SIST EN 13615:2004

2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.Verfahren für die Analyse von Zinn in Masseln - Bestimmung des Gehaltes an Verunreinigungselementen in Zinn der Reinheitsgrade 99,90 % und 99,85 % durch AtomspektrometrieMéthodes d'analyse des lingots d'étain - Détermination des teneurs en impuretés dans l'étain de qualité 99,90 % et 99,85 % par spectrométrie atomiqueMethods for the analysis of ingot tin - Determination of impurity element contents in tin grades 99,90 % and 99,85 % by atomic spectrometry77.150.60L]GHONLLead, zinc and tin products77.040.30Kemijska analiza kovinChemical analysis of metalsICS:Ta slovenski standard je istoveten z:EN 13615:2001SIST EN 13615:2004en01-januar-2004SIST EN 13615:2004SLOVENSKI
STANDARD



SIST EN 13615:2004



EUROPEAN STANDARDNORME EUROPÉENNEEUROPÄISCHE NORMEN 13615December 2001ICS 77.040.30; 77.150.60English versionMethods for the analysis of ingot tin - Determination of impurityelement contents in tin grades 99,90 % and 99,85 % by atomicspectrometryMéthodes pour l'analyse des lingots d'étain - Déterminationdes teneurs en impuretés dans l'étain de qualité 99,90 % et99,85 % par spectrométrie atomiqueVerfahren für die Analyse von Zinn in Masseln -Bestimmung des Gehaltes an Verunreinigungselementen inZinn der Reinheitsgrade 99,90 % und 99,85 % durchAtomspektrometrieThis European Standard was approved by CEN on 5 October 2001.CEN members are 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 the 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 Management Centre has the same status as the officialversions.CEN members are the national standards bodies of Austria, Belgium, Czech Republic, Denmark, Finland, France, Germany, Greece,Iceland, Ireland, Italy, Luxembourg, Netherlands, Norway, Portugal, Spain, Sweden, Switzerland and United Kingdom.EUROPEAN COMMITTEE FOR STANDARDIZATIONCOMITÉ EUROPÉEN DE NORMALISATIONEUROPÄISCHES KOMITEE FÜR NORMUNGManagement Centre: rue de Stassart, 36
B-1050 Brussels© 2001 CENAll rights of exploitation in any form and by any means reservedworldwide for CEN national Members.Ref. No. EN 13615:2001 ESIST EN 13615:2004



EN 13615:2001 (E)2ContentspageForeword.31Scope.32Normative references.33Principle.34Reagents.45Apparatus.66Sampling.67Procedure.67.1Preparation of the solution of the sample under test.67.2Preparation of calibration solutions.67.3Certified reference materials (CRM).77.4Spectrometric measurements.78Expression of results.78.1Determining the metal content.78.2Evaluation of precision.89Test report.8Annex A (normative)
Method for checking atomic absorption spectrometer performance(based on ISO 7530-1:1990).9Annex B (normative)
Method for checking inductively coupled plasma atomic emissionspectrometer performance.12Bibliography.14SIST EN 13615:2004



EN 13615:2001 (E)3ForewordThis European Standard has been prepared by Technical Committee CEN/TC 220 “Tin and tin alloys” thesecretariat of which is held by BSI.This European Standard shall be given the status of a national standard, either by publication of anidentical text or by endorsement, at the latest by June 2002, and conflicting national standards shall bewithdrawn at the latest by June 2002.The annexes A and B are normative.According to the CEN/CENELEC Internal Regulations, the national standards organizations of thefollowing countries are bound to implement this European Standard: Austria, Belgium, CzechRepublic, Denmark, Finland, France, Germany, Greece, Iceland, Ireland, Italy, Luxembourg,Netherlands, Norway, Portugal, Spain, Sweden, Switzerland and the United Kingdom.1 ScopeThis European Standard specifies atomic spectroscopic methods (Atomic Absorption Spectrometry(AAS) or inductively coupled plasma Atomic Emission Spectrometry (ICP-AES)) intended for theanalysis of ingot tin. It is written for use by experienced analysts familiar with atomic spectrometrictechniques.2 Normative referencesThis European Standard incorporates by dated or undated reference, provisions from otherpublications. These normative references are cited at the appropriate places in the text, and thepublications are listed hereafter. For dated references, subsequent amendments to or revisions of anyof these publications apply to this European Standard only when incorporated in it by amendment orrevision. For undated references the latest edition of the publication referred to applies (includingamendments).EN 610, Tin and tin alloys — Ingot tin.3 PrincipleThe test sample is dissolved in hydrochloric acid plus nitric acid and tartaric or citric acid, and theconcentration of the element sought is measured using atomic absorption spectrometry or inductivelycoupled plasma atomic emission spectrometry. Interference is minimised by matching sample andreference materials and by the choice of instrument parameters.SIST EN 13615:2004



