1、 g49g50g3g38g50g51g60g44g49g42g3g58g44g55g43g50g56g55g3g37g54g44g3g51g40g53g48g44g54g54g44g50g49g3g40g59g38g40g51g55g3g36g54g3g51g40g53g48g44g55g55g40g39g3g37g60g3g38g50g51g60g53g44g42g43g55g3g47g36g58copper Electrogravimetric methodICS 73.060.99Copper sulfide concentrates Determination of BRITISH S
2、TANDARDBS ISO 10469:2006BS ISO 10469:2006This British Standard was published under the authority of the Standards Policy and Strategy Committee on 29 September 2006 BSI 2006ISBN 0 580 49147 1Amendments issued since publicationAmd. No. Date Commentscontract. Users are responsible for its correct appl
3、ication.Compliance with a British Standard cannot confer immunity from legal obligations.National forewordThis British Standard was published by BSI. It is the UK implementation of ISO 10469:2006. The UK participation in its preparation was entrusted to Technical Committee NFE/36, Copper lead and zi
4、nc ores and concentrates.A list of organizations represented on NFE/36 can be obtained on request to its secretary.This publication does not purport to include all the necessary provisions of a Reference numberISO 10469:2006(E)INTERNATIONAL STANDARD ISO10469Second edition2006-07-01Copper sulfide con
5、centrates Determination of copper Electrogravimetric method Concentrs de sulfure de cuivre Dosage du cuivre Mthode lectrogravimtrique BS ISO 10469:2006ii iiiContents Page Foreword iv Introduction v 1 Scope . 1 2 Normative references . 1 3 Principle. 1 4 Reagents 2 5 Apparatus 4 6 Sample . 5 6.1 Test
6、 sample . 5 6.2 Test portion . 5 7 Procedure 5 7.1 Number of determinations . 5 7.2 Blank test. 5 7.3 Dissolution of test portion . 5 7.4 Separation of arsenic, antimony, tin, selenium and silver . 5 7.5 Copper separation 6 7.5.1 Sulfide separation. 6 7.5.2 Hydroxide separation . 7 7.6 Electrolytic
7、deposition . 7 7.7 FAAS determination of copper in the electrolyte, filter residues and sulfide precipitates. 8 7.7.1 FAAS determination of copper in the filtrate of the sulfide precipitation. 8 7.7.2 Treatment of hydroxide precipitate in sulfide separation 8 7.7.3 FAAS determination of copper in th
8、e electrolyte, filter residues and precipitates (sulfide separation method). 8 7.8 FAAS determination of copper in the electrolyte, filter residues and precipitates (hydroxide separation method). 9 8 Expression of results . 10 9 Precision 10 9.1 Expression of precision . 10 9.2 Method for obtaining
9、the final result (see Annex B) . 10 9.3 Precision between laboratories. 11 9.4 Check of trueness. 11 9.4.1 Type of certified reference material (CRM) or reference material (RM) 12 10 Test report . 12 Annex A (normative) Procedure for the preparation and determination of the mass of a predried test p
10、ortion 13 Annex B (normative) Flowsheet of the procedure for the acceptance of analytical values for test samples 15 Annex C (informative) Derivation of precision equations 16 BS ISO 10469:2006iv Foreword ISO (the International Organization for Standardization) is a worldwide federation of national
11、standards bodies (ISO member bodies). The work of preparing International Standards is normally carried out through ISO technical committees. Each member body interested in a subject for which a technical committee has been established has the right to be represented on that committee. International
12、 organizations, governmental and non-governmental, in liaison with ISO, also take part in the work. ISO collaborates closely with the International Electrotechnical Commission (IEC) on all matters of electrotechnical standardization. International Standards are drafted in accordance with the rules g
13、iven in the ISO/IEC Directives, Part 2. The main task of technical committees is to prepare International Standards. Draft International Standards adopted by the technical committees are circulated to the member bodies for voting. Publication as an International Standard requires approval by at leas
14、t 75 % of the member bodies casting a vote. Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights. ISO shall not be held responsible for identifying any or all such patent rights. ISO 10469 was prepared by Technical Committee ISO/TC 183,
15、 Copper, lead, zinc and nickel ores and concentrates. This second edition cancels and replaces the first edition (ISO 10469:1994), which has been technically revised. BS ISO 10469:2006vIntroduction ISO 10469:1994 underwent periodical review in 1999. Although the decision was made to confirm the Inte
16、rnational Standard at that time, significant comments were submitted by Japan. These comments were considered at a meeting of ISO/TC 183 in 2000, where it was agreed that Japan would re-draft ISO 10469 to indicate the proposed changes. The most significant change was the elimination of the correctio
17、n for impurities. ISO/TC 183 agreed that the changes made do not warrant a new interlaboratory test programme. Details of the changes are as follows: a) Deletion of the determination of impurities in the deposited copper (7.9 in ISO 10469:1994). b) Adjustment of the expression of dissolution of the
