GOST R 55685-2013

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  ГОСТ Р 55685-2013

GOST R 55685−2013 Copper rough. Methods of analysis

GOST R 55685−2013

NATIONAL STANDARD OF THE RUSSIAN FEDERATION

COPPER ROUGH

Methods of analysis

Blister copper. Methods of analysis

OKS 77.120.30

Date of introduction 2014−09−01

Preface

1 DEVELOPED by the Open joint-stock company «Ural research and design Institute of enrichment and mechanical processing of minerals» (JSC «uralmekhanobr»)

2 SUBMITTED by the Technical Committee for standardization TC 368 «Copper"

3 APPROVED AND put INTO EFFECT by the Federal Agency for technical regulation and Metrology dated 31 October 2013 N 1328-St

4 INTRODUCED FOR THE FIRST TIME


Application rules of this standard are established in GOST R 1.0−2012 (section 8). Information about the changes to this standard is published in the annual (as of January 1 of the current year) reference index «National standards» and the official text changes and amendments — in monthly information index «National standards». In case of revision (replacement) or cancellation of this standard a notification will be published in the upcoming issue of the monthly information index «National standards». Relevant information, notification and lyrics are also posted in the information system of General use — on the official website of the Federal Agency for technical regulation and Metrology on the Internet (gost.ru)

1 Scope

This standard specifies:

General requirements for methods of analysis of blister copper all grades;

— methods of measurements of mass fraction of copper and impurities in blister copper.

2 Normative references

This standard uses the regulatory references to the following standards:

GOST 8.315−97 State system for ensuring the uniformity of measurements. Standard samples of composition and properties of substances and materials. The main provisions of the

GOST 83−79 Reagents. Sodium carbonate. Specifications

GOST 849−2008 Nickel primary. Specifications

GOST 859−2001 Copper. Brand

GOST 860−75 Tin. Specifications

GOST 1027−67 Reagents. Lead (II) acetate 3-water. Specifications

GOST 1089−82 Antimony. Specifications

GOST 1277−75 Reagents. The silver nitrate. Specifications

GOST 1770−74 (ISO 1042−83, ISO 4788−80) Glassware volumetric laboratory glass. Cylinders, beakers, flasks, test tubes. General specifications

GOST 1973−77 arsenious Anhydride. Specifications

GOST 2062−77 Reagents. Acid bromatologica. Specifications

GOST 2713−74 Salt potassium chlorate technical. Specifications

GOST 3118−77 Reagents. Hydrochloric acid. Specifications

GOST 3652−69 Reagents. Citric acid monohydrate and anhydrous. Specifications

GOST 3760−79 Reagents. The aqueous ammonia. Specifications

GOST 3765−78 Reagents. Ammonium molybdate. Specifications

GOST 3778−98 Lead. Specifications

GOST 4108−72 Reagents. Barium chloride 2-water. Specifications

GOST 4109−79 Reagents. Brom. Specifications

GOST 4110−75 Reagents. Bismuth (III) nitrate 5-water. Specifications

GOST 4147−74 Reagents. Iron (III) chloride 6-water. Specifications

GOST 4159−79 Reagents. Iodine. Specifications

GOST 4160−74 Reagents. Potassium bromide. Specifications

GOST 4165−78 Reagents. Copper (II) sulfate 5-water. Specifications

GOST 4197−74 Reagents. Sodium atomistically. Specifications

GOST 4204−77 Reagents. Sulphuric acid. Specifications

GOST 4212−76 Reagents. Methods of preparation of solutions for colorimetric and nephelometric analysis

GOST 4232−74 Reagents. The potassium iodide. Specifications

GOST 4233−77 Reagents. Sodium chloride. Specifications

GOST 4328−77 Reagents. Sodium hydroxide. Specifications

GOST 4461−77 Reagents. Nitric acid. Specifications

GOST 4465−74 Reagents. Nickel (II) sulphate 7-aqueous. Specifications

GOST 4520−78 Reagents. Mercury (II) nitrate 1-water. Specifications

GOST 4689−94 Products refractory periclase. Specifications

GOST 5100−85 Soda ash technical. Specifications

GOST 5456−79 Reagents. Of hydroxylamine hydrochloride. Specifications

GOST 5457−75 Acetylene, dissolved and gaseous. Specifications

GOST 5556−81 Wool medical hygroscopic. Specifications

GOST 5583−78 (ISO 2046−73) Oxygen gas technical and medical. Specifications

GOST 5789−78 Reagents. Toluene. Specifications

GOST 5817−77 Reagents. Acid wine. Specifications

GOST 5828−77 Reagents. Dimethylglyoxime. Specifications

GOST 5845−79 Reagents. Potassium-sodium vinocity 4-water. Specifications

GOST 6344−73 Reagents. Thiourea. Specifications

GOST 6563−75 technical articles made of noble metals and alloys. Specifications

GOST 6613−86 Grids wire woven with square cells. Specifications

GOST 6691−77 Reagents. Urea. Specifications

GOST 6709−72 distilled Water. Specifications

GOST 6835−2002 Gold and alloys on its basis. Brand

GOST 6836−2002 Silver and alloys on its basis. Brand

GOST 7172−76 Reagents. Potassium preservatory

GOST 8429−77 Drill. Specifications

GOST 8677−76 Reagents. Of calcium oxide. Specifications

GOST 9147−80 Glassware and equipment lab porcelain. Specifications

GOST 9849−86 iron Powder. Specifications

GOST 10157−79 Argon gaseous and liquid. Specifications

GOST 10178−85 Portland cement and Portland slag cement. Specifications

GOST 10298−79 Selenium technical. Specifications

GOST 10360−85 periclase sintered Powders for manufacture of products. Specifications

GOST 10929−76 Reagents. Hydrogen peroxide. Specifications

GOST 12026−76 laboratory filter Paper. Specifications

GOST 14261−77 hydrochloric Acid of high purity. Specifications

GOST 16539−79 Reagents. Copper (II) oxide. Specifications

GOST 18300−87 ethyl rectified technical. Specifications

GOST 20015−88 Chloroform. Specifications

GOST 20448−90 liquefied hydrocarbon Gases fuel for household consumption. Specifications

GOST 20478−75 Reagents. Ammonium neccersarily. Specifications

GOST 21241−89 Tweezers medical. General technical requirements and test methods

GOST 22867−77 Reagents. The ammonium nitrate. Specifications

GOST 25086−2011 non-ferrous metals and their alloys. General requirements for methods of analysis

GOST 25336−82 Glassware and equipment laboratory glass. The types, basic parameters and dimensions

GOST 29169−91 (ISO 648−77) oils. Pipette with one mark

GOST 29227−91 (ISO 835−1-81) oils. Pipettes are graduated. Part 1. General requirements

GOST 29251−91 (ISO 385−1-84) oils. Burette. Part 1. General requirements

GOST 31290−2005 Platinum affilirovannaja. Specifications

GOST 31291−2005 Palladium refined. Specifications

GOST R 8.563−2009 State system for ensuring the uniformity of measurements. Techniques (methods) of measurements

GOST R 8.568−97 State system for ensuring the uniformity of measurements. Certification of testing equipment. The main provisions of the

GOST R ISO 5725−1-2002 Accuracy (trueness and precision) of methods and measurement results. Part 1. General provisions and definitions

GOST R ISO 5725−6-2002 Accuracy (correctness and precision) of methods and measurement results. Part 6. The use of precision values in practice

GOST R 52361−2005 Control of the analytical object. Terms and definitions

GOST R 53228−2008 Scales non-automatic actions. Part 1. Metrological and technical requirements. Test

GOST R 54310−2011 Copper rough. Specifications

ST SEV 543−77 Number. Record rules and rounding

Note — When using this standard appropriate to test the effect of reference standards in the information system of General use — on the official website of the Federal Agency for technical regulation and Metrology on the Internet or in the annual information index «National standards» published as on January 1 of the current year, and the editions of the monthly information index «National standards» for the current year. If replaced with a reference standard, which was given an undated reference, then it is recommended to use the current version of this standard, taking into account all enabled in this version modifications. If replaced with a reference standard, which is given a dated reference, it is recommended to use the version of this standard referred to above by year of approval (acceptance). If after approval of this standard in the reference standard, which is given a dated reference, a change affecting a provision to which reference, the provision is recommended to be applied without taking into account this change. If the reference standard is cancelled without replacement, then the situation in which the given link applies to the extent that does not affect this link.

3 Terms and definitions

This standard applies the terminology in accordance with GOST 25086, 52361 GOST R, GOST R 8.563, GOST R ISO 5725−1, GOST R ISO 5725−6.

4 General requirements

4.1 the Selection and preparation of samples of blister copper to measurements carried out in accordance with GOST R 54310.

4.2 General requirements for methods of measurements GOST 25086.

4.3 taking measurements use laboratory scales in accordance with GOST R 53228, accuracy class weights must be specified in a particular method of measurement.

Note — If the class of accuracy is not specified in the method of measurement, weighing of the analyte, the substance for the preparation of solutions of known metal concentrations and precipitation in gravimetric method carried out in the balances of special accuracy class according to GOST R 53228.

4.4 the weight of blister copper is weighed with an accuracy to four decimal places, if there are no instructions in a particular method of measurement.

4.5 For the calcination and fusion used laboratory muffle furnace providing heating temperature up to (1100±5) °C (provided that the measurement technique does not have another temperature). For drying, use laboratory ovens, to ensure the heating temperature is not less than (250±3) °C. For dissolution and evaporation of solutions used electric stoves with a closed heating element for temperature up to 350 °C.

4.6 For measurements use a measuring laboratory glassware not lower than 2nd accuracy class according to GOST 1770, 29169 GOST, GOST 29227, GOST 29251, utensils and equipment according to GOST 25336, crockery and equipment (crucibles, boats, inserts for desiccators, etc.) according to GOST 9147, and jewelry made of platinum according to GOST 6563, dishes made of glassy carbon brand SU-2000.

4.7 Used in the methods of measurement measuring instruments must have valid calibration certificates and/or certificates of calibration test equipment must be certified according to GOST R 8.568.

4.8 Mass fraction of copper and impurities determined in parallel in two or three batches according to the number of parallel measurements, which indicate a particular method of measurement. Simultaneously with the measurements in the same conditions conduct control experience for an amendment to the results of the measurements (with the exception of measurements of mass fraction of copper).

4.9 Used in the methods of measurement the reagents have to have a qualification not lower than «pure for analysis». Allowed the use of the reagents lower qualifications provided that their metrological characteristics of measurement results normalized in the method of measurement. Mandatory application of reagents a higher qualification stipulated in the method of measurement.

4.10 For the preparation of solutions and the analysis used laboratory water is not less pure than distilled water according to GOST 6709, if no other.

4.11 shelf Life of the solutions — in accordance with the requirements of GOST 4212, unless otherwise noted in the measurement procedure.

4.12 verification of the acceptability of measurement results and establishment of final result is carried out in accordance with GOST R ISO 5725−6.

4.13 Control of accuracy of measurement results

Accuracy control of measurement results carried out in accordance with GOST 25086 and subject to GOST R ISO 5725−6.

4.14 the results of the measurements

The results of the measurements are in the form of (at confidence probability of 0.95),

where is the measurement result, % (g/t);

 — characteristics of the measurement error, % (g/t).

The value «» given in a particular method of measurement.

Note — In the case when the final result of the measurement take the median values of critical difference and accuracy specifications calculated in accordance with GOST R ISO 5725−6.

4.15 Rounding of the measurement results is carried out in accordance with the requirements of ST CMEA 543.

4.16 permitted the use of other measurement procedures, certified in the prescribed manner in accordance with GOST R 8.563 and provide metrological characteristics are not worse than specified in this standard.

4.17 in the event of disagreement between the supplier and the consumer on the quality of blister copper of arbitration of the measurement methods are the methods described in this standard.

4.18 safety Requirements methods of measurement — according to GOST 25086.

5 Methods of measurements of mass fraction of copper

5.1 Scope

This section sets electrogravimetry method of measuring the mass fraction of copper (with silver) in the range of 96.00% to 99,85%.

5.2 Requirements on error of measurement

The error of the measurements the mass fraction of copper for a confidence probability of 0.95, should not exceed ±0,15%.

5.3 measurement Means, auxiliary devices, materials, solutions

When performing measurements using the following measuring instruments and auxiliary devices:

installation for electrolysis, providing carrying out the electrolysis while stirring at a current of from 2 to 3 And* and the voltage from 2 to 2.5;
_______________
* Carrying out electrolysis at a current of from 1 to 4 A.


electrodes made of platinum mesh cylindrical GOST 6563;

— laboratory drying oven with thermostatic control, ensuring the heating temperature up to 250 °C;

— spectrophotometer or the photoelectric photometer with all accessories necessary for measurements at a wavelength from 434 to 440 nm;

spectrometer of atomic emission with inductively coupled plasma;

spectrometer atomic absorption of any type, providing the required accuracy of measurement with the radiation source for copper;

— air compressor;

oven muffle with heating temperature up to 1100 °C;

— the stove is electric with a closed heating element for temperature up to 350 °C;

— special laboratory scales of accuracy class according to GOST R 53228;

— porcelain crucibles according to GOST 9147;

— glasses-1−50 TCS In-1−100 TCS-1−200 TCS-1−250 TCS according to GOST 25336;

— funnel VD-1−100 TC GOST 25336;

— volumetric flasks 1−25−2, 1−100−2, 1−200−2, 1−250−2, 1−1000−2, 2−200−2, 2−250−2, 2−500−2, 2−1000−2 according to GOST 1770;

pipettes not lower than 2nd accuracy class according to GOST and GOST 29169 29227;

glass hour.

