ISO 10469:2006

INTERNATIONAL ISO
STANDARD 10469
Second edition
2006-07-01
Copper sulfide concentrates —
Determination of copper —
Electrogravimetric method
Concentrés de sulfure de cuivre — Dosage du cuivre — Méthode
électrogravimétrique
Reference number
©
ISO 2006
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ii © ISO 2006 – All rights reserved

Contents 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 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 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 the 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 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 portion . 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

Foreword
ISO (the International Organization for Standardization) is a worldwide federation of national 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 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 given 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 least 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, 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.
iv © ISO 2006 – All rights reserved

Introduction
ISO 10469:1994 underwent periodical review in 1999. Although the decision was made to confirm the
International 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 correction 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 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 separation 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 method 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 10469:1994. 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 iron to
achieve matrix matching. The preparation method of calibration solution A has been revised to include iron ion
in the revised Standard.
INTERNATIONAL STANDARD ISO 10469:2006(E)

Copper sulfide concentrates — Determination of copper —
Electrogravimetric method
WARNING — This International Standard may involve hazardous 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 electrogravimetric 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 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 for 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 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).
Electrogravimetric 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 determined by flame atomic absorption spectrometry (FAAS) or inductively coupled plasma atomic
emission spectrometry.
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 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 (ρ 1,42 g/ml).
4.2 Nitric acid, diluted 1 + 1.
Slowly add 500 ml of concentrated nitric acid (4.1) to 500 ml of water, while stirring.
4.3 Sulfuric acid, concentrated (ρ 1,84 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 acid, 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 (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) s
...