BS 7317-3-1990 Methods for analysis of high purity copper cathode Cu-CATH-1 - Method for determination of antimony arsenic bismuth selenium tellurium and tin by hydride generation .pdf

1、BRITISH STANDARD BS7317-3: 1990 Methods for Analysis of high purity copper cathode Cu-CATH-1 Part3: Method for determination of antimony, arsenic, bismuth, selenium, tellurium and tin by hydride generation and atomic absorption spectrophotometry UDC669.3.015.4:543.422.062:546.19 + 546.23/.24 + 546.8

2、11 + 546.86/.87BS7317-3:1990 This BritishStandard, having been prepared under the directionof the Non-ferrous Metals Standards Policy Committee, was published underthe authority of the BoardofBSI and comes intoeffecton 31 July1990 BSI12-1999 The following BSI references relate to the work on this st

3、andard: Committee reference NFM/34 Draft for Development DD95-3 ISBN 0 580 18462 5 Committees responsible for this BritishStandard The preparation of this BritishStandard was entrusted by the Non-ferrous Metals Standards Policy Committee (NFM/-) to Technical Committee NFM/34, upon which the followin

4、g bodies were represented: British Bathroom Council British Cable Makers Confederation British Gas plc British Malleable Tube Fittings Association British Non-ferrous Metals Federation British Valve and Actuator Manufacturers Association Copper Development Association London Metal Exchange Non-ferro

5、us Metal Stockists Society of British Aerospace Companies Ltd. Transmission and Distribution Association (BEAMA Ltd.) Coopted members The following bodies were also represented in the drafting of the standard, through subcommittees and panels: BNF Metals Technology Centre British Bronze and Brass In

6、got Manufacturers Association Bureau of Analysed Samples Ltd. Copper Smelters and Refiners Association Ministry of Defence Amendments issued since publication Amd. No. Date of issue CommentsBS7317-3:1990 BSI 12-1999 i Contents Page Committees responsible Inside front cover Foreword ii 1 Scope 1 2 Pr

7、inciple 1 3 Reagents 1 4 Apparatus 3 5 Procedure 3 6 Calculation and expression of results 6 7 Repeatability and reproducibility 6 8 Test report 7 Figure 1 Hydride generator: solution type 2 Figure 2 Silica absorption tube 4 Table 1 Calibration solutions 3 Table 2 Test conditions for the silica tube

8、 hydride method 6 Table 3 Maximum mean differences for impurity elements 6 Table 4 Repeatability of results 7 Table 5 Reproducibility of results 7 Publications referred to Inside back coverBS7317-3:1990 ii BSI 12-1999 Foreword BS7317 has been prepared under the direction of the Non-ferrous Metals St

9、andards Policy Committee. It describes methods for the determination of impurity elements in high purity copper cathode designated Cu-CATH-1, each method being published as a separate Part. The methods are based on those previously issued in the Draft for Development series DD95-1 to DD95-7. Theinfo

10、rmation and experience gained from the practical application of DD95have been taken into account in the methods in BS7317. This Part of BS7317 supersedes DD95-3:1984, which is withdrawn. It is one of a series of methods in BS7317, the others being as follows: Part1: Method for determination of cadmi

11、um, manganese and silver (screening procedure for chromium, cobalt, iron, nickel and zinc) by atomic absorption spectrophotometry; Part2: Method for determination of chromium, cobalt, iron, nickel and zinc by discrete volume nebulization atomic absorption spectrophotometry; Part4: Method for determi

12、nation of antimony, arsenic, bismuth, lead, selenium, tellurium and tin by electrothermal atomization atomic absorption spectrophotometry; Part5: Method for determination of sulphur by hydrogen sulphide evolution and spectrophotometry; Part6: Method for determination of phosphorus and silicon by spe

13、ctrophotometry; Part7: Method for determination of lead by lanthanum hydroxide separation and atomic absorption spectrophotometry. The atomic absorption spectrophotometric procedures in Parts1 and2 are complementary. A sample solution concentration found to be satisfactory for nebulizers in standard

14、 atomic absorptiometers was20g/L. At this concentration the precision obtainable, using the method described in Part1, is only sufficient to allow the determination of cadmium, manganese and silver. Results would be obtained for chromium, cobalt, iron, nickel and zinc that would prove useful in dete

15、cting impurities grossly in excess of the requirements for chemical composition specified in BS6017 for Cu-CATH-1 and would give a guide to the levels to be determined by Part2. The discrete volume nebulization procedure in Part2 was developed to enable a higher equivalent sample solution concentrat

16、ion of100g/L to be used without nebulizer blockage. The method involves no chemical separation, which can give rise to contamination problems, and the extra sensitivity obtained enables the impurities to be determined to an adequate accuracy for the requirements for chemical composition specified in

17、 BS6017 for Cu-CATH-1. Parts1 and2 essentially cover the same impurities. Part4 covers the electrothermal atomization atomic absorption spectrophotometric method and is recommended where the facility is available. Parts1,2,3 and7 are included for use where the electrothermal atomization equipment is