When taking measurements, use the following products and solutions:

— distilled water according to GOST 6709;

— nitric acid according to GOST 4461, diluted 1:4, 3:97, 1:1;

— sulfuric acid according to GOST 4204, diluted 1:1, 5:95;

— a mix of acids for dissolving the sample of blister copper: mix 375 cmof nitric acid and 125 cmof sulfuric acid, was added 500 cmof water;

— ammonia water according to GOST 3760;

— ammonium nitrate according to GOST 22867;

— potassium preservatory according to GOST 7172;

— chloroform according to GOST 20015;

— diethyldithiocarbamate, lead (II) according to [1], the solution of the mass concentration of 0.2 g/lin chloroform;

— technical rectified ethyl alcohol according to GOST 18300;

— copper according to the GOST 859;

— copper (II) sulfate 5-water according to GOST 4165;

— the state standard samples of composition of copper ions;

filters obestochennye [2] or similar;

the filter paper according to GOST 12026, brands, f, FS;

paper universal indicator [3];

— medical absorbent cotton wool GOST 5556;

— solutions of known copper concentration.

5.4 Method of measurement

The method is based on measuring the mass of copper allocated by electrolysis on a platinum mesh cathode in nitric-sulfuric acid solution at a current of from 2 to 3 and a voltage of 2 to 2.5* and the determination of the copper remaining in the electrolyte, photometric or atomic absorption method, method of emission spectrometry with inductively coupled plasma (ICP).
_______________
* Carrying out electrolysis at a current of 1 to 2.5 And with a gradual increase in current strength from 3 to 4 A.

5.5 Preparation for measurements

5.5.1 in the preparation of a solution of lead diethyldithiocarbamate (II) the mass concentration. 0.2 g/lin chloroform the weight of salt mass of 0.2 g is placed in a measuring flask with volume capacity of 1000 cm, a flow from 100 to 200 cmof chloroform, and stirred to dissolve the sample, add chloroform to the mark. Stored in a flask made of dark glass in a dark place. Solution store no more than two weeks.

5.5.2 For the construction of calibration curve prepare solutions of known copper concentration.

In preparing the solution And the mass concentration of copper is 0.2 mg/cma sample of copper with a mass of 0.2000 g placed in a beaker with a capacity of 100 cm, flow 10 to 15 cmof nitric acid, diluted 1:1, and heated to remove oxides of nitrogen and dissolving the sample. Then in a glass pour 50 to 70 cmof water, heated to dissolve the salts, cooled, the resulting solution placed in a measuring flask with volume capacity of 1000 cm, made up to the mark with water and mix.

The same solution may be prepared from sulphate of copper. A sample of copper sulfate weighing 0,7858 g is placed in a measuring flask with volume capacity of 1000 cm, pour 1 cmof sulfuric acid, made up to the mark with water and mix. The shelf life of the solution — not more than three months.

In the preparation of a solution of mass concentration of copper of 0.01 mg/cmof 25 cmof the solution And placed in a volumetric flask with a capacity of 500 cm, pour 2 (3) cmof sulphuric acid diluted 1:1, made up to the mark with water and mix.

When cooking solution To the mass concentration of copper is 0.005 mg/cmof 50 cmof a solution is placed in a volumetric flask with a capacity of 100 cm, made up to the mark with water and mix. Solutions B and C using freshly prepared.

Allowed preparation of the solution And some concentration of copper in solution with subsequent dilution, providing concentrations of solutions B and C.

5.5.3 Construction of calibration curve when using a photometric method of measurement of copper in the electrolyte

For construction of calibration curve six separatory funnels with a capacity of 100 cmeach placed: 0; 0,5; 1,0; 2,0; 3,0; 5,0 cmof solution B. If the mass fraction of copper is less than 0.5 mg, use solution B. all the funnel pour water to a volume of 50 cm, in 5 cmof sulphuric acid diluted 1:1 and continue in 5.6.3.1. According to the obtained results build a graph of optical density by weight of copper.

5.5.4 Construction of calibration curve when using the atomic absorption method of measurement of copper in the electrolyte

To build a calibration curve in a series of volumetric flasks with a capacity of 200 or 250 cmput a solution of A or B in such quantity as to keep the linearity of calibration curve in the range of the designated concentrations.

For constructing a calibration curve allowed to use 3−7 calibration mixtures, but not less than 3.

5.5.5 Construction of calibration curve when using the method of emission spectrometry with inductively coupled plasma

To build a calibration curve in three volumetric flasks with a capacity of 100 cmeach placed 1, 5, 10 cmGSO solution of copper ions or copper solution with a mass concentration of 1 mg/cm, prepared according to GOST 4212, made up to the mark with water, mix and get the calibration solution with a concentration of 10,0, 50,0, 100 µg/cm.

5.6 performance measurement

5.6.1 General requirements for methods of measurements and safety requirements when performing measurements in accordance with section 4.

5.6.2 Electrogravimetry method of measuring the mass fraction of copper (with silver)

The weight of blister copper weighing from 1 to 2 g were placed in a glass with a capacity of 200 or 250 cm, flow 25 to 40 cmof the mixture of acids to dissolve, cover glass glass (cap) and conduct dissolution without first heating, then heated to dissolve the attachment and removal of nitrogen oxides.

Allowed dissolution of the sample in nitric acid, diluted 1:1, followed by adding before the electrolysis is from 5 to 7 cmof sulphuric acid diluted 1:1.

If during the dissolution of formed insoluble residue, the solution is poured 20 cmof water, heated to dissolve the salts and then filtered through a medium density filter «white ribbon», washed six or seven times with hot water, acidified with nitric acid, and five or six times with hot water.

In the case of precipitation measurement acid (after dilution of the sample formed a cloudy solution) the solution is evaporated to a volume of 4 to 5 cm, then add 3 g of ammonium nitrate, pour 100 to 120 cmof hot water, boil the solution for 15−20 min and allowed to stand in a warm place plate to the coagulation of the precipitate (you can leave overnight). The precipitate is then filtered through a dense filter of «blue ribbon» in the cone which is enclosed a little filtrowanie mass, and washed it four or five times with hot nitric acid, diluted 3:97.

The filter with precipitate was placed in a porcelain crucible, dried and burned in a muffle furnace at a temperature of from 400 °C to 500 °C. the Residue is fused with 5 g potassium peacemaking at a temperature of from 800 °C to 850 °C. the Melt is leached in 25 cmof nitric acid, diluted 3:97, and the resulting solution was attached to the main filtrate, which is used for electrolysis.

Allowed connection of the solution after leaching float directly into the beaker with the electrolyte.

The filtrate is diluted with 150−180 cmof water placed in a glass of a platinum mesh electrode (cathode pre-dried at a temperature of from 100 °C to 105 °C and weighed) and covered when necessary, the two halves of the glass or plate. Set the voltage from 2 to 2.5 V and a current of from 2.0 to 2.5 A. Gradually increasing the current up to 3 A, conduct the electrolysis while stirring the solution with or without stirring*.
_______________
* Carrying out electrolysis at a current of 1 to 2.5 And with a gradual increase in current strength from 3 to 4 A.


After deposition of the main mass of copper (after approximately 2 to 2.5 h) check the completeness of its deposition. Add water and, if after 10−15 min on the newly immersed part of the cathode does not appear RAID recovery of copper, electrolysis is complete.

The glass electrolyte is removed and the electrodes washed first with water, then ethyl alcohol (10 g of alcohol per one definition).

If the copper has a dark color, the electrolysis is repeated. For this purpose the cathode with the Deposit of copper is transferred into a beaker with a capacity of 200 to 250 cm, 50 cm pournitric acid, diluted 1:4, and the heated solution. After dissolution of the copper electrode is removed from the beaker, wash it with water over the beaker and the solution is gently boiled to remove oxides of nitrogen. Then add 4 cmof ammonia solution, 5 cmof sulphuric acid diluted 1:1, water to a volume of 100 to 150 cmand repeat the electrolysis.

Washed with water and alcohol, the cathode was dried in a drying Cabinet at a temperature of from 100 °C to 105 °C for 5−10 min, cooled and weighed.

The electrolyte is placed in a volumetric flask with a capacity of 200 or 250 cm, made up to the mark with water and mix. Keep to determine it residual copper and Nickel.

5.6.3 Extraction-photometric method of measuring the mass of copper remaining in the electrolyte

5.6.3.1 From the electrolyte obtained according to 5.6.2, the selected aliquot of the solution of volume from 5 to 25 cm, placed in a separatory funnel with a capacity of 100 cm, pour water up to 50 cm, 10 cmsolution of lead diethyldithiocarbamate and extracted within 2 min. If you use the extractors, then shaken for 3−7 min.

After the separation of the extract was transferred to a beaker with a capacity of 50 cm. The extraction was repeated with 5 cmof a solution of lead diethyldithiocarbamate to obtain a colorless layer. Combine all extracts in the same beaker, transferred to a volumetric flask with a capacity of 50 cm, filtering through cotton wool moistened with chloroform, adjusted to the mark with chloroform and mix.

After 5−30 min, measure the optical density of the chloroform extract at a wavelength of 434 or 440 nm in a cuvette with the thickness of the light absorbing layer 10 or 30 mm.

Solution comparison is the extract of the control experience.

Mass of copper is determined according to the calibration schedule.

5.6.4 Atomic absorption method of measuring the mass of copper remaining in the electrolyte

5.6.4.1 Preparation of spectrometer measurements carried out in accordance with the manual.

5.6.4.2 In accordance with the manual of the spectrometer performs at least two dimensions of the analytical signal of the zero solution, then the corresponding calibration solution.

5.6.4.3 Electrolyte obtained by 5.6.2, injected into the flame of acetylene-air or propane-butane-air and measure the absorbance of copper at a wavelength of 324,7 nm. Measurement conditions selected in accordance with device used.

Mass concentration of copper in the solution found by the calibration schedule.

5.6.5 the Method of emission spectrometry with inductively coupled plasma measurements of the mass fraction of copper remaining in the electrolyte

5.6.5.1 preparation of the spectrometer measurements carried out in accordance with the manual.

5.6.5.2 In accordance with the manual of the spectrometer launch a work program and perform at least two measurements of the analytical signal of the zero solution, then the corresponding calibration solution.

Expect calibration characteristics.

The electrolyte obtained according to 5.6.2, injected into the plasma to measure the mass concentration of copper at a wavelength of 324,7 nm. Measurement conditions selected in accordance with device used.

Mass concentration of copper in the solution found by the calibration schedule.

5.7 the Processing of the measurement results

5.7.1 Mass fraction of copper (with silver) , %, is calculated by the formula

, (1)

where is the mass of the cathode with sediment, g;

 — net weight of the cathode, g;

 — the weight of the portion of blister copper, g;

 — mass fraction of copper found in the electrolyte, %.

5.7.2 Mass fraction of copper that is defined by the photometric method (5.6.3), , %, calculated by the formula

, (2)

where is the mass of copper was found in the calibration graphics mg;

 — capacity volumetric flasks, cm;

 — volume aliquot of the solution, cm;

 — the weight of the portion of blister copper, g;

 — a conversion factor of milligrams to grams.

5.7.3 Mass fraction of copper remaining in the electrolyte, some atomic-absorption method (5.6.4) or by the method of emission spectrometry with inductively coupled plasma (5.6.5), in % is calculated by the formula

, (3)

where is the mass concentration of copper was found in the calibration schedule, µg/cm;

 — capacity volumetric flasks, cm;

 — the weight of the portion of blister copper, g;

 — conversion factor from micrograms to grams.

5.7.4 Mass fraction of copper , %, is calculated by the formula

, (4)

where  — mass fraction of silver, % (see section 9).

5.7.5 For the measurement result take an arithmetic average value of three parallel measurements, provided that the difference between the highest and the lowest results in terms of repeatability with a confidence level of 0.95 does not exceed the limit values of the recurrence:

— blister copper grades МЧ0, МЧ1, МЧ2 — 0,10%;

for other brands — 0,15%.

If the difference between the highest and lowest results of parallel measurements exceeds the limit value of the frequency of occurrence, perform the procedure described in GOST R ISO 5725−6 (paragraph 5.2.2.1).

5.7.6 the Absolute value allowable discrepancies between the two measurement results obtained in different laboratories, should not exceed the value of the reproducibility limit of 0.20% at a confidence probability of 0.95. At default of this condition can be used the procedure described in GOST R ISO 5725−6.

6 Method of measuring the mass fraction of antimony

6.1 Scope

In this section set extraction-photometric method of measuring the mass fraction of antimony in the range of 0,0010% to 0,400%.

6.2 Requirements for measurement uncertainty

The measurement error of the mass fraction of antimony, the limit values of repeatability and reproducibility for a confidence probability of 0.95 should conform to the values given in table 1.