EN 13615:2001 (E)44 Reagents4.1 GeneralDuring the analysis, unless otherwise stated, use only reagents of recognised analytical grade andonly distilled water or water of equivalent purity.4.2Hydrochloric acid, concentrated (
1,18 g/ml).4.3Dilute hydrochloric acid (1 + 1). Dilute 100 ml hydrochloric acid (4.2) with 100 ml water.WARNINGThe acid should added to the water for safety reasons.4.4Dilute hydrochloric acid (1 + 19). Dilute 10 ml hydrochloric acid (4.2) with 190 ml water.4.5Nitric acid, (
1,42 g/ml).4.6Sulphuric acid, (
1,84 g/ml).4.7Tartaric acid or citric acid.4.8Acid mixture. Add 250 ml hydrochloric acid (4.2) to 250 ml water. Cool. Add 250 ml nitric acid (4.5)and 50 g tartaric (or citric) acid (4.7). Dilute to 1 l with water.4.9Dilute nitric acid (1 + 1). Add 100 ml nitric acid (4.5) to 100 ml water.4.10Dilute nitric acid (1 + 4). Add 50 ml nitric acid (4.5) to 200 ml water.4.11Dilute nitric acid (1 + 9). Add 25 ml nitric acid (4.5) to 225 ml water.4.12Dilute nitric acid (1 %). Dilute 5 ml nitric acid (4.5) up to 500 ml.4.13Standard solutions of metals. Freshly purchased standard metal solutions may be used orstandard metal solutions should be made up as follows (4.13.1 to 4.13.25).4.13.1Standard antimony solution (1 ml contains 1 mg Sb). Place 0,10 g Sb in 5 ml sulphuricacid (4.6) and heat to complete dissolution. Cool. Carefully add approximately 10 ml water and coolagain. Transfer to a 100 ml volumetric flask with dilute hydrochloric acid (1 + 1) (4.3).4.13.2Standard antimony solution (1 ml contains 0,2 mg Sb). Transfer 10,00 ml of Sb solution 4.13.1to a 50 ml volumetric flask and make up to volume with dilute hydrochloric acid (1 + 1) (4.3).4.13.3Standard copper solution (1 ml contains 1 mg Cu). Dissolve 0,10 g Cu in 10 ml dilute nitricacid (1 + 4) (4.9) and transfer to a 100 ml volumetric flask. Make up to volume with water and mix.4.13.4Standard copper solution (1 ml contains 0,2 mg Cu). Transfer 10,00 ml of Cu solution 4.13.3to a 50 ml volumetric flask and make up to volume with water and mix.4.13.5Standard lead solution (1 ml contains 1 mg Pb). Dissolve 0,10 g Pb in 10 ml dilute nitric acid(1 + 4) (4.10) and transfer to a 100 ml volumetric flask. Make up to volume with water and mix.4.13.6Standard lead solution (1 ml contains 0,1 mg Pb). Transfer 5,00 ml of Pb solution 4.13.5 to a50 ml volumetric flask and make up to volume with water and mix.4.13.7Standard bismuth solution (1 ml contains 1 mg Bi). Dissolve 0,10 g Bi in 10 ml dilute nitricacid (1 + 1) (4.9) and transfer to a 100 ml volumetric flask. Make up to volume with water and mix.SIST EN 13615:2004



EN 13615:2001 (E)54.13.8Standard bismuth solution (1 ml contains 0,1 mg Bi). Transfer 5,00 ml of bismuth solution 4.13.7to a 50 ml volumetric flask and make up to volume with dilute hydrochloric acid (1 + 1) (4.3).4.13.9Standard cadmium solution (1 ml contains 1 mg Cd). Dissolve 0,10 g Cd in 10 ml dilute nitricacid (1 + 4) (4.10) and transfer to a 100 ml volumetric flask. Make up to volume with water and mix.4.13.10Standard cadmium solution (1 ml contains 0,01 mg Cd). Transfer 1,00 ml of cadmiumsolution 4.13.9 to a 100 ml volumetric flask and make up to volume with water and mix.4.13.11Standard zinc solution (1 ml contains 1 mg Zn). Dissolve 0,10 g Zn in 10 ml nitric acid(1 + 4) (4.10) and transfer to a 100 ml volumetric flask. Make up to volume with water and mix.4.13.12Standard zinc solution (1 ml contains 0,01 mg Zn). Transfer 1,00 ml of zinc solution 4.13.11to a 100 ml volumetric flask. Make up to volume with water and mix.4.13.13Standard iron solution (1 ml contains 1 mg Fe). Dissolve 0,10 g Fe wire (free from rust) in10 ml of nitric acid (1 + 4) (4.10) and transfer to a 100 ml volumetric flask. Make up to volume withwater and mix.4.13.14Standard iron solution (1 ml contains 0,02 mg Fe). Transfer 1,00 ml of iron solution 4.13.13to a 50 ml volumetric flask. Make up to volume with water and mix.4.13.15Standard arsenic solution (1 ml contains 1 mg As). Dissolve 0,1 320 g of As203 in a littlesodium hydroxide solution (1 mol/l) and transfer to a 100 ml volumetric flask. Make up to volume withwater and mix.4.13.16Standard arsenic solution (1 ml contains 0,1 mg As). Transfer 5,00 ml arsenic solution 4.13.15to a 50 ml volumetric flask. Make up to volume with water and mix.4.13.17Standard aluminium solution (1 ml contains 1 mg Al). Dissolve 0,100 g Al metal in 10 mlnitric acid (4.10) and transfer to a 100 ml volumetric flask. Make up to volume with water and mix.4.13.18Standard aluminium solution (1 ml contains 0,05 mg Al). Transfer 5,00 ml of aluminiumsolution 4.13.17 to a 100 ml volumetric flask and make up to volume with dilute nitric acid (1 %)(4.12).4.13.19Standard aluminium solution (1 ml contains 0,005 mg Al). Transfer 5,00 ml of aluminiumsolution 4.13.18 to a 50 ml volumetric flask and make up to volume with dilute nitric acid (1 %) (4.12).4.13.20Standard silver solution (1 ml contains 1 mg Ag). Dissolve 0,787 g silver nitrate in 50 mlwater. Transfer to a 500 ml volumetric flask and make up to volume with nitric acid (1 %) (4.12).4.13.21Standard silver solution (1 ml contains 0,1 mg Ag). Transfer 5,00 ml of silver solution (4.13.20)to a 50 ml volumetric flask and make up to volume with water and mix.4.13.22Standard nickel solution (1 ml contains 1,0 mg Ni). Dissolve 0,100 g of nickel in 10 ml ofnitric acid (1 + 4) (4.10) and transfer to a 100 ml volumetric flask and make up to volume with waterand mix.4.13.23Standard nickel solution (1 ml contains 0,1 mg Ni). Transfer 5,00 ml of nickel solution 4.13.22to a 50 ml volumetric flask and make up to volume with water and mix.4.13.24Standard indium solution (1 ml contains 1,0 mg In). Dissolve 0,100 g of indium in 10 ml ofnitric acid (1 + 4) (4.10) and transfer to a 100 ml volumetric flask and make up to volume with waterand mix.4.13.25Standard indium solution (1 ml contains 0,1 mg In). Transfer 5,00 ml of indium solution 4.13.24to a 50 ml volumetric flask and make up to volume with dilute nitric acid (1 %) (4.12).SIST EN 13615:2004



