BS-EN-12441-3-2002.pdf
BRITISH STANDARD BS EN 12441-3:2002 Zinc and zinc alloys Chemical analysis Part 3: Determination of lead, cadmium and copper Flame atomic absorption spectrometric method The European Standard EN 12441-3:2001 has the status of a British Standard ICS 77.120.60; 77.040.30 NO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAW Licensed Copy: sheffieldun sheffieldun, na, Sat Oct 28 07:06:01 GMT+00:00 2006, Uncontrolled Copy, (c) BSI BS EN 12441-3:2002 This British Standard, having been prepared under the direction of the Engineering Sector Policy and Strategy Committee, was published under the authority of the Standards Policy and Strategy Committee on 23 January 2002 © BSI 23 January 2002 ISBN 0 580 38163 3 National foreword This British Standard is the official English language version of EN 12441-3:2001. It supersedes BS 3630-7:1967, BS 3630-8:1971, BS 3630-9:1969, BS 3630-13:1972 and BS 3630-14:1972 which are withdrawn. The UK participation in its preparation was entrusted by Technical Committee NFE/8, Zinc and zinc alloys, to Subcommittee NFE/8/4, Sampling and analysis of zinc and zinc alloys, which has the responsibility to: A list of organizations represented on this subcommittee can be obtained on request to its secretary. Cross-references The British Standards which implement international or European publications referred to in this document may be found in the BSI Standards Catalogue under the section entitled “International Standards Correspondence Index”, or by using the “Find” facility of the BSI Standards Electronic Catalogue. A British Standard does not purport to include all the necessary provisions of a contract. Users of British Standards are responsible for their correct application. Compliance with a British Standard does not of itself confer immunity from legal obligations. aid enquirers to understand the text; present to the responsible European committee any enquiries on the interpretation, or proposals for change, and keep the UK interests informed; monitor related international and European developments and promulgate them in the UK. Summary of pages This document comprises a front cover, an inside front cover, the EN title page, pages 2 to 12, an inside back cover and a back cover. The BSI copyright date displayed in this document indicates when the document was last issued. Amendments issued since publication Amd. No. DateComments Licensed Copy: sheffieldun sheffieldun, na, Sat Oct 28 07:06:01 GMT+00:00 2006, Uncontrolled Copy, (c) BSI EUROPEAN STANDARD NORME EUROPÉENNE EUROPÄISCHE NORM EN 12441-3 October 2001 ICS 77.040.30; 77.120.60 English version Zinc and zinc alloys - Chemical analysis - Part 3: Determination of lead, cadmium and copper - Flame atomic absorption spectrometric method Zinc et alliages de zinc - Analyse chimique - Partie 3: Dosages du plomb, du cadmium et du cuivre - Méthode par spectrométrie d'absorption atomique dans la flamme Zink und Zinklegierungen - Chemische Analyse - Teil 3: Bestimmung von Blei, Cadmium und Kupfer - FAAS- Verfahren This European Standard was approved by CEN on 11 August 2001. 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 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 Management Centre has the same status as the official versions. 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 STANDARDIZATION COMITÉ EUROPÉEN DE NORMALISATION EUROPÄISCHES KOMITEE FÜR NORMUNG Management Centre: rue de Stassart, 36 B-1050 Brussels © 2001 CENAll rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 12441-3:2001 E Licensed Copy: sheffieldun sheffieldun, na, Sat Oct 28 07:06:01 GMT+00:00 2006, Uncontrolled Copy, (c) BSI EN 12441-3:2001 (E) 2 Contents page Foreword3 1Scope 4 2Normative references 4 3Terms and definitions4 4Principle4 5Reagents.5 6Apparatus .7 7Sampling.7 8Procedure .7 9Calculation and expression of results.11 10Test report 11 Licensed Copy: sheffieldun sheffieldun, na, Sat Oct 28 07:06:01 GMT+00:00 2006, Uncontrolled Copy, (c) BSI EN 12441-3:2001 (E) 3 Foreword This European Standard has been prepared by Technical Committee CEN/TC 209, “Zinc and zinc alloys“, the secretariat of which is held by AFNOR. 