British Standard cannot confer immunity from legal obligations This British Standard was published under the authority of the Standards Policy and Strategy Committee on 31 January 2012 Amendments issued since publication Date Text affected BS EN 15492:2012 EN 15492 EUROPEAN STANDARD NORME EUROPÉENNE EUROPÄISCHE NORM January 2012 ICS 71.080.60; 75.160.20 Supersedes EN 15492:2008 English Version Ethanol as a blending component for petrol - Determination of inorganic chloride and sulfate content - Ion chromatographic method Éthanol comme base de mélange l'essence Détermination de la teneur en chlorures minéraux et en sulfates - Méthode par chromatographie ionique Ethanol zur Verwendung als Blendkomponente in Ottokraftstoff - Bestimmung des Gehaltes an anorganischem Chlor und Sulfat - Ionenchromatographie This European Standard was approved by CEN on 26 November 2011 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 and 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 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, 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 COMITÉ EUROPÉEN DE NORMALISATION EUROPÄISCHES KOMITEE FÜR NORMUNG Management Centre: Avenue Marnix 17, B-1000 Brussels © 2012 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members Ref No EN 15492:2012: E BS EN 15492:2012 EN 15492:2012 (E) Contents Page Foreword 3 Scope 4 Normative references 4 Principle 4 Reagents 4 Apparatus .5 Sampling 6 7.1 7.2 Preparation of calibration solutions 6 Intermediate calibration solutions .6 Calibration solutions .6 8.1 8.2 Preparation of apparatus 7 Setting up the instrument .7 Calibration 7 9.1 9.2 Procedure .8 Sample preparation .8 Sample analysis .8 10 Calculations 9 11 Expression of results 9 12 12.1 12.2 12.3 Precision 9 General 9 Repeatability, r .9 Reproducibility, R 10 13 Test report 10 Bibliography 11 BS EN 15492:2012 EN 15492:2012 (E) Foreword This document (EN 15492:2012) 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 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 July 2012, and conflicting national standards shall be withdrawn at the latest by July 2012 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 rights This document supersedes EN 15492:2008 The method described in this document was originally based on a method from a European Regulation on wine [1] This method has been developed and revised in 2008 to suit the needs as expressed in the ethanol specification (EN 15376:2011 [2]), also drafted by CEN/TC 19 The precision and range of application for both inorganic chloride and sulfate have again been updated based on a second interlaboratory study done by CEN/TC 19/WG 27 on “Elemental analysis” Small parts of the procedure have been updated according to laboratory practice and a density correction has been included in order to be able to report the result of the test in mass fraction 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, Croatia, 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, Turkey and United Kingdom BS EN 15492:2012 EN 15492:2012 (E) Scope This European Standard specifies an ion chromatographic (IC) method for the determination of inorganic chloride content in ethanol from about mg/kg to about 30 mg/kg and of sulfate content in ethanol from about mg/kg to about 20 mg/kg NOTE Sulfate content can be determined from 0,5 mg/kg to 1,0 mg/kg However, the precision was not established as no samples with sulfate content in this range were included in the interlaboratory test WARNING — Use of this method may involve hazardous equipment, materials and operations 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 Normative references The following referenced documents are indispensable for the application 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 15486:2007, Ethanol as a blending component for petrol — Determination of sulfur content — Ultraviolet fluorescence method EN ISO 1042, Laboratory glassware — One-mark volumetric flasks (ISO 1042) EN ISO 3170, Petroleum liquids — Manual sampling (ISO 3170) EN ISO 3675, Crude petroleum and liquid petroleum products — Laboratory determination of density — Hydrometer method (ISO 3675) EN ISO 3696, Water for analytical laboratory use — Specification and test methods (ISO 3696) EN ISO 12185, Crude petroleum and petroleum products — Determination of density — Oscillating U-tube method (ISO 12185) Principle A test portion of ethanol sample is evaporated on a water bath The dry residue is dissolved in water The chloride and sulfate ion contents are determined by comparing the peak area in the chromatogram of the aqueous solution of the test portion with the curve of the calibration standards The calibration standards are prepared from suitable compounds in aqueous solution Reagents Use only reagents of recognized analytical grade, such as “Ionic Chromatography grade”, unless otherwise specified 4.1 Sodium chloride (NaCl), molar mass 58,44 g/mol 4.2 Sulfuric acid (H2SO4), aqueous solution at 0,1 mol/l The concentration of sulfuric acid shall be verified by titration, or shall be certified in case of commercially available product BS EN 15492:2012 EN 15492:2012 (E) 4.3 Water, for analytical laboratory