18、test portion according to ISO 10258:1994, Copper sulfide concentrates Determination of copper content Titrimetric methods. c) Adjustment of the expression of the sulfide separation method according to ISO 10258:1994. d) In the case of contained bismuth or tellurium, modification of the sulfide separ
19、ation procedure. The method described in ISO 10469:1994 included a lot of copper in the iron hydroxide precipitation, which will lead to incorrect results. The method described in ISO 13658:2000, Zinc sulfide concentrates Determination of zinc content Hydroxide precipitation and EDTA titrimetric met
20、hod has less copper in the iron hydroxide precipitation than the method described in ISO 10469:1994, so the method described in ISO 10469:1994 has now been modified with reference to ISO 13658. e) The procedure of treatment of the iron hydroxide precipitation (contained copper) is not given in ISO 1
21、0469:1994. The procedure of treatment has been added to the revised Standard. Calibration solution A (4.34.1 in ISO 10469:1994) will be used in 7.7.1 (FAAS determination of copper in the filtrate of the sulfide precipitation). This filtrate contains iron ion, so calibration solution A should contain
22、 iron to achieve matrix matching. The preparation method of calibration solution A has been revised to include iron ion in the revised Standard. BS ISO 10469:2006blank1Copper sulfide concentrates Determination of copper Electrogravimetric method WARNING This International Standard may involve hazard
23、ous materials, operations and equipment. It is the responsibility of the user of this International Standard to establish appropriate health and safety practices and determine the applicability of regulatory limitations prior to use. 1 Scope This International Standard specifies an electrogravimetri
24、c method for the determination of the mass fraction of copper in copper sulfide concentrates in the range 15 % to 50 %. 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
25、references, the latest edition of the referenced document (including any amendments) applies. ISO 385, Laboratory glassware Burettes ISO 648, Laboratory glassware One-mark pipettes ISO 1042, Laboratory glassware One-mark volumetric flasks ISO 4787, Laboratory glassware Volumetric glassware Methods f
26、or use and testing of capacity ISO 9599, Copper, lead and zinc sulfide concentrates Determination of hygroscopic moisture in the analysis sample Gravimetric method 3 Principle The test portion is decomposed in nitric and sulfuric acids, and copper is separated from interfering elements: from silver
27、by precipitation of silver chloride; from arsenic, antimony, selenium and tin by fuming with hydrobromic acid; from iron by precipitation of copper sulfide with sodium thiosulfate or by precipitation of iron(III) oxide hydrate (bismuth and tellurium are also separated in this way). Electrogravimetri
28、c deposition of copper occurs in the presence of nitric acid, sulfuric acid and traces of chloride. Under these conditions, coprecipitation of molybdenum does not occur. Traces of copper in the electrolyte, the filtrate of the copper sulfide precipitation, all precipitates and residues are determine
29、d by flame atomic absorption spectrometry (FAAS) or inductively coupled plasma atomic emission spectrometry. BS ISO 10469:20062 The normal mass fraction of mercury in copper concentrates does not usually affect the copper result. At a level of 0,005 % or greater, the mass fraction of mercury in the
30、copper deposit should be checked. This procedure is not described in this International Standard. 4 Reagents During the analysis, use only reagents of recognized analytical grade and distilled water or water of equivalent purity. 4.1 Nitric acid, concentrated (201,42 g/ml). 4.2 Nitric acid, diluted
31、1 + 1. Slowly add 500 ml of concentrated nitric acid (4.1) to 500 ml of water, while stirring. 4.3 Sulfuric acid, concentrated (201,84 g/ml). 4.4 Sulfuric acid, diluted 1 + 1. Slowly add 500 ml of concentrated sulfuric acid (4.3) to 500 ml of water, while stirring. Cool the solution. 4.5 Sulfuric ac
32、id, diluted 1 + 4. Slowly add 200 ml of concentrated sulfuric acid (4.3) to 800 ml of water, while stirring. Cool the solution. 4.6 Sodium thiosulfate pentahydrate, (450 g/l) solution. 4.7 Nitration mixture. Slowly add 250 ml of concentrated sulfuric acid (4.3) to 250 ml of concentrated nitric acid
33、(4.1). 4.8 Sodium chloride, 10 g/l solution. 4.9 Sodium chloride, 0,5 g/l solution. 4.10 2-propanol. 4.11 Ethanol, minimum purity 95 % (V/V). 4.12 Methanol, minimum purity 95 % (V/V). 4.13 Ammonium iron(III) sulfate solution. Add 50 ml of dilute sulfuric acid (4.4) and 43 g of ammonium iron(III) sul
