1、DD CEN/TS15022-2:2009ICS 77.120.30NO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAWDRAFT FOR DEVELOPMENTCopper and copperalloys Determinationof tin contentPart 2: Spectrophotometric methodLicensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 17/06/2010 07:05, Uncontrolled Copy,
2、 (c) BSIThis Draft for Developmentwas published under theauthority of the StandardsPolicy and StrategyCommittee on 28 February2010. BSI 2010ISBN 978 0 580 61868 0Amendments/corrigenda issued since publicationDate CommentsDD CEN/TS 15022-2:2009National forewordThis Draft for Development is the UK imp
3、lementation of CEN/TS15022-2:2009.This publication is not to be regarded as a British Standard.It is being issued in the Draft for Development series of publications andis of a provisional nature. It should be applied on this provisional basis,so that information and experience of its practical appl
4、ication can beobtained.Comments arising from the use of this Draft for Development arerequested so that UK experience can be reported to the internationalorganization responsible for its conversion to an international standard.A review of this publication will be initiated not later than 3 years aft
5、erits publication by the international organization so that a decision can betaken on its status. Notification of the start of the review period will bemade in an announcement in the appropriate issue of Update Standards.According to the replies received by the end of the review period,the responsib
6、le BSI Committee will decide whether to support theconversion into an international Standard, to extend the life of theTechnical Specification or to withdraw it. Comments should be sent tothe Secretary of the responsible BSI Technical Committee at BritishStandards House, 389 Chiswick High Road, Lond
7、on W4 4AL.The UK participation in its preparation was entrusted to TechnicalCommittee NFE/34, Copper and copper alloys.A list of organizations represented on this committee can be obtained onrequest to its secretary.This publication does not purport to include all the necessary provisionsof a contra
8、ct. Users are responsible for its correct application.Compliance with a British Standard cannot confer immunityfrom legal obligations.Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 17/06/2010 07:05, Uncontrolled Copy, (c) BSIDD CEN/TS 15022-2:2009TECHNICAL SPECIFICATION SPCIFICATION TECHNIQU
9、E TECHNISCHE SPEZIFIKATION CEN/TS 15022-2 December 2009 ICS 77.120.30 English Version Copper and copper alloys - Determination of tin content - Part 2: Spectrophotometric method Cuivre et alliages de cuivre - Dosage de ltain - Partie 2 : Mthode spectrophotomtrique Kupfer und Kupferlegierungen - Best
10、immung des Zinngehaltes - Teil 2: Spektrophotometrisches Verfahren This Technical Specification (CEN/TS) was approved by CEN on 15 September 2009 for provisional application. The period of validity of this CEN/TS is limited initially to three years. After two years the members of CEN will be request
11、ed to submit their comments, particularly on the question whether the CEN/TS can be converted into a European Standard. CEN members are required to announce the existence of this CEN/TS in the same way as for an EN and to make the CEN/TS available promptly at national level in an appropriate form. I
12、t is permissible to keep conflicting national standards in force (in parallel to the CEN/TS) until the final decision about the possible conversion of the CEN/TS into an EN is reached. CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Cyprus, Czech Republic, Denmark, Eston
13、ia, 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 COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROP
14、ISCHES 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. CEN/TS 15022-2:2009: ELicensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 17/06/2010 07:05, Uncontr
15、olled Copy, (c) BSIDD CEN/TS 15022-2:2009CEN/TS 15022-2:2009 (E) 2 Contents Page Foreword 31 Scope 42 Normative references 43 Principle 44 Reagents .45 Apparatus .56 Sampling .57 Procedure .68 Expression of results 89 Precision .810 Test report 9Bibliography . 10Licensed Copy: Wang Bin, ISO/EXCHANGE
16、 CHINA STANDARDS, 17/06/2010 07:05, Uncontrolled Copy, (c) BSIDD CEN/TS 15022-2:2009CEN/TS 15022-2:2009 (E) 3 Foreword This document (CEN/TS 15022-2:2009) has been prepared by Technical Committee CEN/TC 133 “Copper and copper alloys”, the secretariat of which is held by DIN. Attention is drawn to th