Table 1

Percentage

Measurement range of mass fraction of antimony	Characterization of the measurement error	Limit
		repeatability (2)	reproducibility
From to 0,0010 0,0030 incl.	0,0007	0,0007	0,0010
SV. 0,0030 «0,0100 «	0,0020	0,0015	0,0030
«0,010» 0,030 «	0,004	0,003	0,006
«0,030» to 0,060 «	0,008	0,006	0,012
«0,060» 0,150 «	0,011	0,008	0,016
«0,150» 0,400 «	0,014	0,010	0,020

6.3 measurement Means, auxiliary devices, materials, solutions

When performing measurements using the following measuring instruments and auxiliary devices:

— spectrophotometer or the photoelectric photometer with all accessories necessary for measurements at a wavelength from 434 nm to 450 nm, from 590 to 608 and 644 nm to 670 nm;

— special laboratory scales of accuracy class according to GOST R 53228;

— volumetric flasks 1−100−2, 1−200−2, 2−100−2, 2−1000−2 according GOST 1770;

— flasks KN-1−250−19/26 TCS GOST 25336;

— glasses-1−100 TCS according to GOST 25336;

— funnel VD-1−100 TC GOST 25336;

— dephlegmator 250−14/23 TC GOST 25336;

pipettes not lower than 2nd accuracy class according to GOST and GOST 29169 29227;

— funnel filtering laboratory according to GOST 25336;

glass hour.

When taking measurements, use the following products and solutions:

— distilled water according to GOST 6709;

— nitric acid according to GOST 4461, diluted 3:97;

— sulfuric acid according to GOST 4204, diluted 1:1, 1:10 and 1:5;

— hydrochloric acid according to GOST 3118 diluted 7:3 and 3:1;

— ammonium nitrate according to GOST 22867, solution mass concentration of 150 g/DM;

— crystal violet [4], the solution of the mass concentration of 6 g/DM;

— brilliant green, solution mass concentration of 2 g/lin ethanol: 0.5 g of reagent was dissolved in 100 cmof a mixture of ethyl alcohol with water in the ratio 1:3;

— thiourea according to GOST 6344, solution mass concentration of 100 g/DM;

— urea according to GOST 6691, a saturated solution of 50 g of urea is dissolved by heating in 50 cmof water, the solution was then filtered;

sodium atomistically according to GOST 4197, solution mass concentration of 100 g/DM;

— tin GOST 860;

— tin (II) chloride 2-water (tin dichloride) in [5], the solution of the mass concentration of 100 g/lin hydrochloric acid, diluted 1:1;

— toluene according to GOST 5789, distilled;

— antimony GOST 1089;

— antimony trioxide;

filters obestochennye [2] or similar;

the filter paper according to GOST 12026, brands, f, FS;

— antimony solutions of known concentration.

6.4 Method of measurement

The method is based on measuring the optical density of the complex compound of antimony (V) with crystal violet or brilliant green. Previously antimony Coosada with metalbands acid and oxidize the antimony (III) atomistically sodium.

6.5 Preparing for performance measurements

6.5.1 For the construction of calibration curve prepare solutions of known concentration of antimony.

In preparing the solution And the mass concentration of antimony 0.1 mg/cm(from antimony) a portion of the antimony mass 0,1000 g is placed in a conical flask with a capacity of 250 cmand dissolved by heating in 20 cmof sulfuric acid. The solution was cooled, poured into a measuring flask with volume capacity of 1000 cm, made up to the mark with sulfuric acid diluted 1:10, and stirred.

In preparing the solution And the mass concentration of antimony 0.1 mg/cm(from antimony trioxide) a portion of the antimony trioxide by weight 0,1200 g is placed in a conical flask with a capacity of 1,000 cmwith a ground joint and with reflux condenser and dissolved by heating in 200 cmof hydrochloric acid diluted 7:3. Then, the resulting solution was evaporated to a volume of 5 to 10 cm, placed in a volumetric flask with a capacity of 1000 cm, made up to the mark with sulfuric acid diluted 1:10, and stirred.

In the preparation of a solution of mass concentration of antimony 0.01 mg/cm10 cmsolution And placed in a volumetric flask with a capacity of 100 cm, made up to the mark with sulfuric acid diluted 1:10, and stirred.

6.5.2 Construction of calibration curve

Six glasses with a capacity of 100 cmeach placed respectively: 0; 1,0; 2,0; 4,0; 6,0 and 8.0 cmof a solution, pour 10 cmof hydrochloric acid (or 25 cmof sulphuric acid, diluted 1:5) and then continue on 6.6.3.

According to the obtained results build a calibration graph of optical density of the solution by weight of antimony.

A solution of comparison used toluene.

6.6 performance measurement

6.6.1 General requirements for measuring methods and safety requirements when performing measurements in accordance with section 4.

6.6.2 the weight of the portion of blister copper, with a capacity for volumetric flasks, the volume of the aliquot (depending on the mass fraction of antimony in blister copper) are shown in table 2.


Table 2

Mass fraction of SB, %	The mass of charge, g	Capacity volumetric flasks, cm	The volume of the aliquot, see
To 0.005 incl.	2,0	100	20
SV. 0.005−0.01 cyl.	1,0	100	10
«0,01» 0,06 «	1,0	200	10
«0,06» 0,30 «	1,0	500	5
«0,3» 0,4 «	0,5	500	5

6.6.3 the Charge of blister copper by weight in accordance with table 2 is placed in a flask with a capacity of 250 cm, adding 0,01 (0,02) g of metal tin, pour 25 cmof nitric acid, cover the flask with a watch glass (or a lid) and heated until complete dissolution of the sample. If upon dissolution forms a yellow Wren sulphur, the residue is treated once more with sulphuric acid of 5 to 10 cm.

The solution was boiled to remove oxides of nitrogen, remove the glass (cover), wash it over the bulb with water and evaporated to a volume of 5 to 7 cm. Then pour 100 to 120 cmof hot water, from 20 to 25 cmof ammonium nitrate solution, add a little filtrowanie mass and boiled for 15−20 min. solution and the precipitate leave in a warm place the plate for 2−2. 5 hours.

After that, the solution was filtered through a medium density filter «white ribbon» in the cone which is enclosed a little filtrowanie mass, and wash the flask and filter ten or fifteen times with hot nitric acid, diluted 3:97. The filter with precipitate was placed in a flask in which to carry out the deposition, poured 10 cmof nitric acid and sulfuric acid, cover the flask with glass (cap) and heated to remove oxides of nitrogen. Then the glass (the lid) is removed, wash it with water over the flask and evaporated to the appearance of dense sulphuric acid fumes. If the solution darkens, add 3−5 drops of nitric acid and continue heating until discoloration of the solution. The solution was cooled, poured 30 to 50 cmof hydrochloric acid, diluted 3:1, and placed in a measuring flask with volume capacity in accordance with table 2, made up to the mark with hydrochloric acid, diluted 3:1, and stirred. If further definition of the mass fraction of antimony is carried out with potassium iodide (6.6.3.4), the solution was placed in a volumetric flask with a capacity of 200 cm, made up to the mark with sulfuric acid diluted 1:5, and stirred.

6.6.3.1 Take an aliquot of the solution in accordance with table 2 and added dropwise with stirring a solution of dichloride of tin to the bleaching solution. If the original solution is colorless, add 2−3 drops of solution of tin dichloride. After 1−2 minutes pour 1 cmof a solution of sodium attestatio and leave for 5−7 minutes, then pour 1 cmof the urea solution, mix and add 20 to 30 cmof water.

If the ratio gold: antimony in blister copper is less than 1:4, antimony is determined with the crystal violet; if more than 1:4 — with diamond green. Define with potassium iodide in sulfuric acid solution (6.6.3.4).

6.6.3.2 mass Determination of antimony with crystal violet

The solution obtained according to 6.6.3.1, transferred to a separatory funnel with a capacity of 100 cmand diluted with water to 65 cm. To the solution was added with stirring 0.5 cmof a solution of crystal violet, 30 cmof toluene and extracted for 1 min. the Toluene layer is separated and after 15−20 min, measure the optical density of the extract at a wavelength of from 590 to 608 nm in a cuvette with the thickness of the light absorbing layer 10 mm. as a solution of comparison used toluene.

The mass of antimony in milligrams set by the calibration schedule.

6.6.3.3 determination of the mass of antimony with brilliant green

The solution obtained according to 6.6.3.1, transferred to a separatory funnel with a capacity of 100 cm, add 10 cmof hydrochloric acid, water to a volume of 50 to 60 cm, and 2 cmof a solution of brilliant green, 10 cmsulfuric acid, diluted 1:1, in 20 cmof toluene and extracted for 1 min. the Toluene layer is separated and after 15 to 20 minutes, measure its optical density at a wavelength of from 644 to 670 nm (depending on device type) in a ditch with the thickness of the light absorbing layer 10 mm. as a solution of comparison used toluene.

Mass of antimony is determined according to the calibration schedule.

6.6.3.4 mass Determination of antimony with iodide of potassium

Of volumetric flasks with a capacity of 200 cm(sulfuric acid solution) are selected aliquot of 25 cmand placing it in a volumetric flask with a capacity of 50 cm, pour 2 cmof a solution of thiourea, 5 cmof a solution of potassium iodide and topped to the mark with sulfuric acid diluted 1:5. The solution was stirred. Measure the optical density at a wavelength from 434 nm to 450 nm (depending on device type) in a ditch with the thickness of the light absorbing layer 30 mm. with a Solution of comparison is the solution of the reference experiment.

Mass of antimony is determined according to the calibration schedule.

6.7 Processing of measurement results

6.7.1 Mass fraction of antimony , %, is calculated by the formula

, (5)

where is the mass of antimony, was found in the calibration graphics mg;

 — capacity volumetric flasks, cm;

 — volume aliquot of the solution, cm;

 — the weight of the portion of blister copper, g;

 — a conversion factor of milligrams to grams.

6.7.2 For the measurement result taking the arithmetic mean of two parallel definitions, provided that the absolute difference between them in terms of repeatability does not exceed the values (with confidence probability of 0.95) limit of repeatability in table 1.

If the discrepancy between the results of parallel measurements exceeds the limit value of the frequency of occurrence, perform the procedure described in GOST R ISO 5725−6 (paragraph 5.2.2.1).

6.7.3 Differences between measurements obtained in two laboratories, should not exceed the limit values for the reproducibility given in table 1. In this case, the final result may be decided to their arithmetic mean value. At default of this condition can be used the procedure described in GOST R ISO 5725−6.

7 Method of measuring the mass fraction of bismuth

7.1 Scope

This section is set by the photometric method of measuring the mass fraction of bismuth in the range of 0.0002% to 0,060%.

7.2 Requirements for measurement uncertainty

The measurement error of the mass fraction of bismuth, the values of the limits of repeatability and reproducibility for a confidence probability of 0.95 should conform to the values given in table 3.


Table 3

Percentage

Measurement range of mass fraction of bismuth	Characterization of the measurement error	Limit
		repeatability (2)	reproducibility
From to from 0.0002 to 0.0005 incl.	0,0001	0,0001	0,0002
SV. Of 0.0005 «0,0010 «	0,0003	0,0002	0,0004
«0,0010» 0,0030 «	About 0.0006	0,0004	0,0008
«0,0030» 0,0050 «	0,0007	About 0.0006	0,0010
«0,005» 0,010 «	0,003	0,002	0,004
«0,010» 0,030 «	0,006	0,004	0,008
«0,030» to 0,060 «	0,008	0,006	0,012
«0,060	0,011	0,008	0,016

7.3 measurement Means, auxiliary devices, materials, solutions

When performing measurements using the following measuring instruments and auxiliary devices:

— spectrophotometer or the photoelectric photometer with all accessories necessary for measurements at a wavelength from 434 nm to 450 nm;

— special laboratory scales of accuracy class according to GOST R 53228;

— volumetric flasks 1−200−2, 2−1000−2 according GOST 1770;

— flasks KN-2−25−19/26 TCS, KN-2−200−19/26 TCS, KN-2−250−19/26 TCS GOST 25336;

— glasses-1−100 TCS according to GOST 25336;

pipettes not lower than 2nd accuracy class according to GOST and GOST 29169 29227;

— funnel filtering laboratory according to GOST 25336;

glass hour.

When taking measurements, use the following products and solutions:

— distilled water according to GOST 6709;

— nitric acid according to GOST 4461 diluted 1:99;

— sulfuric acid according to GOST 4204, diluted 1:1, 1:3, 1:9, 5:95;

— hydrochloric acid according to GOST 3118, diluted 1:1, 5:95, 1:5, 1:9;

— tartaric acid according to GOST 5817, solution mass concentration of 200 g/DM;

— ammonia water according to GOST 3760 diluted 1:99;

— ascorbic acid by [6], the solution of the mass concentration of 50 g/DM;

— thiourea according to GOST 6344, solution mass concentration of 100 g/DM;

— potassium iodide according to GOST 4232, solution mass concentration of 200 g/DM;

— tin (II) chloride 2-water (tin dichloride) in [5], the solution of the mass concentration of 200 g/lin hydrochloric acid, diluted 1:1;

— iron (III) chloride 6-water according to GOST 4147, solution mass concentration 10 g/DMsolution of hydrochloric acid molar concentration of 0.2 mol/DM;

— bismuth (III) nitrate 5-water according to GOST 4110;

— selenium GOST 10298;

filters obestochennye [2] or similar;

the filter paper according to GOST 12026, brands, f, FS;

— bismuth solutions of known concentration.

7.4 Method of measurement

The method is based on measuring the optical density of the colored godenovo complex of bismuth formed in sulfuric acid or hydrochloric acid solution after the preliminary separation of bismuth by coprecipitation on iron hydroxide.

7.5 Preparation for measurements

7.5.1 To construct the calibration curve, prepare solutions of known concentration of bismuth.

In preparing the solution And the mass concentration of bismuth 0.1 mg/cma portion of the bismuth mass 0,1000 g placed in a beaker with a capacity of 100 cm, is dissolved by heating in a volume of 10 to 15 cmof nitric acid and evaporated to a volume of 2 to 3 cm. Then add 50 to 60 cmof sulphuric acid, diluted 1:9 (or 65 cmof nitric acid), transfer the resulting solution into a measuring flask with volume capacity of 1000 cm, made up to the mark with sulfuric acid diluted 1:9 (or water in the case of using nitric acid) and mixed.