EN 13615:2001 (E)64.14Tin, min. purity 99,99 %.5 Apparatus5.1Ordinary laboratory apparatus. Use grade A glassware.5.2Burette, of capacity 5 ml, graduated in 0,02 ml.5.3Atomic absorption spectrometer or inductively coupled plasma atomic emission spectrometer,conforming to the performance requirements in normative annexes A and B.5.4Hollow cathode lamps or electrodeless discharge tubes for antimony, bismuth, cadmium,copper, lead, silver, iron, zinc, arsenic, nickel, aluminium, indium, gold and cobalt.NOTEThe presence of other elements may also need to be ascertained.6 SamplingThe sample for analysis shall be obtained as described in EN 610.7 Procedure7.1 Preparation of the solution of the sample under test7.1.1Weigh 1,0 g ± 0,1 g of the sample and transfer to a 250 ml beaker. Add 20 ml of the acidmixture (4.8), heat to complete dissolution and cool. Transfer to a 100 ml volumetric flask and makeup to the volume with dilute hydrochloric acid (1 + 19) (4.4) and mix.7.1.2Prepare a blank test solution following the procedure described in 7.1.1, but using 1,0 g ofhigh purity tin (4.14) instead of the sample.7.2 Preparation of calibration solutionsFor the determination of the impurities, weigh 1,0 g
0,1 g high purity tin (4.14) into each of 7 250 mlbeakers. Add 20 ml of the acid mixture (4.8) and warm to dissolve. Cool and transfer to a 100 mlvolumetric flask and add the amounts of the standard metal solutions shown in Table 1.Finally make up to the mark with dilute hydrochloric acid (4.4).SIST EN 13615:2004



EN 13615:2001 (E)7Table 1 — Volume of standard metal solutions usedin the preparation of the calibration solutionsFlask No.Standard metal solutionmlSbCuPbBiCdZn4.13.24.13.44.13.64.13.84.13.104.13.1210,00,00,00,00,00,020,50,50,50,50,50,531,01,01,01,01,01,042,02,02,02,02,02,053,03,03,04,03,03,064,04,04,06,04,04,075,05,05,08,05,05,0Flask No.Standard metal solutionmlFeAsAlAgNiIn4.13.144.13.164.13.184.13.214.13.234.13.2510,00,00,00,00,00,021,01,01,01,01,01,032,02,02,02,02,02,044,03,03,03,03,03,056,04,04,04,04,04,068,05,05,05,05,05,0710,06,06,06,06,06,0For the determination of antimony in all samples and for copper in sample numbers 1,2,3 and 6transfer 10,0 ml of the solutions to a 100 ml flask and dilute to the mark with dilute hydrochloricacid (4.4).7.3 Certified reference materials (CRM)Where CRM of similar matrix to the sample under test is available, treat an appropriate sample of theCRM in exactly the same way as the sample under test (7.1).7.4 Spectrometric measurementsSet up the spectrometer (AAS, ICP-AES) using the wavelengths given in A.3.5 or B.3.3, asappropriate. A minimum of two runs of the
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