18、 not available. The method described in this Part has been developed from analytical work in which various types of commercially available apparatus have been used. Consequently, although every reasonable effort has been made to draft the method in a form that is practicable irrespective of the type

19、 of apparatus, information on the actual test conditions for particular types of apparatus that have been found to yield satisfactory results may be available. Requests for such information should be sent to Enquiry Section (Milton Keynes), British Standards Institution, enclosing a stamped addresse

20、d envelope for reply. Subject to availability, information will be supplied provided that the type, i.emanufacturer/model, of apparatus for which the information is required is clearly stated in the request.BS7317-3:1990 BSI 12-1999 iii DD95-3 described two methods for generating the impurity elemen

21、t hydrides: a) the direct flame hydride method; and b) the silica tube hydride method. Experience gained in the use of DD95-3 led to the conclusion that the sensitivity of the direct flame method was significantly less than the silica tube method. Thedirect flame method has therefore been deleted in

22、 this Part of BS7317. Revised techniques for the preparation of the primary calibration solutions for arsenic, selenium and tellurium have been introduced. A British Standard does not purport to include all the necessary provisions of a contract. Users of British Standards are responsible for their

23、correct application. Compliance with a British Standard does not of itself confer immunity from legal obligations. Summary of pages This document comprises a front cover, an inside front cover, pagesi toiv, pages1to8, an inside back cover and a back cover. This standard has been updated (see copyrig

24、ht date) and may have had amendments incorporated. This will be indicated in the amendment table on the inside front cover.iv blankBS7317-3:1990 BSI 12-1999 1 1 Scope This Part of BS7317 describes methods for the determination of the actual amounts of the impurity elements antimony, arsenic, bismuth

25、, selenium, tellurium and tin present in high purity copper cathode (designated Cu-CATH-1), by hydride generation and atomic absorption spectrophotometry. It is applicable to concentrations of the impurity elements not exceeding the following limits. 2 Principle Test solutions are prepared by separa

26、ting the impurity elements from the sample of Cu-CATH-1 by double co-precipitation with lanthanum hydroxide. An aliquot of each test solution is introduced into a hydride generation assembly where reaction with sodium borohydride liberates hydrogen and volatile hydrides which are transferred into th

27、e optical path of an atomic absorption spectrophotometer. The hydrides are thermally dissociated and the absorbances due to the impurity elements are measured. The determinations are carried out by the silica tube hydride method, in which sodium borohydride solution is used to generate the impurity

28、element hydrides. The generated hydrogen and the hydrides are introduced into a silica dissociation tube that is heated by a normal acetylene/air burner. 3 Reagents 3.1 General During the analysis, use only reagents of recognized analytical quality or higher purity and only distilled water, deionize

29、d water, or water of equivalent purity that has no detectable levels of the particular elements to be determined. NOTEUnless otherwise stated, all solutions are aqueous solutions. 3.2 Copper 1) , a certified reference material of a minimum of99.999% copper, containing less than0.54g/g of each of the

30、 impurity elements. 3.3 Hydrochloric acid, 1.18g/mL. 3.4 Hydrochloric acid, 1.18g/mL,50%V/V solution. 3.5 Hydrochloric acid, 1.18g/mL,20%V/V solution. 3.6 Hydrochloric acid, 1.18g/mL,5%V/V solution. 3.7 Hydrochloric acid, 1.18g/mL,4%V/V solution. 3.8 Nitric acid, 1.42g/mL. 3.9 Nitric acid, 1.42g/mL,

31、50%V/V solution. 3.10 Lanthanum nitrate solution, prepared by dissolving50g lanthanum nitrate in1L of water. 3.11 Ammonium hydroxide, 0.880g/mL. 3.12 Ammonium hydroxide, 0.880g/mL,10%V/V solution. 3.13 Potassium hydroxide solution, prepared by dissolving2g potassium hydroxide in100mL of water. 3.14

32、Sodium borohydride solution containing1g sodium hydroxide and3g sodium borohydride (NaBH 4 ) in100mL of water, prepared by dissolving first the sodium hydroxide and then the sodium borohydride. Filter the solution. Prepare daily. 3.15 Boric acid solution, prepared by dissolving40g boric acid (H 3 BO

33、 3 ) in1L of water. 3.16 Primary calibration solutions, as given in3.16.1 to3.16.6. These are acidified solutions containing1.0 0.0005g/L of the appropriate element. 3.16.1 Antimony. Dissolve2.669g antimony potassium tartrate K(SbO)C 4 H 4 O 6 in a minimum amount of distilled water and dilute to1L w

34、ith20%V/V hydrochloric acid solution(3.5). 3.16.2 Arsenic. Dissolve4.165g sodium arsenate (Na 2 HAsO 4 .7H 2 O) in water and dilute to1L with water. 3.16.3 Bismuth. Dissolve1.000g bismuth in a minimum amount of nitric acid solution(3.9) and dilute to1L with20%V/V hydrochloric acid solution(3.5). 3.1