In the preparation of a solution of mass concentration of bismuth 0.01 mg/cmto 20 cmof solution A is placed in a volumetric flask with a capacity of 200 cm, made up to the mark with sulphuric acid, diluted with 5:95 or 1:5 (or pour 2 to 3 cmof nitric acid), made up to the mark with water and mix.

The solution is ready for use within 5 hours.

7.5.2 Construction of calibration curve for determining the mass fraction of bismuth in sulfuric acid solution

Six glasses with a capacity of 100 cmeach placed respectively: 0; 0,5; 1,0; 3,0; 5,0 and 7.0 cmof solution B. the Solutions were evaporated to dryness, added 2.2 cmof sulphuric acid, diluted 1:3, heated to boiling, cooled and transferred to a flask with a capacity of 25 cmand then continue in 7.6.2.1.

According to the obtained results build a calibration graph of optical density by weight of bismuth.

Solution comparison is the solution of the reference experiment.

7.5.3 Construction of calibration curve for determining the mass fraction of bismuth in hydrochloric acid solution

In six conical flasks with a capacity of 250 cm, each placed respectively: 0; 1,0; 2,0; 3,0; 4,0 and 5.0 cmof a solution, poured in 5 cmof nitric acid, at 20 cmof hydrochloric acid and is evaporated under heating to a volume of 3 to 5 cm. Poured from 100 to 150 cmof water and then continue in 7.6.2.2.

According to the obtained results build a calibration graph of optical density of the solution by weight of bismuth.

Solution comparison is the solution of the reference experiment.

7.6 performance measurement

7.6.1 General requirements for methods of measurements and safety requirements when performing measurements in accordance with section 4.

7.6.2 the weight of blister copper weight from 0.5 to 5.0 g (depending on the mass fraction of bismuth) is placed in a conical flask with a capacity of 250 cm, flow 10 to 15 cmof nitric acid, cover the flask with a watch glass (or a lid) and allowed to stand without heating until the termination of allocation of oxides of nitrogen. Glass (cover) is removed, wash it over with a flask of water, poured from 20 to 25 cmof hydrochloric acid and continue the dissolution of the sample when heated. The solution was evaporated to a volume of 3 to 5 cm. Poured from 25 to 30 cmof water and, if present, the insoluble residue, the solution was filtered through a dense filter of «blue ribbon» and washed the residue three to five times with nitric acid, diluted 1:99. The filter residue is discarded.

The filtrate is adjusted with water to a volume of 100 to 150 cm, pour 5 cmof a solution of trichloride iron, heat the solution to a temperature from 60 °C to 70 °C and poured a solution of ammonia in such quantity that the whole of the copper passed into the ammonia complex, and then another 10 cm. Leave the solution to precipitate in a warm place for 10−15 minutes to coagulate the precipitate.

Solution and the precipitate was filtered through a medium density filter «white ribbon» and washed the residue three to five times a hot ammonia diluted 1:99.

Wash the precipitate from the filter with water into the flask in which the precipitation was carried out, and dissolved in a volume of 15 to 20 cma hot hydrochloric acid diluted 1:1. The filtrate is poured in water to a volume of 100 to 150 cmand repeat the precipitation of iron hydroxide with ammonia.

When the mass fraction of bismuth of more than 0.01% solution after dissolving the sample is placed in a volumetric flask with a capacity of 200 cm, made up to the mark with water, mix and select for further measurement of the sample volume from 10 to 20 cm, the precipitated hydroxide of iron in the aliquot solution.

The precipitate of iron hydroxide obtained after re-deposition, dissolved in a volume of 15 to 20 cma hot hydrochloric acid diluted 1:1, then the filter is washed two or three times with hot water.

This was followed by the separation of selenium and tellurium. The solution is heated to a temperature of from 40 °C to 50 °C and add dropwise a solution of tin dichloride to darkening of the solution and 1 cm. Add a little filtrowanie mass is heated to the boil and leave for 10−15 min. Then the precipitate is filtered on a filter of dense «blue ribbon» in the cone which is enclosed a little filtrowanie mass, and washed two or three times with hot water. Filter the precipitate discarded. The filtrate volume should not exceed 30 (35) cm.

Further, the determination of the mass fraction of bismuth is carried out in two ways:

a) determination of the mass fraction of bismuth in sulfuric acid solution

The filtrate obtained in 7.6.2, evaporated on a water bath to wet salts. To the residue poured 2.2 cmof sulphuric acid, diluted 1:3, heated to dissolve the residue is cooled, add 5 cmof tartaric acid solution and transfer the solution into volumetric flask with a capacity of 25 cm. Into the flask pour 1 cmof potassium iodide, 1 cmof a solution of thiourea and tested for absence of free iodine with ikramullah paper. If the paper changes color, then pour another 1 to 2 cmof a solution of thiourea. The volume of the solution was adjusted to the mark with water and after 10 to 15 min measure the optical density at a wavelength from 434 nm to 450 nm (depending on device type) in a ditch with the thickness of the light absorbing layer 50 mm. Solution comparison is the solution of the reference experiment;

b) determine the mass fraction of bismuth in hydrochloric acid solution

To the filtrate obtained in 7.6.2, add 4 cmof tartaric acid solution, 5 cmof a solution of iodide of potassium, 1 to 1.5 cmof the ascorbic acid solution, transfer the solution into a volumetric flask with a capacity of 50 cmand top up with water to the mark. After 10 to 15 min measure the optical density at 7.6.2.1.

7.7 Processing of measurement results

7.7.1 Mass fraction of bi , %, is calculated by the formula

, (6)

where  — weight of bismuth, was found in the calibration graphics mg;

 — capacity volumetric flasks, cm;

 — volume aliquot of the solution, cm;

 — the weight of the portion of blister copper, g;

 — a conversion factor of milligrams to grams.

7.7.2 For the measurement result taking the arithmetic mean of two parallel definitions, provided that the absolute difference between them in terms of repeatability does not exceed the values (with confidence probability of 0.95) limit of repeatability are given in table 3.

If the discrepancy between the results of parallel measurements exceeds the limit value of the frequency of occurrence, perform the procedure described in GOST R ISO 5725−6 (paragraph 5.2.2.1).

7.7.3 Differences between measurements obtained in two laboratories, should not exceed the limit values repeatability, are shown in table 3. In this case, the final result may be decided to their arithmetic mean value. At default of this condition can be used the procedure described in GOST R ISO 5725−6.

8 Methods of measurements of mass fraction of Nickel

8.1 Scope

In this section, established methods of measuring the mass fraction of Nickel: photometric — in the range from 0.010% to 1.20%, atomic absorption in the range from 0.010% to 3.00%.

8.2 Requirements for measurement uncertainty

The measurement error of the mass fraction of Nickel, the limit values of repeatability and reproducibility for a confidence probability of 0.95 should conform to the values given in table 4.


Table 4

Percentage

Measurement range of mass fraction of Nickel	Characterization of the measurement error	Limit
		repeatability (2)	reproducibility
From 0,010 to 0,030 incl.	0,003	0,002	0,004
SV. 0,030 «0,100 «	0,006	0,004	0,008
«0,100» 0,300 «	0,028	0,020	0,040
«Of 0.30» to 0.60 «	0,06	0,04	0,08
«0,60» 1,50 «	0,08	0,06	0,12
«Of 1.50» to 3.00 «	0,21	0,15	0,30

8.3 Photometric method

8.3.1 measurement Means, auxiliary devices, materials, solutions

When performing measurements using the following measuring instruments and auxiliary devices:

installation for electrolysis, providing carrying out the electrolysis while stirring at a current density of from 1 to 4 and the voltage from 2 to 2.5;

electrodes made of platinum mesh cylindrical GOST 6563;

— laboratory drying oven with thermostatic control, ensuring the heating temperature up to 250 °C;

— spectrophotometer or the photoelectric photometer with all accessories necessary for measurements at a wavelength of from 440 to 450 nm;

oven muffle with heating temperature up to 1000 °C;

— the stove is electric with a closed heating element for temperature up to 350 °C;

— special laboratory scales of accuracy class according to GOST R 53228;

— porcelain crucibles according to GOST 9147;

— glasses-1−200 TCS-1−250 TCS according to GOST 25336;

— volumetric flasks 1−25−2, 1−50−2; 1−100−2; 1−200−2, 1−250−2, 1−1000−2, 2−200−2, 2−250−2, 2−500−2, 2−1000−2 according to GOST 1770;

pipettes not lower than 2nd accuracy class according to GOST and GOST 29169 29227;

glass hour;

— flasks KN-2−250−19/26 TCS GOST 25336;

— funnel filtering laboratory according to GOST 25336.

When taking measurements, use the following products and solutions:

— distilled water according to GOST 6709;

— nitric acid according to GOST 4461, diluted 2:1; 1:1;

— sulfuric acid according to GOST 4204, diluted 1:1;

— hydrochloric acid according to GOST 3118;

— potassium-sodium vinocity 4-water (Sagatova salt) according to GOST 5845, solution mass concentration of 200 g/DM;

— sodium hydroxide (sodium hydroxide) according to GOST 4328, solutions of the mass concentrations of 50, 100 and 200 g/DM;

— sodium carbonate according to GOST 83, a saturated solution;

— ammonium neccersarily according to GOST 20478, solution mass concentration of 30 g/DM;

— iodine according to GOST 4159, solution in ethyl alcohol mass concentration 10 g/DM;

— dimethylglyoxime according to GOST 5828, solution mass concentration 10 g/DMsolution of sodium hydroxide mass concentration of 50 g/DMor solution of the mass concentration of 80 g/lin ethanol;

— citric acid according to GOST 3652, solution mass concentration of 500 g/DM;

— Nickel (II) sulfate 7-water according to GOST 4465;

— Nickel GOST 849;

— a mixture of hydrochloric and nitric acids 3:1;

filters obestochennye [2] or similar;

the filter paper according to GOST 12026, brands, f, FS;

the Nickel solutions of known concentration.

8.3.2 Method of measurement

The method is based on measuring the optical density of the coloured compounds of Nickel with dimethylglyoxime formed in alkaline medium in the presence of an oxidant — ammonium naternicola.

8.3.3 Preparing to run measurements

8.3.3.1 To build a calibration curve, prepare solutions of known concentration of Nickel.

In preparing the solution And the mass concentration of Nickel 0.1 mg/cmof Nickel of a portion of the Nickel mass 0,1000 g placed in a beaker with a capacity of 200 cm, flow 10 cmof nitric acid, diluted 2:1, heated to obtain a volume of 2 to 3 cm. Cooled, poured 10 cmof sulphuric acid diluted 1:1, and heated to release vapors of sulfuric acid. Again cooled, poured 10 cmof water and repeat evaporation to fumes of sulfuric acid. After cooling, poured from 100 to 120 cmof water, heated to dissolve the salts, transfer the solution into a measuring flask with volume capacity of 1000 cm, made up to the mark with water and mix.

In preparing the solution And the mass concentration of Nickel 0.1 mg/cmof Nickel sulfate suspension sulfate Nickel mass 0,4784 g is placed in a measuring flask with volume capacity of 1000 cm, a flow from 100 to 200 cmwater, 1 cmof sulfuric acid, made up to the mark with water and mix.

In the preparation of a solution of mass concentration of Nickel 0.01 mg/cm10 cmsolution And placed in a volumetric flask with a capacity of 100 cm, made up to the mark with water and mix.

When cooking solution To the mass concentration of Nickel 0.001 mg/cmof 10 cmof a solution is placed in a volumetric flask with a capacity of 100 cm, made up to the mark with water and mix.

8.3.3.2 Construction of calibration curve

In six volumetric flasks with a capacity of 50 or 25 cmeach are placed accordingly: 0; 1,0; 3,0; 5,0; 8,0 and 10.0 cmof solution B. If the Nickel in the measured solution is at least 0.01 mg, then build a calibration curve using a solution V. In the flask consistently pour the solutions of the reagents listed in 8.3.4.2, and measure the optical density of the solution.

According to the obtained results build a calibration graph of optical density by weight of Nickel.

As a solution comparison using the solution in the reference experiment.

8.3.4 performance measurement

8.3.4.1 General requirements for methods of measurements and safety requirements when performing measurements in accordance with section 4.

8.3.4.2 the weight of blister copper (at a mass fraction of Nickel in excess of 0.5%) by weight of from 0.5 to 1.0 g was placed in a beaker or conical flask with a capacity of 250 cm, flow 20 to 25 cmof a mixture of hydrochloric and nitric acids (ratio 3:1), covered with glass (lid), leave without heating until the cessation of the violent reaction of the allocation of nitrogen oxides. Then heated to dissolve the sample, evaporating the solution to wet salts.

To the moist residue is poured 5 to 10 cmof sulphuric acid diluted 1:1, and evaporated to release thick vapors of sulfuric acid. Cooled, poured 5 to 10 cmof water and again heated to release vapors of sulfuric acid. Add from 30 to 50 cmof water, boil to dissolve the salt and filter the insoluble residue on the dense filter of «blue ribbon» in the cone which is enclosed a little filtrowanie mass. Filter and the residue is washed four or five times with hot water.