use, conforming to grade of EN ISO 3696 4.4 Eluent compounds 4.4.1 Sodium carbonate (Na2CO3), molar mass 105,99 g/mol 4.4.2 Sodium hydrogen carbonate (NaHCO3), molar mass 84,01 g/mol 4.4.3 Potassium hydroxide (KOH), molar mass 56,11 g/mol 4.5 Nitric acid (HNO3) aqueous solution, c(HNO3) ≈ 0,75 mol/l Cautiously add 50 ml ± ml of nitric acid (ρ = 1,40 g/ml) to 500 ml ± 10 ml water (4.3) Mix and allow to cool to room temperature Make up to 000 ml in a volumetric flask (5.3) with water (4.3) Apparatus Before use, wash glassware (5.3) and evaporating dish (5.6) with nitric acid solution (4.5) and rinse thoroughly with water (4.3) 5.1 Ion chromatograph equipped with the following components 5.1.1 Injection system, manual or automatic, with a sampling loop with minimum capacity of 25 µl 5.1.2 Pumping system, capable of delivering mobile phase flows between 0,5 ml/min and 1,5 ml/min with a precision better than % 5.1.3 Chromatographic column, of which the following conditions have been found satisfactory: Column Type Dimension Mesh size anion exchange resin 4,0 mm ì 250 mm 9,0 àm Eluent Composition Flow rate mmol/l Na2CO3 + mmol/l NaHCO3 1,0 ml/min NOTE A 25 mmol/l KOH eluent may be used instead of the carbonate eluent It is also possible to use a precolumn (4,0 mm × 50,0 mm) with the same anion exchange resin and, if necessary, equipped with suppressors to remove interference from eluent The thermal regulation of the system is not required, as the acceptable temperature of the column is in the range from 15 °C to 30 °C 5.1.4 Conductivity detector, if necessary equipped with suppressor 5.1.5 Integrator or computer, capable of measuring peak areas and retention times and correct the data according to the baseline of the chromatogram 5.2 Balance, capable of weighing with an accuracy of 0,01 mg 5.3 Glassware: 25 ml, 50 ml, 100 ml and 000 ml volumetric flasks, according to EN ISO 1042, and 25 ml and 50 ml graduated cylinders 5.4 Graduated pipettes, of ml and ml capacity or variable volume automatic pipettes fitted with disposable polypropylene tips BS EN 15492:2012 EN 15492:2012 (E) 5.5 Warm water bath NOTE In order to avoid potential external contamination, the warm water bath should be exempt of chloride and sulfates, as during the evaporation process water can potentially be mixed into a certain extent with the ethanol samples 5.6 Evaporating dish, capacity 100 ml to 250 ml 5.7 Desiccator, containing freshly activated silica gel (or equivalent desiccant) with moisture content indicator 5.8 Oven, thermostatically controlled at (105 ± 2) °C 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 containers shall be used The containers shall be carefully cleaned and rinsed with water (4.3) to avoid contamination Samples should be analysed as soon as possible after removal from bulk supplies to prevent loss of ethanol 7.1 Preparation of calibration solutions Intermediate calibration solutions 7.1.1 Approximately 50 mg/l chloride solution Weigh 82,4 mg of sodium chloride (4.1) in a 100 ml volumetric flask (5.3) Bring to the mark with water (4.3) and homogenise Dilute this solution 1:10 with water (4.3) and homogenise 7.1.2 Approximately 150 mg/l sulfate solution Add 1,5 ml of sulfuric acid (4.2) in a 100 ml flask (5.3) Bring to the mark with water (4.3) and homogenise 7.1.3 The actual concentration of chloride and sulfate used shall be known to calculate the concentration of each ion in the solution, as 50 mg/l and 150 mg/l only represent target concentrations NOTE Alternatively, commercially available stock calibration solutions may be used, provided that the solutions are traceable to primary stock solutions or Certified Reference Materials and are free from other analytes if single ion solutions are employed 7.2 Calibration solutions Dilute the intermediate calibration solutions (7.1) with water (4.3) in five volumetric flasks to obtain calibration solutions having the ion contents as given in Table Fresh solutions shall be prepared daily BS EN 15492:2012 EN 15492:2012 (E) Table — Ion contents for calibration solutions Solution 8.1 Sulfate Chloride mg/l mg/l (blank) 0 1,0 2,0 2,0 5,0 5,0 10,0 10,0 20,0 Preparation of apparatus Setting up the instrument Since instruments from different manufacturers have different configurations and settings, it is difficult to specify an exact procedure Follow the manufacturer's instructions for setting up the instrument with aqueous solutions 8.2 Calibration Inject a minimum of 25 µl (5.1.1) of each calibration solution (7.2) in the chromatograph and measure the areas of the peaks corresponding to chloride and sulfate ions Carry out two measurements for each solution and calculate the mean of the peak areas corresponding to each ion Construct the calibration curve of chloride and the calibration curve of sulfate using the linear regression by plotting the peak area values against the values of the respective ion concentrations A chromatogram of a calibration solution containing mg/l each of chloride and sulfate ions is shown in Figure NOTE If the plot of the peak area values against the ion concentrations is not linear (correlation coefficient R2 less than 0,99) then the procedure should