34、fate dodecahydrate NH4Fe(SO4)212H2O to 950 ml of water. 4.14 Iron(III) nitrate solution. Add 30 g of iron(III) nitrate nonahydrate Fe(NO3)39H2O to 100 ml of water. 4.15 Ammonia solution (200,91 g/ml). 4.16 Ammonia solution, diluted 1 + 99. 4.17 Hydrobromic acid (201,50 g/ml). 4.18 Perchloric acid (2
35、01,53 g/ml). BS ISO 10469:200634.19 Hydrofluoric acid (201,14 g/ml). 4.20 Copper metal, minimum purity 99,999 %. 4.21 Sodium sulfate (Na2SO4), anhydrous. 4.22 Hydrochloric acid, concentrated (201,16 g/ml to 1,18 g/ml). 4.23 Hydrochloric acid, diluted 1 + 1. Slowly add 500 ml of concentrated hydrochl
36、oric acid (4.22) to 500 ml of water, while stirring. 4.24 Bromine. 4.25 Copper standard solution, 1 ml contains 0,1 mg of Cu. Dissolve 0,1 000 g of copper metal (4.20) in 10 ml of warm dilute nitric acid (4.2) and heat to evaporate to approximately 5 ml to remove nitrogen oxides. Transfer to a 1 000
37、 ml volumetric flask, fill up nearly to the mark with water, mix and equilibrate at room temperature; then fill up exactly to the mark and mix again. Standard solutions should be prepared at the same ambient temperature as that at which the determinations will be conducted. 4.26 Calibration solution
38、s. Calibration solutions should be prepared at the same ambient temperature as that at which the determination will be conducted. Calibration solutions should be prepared freshly before use. 4.26.1 Calibration solutions A. Pipette 0,0 ml, 10,00 ml, 20,00 ml, 30,00 ml and 40,00 ml of copper standard
39、solution (4.25) into a series of 500 ml one-mark volumetric flasks. Add 40 ml of dilute sulfuric acid (4.4), 13 g of sodium sulfate (4.21) and 50 ml (see third paragraph) of ammonium iron(III) sulfate (4.13) (corresponding to approximately 250 mg of iron) to each flask. Dilute with water, stir to di
40、ssolve the salts, fill up nearly to the mark, mix and equilibrate at room temperature, then fill up exactly to the mark and mix again. These solutions contain 0 mg of Cu, 1 mg of Cu, 2 mg of Cu, 3 mg of Cu and 4 mg of Cu in a 500 ml volume. If the test solution contains less than 50 mg of iron, only
41、 10 ml of ammonium iron(III) sulfate (4.13) should be added to each flask. In situations where the test solution contains more than 4 mg of Cu, dilute with the calibration solution containing 0,0 mg of Cu, until the copper concentration in the test solution is below 4 mg/500 ml. 4.26.2 Calibration s
42、olutions B. Pipette 0,0 ml, 10,00 ml, 20,00 ml, 30,00 ml and 40,00 ml of copper standard solution (4.25) into a series of 500 ml one-mark volumetric flasks. Add 30 ml of dilute sulfuric acid (4.4), 10 ml of dilute nitric acid (4.2), 15 ml of dilute hydrochloric acid (4.23) and 25 ml of ammonium iron
43、(III) sulfate solution (4.13) to each flask. Fill up nearly to the mark with water, mix and equilibrate at room temperature; then fill up exactly to the mark and mix again. These solutions contain 0 mg of Cu, 1 mg of Cu, 2 mg of Cu, 3 mg of Cu and 4 mg of Cu in a 500 ml volume. BS ISO 10469:20064 In
44、 situations where the test solution contains more than 4 mg of Cu, dilute with the calibration solution containing 0,0 mg of Cu, until the copper concentration in the test solution is below 4 mg/500 ml. 4.26.3 Calibration solutions C. Pipette 0,0 ml, 10,00 ml, 20,00 ml, 30,00 ml and 40,00 ml of copp
45、er standard solution (4.25) into a series of 500 ml one-mark volumetric flasks. Add 20 ml of dilute sulfuric acid (4.4), 10 ml of dilute nitric acid (4.2) and 50 ml (see third pargraph) of ammonium iron(III) sulfate solution (4.13) (corresponding to approximately 250 mg of Fe) to each flask. Fill up
46、 nearly to the mark with water, mix and equilibrate at room temperature; then fill up exactly to the mark and mix again. These solutions contain 0 mg of Cu, 1 mg of Cu, 2 mg of Cu, 3 mg of Cu and 4 mg of Cu in a 500 ml volume. If the test portion contains less than 50 mg of Fe (18) If this condition
47、 exists, the difference between the reported result and the certified value is statistically significant. BS ISO 10469:200612 In Equations (17) and (18), the symbols have the following meanings: cis the final result, expressed as a percentage by mass of copper, of the certified reference material; A
48、cis the certified value, expressed as a percentage by mass of copper, of the certified reference material; C is a quantity, expressed as a percentage by mass of copper, depending on the type of the certified reference material used, as defined in 9.4.1. 9.4.1 Type of certified reference material (CR
49、M) or reference material (RM) The reference materials used for this purpose should be prepared and certified in accordance with ISO Guide 35:2006, Reference materials General and statistical principles for certification. 9.4.1.1 Reference material certified/characterized by an interlaboratory test programme The quantity C (see 9.4), expressed as a percentage by mass of copper, is given by the following equation: 22 2Lc2/rCssnSA=+ (19) where S2Ac is the variance of the certified value