35、6.4 Selenium. Dissolve1.000g selenium in a minimum amount of nitric acid solution(3.9) and dilute to1L with water. 3.16.5 Tellurium. Dissolve1.000g tellurium in40mL nitric acid solution(3.9) and dilute to1L with water. 3.16.6 Tin. Dissolve1.000g tin in20%V/V hydrochloric acid solution(3.5) and dilut

36、e to1L with20%V/V hydrochloric acid solution(3.5). antimony 64g/g(0.0006%m/m) maximum for each element arsenic bismuth 34g/g(0.0003%m/m) maximum for each element selenium tellurium tin 204g/g(0.0020%m/m) maximum NOTEThe titles of the publications referred to in this Part of BS7317 are listed on the

37、inside back cover. 1) For information on the availability of copper of suitable purity, apply to Enquiry Section, BSI, Linford Wood, Milton Keynes, MK146LE, enclosing a stamped addressed envelope for reply. BS7317-3:1990 2 BSI 12-1999 NOTEConical ground glass joints complying with BS572. Figure 1 Hy

38、dride generator: solution typeBS7317-3:1990 BSI 12-1999 3 4 Apparatus 4.1 Atomic absorption spectrophotometer, incorporating a 10 scale expansion facility, fitted with a burner for use with argon/hydrogen or acetylene/air, a strip chart or other recording system for peak measurement, and electrodele

39、ss discharge (ED) or hollow cathode (HC) lamps. NOTEElectrodeless discharge tube equipment is preferred for the determination of all elements, but hollow cathode lamps may be adequate for the determination of antimony, bismuth and tin. 4.2 Hydride generator, a purpose-built solution generator, such

40、as that shown in Figure 1, constructed from borosilicate or similar heat-resistant glass, or a commercially available generator. NOTEAlthough this method describes the use of a purpose-built generator, the use of a commercial hydride system constructed of all plastics material could require less “co

41、nditioning” before reproducible results are obtained. 4.3 Silica absorption tube, as shown in Figure 2, constructed from silica tube. The tube may be either purpose-built or as supplied with a commercially available hydride generator. The length of the tube is dependent on the flame length of the bu

42、rner in the atomic absorption spectrophotometer(4.1); it should be longer than the flame length by not more than10mm. 4.4 Laboratory glassware NOTEIt is recommended that new glassware, dedicated to this specific purpose, be used. 4.5 Paper pulp pad 4.6 110mm hardened, rapid filter paper 5 Procedure

43、5.1 General Scrupulously clean all glassware in aqua regia, i.e.1part concentrated nitric acid(3.8) and3 parts concentrated hydrochloric acid(3.3) for16h, rinse with distilled water and dry, immediately before use. 5.2 Preparation of solutions 5.2.1 Stock reference solutions. Prepare six stock refer

44、ence solutions (solutions5.2.1.1 to5.2.1.6) by the following method and use within24h to avoid deterioration. Into six separate1L volumetric flasks transfer, using a pipette,10mL of the antimony(3.16.1), arsenic(3.16.2) and tin(3.16.6) primary calibration solutions and5mL of the bismuth(3.16.3), sel

45、enium(3.16.4) and tellurium(3.16.5) primary calibration solutions. Dilute each solution to the mark with water and mix well. NOTEThe concentrations of the resulting stock reference solutions will be such that1mL is equivalent in each case to: Table 1 Calibration solutions 5.2.2 Calibration solutions

46、. Prepare six calibration solutions (solutions5.2.2.1 to5.2.2.6) by the following method, and use them in the same time period as that in which the test portions(see5.2.4) and the reagent blanks(see5.2.5) are prepared and measured. Weigh and transfer approximately35g of copper(3.2) into a1L beaker,

47、add250mL of50%V/V hydrochloric acid solution(3.4), cover and boil for1min. Decant the acid solution and wash the copper several times with water. Dry. Weigh and transfer six5.0g portions of the cleaned and dried copper(3.2) into separate600mL beakers. Add40mL nitric acid solution(3.9) and heat gentl

48、y to dissolve. Boil gently to expel nitrous fumes and dilute to approx.200mL with distilled water. Add to each beaker the amounts of each stock reference solution(5.2.1.1 to5.2.1.6) given in Table 1. 5.2.3 Separation procedures 5.2.3.1 Carry out the procedures in5.2.3.2 to5.2.3.4 for each calibratio

49、n solution(5.2.2.1 to5.2.2.6), for each test portion(5.2.4.1 to5.2.4.6) and for each reagent blank(5.2.5.1 to5.2.5.3). 5.2.3.2 Add10mL of lanthanum nitrate solution(3.10) and mix well. Add40mL of ammonium hydroxide(3.11) while stirring, heat to boiling and simmer for1min. Allow to settle for1min. antimony (5.2.1.1) 104g arsenic (5.2.1.2) tin (5.2.1.6) bismuth (5.2.1.3) 54g selenium (5.2.1.4) tellurium (5.2.1.5) Calibration solution Addition of stock reference solution Equivalent concentration for a5g sampl