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 April 2002, and conflicting national standards shall be withdrawn at the latest by April 2002. Within its program of work, Technical Committee CEN/TC 209 entrusted CEN/TC 209/WG 6 “Methods of analysis and testing” with the preparation of the following document: prEN 12441-3, Zinc and zinc alloys - Chemical analysis - Part 3: Determination of lead, cadmium and copper - Flame atomic absorption spectrometric method. This standard is part of a series of eleven standards. The other standards are: ? Part 1 : Determination of aluminium in zinc alloys Titrimetric method ? Part 2 : Determination of magnesium in zinc alloys Flame atomic absorption spectrometric method ? Part 4 : Determination of iron in zinc alloys - Spectrophotometric method ? Part 5 : Determination of iron in primary zinc - Spectrophotometric method ? Part 6 : Determination of aluminium and iron - Flamme atomic absorption spectrometry method ? Part 7 : Determination of tin - Flame atomic absorption spectrometric method after extraction ? Part 8 : Determination of tin in secondary zinc - Flame atomic absorption spectrometric method ? Part 9 : Determination of nickel in zinc alloys - Flame atomic absorption spectrometric method ? Part 10 : Determination of chromium and titanium in zinc alloys Spectrophotometric method ? Part 11 : Determination of silicon in zinc alloys - Spectrophotometric method According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following countries are bound to implement this European Standard: Austria, Belgium, Czech Republic, Denmark, Finland, France, Germany, Greece, Iceland, Ireland, Italy, Luxembourg, Netherlands, Norway, Portugal, Spain, Sweden, Switzerland and the United Kingdom. Licensed Copy: sheffieldun sheffieldun, na, Sat Oct 28 07:06:01 GMT+00:00 2006, Uncontrolled Copy, (c) BSI EN 12441-3:2001 (E) 4 1 Scope This European Standard specifies a flame atomic absorption spectrometry method for the determination of lead, copper and cadmium in zinc and zinc alloys. It is applicable to the products specified in EN 988, EN 1179, EN 1774, EN 12844 and prEN 13283. It is suitable for the determination of lead contents (mass fractions) between 0,000 5 % and 2,5 %, cadmium contents (mass fractions) between 0,000 5 % and 0,3 %, and copper mass fractions between 0,000 5 % and 4 %. 2 Normative references This European Standard incorporates by dated or undated reference, provisions from other publications. These normative references are cited at the appropriate places in the text, and the publications are listed hereafter. For dated references, subsequent amendments to or revisions of any of these publications apply to this European Standard only when incorporated in it by amendment or revision. For undated references the latest edition of the publication referred to applies (including amendments). EN 988, Zinc and zinc alloys Specifications for rolled flat products for building. EN 1179, Zinc and zinc alloys Primary zinc. EN 1774, Zinc and zinc alloys Alloys for foundry purposes Ingot and liquid. EN 12060, Zinc and zinc alloys Method of sampling Specifications. EN 12844, Zinc and zinc alloys Castings - Specifications. prEN 13283, Zinc and zinc alloys Secondary zinc. 3 Terms and definitions For the purposes of this standard, the terms and definitions given in EN 12060 and the following apply. 3.1 flame atomic absorption spectrometry measurement of the absorption of electromagnetic radiation, emitted by an element at a determined wavelength, by an absorbent medium (flame) formed of atoms of the same element that are in the ground state. Each element absorbs radiation of specific wavelengths and the intensity of the absorbed radiation is proportional to the concentration of said element 4 Principle A sample of the metal or alloy is dissolved in a mixture of hydrochloric acid and nitric acid and, after adequate dilution and atomization of the solution into an airacetylene flame, the content of the particular element is determined by flame atomic absorption spectrometry. Sample(s) of secondary zinc containing tin are dissolved in hydrochloric acid/hydrogen peroxide. NOTEFor lead contents (mass fractions) between 0,000 5 % and 0,005 %, the determination could be preceded by an enrichment of the lead by simultaneous precipitation with copper sulphide as a trace impurity scavenger from ammoniacal solution in the presence of ammonium fluoride, a specified amount of thioacetamide being used as precipitating agent. Licensed Copy: sheffieldun sheffieldun, na, Sat Oct 28 07:06:01 GMT+00:00 2006, Uncontrolled Copy, (c) BSI EN 12441-3:2001 (E) 5 5 Reagents 5.1 General During the test, use only reagents of known or analytical grade and distilled or demineralized water. 5.2 Hydrochloric acid, ?1,19 g/ml 5.3 Nitric acid, ? = 1,4 g/ml 5.4 Hydrochloric acid-nitric acid mixture Mix 180 volumes of hydrochloric acid (5.2) with 4 volumes of nitric acid (5.3). This mixture shall be freshly prepared just before use 5.5 Hydrochloric acid (1 + 6) Mix 1 volume of hydrochloric acid (5.2) with 6 volumes of water. 5.6 Zinc powder Zinc powder of particle size less than 60 ?m, prepared from zinc having a purity of not less than 99,995 %. 