be inspected for errors and, if necessary, the calibration should be repeated starting from Clause 7 BS EN 15492:2012 EN 15492:2012 (E) Key A chloride X-axis time (min.) B sulfate Y-axis detector response (µS) Figure — Example of a chromatogram of a solution Procedure 9.1 Sample preparation In order to avoid contamination, all sampling operations are carried out using polypropylene pipettes or automatic pipettes having disposable tips Manually shake the sample containers immediately prior to sampling of the test portions Add 25 ml (VE) of test portion, or 50 ml (VE) if the chloride content is expected to be lower than mg/kg, to the evaporating dish (5.6) using a graduated cylinder (5.3) Place the dish with sample on the boiling warm water bath (5.5) and allow to dry Place the dish in the oven (5.8) at 105 °C for 30 and then transfer the dish in a desiccator (5.7) Allow the dish to cool for 30 Add ml of water (4.3) to the dish and heat gently to dissolve the dry residue Collect the treatment water in a 25 ml (VS) volumetric flask Repeat the treatment with water (4.3) three times Fill the flask to the mark with water (4.3) NOTE 9.2 The time usually required to obtain the dry residue is about h Sample analysis IMPORTANT —Ethanol as a blending component for petrol can contain denaturants (i.e petrol) These can leave water insoluble residues after evaporation, which may cause analytical determination problems Inject a minimum of 25 µl of sample solution (9.1) in the chromatograph and measure the areas of the peaks corresponding to chloride and sulfate ions Carry out two measurements and calculate the mean of the peak areas corresponding to each ion BS EN 15492:2012 EN 15492:2012 (E) If the ion concentration exceeds that of the highest calibration solution, dilute appropriately the sample solution with deionised water (4.3) and repeat the sample analysis Take into account the dilution factor F in the calculation of the ion content in the ethanol sample 10 Calculations Determine, according to the calibration curve of chloride and to the calibration curve of sulfate, respectively the concentration E of chloride and of sulfate in the sample solution, expressed in mg/l Calculate the content C of chloride and of sulfate in the ethanol sample, expressed in mg/kg, using Equation (1): C= E × F × VS VE × ρ (1) where E is the ion concentration of the sample solution in mg/l; F is the dilution factor (9.2); VS is the volume of aqueous sample solution in ml (9.1); VE is the volume of the test portion in ml (9.1); ρ is the density of the test portion (9.1), expressed in g/ml, and measured according to EN ISO 3675 or EN ISO 12185, or obtained from EN 15486:2007, Table A.1 11 Expression of results Report the content of chloride and the content of sulfate rounded to the nearest 0,1 mg/kg 12 Precision 12.1 General The precision given in 12.1 and 12.2 was determined by statistical examination (see EN ISO 4259:2006 [3]) of interlaboratory test results 12.2 Repeatability, r The difference between two test results, obtained by the same operator with the same apparatus under constant operating conditions on identical test material, would in the long run, in the normal and correct operation of the test method, exceed the value calculated from Equations (2) and (3) only in one case in twenty: chloride r = 0,029 X + 0,189 (2) sulfate r = 0,074 X + 0,055 (3) where X is the average of the two results being compared, in mg/kg BS EN 15492:2012 EN 15492:2012 (E) 12.3 Reproducibility, R The difference between two single and independent test results, obtained by different operators working in different laboratories on identical test material, would in the long run, in the normal and correct operation of the test method, exceed the value calculated from Equations (4) and (5) only in one case in twenty: chloride R = 0,075 X + 0,500 (4) sulfate R = 0,207 X + 0,153 (5) where X is the average of the two results being compared, in mg/kg 13 Test report The test report shall specify the following: a) the type and identification of the product under test; b) a reference to this European Standard, i.e EN 15492; c) the method of sampling (see Clause 6); d) the result of the test (see Clause 11); e) any deviation from the procedure described; f) the date of the test 10 BS EN 15492:2012 EN 15492:2012 (E) Bibliography [1] Method 10, Determination of dry residue of alcohol, Annex I of Commission Regulation (EC) No 625/2003, of April 2003, amending Regulation (EC) No 1623/2000 laying down detailed rules for implementing Council Regulation (EC) No 1493/1999 on the common organization of the market in wine with regards to market mechanism, OJ L 90, 8.4.2003, p 4–31 [2] EN 15376:2011, Automotive fuels — Ethanol as a blending component for petrol — Requirements and test methods [3] EN ISO 4259:2006, Petroleum products — Determination and application of precision data in relation to methods of test (ISO 4259:2006) 11 BS 2000 Series Energy Institute Buying Parts of BS 2000 Orders for BS 2000 publications should be addressed to either: Energy Institute – Library and Information Service 61 New Cavendish Street London W1G 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