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 methodThis Draft for Developmentwas published under theauthority of the StandardsPolicy and Strat
2、egyCommittee 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 implementation of CEN/TS15022-2:2009.This publication is not to be regarded as a British Standard.It i
3、s 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 application can beobtained.Comments arising from the use of this Draft for Development arerequested so
4、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 afterits publication by the international organization so that a decision can betaken on its status. N
5、otification 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 responsible BSI Committee will decide whether to support theconversion into an international Standard, to ex
6、tend 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, London W4 4AL.The UK participation in its preparation was entrusted to TechnicalCommittee NFE/34, Coppe
7、r 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 contract. Users are responsible for its correct application.Compliance with a British Standard cannot con
8、fer immunityfrom legal obligations.DD CEN/TS 15022-2:2009TECHNICAL SPECIFICATION SPCIFICATION TECHNIQUE 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 d
9、e cuivre - Dosage de ltain - Partie 2 : Mthode spectrophotomtrique Kupfer und Kupferlegierungen - Bestimmung 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
10、of this CEN/TS is limited initially to three years. After two years the members of CEN will be requested 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
11、way as for an EN and to make the CEN/TS available promptly at national level in an appropriate form. It 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 a
12、re 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, Slovakia, Slovenia, Spain, Sweden, Switz
13、erland and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES 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.
14、CEN/TS 15022-2:2009: EDD 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 . 10DD CEN/TS 15022-2:2009CEN/TS 15022
15、-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 the possibility that some of the elements of this document may be the subject of patent rights. CE
16、N 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 Technical Specification: This is one of four parts of the Standard/Technical Specification for
17、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 subject of future work); EN 15022-3, Copper and copper alloys Determination of tin content Part 3: Low
18、 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 method (FAAS). According to the CEN/CENELEC Internal Regulations, the national standards organization
19、s 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, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Roma
20、nia, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom. DD CEN/TS 15022-2:2009CEN/TS 15022-2:2009 (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,
21、 wrought and cast products. The method is applicable to products having tin mass fractions between 0,005 % 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 re
22、ferences, the latest edition of the referenced document (including any amendments) applies. ISO 1811-1, Copper 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 sa
23、mples for chemical analysis Part 2: Sampling of wrought products and castings 3 Principle Extraction into 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 analyti
24、cal grade and only distilled water or water of equivalent purity. 4.1 Hydrochloric acid, HCl ( = 1,19 g/ml). 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
25、 hydrochloric acid (4.1) to 50 ml of water. 4.6 Sulphuric acid, H2SO4( = 1,84 g/ml). 4.7 Sulphuric acid solution, 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. DD CEN/TS 15022-2:
26、2009CEN/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 o
27、ne-mark 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
28、 of hydrochloric 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 standar
29、d solution, 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 elec
30、trolytic 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
31、flask. 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
32、 of 0,5 mm. DD 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 fraction of the test sample, a test portion according to Table 1. Table 1 Test portion mass Expecte
33、d 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 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 po
34、rtion 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 solution (4.4), in small portions. It is necessary to dissolve slowly to avoid loss of tin chlor
35、ide. 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 test Carry out a blank test simultaneously with the determination, following the same procedure
36、 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 the result from the blank test. 7.3 Check test Make a preliminary check of the apparatus by p
37、reparing 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. DD CEN/TS 15022-2:2009CEN/TS 15022-2:2009 (E) 7 7.4 Establishment of the calibration curve 7.4.
38、1 Preparation of the calibration solutions 7.4.1.1 General The tin concentration of the calibration solutions 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 stra
39、ight 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 seven 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 m
40、l 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 7.5.2, 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, ag
41、ainst methyl-isobutyl ketone at 440 nm. 7.4.3 Calibration curve Establish the calibration curve using measured absorbances, after correcting the results for the zero solution and corresponding analyte amounts. Use appropriate spectrophotometer software or off-line computer for regression calibration
42、 or prepare a graphical representation. 7.5 Determination 7.5.1 The analyses shall be carried out independently, 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 w
43、ell. Transfer the prescribed aliquot portion to a 200 ml one-mark volumetric flask. 7.5.2 Neutralize with the 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 o
44、f the hydrochloric acid. Allow to cool, dilute to the mark with water and mix well. 7.5.3 Introduce successively 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)
45、 10,0 ml of the test portion solution while mixing; e) 20,0 ml of the methyl isobutyl ketone (4.2). 7.5.4 Shake 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 th
46、e sulphuric acid solution. Shake for 30 s. During shaking avoid too close an intermixture of the phases; this 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
47、 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. DD CEN/TS 15022-2:2009CEN/TS 15022-2:2009 (E) 8 8 Expression of results By means of the calibration cur
48、ve (7.4.3) determine the mass of tin, in micrograms, corresponding to the measured absorbance value (after correction for the blank) and calculate the tin mass fraction in percent (%), according to one of the following formulae: a) without predilution: 041061Sn1010010mmmmw= (1) b) with predilution:
49、VmmVmmw=021061Sn10210020010(2) where m0is the mass of the test portion (Table 1), in grams (g); m1is the mass of tin, found in the test portion solution, in micrograms (g); 200 is the diluted volume of the aliquot portion taken for the determination (Table 1), in millilitres (ml); V is the volume of the aliquot portion taken for the determination (Table 1) in millilitres (ml). 9 Precision One laboratory tested this method and obtained the results summarized in Table 2 and Fi