17、e possibility that some of the elements of this document may be the subject of patent rights. CEN shall not be held responsible for identifying any or all such patent rights. Within its programme of work, Technical Committee CEN/TC 133 requested CEN/TC 133/WG 10 “Methods of analysis“ to prepare this
18、 Technical Specification: This is one of four parts of the Standard/Technical Specification for the determination of tin content in copper and copper alloys. The other parts are: prEN 15022-1, Copper and copper alloys Determination of tin content Part 1: Titrimetric method (Part 1 will be the subjec
19、t of future work); EN 15022-3, Copper and copper alloys Determination of tin content Part 3: Low tin content Flame atomic absorption spectrometry method (FAAS); CEN/TS 15022-4, Copper and copper alloys Determination of tin content Part 4: Medium tin content Flame atomic absorption spectrometry metho
20、d (FAAS). According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following countries are bound to announce this Technical Specification: Austria, Belgium, Bulgaria, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, I
21、reland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom. Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 17/06/2010 07:05, Uncontrolled Copy, (c) BSIDD CEN/TS 15022-2:2009CEN/TS 1502
22、2-2:2009 (E) 4 1 Scope This part of this Technical Specification specifies the spectrophotometric method for the determination of tin content of copper and copper alloys in the form of unwrought, wrought and cast products. The method is applicable to products having tin mass fractions between 0,005
23、% and 0,5 %. 2 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. ISO 1811-1, C
24、opper and copper alloys Selection and preparation of samples for chemical analysis Part 1: Sampling of cast unwrought products ISO 1811-2, Copper and copper alloys Selection and preparation of samples for chemical analysis Part 2: Sampling of wrought products and castings 3 Principle Extraction into
25、 methyl isobutyl ketone and spectrophotometric determination of the yellow tin-quercetin complex at a wavelength of 440 nm. 4 Reagents During the analysis, use only reagents of recognized analytical grade and only distilled water or water of equivalent purity. 4.1 Hydrochloric acid, HCl ( = 1,19 g/m
26、l). 4.2 Methyl isobutyl ketone. 4.3 Ammonia solution, NH4OH ( = 0,91 g/ml). 4.4 Hydrogen peroxide solution, H2O2, 30 % (mass fraction). 4.5 Hydrochloric acid solution, diluted 1 + 1. Add 50 ml of hydrochloric acid (4.1) to 50 ml of water. 4.6 Sulphuric acid, H2SO4( = 1,84 g/ml). 4.7 Sulphuric acid s
27、olution, diluted 1 + 19. Add 50 ml of sulphuric acid (4.6) to 950 ml of water. 4.8 Thiourea solution, NH2CSNH2(60 g/l). Dissolve 15 g of thiourea in water and dilute to 250 ml. Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 17/06/2010 07:05, Uncontrolled Copy, (c) BSIDD CEN/TS 15022-2:2009CE
28、N/TS 15022-2:2009 (E) 5 4.9 Ascorbic acid solution, C6H8O6(20 g/l). Dissolve 1 g of ascorbic acid in water and dilute to 50 ml. Use a freshly prepared solution. 4.10 Quercetin acid ethanol solution, (1 g/l). Dissolve 500 mg of quercetin in 300 ml of 95 % (volume fraction) ethanol in a 500 ml one-mar
29、k volumetric flask. The dissolution takes some hours. Add 25 ml of the hydrochloric acid (4.1), dilute to the mark with water and mix well. Filter off any residue. 4.11 Tin stock solution, 0,5 g/l Sn. Weigh (0,5 0,001) g of pure tin (Sn 99,99 %) and transfer it into a 400 ml beaker. Add 100 ml of hy
30、drochloric acid (4.1) and cover with a watch glass. Heat gently until the metal is dissolved. After cooling, transfer the solution quantitatively into a 1 000 ml one-mark volumetric flask, dilute to the mark with water and mix well. 1 ml of this solution contains 0,5 mg of Sn. 4.12 Tin standard solu
31、tion, 0,050 g/l Sn. Transfer 10,0 ml of the tin stock solution (4.11) to a 100 ml one-mark volumetric flask. Add 20 ml of the hydrochloric acid (4.1). Dilute to the mark with water and mix well. 1 ml of this solution contains 50 g of Sn. 4.13 Copper base solution, 5 g/l. Dissolve 5,0 g of electrolyt
32、ic tin-free copper in 100 ml of the hydrochloric acid (4.1). Add 5 ml portions of the hydrogen peroxide solution (4.4) until the copper is completely dissolved then add 200 ml of water and boil to destroy the excess of the hydrogen peroxide. Cool and transfer to a 1 000 ml one-mark volumetric flask.