The filter with residue placed in a porcelain crucible, dried, and incinerated in a muffle furnace and fused with potassium pyroterrorism weighing 5 to 6 g at a temperature of from 700 °C to 800 °C for 15−20 min. the Melt is leached in 20−30 cmof water, add 5 cmof sulphuric acid diluted 1:1, heated to dissolve the melt, then the solution attached to the main filtrate.

The filtrate is boiled, cooled and leave for 2−2,5 h. the precipitate was filtered on a dense filter «blue ribbon» in the cone which is enclosed a little filtrowanie mass, washed the filter three or four times with hot water, collecting the filtrate in a beaker with a capacity of 250 cm. The filter is discarded.

The filtrate is diluted with water to a volume of 150 cm, placed in it the platinum electrodes and covered with a glass the two halves of the glass, conduct electrolysis at a current of from 1 to 4 A and a voltage of 2 to 2.5 V. After the electrolysis, the electrodes are removed from solution, washed with water over a Cup.

Allowed the use of the electrolyte after separation of copper by 5.6.2.

The electrolyte obtained as described above, or 5.6.2, add 5 cmof sulphuric acid diluted 1:1, and the solution is evaporated to release vapors of sulfuric acid, cooled, poured 5 to 10 cmof water and the evaporation repeated.

To the cooled residue poured from 30 to 50 cmof water, boil for 5−7 minutes, cooled and filtered the insoluble residue on the dense filter of «blue ribbon» in the cone which is enclosed a little filtrowanie mass, collecting the filtrate in a volumetric flask with a capacity of 250 or 500 cm, made up to the mark with water and mix. Further characterization of Nickel is carried out in two ways.

An aliquot of the solution from 5 to 20 cmof volumetric flasks with a capacity of 500 cmis placed in a volumetric flask with a capacity of 50 cm, pour 2.5 cmof a solution of Rochelle salt, 7.5 cmof sodium hydroxide solution mass concentration of 100 g/DMor a saturated solution of sodium carbonate, 10 cmsolution naternicola ammonium or iodine solution, 10 cmdimethylglyoxime alkaline solution, made up to the mark with water and mix.

An aliquot of the solution of volume from 1 to 2 cmof volumetric flasks with a capacity of 250 cmis placed in a volumetric flask with a capacity of 25 cm, pour 1 cmof solution of citric acid, neutralized with sodium hydroxide solution the mass concentration of 200 g/DM, add 2.5 cmof sodium hydroxide solution mass concentration of 50 g/DM, then 2.5 cmof the solution naternicola ammonium, 2.5 cmdimethylglyoxime alkaline solution, made up to the mark with water and mix.

After 15−20 min, measure the optical density of the solutions at a wavelength of from 440 to 450 nm (depending on device type) in a ditch with the thickness of the light absorbing layer 30 mm.

Solution comparison is the solution of the reference experiment.

8.3.5 Processing of measurement results

8.3.5.1 Mass fraction of Nickel , %, is calculated by the formula

, (7)

where is the mass of Nickel was found in the calibration graphics mg;

 — capacity volumetric flasks, cm;

 — volume aliquot of the solution, cm;

 — the weight of the portion of blister copper, g;

 — a conversion factor of milligrams to grams.

8.3.5.2 For the measurement result taking the arithmetic mean of two parallel definitions, provided that the absolute difference between them in terms of repeatability does not exceed the values (with confidence probability of 0.95) limit of repeatability shown in table 4.

If the discrepancy between the results of parallel measurements exceeds the limit value of the frequency of occurrence, perform the procedure described in GOST R ISO 5725−6 (paragraph 5.2.2.1).

8.3.5.3 the Discrepancy between the results of measurements obtained in two laboratories, should not exceed the limit values repeatability, are given in table 4. In this case, the final result may be decided to their arithmetic mean value. At default of this condition can be used the procedure described in GOST R ISO 5725−6.

8.4 Atomic absorption method of measuring the mass fraction of Nickel

8.4.1 measurement Means, auxiliary devices, materials, solutions

When performing measurements using the following measuring instruments and auxiliary devices:

spectrometer atomic absorption, comprising a radiation source for Nickel of any type;

— air compressor;

— acetylene according to GOST 5457;

— propane-butane according to GOST 20448;

— glasses-1−200 TCS according to GOST 25336;

pipettes not lower than 2nd accuracy class according to GOST and GOST 29169 29227;

— volumetric flasks 1−25−2, 1−50−2; 1−100−2; 1−200−2, 1−250−2, 1−1000−2, 2−200−2, 2−250−2, 2−500−2, 2−1000−2 according to GOST 1770;

— flasks KN-2−100−19/26 TCS, KN-2−250−19/26 TCS GOST 25336;

— funnel filtering laboratory according to GOST 25336;

glass hour.

When taking measurements, use the following products and solutions:

— nitric acid according to GOST 4461, diluted 1:1, 1:9;

— hydrochloric acid according to GOST 3118, diluted 1:1;

— copper according to GOST 859, solution mass concentration of 100 g/DM: a sample of copper with a mass of 10 g was dissolved with heating in 70 cmof nitric acid, diluted 1:1, prior to the removal of oxides of nitrogen, cooled and transferred to a volumetric flask with a capacity of 100 cm, made up to the mark with water;

— Nickel GOST 849;

the Nickel solutions of known concentration.

8.4.2 Method of measurement

The method is based on measuring absorption of atomic resonance lines of Nickel in the introduction of the analyzed solution in the flame acetylene-air or propane-butane-air.

8.4.3 Preparation for measurements

8.4.3.1 For the construction of calibration curve prepare solutions of known concentration of Nickel.

In preparing the solution And the mass of Nickel concentration of 1 mg/cma portion of the Nickel mass 1,0000 g was dissolved with heating in 10−20 cmof nitric acid, diluted 1:1, evaporated to wet salts, cooled, placed in a volumetric flask with a capacity of 1000 cm, add 50 cmof nitric acid, diluted 1:1, made up to the mark with water and mix.

The same solution can be prepared as follows: 1,0000 g Nickel dissolved in 10−20 cmof nitric acid, diluted 1:1, and the solution is evaporated to wet salts. Then treat the residue twice 10−15 cmof hydrochloric acid diluted 1:1, each time evaporating to wet salts. Cooled, the residue is dissolved in 50 cmof hydrochloric acid diluted 1:1 was placed in a volumetric flask with a capacity of 1000 cm, made up to the mark with water and mix.

In the preparation of a solution of mass concentration of Nickel 0.1 mg/cm10 cmsolution And placed in a volumetric flask with a capacity of 100 cm, made up to the mark with hydrochloric (or nitric acid), diluted 1:9, and stirred.

8.4.3.2 Construction of calibration curve

In a series of volumetric flasks with a capacity of 100 cmeach placed solution B or in such amount as to respect the linearity of the calibration graphs in the range of detectable concentrations of Nickel, made up to the mark with hydrochloric (or nitric acid), diluted 1:9, and stirred.

For constructing a calibration curve allowed to use 3−7 calibration mixtures, but not less than 3.

In the calibration solutions are poured 10 cmof a solution of copper mass concentration of 100 g/DM(for alignment of the copper content in the calibration and initial solutions).

8.4.4 performance measurement

8.4.4.1 General requirements for methods of measurements and safety requirements when performing measurements in accordance with section 4.

8.4.4.2 in the determination of Nickel in nitric acid solution, the charge of blister copper weight from 0.5 to 1.0 g was placed in a conical flask with a capacity of 100 cmand dissolved by heating in 10−15 cmof nitric acid. If, after the dissolution of copper remained insoluble residue of black color, the solution is poured 1 to 2 cmof hydrochloric acid, is evaporated to wet salts, cooled, poured 10 to 20 cmof water and boil to dissolve the salts. After cooling, the solution is transferred to a volumetric flask with a capacity of 100 or 200, or 500 cm(depending on the weight of Nickel), made up to the mark with water, mix.

8.4.4.3 in the determination of Nickel in hydrochloric acid solution, the charge of blister copper weight from 0.5 to 1.0 g was placed in a conical flask with a capacity of 100 cm, flow 20 cmof a mixture of nitric and hydrochloric acids (in the ratio 3:1), cover with a watch glass (cap) and dissolve with a moderate heat for 30−40 minutes, then the glass (the lid) is removed, washed with water over the flask and evaporate the solution to wet salts. Salt is dissolved by heating in 5−10 cmof hydrochloric acid diluted 1:1, cooled, placed in a volumetric flask with a capacity of 100 or 200, or 500 cm, made up to the mark with water and mix.

8.4.4.4 the resulting solutions for 8.4.4.2 and 8.4.4.3 sprayed in the flame of acetylene-air or propane-butane-air and record the absorbance at the wavelength or 352,4 232,0 nm.

Measurement conditions selected in accordance with device used.

The absorbance of each solution is measured at least twice and for calculating take arithmetic mean value. When changing solutions, the spray system was washed with water to obtain the zero readings. The recommended maximum value of the measured absorbance of approximately 0.5 units. If necessary to reduce its value is allowed to carry out measurements at less sensitive wavelengths or deploy the burner.

Mass of Nickel is determined according to the calibration schedule.

8.4.4.5 allowed the use of the electrolyte after separation of copper by 5.6.2.

For this part of the electrolyte (depending on the mass fraction of Nickel) was placed in a volumetric flask with a capacity of 100 cm, adjusted to the mark with water and measure the absorbance at the wavelength or 352,4 232,0 nm in the flame acetylene-air or propane-butane-air.

8.4.5 Processing of measurement results

8.4.5.1 Mass fraction of Nickel , %, is calculated by the formula

, (8)

where is the mass of Nickel was found in the calibration graphics mg;

 — capacity volumetric flasks, cm;

 — volume aliquot of the solution, cm;

 — the weight of the portion of blister copper, g;

 — a conversion factor of milligrams to grams.

8.4.5.2 For the measurement result taking the arithmetic mean of two parallel definitions, provided that the absolute difference between them in terms of repeatability does not exceed the values (with confidence probability of 0.95) limit of repeatability shown in table 4.

If the discrepancy between the results of parallel measurements exceeds the limit value of the frequency of occurrence, perform the procedure described in GOST R ISO 5725−6 (paragraph 5.2.2.1).

8.4.5.3 Differences between measurements obtained in two laboratories, should not exceed the limit values repeatability, are given in table 4. In this case, the final result may be decided to their arithmetic mean value. At default of this condition can be used the procedure described in GOST R ISO 5725−6.

9 Methods of measurement of mass fraction of gold and silver

9.1 Scope

In this section, established methods of measuring a mass fraction of silver and gold: fire assay-gravimetric — when the mass fraction of gold from 0.5 500.0 g/t and the mass fraction of silver from 10 to 10000 ppm, atomic absorption — when the mass fraction of gold from 10 to 300 g/t and the mass fraction of silver from 100 to 4000 g/t.

9.2 Requirements for measurement uncertainty

The error of measurement of mass fraction of gold and silver, the limit values of repeatability and reproducibility for a confidence probability of 0.95 should conform to the values given in tables 5 and 6.


Table 5

In grams per ton

Measurement range of mass fraction of gold	Characterization of the measurement error	Limit
		repeatability (3)	reproducibility
From 0.5 to 1.0, incl.	0,4	0,3	0,5
SV. Of 1.0 «to 2.5 «	0,7	0,6	1,0
Of «2.5 «to 4.0 «	0,9	0,8	1,3
«4,0» 6,0 «	1,1	0,9	1,5
«Of 6.0» to 9.0 «	1,2	1,0	1,7
«To 9.0» to 14.0 «	1,4	1,2	2,0
«14,0» 20,0 «	1,6	1,4	2,2
«20,0» 25,0 «	1,6	1,6	2,3
«25,0» 30,0 «	1,8	1,8	2,5
«30,0» 35,0 «	2,0	2,0	2,8
«35,0» 40,0 «	2,2	2,2	3,1
«40,0» 45,0 «	2,4	2,4	3,4
«45,0» 55,0 «	2,5	2,6	3,6
«55,0» 70,0 «	2,8	2,8	3,9
«70,0» 85,0 «	3,0	3,1	4,3
«85,0» 100,0 «	3,4	3,4	4,8
«100,0» 115,0 «	3.7 V	3.7 V	5,2
«115,0» 130,0 «	4,0	4,0	5,6
«130,0» 150,0 «	4,5	4,5	6,3
«150,0» 180,0 «	5,0	5,0	7,0
«180,0» 225,0 «	5,5	5,5	7,7
«225,0» 275,0 «	6,0	6,0	8,4
«275,0» 340,0 «	6,4	6,5	9,1
«340,0» 400,0 «	7,0	7,0	9,8
«400,0» 450, 0 «	7,4	7,5	10,5
«450,0» 500,0 «	8,0	8,0	11,2
«500,0	9,9	10,0	14,0

Table 6

In grams per ton

Measurement range of mass fraction of silver	Characterization of the measurement error	Limit
		repeatability (3)	reproducibility
From 10 to 20 incl.	5	4	7
SV. 20 «50 «	9	8	13
«50» 100 «	19	16	27
«100» 200 «	24	20	34
«200» 300 «	26	22	37
«300» 400 «	28	24	40
«400» 500 «	31	26	44
«500» 600 «	33	28	47
«600» 700 «	35	30	50
«700» 800 «	39	33	55
«800» 900 «	42	36	60
«900» 1000 «	46	39	65
«1000» 1100 «	50	42	70
«1100» 1200 «	53	45	75
«1200» 1300 «	57	48	80
«1300» 1400 «	60	51	85
«1400» 1500 «	63	54	89
«1500» 1600 «	64	57	91
«1600» 1700 «	66	60	93
«1700» 1800 «	67	63	95
«1800» 1900 «	68	66	96
«1900» 2000 «	69	69	97
«2000» 2100 «	72	72	102
«2100» 2200 «	74	74	104
«2200» 2300 «	76	76	107
«2300» 2400 «	78	78	110
«2400» 2500 «	80	80	113
«2500» 2700 «	82	82	116
«2700» 2900 «	84	84	119
«2900» 3100 «	86	86	122
«3100» 3300 «	88	88	124
«3300» 3500 «	90	90	127
«3500» 3700 «	95	95	134
«3700» 4000 «	100	100	141
«4000» 5000 «	130	130	184
«5000» 6000 «	155	155	219
«6000» 7000 «	170	170	240
«7000» 10000 «	185	185	261
«10000	210	210	297