5.7 Zinc chloride solution, 200 g /l Introduce 200 g of zinc (minimum purity 99,995 %) into a 2 l beaker. Add 100 ml of water and 700 ml of hydrochloric acid (5.2) carefully in small amounts to control the rate of reaction. After dissolution evaporate carefully to a syrupy consistency. After cooling, take up with about 800 ml water and warm gently to dissolve any salts. Add 20 g of zinc powder (5.6) and shake from time to time for not less than 30 min. Transfer into a 1 l volumetric flask, dilute to the mark with water and mix. Allow to settle and filter the solution without washing the residue. Store in a polyethylene bottle. 1 ml of this solution contains approximately 200 mg of zinc. NOTEIf zinc with a purity of not less than 99,9999 % is used, the treatment with zinc powder may be omitted. 5.8 Lead, cadmium or copper, 1 g/l solutions Introduce 0,500 g of lead, cadmium or copper (in all cases with a purity of not less than 99,9 %) into a 100 ml beaker fitted with a watch-glass, and add about 10 ml of water. Dissolve by carefully adding 5 ml of nitric acid (5.3). After dissolution, heat the solution until no further nitrous gas is evolved. Cool and transfer to a 500 ml volumetric flask, dilute to the mark with water and mix. 1 ml of this solution contains 1 mg of lead, cadmium or copper. 5.9 Standard solutions of lead, cadmium or copper Transfer 25,00 ml of each of the solutions, prepared as described in 5.8, into a series of 1 000 ml volumetric flasks. Dilute to the mark with water and mix. 1 ml of each of these solutions contains 0,025 mg of lead, cadmium or copper. 5.10 Hydrochloric acid (1 + 1) Mix 1 volume of hydrochloric acid (5.2) with 1 volume of water. Licensed Copy: sheffieldun sheffieldun, na, Sat Oct 28 07:06:01 GMT+00:00 2006, Uncontrolled Copy, (c) BSI EN 12441-3:2001 (E) 6 5.11 Ammonia solution, ? = 0,91 g/ml 5.12 Perchloric acid, 60 % (mass fraction) 5.13 Chloroform 5.14 Hydrogen peroxide, 30 % (mass fraction) 5.15 Copper, 5 g/l solution Dissolve 1 g of high purity copper containing not more than 5 ?g/g of lead in 15 ml of hydrochloric acid solution (1 + 1) (5.10). Add hydrogen peroxide (5.14) dropwise and heat gently on a hotplate until dissolution. Evaporate to a syrupy consistency. Take up in water and transfer quantitatively to a 200 ml volumetric flask. Dilute to the mark with water and mix. 1 ml of this solution contains 5 mg of copper. 5.16 Thioacetamide solution Fresh solution, prepared immediately before use by dissolving 300 mg of thioacetamide in water and made up to 100 ml. 5.17 Dithizone solution Dissolve 40 mg of dithizone in 1 l of chloroform (5.13). Protect this solution from light and keep it in a brown glass bottle. 5.18 Purified ammonium fluoride solution Dissolve 50 g of ammonium fluoride, NH4F, in about 300 ml of water in a plastic beaker. Adjust the pH of the solution to 7,5 ± 0,1 using ammonia solution (5.11), and transfer to a 500 ml shaking funnel. Now shake, while adding dithizone solution (5.17) in 15 ml portions, discarding the extract each time until the final extract retains the pure green colour of the dithizone solution. Remove residual dithizone by shaking several times with 15 ml of pure chloroform (5.13). Drain the purified ammonium fluoride solution into a plastic beaker and adjust its pH value to between 9,8 and 10,0 with ammonia solution (5.11). Transfer the solution to a 500 ml volumetric flask, and make up to the mark with water. Mix and transfer to a plastic bottle for storage. 5.19 Aqua regia Mix 3 volumes of hydrochloric acid (5.2) with 1 volume of nitric acid (5.3). 5.20 Aluminium, 50 g/l solution Introduce 50 g of aluminium, with a minimum purity of 99,995 % and free of lead, cadmium and copper into a 1 l beaker. Add 200 ml of water and 200 ml of hydrochloric acid (5.2). After dissolution evaporate carefully to a syrupy consistency. After cooling, take up with about 800 ml of water and transfer to a 1 l volumetric flask. Add 20 g of aluminium-turnings and shake from time to time for not less than 60 minutes. Transfer to a 1 l volumetric flask, dilute to the mark with water and mix. Allow to settle and filter the solution without washing the residue. Store in a polyethylene bottle. 1 ml of this solution contains approximately 50 mg of aluminium. Licensed Copy: sheffieldun sheffieldun, na, Sat Oct 28 07:06:01 GMT+00:00 2006, Uncontrolled Copy, (c) BSI EN 12441-3:2001 (E) 7 6 Apparatus 6.1 General All glassware used for the preparation of the solutions and for the implementation of the method shall be cleaned with boiling aqua regia (5.19) prior to use. 6.2 Specific equipment In addition to standard laboratory apparatus, t