33、 Dilute to the mark with water and mix well. 5 Apparatus 5.1 Spectrophotometer, with 20 mm cells. 6 Sampling Sampling shall be carried out in accordance with ISO 1811-1 or ISO 1811-2 as appropriate. Test samples shall be in the form of fine drillings, chips or millings with a maximum thickness of 0,
34、5 mm. Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 17/06/2010 07:05, Uncontrolled Copy, (c) BSIDD CEN/TS 15022-2:2009CEN/TS 15022-2:2009 (E) 6 7 Procedure 7.1 Preparation of the test portion solution 7.1.1 Test portion Weigh to the nearest 0,001 g, according to the expected tin mass fracti
35、on of the test sample, a test portion according to Table 1. Table 1 Test portion mass Expected tin mass fraction of test sample Mass of test portion ( 0,001 g) Predilution aliquot volume taken diluted to % g ml ml0,005 to 0,010 2 without predilution 0,01 to 0,02 1 0,02 to 0,04 1 100 200 0,04 to 0,08
36、 1 50 200 0,08 to 0,16 1 25 200 0,16 to 0,30 0,5 25 200 0,30 to 0,50 0,4 20 200 7.1.2 Test portion solution Transfer the test portion to a 250 ml conical flask. Under cold running water, dissolve the test portion in 20 ml of the hydrochloric acid solution (4.5) and 10 ml of the hydrogen peroxide sol
37、ution (4.4), in small portions. It is necessary to dissolve slowly to avoid loss of tin chloride. Complete the dissolution by heating gently. Add 10 ml of water and boil to destroy the excess of hydrogen peroxide. Transfer the test portion solution to a 200 ml one-mark volumetric flask. 7.2 Blank te
38、st Carry out a blank test simultaneously with the determination, following the same procedure and using the same quantities of all reagents as used for the determination, but substituting pure copper for the test portion (7.1.1). Correct the result obtained from the determination in accordance with
39、the result from the blank test. 7.3 Check test Make a preliminary check of the apparatus by preparing a solution of standard material or a synthetic sample containing a known amount of tin and of composition similar to the material to be analysed. Carry out the procedure specified in 7.1 and 7.5. Li
40、censed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 17/06/2010 07:05, Uncontrolled Copy, (c) BSIDD CEN/TS 15022-2:2009CEN/TS 15022-2:2009 (E) 7 7.4 Establishment of the calibration curve 7.4.1 Preparation of the calibration solutions 7.4.1.1 General The tin concentration of the calibration solution
41、s was adjusted to meet the sensitivity of common apparatus, so that the curve of integrated absorbance as a function of concentration is a straight line. If the calibration curve is not a straight line, use a 10 mm cell. 7.4.1.2 Tin mass fraction between 0,005 % and 0,5 % Into each of a series of se
42、ven 200 ml one-mark volumetric flasks introduce 50 ml of the copper base solution (4.13) and 10 ml of water. Add of the tin standard solution (4.12) 0 ml, 0,5 ml, 1,0 ml, 2,0 ml, 3,0 ml, 4,0 ml and 5,0 ml, equivalent to 0 g, 25 g, 50 g, 100 g, 150 g, 200 g and 250 g of tin. Proceed as specified in 7
43、.5.2, 7.5.3 and 7.5.4. 7.4.2 Spectrophotometric measurements of the calibration solutions Measure the absorbance of the solutions using the spectrophotometer (5.1) fitted with a 20 mm cell, against methyl-isobutyl ketone at 440 nm. 7.4.3 Calibration curve Establish the calibration curve using measur
44、ed absorbances, after correcting the results for the zero solution and corresponding analyte amounts. Use appropriate spectrophotometer software or off-line computer for regression calibration or prepare a graphical representation. 7.5 Determination 7.5.1 The analyses shall be carried out independen
45、tly, in duplicate. If, according to the Table 1, no dilution is to be made, proceed as directed in 7.5.2, 7.5.3 and 7.5.4. If a predilution is to be made, dilute to 200 ml with water and mix well. Transfer the prescribed aliquot portion to a 200 ml one-mark volumetric flask. 7.5.2 Neutralize with th
46、e ammonia solution (4.3) just to the point where a precipitate appears and remains. Dissolve the precipitate with the hydrochloric acid (4.1) added drop by drop. Add 20 ml of water and 30 ml of the hydrochloric acid. Allow to cool, dilute to the mark with water and mix well. 7.5.3 Introduce successi
47、vely into a 125 ml separating funnel: a) 25 ml of the thiourea solution (4.8); b) 5 ml of the ascorbic acid solution (4.9); c) 10,0 ml of the quercetin acid ethanol solution (4.10) and mix; d) 10,0 ml of the test portion solution while mixing; e) 20,0 ml of the methyl isobutyl ketone (4.2). 7.5.4 Sh
48、ake for 1 min and allow the layers to separate for 3 min. Discard the aqueous layer. Add 5 ml of the sulphuric acid solution (4.7), without mixing. Drain off the acid phase and add 20 ml of the sulphuric acid solution. Shake for 30 s. During shaking avoid too close an intermixture of the phases; thi
49、s will prolong the separation time. After 3 min, drain off and discard the acid phase and a little of the organic phase. Transfer the remainder of the organic phase through a small, dry, rapid filter paper into a dry, stoppered flask. After 10 min, measure the absorbance of the solution using a spectrophotometer (5.1), fitted with a 20 mm cell, against methyl isobutyl ketone at 440 nm. Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 17/06/2010 07:05, Uncontrolled Copy, (c) BSIDD CEN/T