9.3 Assay-gravimetric method of measuring a mass fraction of silver and gold

9.3.1 measurement Means, auxiliary devices, materials, solutions

When performing measurements using the following measuring instruments and auxiliary devices:

— muffle furnace (smelting) with a thermostat, ensuring the heating temperature up to 1000 °C;

oven cooperational with the heating temperature up to 1000 °C;

— the stove is electric with a closed heating element for temperature up to 350 °C;

— a mold of cast iron or steel;

— special laboratory scales of accuracy class according to GOST R 53228 increments of 0.0001, 0,00001, 0,000001 g;

— hammer and anvil steel working lead alloy;

— hammer and anvil steel polished to raskopki Korolkov;

— Curling of serburov;

— tongs for anything;

— glazed porcelain crucible according to GOST 9147;

— surbery an inner diameter of from 50 to 60 mm, height from 23 to 35 mm (if necessary, pre-glazed);

— Cappel magnesite, prepared from a mixture consisting of 85% of periclase powder according to GOST 10360 brands of PPI 8891 PPI, PPTI 92 (or other regulations) or magnesite powder according to GOST 4689 and 15% of Portland cement according to GOST 10178 grade not lower than 400 (crushed to a particle size passing through a sieve 0,071 according to GOST 6613) with the addition of 10% water. Before use, the drops should be dried.

Note — it is possible to produce anything of a different composition, providing measurements with a set accuracy;


— flasks KN-2−750−29/32 TCS GOST 25336;

— glasses-1−800 TCS In-1−1000 TCS according to GOST 25336;

— funnel In-100−150 MS, In-150−230 TC GOST 25336.

When taking measurements, use the following products and solutions:

— nitric acid according to GOST 4461, diluted 1:1, 1:3, 1:4, 1:7 (tested for chloride ion with a solution of silver nitrate. If a chloride ion, the acid is distilled);

— sulfuric acid according to GOST 4204;

— lead according to GOST 3778 or other regulatory documents;

— dense and light soda ash according to GOST 5100;

— quartz or crushed glass;

— the charge for Sherburne bottoms, consisting of two parts by weight of calcined borax and one part by weight of soda. 10 kg of the mixture is added 3 kg of quartz or crushed glass. One sample of the sample spend between 6 to 8 g of the charge;

— lead foil with a thickness of 0.1 to 0.3 mm, is made of lead according to GOST 3778 (or other regulatory documents);

— gold GOST 6835 or other regulatory documents;

— silver GOST 6836 or other regulatory documents;

— mercury (II) nitrate according to GOST 4520, solution mass concentration of 26 g/DM;

sodium chloride according to GOST 4233 and solution mass concentration of 20 g/DM;

— borax according to GOST 8429 (calcined);

— lead (II) acetate 3-water according to GOST 1027, solution mass concentration of 200 g/DM;

— distilled water according to GOST 6709;

filters obestochennye [2] or similar;

the filter paper according to GOST 12026, brands f, FS.

9.3.2 Method of measurement

The method is based on measurement of the mass of the gold-silver bead obtained after Sherburne melting and copilasii lead alloy.

9.3.3 performance measurement

9.3.3.1 General requirements for methods of measurements and safety requirements when performing measurements in accordance with section 4.

9.3.3.2 the weight of blister copper mass of 25.00 or the 50.00 g was placed in a conical flask or beaker with a capacity of 750 inches(800 cm), flow from 30 to 35 cmof water and 10 to 20 cmof nitrate of mercury was stirred until complete amalgamation of the whole chip of copper. Then the flask was poured from 100 to 125 cmof sulfuric acid, if necessary, close the flask with the glass (with a lid) and heat for at least 2 hours to dissolve the sample copper. If the color of the solution changed from dark green to light blue, then the solution is complete. The solution was cooled, diluted with water to 500 cmand stirred to dissolve the copper sulphate. Heated to boiling and poured from 10 to 30 cmof a solution of sodium chloride and from 1 to 10 cmof a solution of acetate of lead solution, boil the solution for 5−10 minutes, cool and leave to coagulate the precipitate.

The solution was filtered through a double filter of «white» or «blue ribbon» in the cone which is enclosed a little filtrowanie mass, washed the walls of the bulb (glass) with water, remove the remains of the sludge with a piece of the filter and attach this piece to the main residue on the filter and washed the filter cake and the filter repeatedly with hot water to remove copper sulphate from the filter. The filtrate is discarded.

The filter with the precipitate is transferred in serber, dried, placed in a muffle furnace, was dried and burned at a temperature of from 400 °C to 500 °C, for blister copper grades МЧ3-МЧ6 with a high content of impurities of the above-mentioned operation must be performed at a temperature of 600 °C. Then, server add 30 g of lead, the charge for Sherburne bottoms, placed in a muffle furnace, heated to a temperature of from 950 °C to 1000 °C. Melting the original lead with the door closed (the damper) muffle furnace until complete melting of the sample and the appearance of the «eye» of lead. Then the door (flap) muffle furnace if necessary, open and continue the process of oxidation and slagging at temperatures below 950 °C till the complete closing lead of a highlight (eyes) slag.

The contents of servera poured into a mold, cooled, and separating the lead alloy from the slag. Give the alloy the shape of a cube, place it on drops, preheated to a temperature of from 950 °C to 980 °C, and incubated with the door closed (the damper) muffle furnace for 5−10 minutes Then spend the cupellation when the door is open (throttle) for 15−20 min. while the Temperature should not be below 950 °C. When the amount of lead will remain insignificant, the temperature was raised to 980 °C. At the end of cupellation is the flare, then darkening and hardening of gold-silver bead.

Then drops removed from a muffle furnace, cooled, clean the bead from adhering particles of the drops crushed on the anvil in the plate, which is then weighed. The resulting mass is the amount of gold and silver .

The plate is placed in a porcelain crucible, where the pre-pour 2/3 of the height of the crucible nitric acid, diluted 1:4 or 1:7, heated to a temperature of from 70 °C to 90 °C. the Crucible is heated for 15−20 minutes (avoid boiling acid) to form a Golden squat dark color. The solution is decanted by decantation, pour the nitric acid diluted 1:1, and heated for 15−20 min.

When the ratio of gold to silver is more than 1:6 used nitric acid, diluted 1:4 or 1:7; at a ratio less than 1:6 the dissolution is carried out first in nitric acid, diluted 1:3, and then diluted 1:1.

When the ratio of gold to silver is 1:3 to the bead adds metallic silver in quantity, giving a ratio of 1:6. Then the willow-Wren with the silver wrapped in a lead foil weighing between 2 and 3 g and placed in a muffle furnace for cupellation. The resulting gold-silver Regulus treated with nitric acid as described above.

Golden kartochku washed three times by decantation with hot water, dried, calcined at temperatures from 400 °C to 500 °C for 3−5 min, and after cooling weighed.

Weight of silver is determined by difference between the mass of a goldcrest and a lot of gold .

Simultaneously with the measurement of each batch of samples of blister copper is carried out, the control experience to determine the amendment (hereinafter — amendments TO) to the measurements, using two control samples (with silver content above 200 g/ton and any gold content). A test sample composed of gold and silver, taken in an amount roughly equal to the content of components in the analyzed samples, and carried through all stages of the measurements, starting with the process of servirovane. Placing the reference sample in the beginning and at the end of the series of samples of blister copper.

The result of the amendment TO the for gold (and silver) is defined as the arithmetic mean value of the two obtained results of measurements of control samples and take into account the appropriate sign in the calculations of the measurement results of the sample of blister copper.

Notes

1 a Series of samples is the number of samples analysed in terms of repeatability (without changing the laboratory, equipment, operator).

2 are allowed to change (increase) the frequency of determining the alterations TO be made for gold and silver on the basis of statistical data about the stability of the amendment TO the definition of a mass fraction of gold and silver.

3 in determining the alterations TO be made for gold and silver control experience with each series of samples to make corrections for contamination of the reagents precious metals is not carried out.

9.3.4 Processing of measurement results

9.3.4.1 Mass fraction of gold , g/t, calculated by the formula

, (9)

where is the mass of gold, mg;

 — amendment of the control of gold and a measurement of the control sample, mg;

 — the weight of the portion of blister copper,

Mass fraction of silver , g/t, calculated by the formula

, (10)

where is the mass amounts of gold and silver, mg;

 — the mass of gold, mg;

 — amendment of the control and experience to the silver and a measurement of the control sample, mg;

 — the weight of the portion of blister copper,

9.3.4.2 For the measurement result take an arithmetic average value of three parallel measurements, provided that the difference between the highest and the lowest results in terms of repeatability with a confidence level of 0.95 does not exceed the limit values of the frequency of occurrence , are shown in tables 5 and 6.

If the difference between the highest and lowest results of parallel measurements exceeds the limit value of the frequency of occurrence, perform the procedure described in GOST R ISO 5725−6 (paragraph 5.2.2.1).

9.3.4.3 the Discrepancy between the results of measurements obtained in two laboratories, should not exceed the limit values of reproducibility are given in tables 5 and 6. In this case, the final result may be decided to their arithmetic mean value. At default of this condition can be used the procedure described in GOST R ISO 5725−6.

9.4 Atomic absorption method of measuring a mass fraction of gold and silver

9.4.1 measurement Means, auxiliary devices, materials, solutions

When performing measurements using the following measuring instruments and auxiliary devices:

spectrometer of atomic absorption with flame atomizer and a radiation source for gold and silver;

— air compressor;

— muffle furnace with thermostatic control, ensuring the heating temperature of 1050 °C;

— special laboratory scales of accuracy class according to GOST R 53228 with a readability of 0.0001 g;

— acetylene according to GOST 5457;

— propane-butane according to GOST 20448;

— porcelain crucibles according to GOST 9147;

— flasks KN-2−100−19/26 TCS, KN-2−250−19/26 TCS GOST 25336;

— glasses-1−100 TCS In-1−400 TCS according to GOST 25336;

— volumetric flasks 1−100−2, 1−200−2, 1−1000−2, 2−25−2 according GOST 1770;

pipettes not lower than 2nd accuracy class according to GOST and GOST 29169 29227.

When performing measurements, use the following materials, solutions:

— nitric acid according to GOST 4461 (tested for chloride ion with a solution of silver nitrate), diluted 1:6;

— hydrochloric acid according to GOST 3118, diluted 2:3 and 1:4, and solutions of molar concentrations of 2 and 6 mol/DM;

— a mixture of hydrochloric and nitric acids in the ratio 3:1;

acid bromatological according to GOST 2062;

— a mixture of nitric and bromatological acids in the ratio 1:1;

— bromine according to GOST 4109;

sodium chloride according to GOST 4233;

— copper according to GOST 859, solution mass concentration of 0.2 g/lsolution of hydrochloric acid molar concentration of 2 mol/DM;

— gold GOST 6835 or other regulatory documents;

— solutions of gold of known concentration;

— silver nitrate according to GOST 1277, solution mass concentration of 20 g/DM;

— silver GOST 6836 or other regulatory documents;

— a solution of silver of known concentration;

— distilled water according to GOST 6709;

filters obestochennye [2] or similar;

the filter paper according to GOST 12026, brands f, FS.

9.4.2 Method of measurement

The method is based on measuring absorption of atomic resonance lines of gold at a wavelength of 242,4 nm of silver at a wavelength of 328,1 nm with the introduction of the analyzed solution in the flame acetylene-air or propane-butane-air.

9.4.3 Preparation for measurements

9.4.3.1 in preparing the solution of copper mass concentration of 0.2 g/DM, the linkage of copper with a mass of 40 g were placed in a glass with a capacity of 400 cm, 100 cm pourednitric acid. After the cessation of rapid evolution reaction of nitrogen oxides to the solution flow of 100 cmmixture of nitric and bromatological acids in a ratio of 1:1 or ten drops of bromine and allowed to stand without heating 10 to 15 min. the solution is Evaporated to a volume of 3 to 5 cm, 30 cm, pouredhydrochloric acid and again evaporated to moist salts. Place the solution in a volumetric flask with a capacity of 200 cm, adjusted to the mark with hydrochloric acid molar concentration of 2 mol/land stirred.

9.4.3.2 For the construction of calibration curve prepare solutions of known gold concentrations.

In preparing the solution And the mass concentration of gold is 0.1 mg/cma sample of gold with mass 0,1000 g was dissolved with heating in a volume of 10 to 15 cmof a mixture of hydrochloric and nitric acids, add 0.1 g of sodium chloride, 2 to 3 cmof hydrochloric acid and evaporated to moist salts. After cooling, pour 60 to 80 cmof water, transfer the resulting solution into a measuring flask with volume capacity of 1000 cm, adjusted to the mark with hydrochloric acid, diluted 2:3, and mixed.

In the preparation of a solution of mass concentration of gold is 0.01 mg/cm10 cmsolution And placed in a volumetric flask with a capacity of 100 cm, made up to the mark with hydrochloric acid diluted 1:4, and stirred.

In seven volumetric flasks with a capacity of 100 cmeach placed: 0; 0,5; 1,0; 3,0; 5,0; 10,0 and 30 cmof a solution and the copper solution, an amount corresponding to the sample taken samples, made up to the mark with hydrochloric acid 2 mol/cmand stirred. The resulting solutions contain 0; 0,05; 0,1; 0,3; 0,5; 1,0 and 3.0 µg/cmof gold.

Note — Concentrations of the calibration solutions of gold are Advisory in nature and depend on the characteristics of the used atomic absorption spectrometer, the interval defined concentrations. For constructing a calibration curve allowed to use 3−7 calibration mixtures, but not less than 3.

9.4.3.3 For the construction of calibration curve prepare solutions of known silver concentration.

In preparing the solution And the mass concentration of silver is 1 mg/cma portion of the silver weight 1,0000 g was dissolved with heating in 30 cmof nitric acid. Then pour 25 cmof water, from 100 to 120 cmof hydrochloric acid, transfer the solution into a measuring flask with volume capacity of 1000 cm, made up to the mark with hydrochloric acid 6 mol/land stirred.

In the preparation of a solution of mass concentration of silver is 0.1 mg/cm10 cmsolution And placed in a volumetric flask with a capacity of 100 cm, made up to the mark with hydrochloric acid 2 mol/land stirred.

In seven volumetric flasks with a capacity of 100 cmeach placed respectively: 1,5; 3,0; 5,0; 7,0 and 10 cmof a solution; 2.0 and 4.0 cmof solution A and pour to the mark with hydrochloric acid 2 mol/land stirred.

For construction of calibration curve the prepared solutions were sprayed into the flame of acetylene-air or propane-butane-air, as specified in 9.4.4.2

9.4.4 measurements

9.4.4.1 General requirements for methods of measurements and safety requirements when performing measurements in accordance with section 4.

9.4.4.2 the weight of blister copper by weight from 1 to 5 grams (depending on the mass fraction of gold and silver) was placed in a conical flask with a capacity of 250 cm, 30 cm, pour themixture of hydrochloric and nitric acid, cover the flask with a cover glass (lid) and allowed to stand without heating until the cessation of the violent reaction of the allocation of nitrogen oxides. Then solution is heated and evaporated up to wet salts. Poured from 30 to 50 cmof hydrochloric acid molar concentration of 2 mol/l, heated to dissolve the salts, cooled, transferred to a volumetric flask with a capacity of 100 cmand then filled to the mark with the same acid.

The resulting solutions are sprayed in the flame of acetylene-air or propane-butane-air and record the absorbance at wavelengths for gold — 242,8 nm and for silver — 328,1 nm.

Measurement conditions selected in accordance with device used.

Masses of gold and silver is determined by the calibration graphs.

The absorbance of each solution is measured at least twice and for calculating take arithmetic mean value. When changing solutions, the spray system was washed with water to obtain the zero readings. The recommended maximum value of the measured absorbance of approximately 0.5 units. If necessary to reduce its value is allowed to carry out measurements at less sensitive wavelengths or deploy the burner.

The found value of the absorbance of the analyzed solution minus the absorbance of the solution in the reference experiment find a content-defined component for the calibration schedule.

9.4.5 Processing of measurement results

9.4.5.1 fraction of total Mass of gold or silver , g/t, calculated by the formula

, (11)

where is the mass concentration of the component was found in the calibration schedule, µg/cm;

 — capacity volumetric flasks, cm;

 — the weight of the portion of blister copper,

9.4.5.2 For the measurement result take an arithmetic average value of three parallel measurements, provided that the difference between the highest and the lowest results in terms of repeatability with a confidence level of 0.95 does not exceed the limit values of the frequency of occurrence , are shown in tables 5 and 6.

If the difference between the highest and lowest results of parallel measurements exceeds the limit value of the frequency of occurrence, perform the procedure described in GOST R ISO 5725−6 (paragraph 5.2.2.1).

9.4.5.3 Differences between measurements obtained in two laboratories, should not exceed the limit values of reproducibility are given in tables 5 and 6. In this case, the final result may be decided to their arithmetic mean value. At default of this condition can be used the procedure described in GOST R ISO 5725−6.

10 the Method of measuring the mass fraction of arsenic

10.1 Scope

This section is set by the photometric method of measuring the mass fraction of arsenic in the range of 0,0010% to 0.50%.

10.2 Requirements for measuring errors

The measurement error of the mass fraction of arsenic, the limit values of repeatability and reproducibility for a confidence probability of 0.95 should conform to the values given in table 7.


Table 7

Percentage

Measurement range of mass fraction of arsenic	Characterization of the measurement error	Limit
		repeatability (2)	reproducibility
From to 0,0010 0,0030 incl.	0,0007	0,0005	0,0010
SV. 0,0030 «0,0050 «	0,0011	0,0008	0.0016 inch
«0,0050» 0,0100 «	0,0021	0,0015	0,0030
«0,010» 0,030 «	0,004	0,003	0,006
«0,030» 0,100 «	0,007	0,005	0,012
«To 0.10» to 0.30 «	0,04	0,03	0,06
«To 0.30» to 0.50 «	0,07	0,05	0,010

10.3 measurement Means, auxiliary devices, materials, solutions

When performing measurements using the following measuring instruments and auxiliary devices:

— a device for distillation of arsenic;

— spectrophotometer or the photoelectric photometer with all accessories necessary for measurements at a wavelength of from 630 to 670 or 750 nm;

— special laboratory scales of accuracy class according to GOST R 53228;

— laboratory drying oven with thermostatic control, ensuring the heating temperature up to 250 °C;

— the stove is electric with a closed heating element for temperature up to 350 °C;

— volumetric flasks 1−50−2, 1−100−2, 1−250−2, 2−250−2, 2−1000−2 according GOST 1770;

— glasses-1−100 TCS-1−250 TCS according to GOST 25336;

pipettes not lower than 2nd accuracy class according to GOST and GOST 29169 29227;

— funnel filtering laboratory according to GOST 25336;

glass hour.

When taking measurements, use the following products and solutions:

— distilled water according to GOST 6709;

— nitric acid according to GOST 4461, diluted 1:1;

acid salt of high purity according to GOST 14261, or hydrochloric acid according to GOST 3118 (purified from arsenic), diluted 1:1;

— sulfuric acid according to GOST 4204, diluted 1:1, and the solution molar concentration of 2 mol/DM;

— ammonium molybdate according to GOST 3765, solution mass concentration 10 g/DM;

— hydrazine sulphate, solution mass concentration of 1.5 g/DM;

— sodium hydroxide (sodium hydroxide) according to GOST 4328, solution mass concentration of 100 g/DM;

— potassium bromide according to GOST 4160;

— bromine according to GOST 4109;

— the reaction mixture;

— arsenious anhydride according to GOST 1973.

10.4 Method of measuring

The method is based on measuring the optical density of the colored michalopolous connection after separation of arsenic from copper and interfering elements by distillation in the form of trichloride arsenic.

10.5 Preparation for measurements

10.5.1 in the preparation of a solution of molybdate of ammonium mass concentration of 10 g/DMthe weight of salt mass of 10 g is dissolved in sulfuric acid solution the molar concentration of 2 mol/DM, the solution is filtered, transferred to a measuring flask with volume capacity of 1000 cm, made up to the mark with the same acid and mix.

10.5.2 in the preparation of the reaction mixture in a volumetric flask with a capacity of 100 cmare placed 50 cmof ammonium molybdate solution and 5 cmof hydrazine solution, made up to the mark with water and mix. The mixture is prepared immediately before use.

10.5.3 For the construction of calibration curve prepare solutions of known arsenic concentrations.

In preparing the solution And the mass concentration of arsenic of 0.1 mg/cma portion of the arsenious anhydride weight 0,1320 g is placed in a measuring flask with volume capacity of 1000 cm, flow 10 cmof sodium hydroxide solution, made up to the mark with water and mix.

In the preparation of a solution of mass concentration of arsenic 0.02 mg/cm50,0 cmsolution And placed in a volumetric flask with a capacity of 250 cm, made up to the mark with water and mix.

10.5.4 Construction of calibration curve

In five glasses with a capacity of 100 cmeach placed: 0; 0,5; 1,0; 3,0 and 4,0 cmof solution B. In glasses added 5 cmof nitric acid, evaporated to dryness and then the measurement is continued as specified in 10.6.2. According to the obtained results build a calibration curve.

Solution comparison is the solution of the reference experiment.

10.6 performance measurement

10.6.1 General requirements for methods of measurements and safety requirements when performing measurements in accordance with section 4.

10.6.2 the weight of blister copper by weight in accordance with table 8 were placed in a glass with a capacity of 250 cmand go from 10 to 50 cmof nitric acid, diluted 1:1.


Table 8

Mass fraction of arsenic, %	The mass of charge, g	The amount of acid cm	Capacity volumetric flasks, cm	An aliquot of solution, cm
From 0.001 to 0.005 incl.	5	50	100	20
SV. Of 0.005 «to 0.05 «	2	40	250	20
«0,05» 0,1 «	1	20	250	10
«0,1» 0,5 «	0,5	10	250	5

Glass cover glass (lid) and heat for 20−30 min until the cessation of the violent reaction of the allocation of nitrogen oxides. Glass (cover) is removed, wash it with water over the glass and evaporate the solution until a volume of 3 to 5 cm. If seen goldcrests sulfur to the solution add from 2 to 3 cmof bromine, cover glass (the cover) and leave without heat for 10−15 minutes, then evaporated to wet salts.

To the residue poured 20 cmof sulphuric acid diluted 1:1, and is evaporated prior to the allocation of sulphuric acid fumes. Cool, add 5 to 10 cmof water and the evaporation repeated.

To the residue poured from 40 to 50 cmof water and transfer the solution into a flask for distillation. Added to a flask, 4 g of hydrazine, 1 g of potassium bromide and the flask quickly stoppered, fitted with a drip funnel and nozzle. In the receiver pour 30 cmof water and connect all the parts of the device, control the receiver poured such a volume of water, the level was at 1 (2) mm above the end of the tube.

In the distillation flask containing the solution, is introduced through the drip funnel 100 cmof hydrochloric acid, heated to boiling and then distilled 2/3 of the volume of the liquid.

Wash out fridge with water and transfer the solutions from the receivers in a volumetric flask with a capacity from 100 to 250 cmand for measurements taken of the sample solution in accordance with table 8.

An aliquot of the solution was placed in a beaker with a capacity of 100 cm, flow 10 to 15 cmof nitric acid and evaporated to dry salts at a temperature of from 120 °C to 130 °C. For complete removal of residual nitric acid in the beaker put into an oven and dried at a temperature of from 130 °C to 135 °C for 1−1,5 h. the Residue was cooled and moistened with 2 drops of sodium hydroxide solution. After 10−12 min, poured to the residue, 30 cmof hot water and 4 cmof the reaction mixture. Heated to boiling and boiled for 5−6 min. After cooling, the solution is transferred to a volumetric flask with a capacity of 50 cm, made up to the mark with water and mix.

Measure the optical density of the solution at a wavelength of from 630 to 670 nm or 750 nm (depending on device type) in a ditch with the thickness of the light absorbing layer 30 mm.

Solution comparison is the solution of the reference experiment.

Mass of arsenic is determined by calibration schedule.

10.7 Processing of measurement results

10.7.1 Mass fraction of arsenic , %, is calculated by the formula

, (12)

where is the mass of arsenic, was found in the calibration graphics mg;

 — capacity volumetric flasks, cm;

 — volume aliquot of the solution, cm;

 — the weight of the portion of blister copper, g;

 — a conversion factor of milligrams to grams.

10.7.2 For the measurement result taking the arithmetic mean of two parallel definitions, provided that the absolute difference between them in terms of repeatability does not exceed the values (with confidence probability of 0.95) limit of repeatability are given in table 7.

If the discrepancy between the results of parallel measurements exceeds the limit value of the frequency of occurrence, perform the procedure described in GOST R ISO 5725−6 (paragraph 5.2.2.1).

10.7.3 the Discrepancy between the results of measurements obtained in two laboratories, should not exceed the values of the limit of reproducibility shown in table 7. In this case, the final result may be decided to their arithmetic mean value. At default of this condition can be used the procedure described in GOST R ISO 5725−6.

11 Methods for measuring the mass fraction of sulfur

11.1 Scope

In this section, established methods of measuring the mass fraction of sulfur: gravity — in the range from 0.03% to 1.00%, and infrared spectrometry in the range from 0.010% to 1.00%.

11.2 Requirements for measurement uncertainty

The measurement error of the mass fraction of sulphur limit values of repeatability and reproducibility for a confidence probability of 0.95 should conform to the values given in tables 9 and 10.


Table 9 — Gravimetric method

Percentage

Measurement range of mass fraction of sulfur	Characterization of the measurement error	Limit
		repeatability (2)	reproducibility
From 0.03 to 0.10 incl.	0,02	0,02	0,03
SV. Of 0.10 «to 0.30 «	0,05	0,05	0,07
«0,30» to 1.00 «	0,08	0,08	0,1

Table 10 — infrared spectrometric Method.

Percentage

Measurement range of mass fraction of sulfur	Characterization of the measurement error	Limit
		repeatability (2)	reproducibility
From 0,010 to 0,030 incl.	0,003	0,003	0,004
SV. 0,030 «0,100 «	0,005	0,005	0,007
«To 0.10» to 0.30 «	0,02	0,01	0,03
«0,30» to 1.00 «	0,04	0,03	0,05

11.3 Gravimetric method

11.3.1 measurement Means, auxiliary devices, materials, solutions

When performing measurements using the following measuring instruments and auxiliary devices:

— muffle furnace with a thermostat that provides temperature 900 °C;

— the stove is electric with a closed heating element for temperature up to 350 °C;

— porcelain crucibles according to GOST 9147;

— flasks KN-2−500−19/26 TCS GOST 25336;

— glasses-1−250 TCS according to GOST 25336;

pipettes not lower than 2nd accuracy class according to GOST and GOST 29169 29227;

— desiccator with GOST 25336 filled with calcium oxide or calcium chloride.

When taking measurements, use the following products and solutions:

— calcium oxide according to GOST 8677, pre-calcined at a temperature of from 970 °C to 1050 °C;

— calcium chloride [7];

— nitric acid according to GOST 4461, diluted 1:1;

— hydrochloric acid according to GOST 3118, diluted 1:1, 1:9;

— bromine according to GOST 4109;

— potassium bromide according to GOST 4160;

— potassium chlorate (potassium chlorate salt) according to GOST 2713;

— hydroxylamine hydrochloride according to GOST 5456, solution mass concentration of 100 g/DM, the solution is kept for seven days.

— barium chloride 2-water according to GOST 4108, solution mass concentration of 20 g/DMpre-filtered solution stored for one year;

— silver nitrate according to GOST 1277, solution mass concentration 10 g/DM, acidified with nitric acid, the solution is kept for one year, storage conditions according to GOST 4212.

11.3.2 Method of measurement

The method is based on decomposition of a sample of blister copper nitric and hydrochloric acids, followed by precipitation of sulfur in the form of barium sulfate and the determination of the mass of the latter.

11.3.3 measurements

11.3.3.1 General requirements for methods of measurements and safety requirements when performing measurements in accordance with section 4.

11.3.3.2 Sample of blister copper weighing from 1 g to 5 g were placed in a glass with a capacity of 250 cm, add 2 to 3 drops of bromine (or 1 to 2 g of potassium bromide or potassium chlorate), from 15 to 25 cmof nitric acid, diluted 1:1, covered with glass and leave you without heating for 15−20 minutes until the cessation of the violent reaction of the allocation of nitrogen oxides.

Then placed on a warm plate place, slowly evaporated the solution to a syrupy state. Remove the glass (cover), wash it with water over the beaker, pour 10 to 15 cmof hydrochloric acid and evaporated almost to dryness. Add 5 cmof hydrochloric acid and again evaporated to dryness. This operation is repeated one more time. The residue is dried at a temperature of from 130 °C to 150 °C to remove the smell of hydrochloric acid.

The dry residue moistened with 5 cmof hydrochloric acid diluted 1:1, pour 50 to 70 cmof hot water and boiled under glass for 5−10 min. the Solution was filtered (if any insoluble residue) through the dense filter of «blue ribbon» in the cone which is enclosed a little filtrowanie mass, and washed five or six times with hot hydrochloric acid, diluted 1:99.

The filtrate and the washings collected in a conical flask with a capacity of 500 cm. The volume of the solution should be from 250 to 300 cm. Poured into flask 2 cmof a solution of hydroxylamine, close the flask with a lid and boil for 5−7 min.

In heated to boiling, the solution is poured with constant stirring with a constant flow of 100 cmof hot solution of barium chloride. Boil for 10−15 minutes and leave until the next day on a warm plate place.

The solution was filtered through a tight double filter of «blue ribbon», trying not to move him precipitate. Into the flask pour 25 cmof hot water, shaken and poured on filter. Repeat this operation two more times. The walls of the bulb is wiped with a piece of filter, which is placed on the filter with the sediment. Then wash the flask and filter repeatedly with hot water until no reaction to chloride ions in the washing waters (with a solution of silver nitrate).

The filter with precipitate was placed in preheated and weighed porcelain crucible, dried, and incinerated in a muffle furnace and calcined at a temperature from 850 °C to 900 °C to obtain constant weight. Then the crucible was placed in a desiccator, cooled and weighed.

11.3.4 Processing of measurement results

11.3.4.1 Mass fraction of sulfur , %, is calculated by the formula

, (13)

where the weight of the precipitate of barium sulphate, g;

factor of recalculation of the mass of barium sulfate on sulfur;

 — the weight of the portion of blister copper,

11.3.4.2 For the measurement result taking the arithmetic mean of two parallel definitions, provided that the absolute difference between them in terms of repeatability does not exceed the values (with confidence probability of 0.95) limit of repeatability are given in table 9.

If the discrepancy between the results of parallel measurements exceeds the limit value of the frequency of occurrence, perform the procedure described in GOST R ISO 5725−6 (paragraph 5.2.2.1).

11.3.4.3 the Discrepancy between the results of measurements obtained in two laboratories, should not exceed the limit values for the reproducibility given in table 9. In this case, the final result may be decided to their arithmetic mean value. At default of this condition can be used the procedure described in GOST R ISO 5725−6.

11.4 infrared spectrometric Method.

11.4.1 measurement Means, auxiliary devices, materials, solutions

When performing measurements using the following measuring instruments and auxiliary devices:

— sulfur analyzer based on the principle of infrared spectrometry;

— induction or high-frequency tube furnace providing heating temperature not less than 1100 °C;

— boats or crucibles, of refractory ceramic, calcined at temperatures from 900 °C to 1100 °C for at least 1 h;

— standard samples according to GOST 8.315 composition of copper or alloys based on copper or iron;

— medical forceps according to GOST 21241.

When performing measurements using the following materials:

— technical oxygen gas according to GOST 5583;

magnesium rate (anhydro) [8] or other technical documentation;

— sodium hydroxide (sodium hydroxide) according to GOST 4328 or other regulatory documents;

— copper (II) oxide according to GOST 16539 or other regulatory documents;

reagents in accordance with the instructions for the analyzer;

marshes: tungsten [9] and other substances, providing the combustion and the results of control of the experience outlined in 11.4.4.

11.4.2 Method of measurement

The method is based on measuring the absorption of gaseous sulfur dioxide (IV) in the infrared region of the spectrum after selecting it from a sample of metal combustion in high-frequency or induction tube furnace in flowing oxygen.

11.4.3 Preparation for measurements

Preparing the analyzer to work and his grading is carried out in accordance with the operation manual. For calibration you must use the standard samples for composition of copper, alloys of copper-based or iron-based.

11.4.4 measurements

General requirements for methods of measurements and safety requirements when performing measurements in accordance with section 4.

Mass fraction of sulfur is determined simultaneously from the two batches.

In the boat or crucible is placed a portion of the sample weighing between 0,1000 up to 1,000 g, add the flux, the weight of which must be the same when conducting the reference experiment, the calibration and analysis, and conduct measurement as specified in the supplied instructions.

Directly before measuring sample of the sample hold control experience. To do this in the boat or crucible is placed a portion of the beach that mass, which is used in the analysis of samples and measurements taken as stated above.

Control experience should be considered satisfactory if the readings of the mass fraction of sulfur on the digital scoreboard do not exceed the values of the accuracy specifications of the measurement method (table 10). The inaccuracy of the measurement method consider the error of the lower range determined intervals a mass fraction of sulfur.

11.4.5 Processing of measurement results

The results of measurements of sulphur mass fraction in percent is displayed on the scoreboard, printer, or automated analyzer.

The measurement results take the arithmetic mean of two parallel definitions, provided that the absolute difference between them in terms of repeatability does not exceed the values (with confidence probability of 0.95) limit of repeatability , is given in table 10.

If the discrepancy between the results of parallel measurements exceeds the limit value of the frequency of occurrence, perform the procedure described in GOST R ISO 5725−6 (paragraph 5.2.2.1).

Discrepancies between measurements obtained in two laboratories, should not exceed the limit values for the reproducibility given in table 10. In this case, the final result may be decided to their arithmetic mean value. At default of this condition can be used the procedure described in GOST R ISO 5725−6.

12 Atomic-absorption method of measuring the mass fraction of lead

12.1 Scope

In this section, the set of atomic-absorption method of measuring the mass fraction of lead in the range from 0.002% to 3.0%.

12.2 Requirements for measurement uncertainty

The measurement error of the mass fraction of lead, the limit values of repeatability and reproducibility for a confidence probability of 0.95 should conform to the values given in table 11.


Table 11

Percentage

Measurement range of mass fraction of lead	Characterization of the measurement error	Limit
		repeatability (2)	reproducibility
From 0.002 to 0.005 incl.	0,001	0,001	0,002
SV. 0,005 «0,010 «	0,003	0,003	0,004
«0,010» 0,030 «	0,005	0,005	0,007
«0,030» 0,100 «	0,028	0,025	0,04
«To 0.10» to 0.50 «	0,04	0,04	0,06
«0,5» 1,0 «	0,1	0,1	0,2
«Of 1.0» to 3.0 «	0,3	0,2	0,4

12.3 measurement Means, auxiliary devices, materials, solutions

When performing measurements using the following measuring instruments and auxiliary devices:

spectrometer of atomic absorption with flame atomizer and the radiation source to the lead;

— air compressor;

— special laboratory scales of accuracy class according to GOST R 53228;

— volumetric flasks 2−100−2, 2−200−2, 2−250−2, 2−1000−2 according GOST 1770;

— glasses-1−100 TCS-1−250 TCS according to GOST 25336;

— flasks KN-2−100−19/26 TCS, KN-2−250−19/26 TCS GOST 25336;

pipettes not lower than 2nd accuracy class according to GOST and GOST 29169 29227.

When taking measurements, use the following products and solutions:

— air compressed under a pressure of 2·10-6·10PA;

— acetylene according to GOST 5457;

— propane-butane according to GOST 20448;

— distilled water according to GOST 6709;

— hydrochloric acid according to GOST 3118 or diluted 1:1, 1:9 and 1:95;

— nitric acid according to GOST 4461 or diluted 1:9 and 1:95;

— iron according to GOST 9849, solution mass concentration of 15 g/DMnitric acid molar concentration of 0.1 mol/DM;

— ammonia water according to GOST 3760;

— hydrogen peroxide according to GOST 10929;

— lead according to GOST 3778, marks S0 and S1;

— lead solutions of known concentration;

— calibration solutions of lead;

filters obestochennye [2] or similar;

— lanthanum chloride or nitrate or lanthanum oxide in [10], [11], [12]; the solution, the mass concentration of 2 mg/cm.

12.4 Method of measuring

The method is based on measuring absorption of atomic resonance line of lead at a wavelength is 283.3 nm after the introduction of the analyzed solution in the flame acetylene-air or propane-butane-air. For the mass concentration of lead is less than 0.01% of its Coosada on the iron hydroxide or lanthanum.

12.5 Preparation for measurements

12.5.1 in the preparation of a solution of lanthanum mass concentration of 2 mg/cmweighed lanthanum nitrate weighing 3.1 g or lanthanum oxide with a mass of 2.4 g, chloride or lanthanum weighing 5.4 g was dissolved in a volume of 10 to 15 cmof hydrochloric acid diluted 1:1, the resulting solution placed in a measuring flask with volume capacity of 1000 cm, made up to the mark with water and mix.

12.5.2 For the construction of calibration curve prepare solutions of known lead concentrations.

In preparing the solution And the mass concentration of lead of 0.1 mg/cma portion of the lead mass 0,1000 g dissolved in a volume of 10 to 15 cmof nitric acid, diluted 1:1, evaporated to wet salts. Pour 50 cmof nitric acid was placed in a volumetric flask with a capacity of 1000 cm, made up to the mark with water and mix.

In the preparation of a solution of mass concentration of lead is 0.01 mg/cm10 cmsolution And placed in a volumetric flask with a capacity of 100 cm, made up to the mark with nitric acid, diluted 1:9 or 1:95 and stirred.

In preparing the solution In the mass concentration of 0.002 mg/cmof 20 cmof solution B is placed in a volumetric flask with a capacity of 100 cm, made up to the mark with nitric acid, diluted 1:9 or 1:95 and stirred.

12.5.3 Construction of calibration curve

To build a calibration curve in a series of volumetric flasks with a capacity of 100 cmeach placed In solution B or in the volume, to respect the linearity of the graph, poured 10 cmof hydrochloric (nitric) acid diluted 1:1, made up to the mark with water and mix. Next, keep in 12.6.2. According to the obtained results build a calibration curve (used for the mass fraction of lead more than 0.01%).

To build a calibration curve in the number of cups (conical flasks) with a capacity from 100 to 250 cmis placed In a solution or in the volume, to respect the linearity of the graph. Then in beakers (flasks) pour from 3 to 5 cmof a solution of iron (Lantana), from 5 to 10 cmof nitric acid, diluted 1:1, 3 to 5 cmof hydrogen peroxide solution, 80 to 100 cmof water and heat the solution to boiling. Next, keep in 12.6.2. According to the obtained results build a calibration curve (used for the mass concentration of lead is less than 0.01%).

12.6 performance measurement

12.6.1 General requirements for methods of measurements and safety requirements when performing measurements in accordance with section 4.

12.6.2 for the mass concentration of lead is less than 0.01%

The weight of blister copper weighing from 1 to 2 g were placed in a glass (or conical flask) with a capacity of 250 cm, flow 10 to 15 cmof nitric acid, diluted 1:1, and heated to remove oxides of nitrogen, evaporating to a volume of 1 to 2 cm. Poured from 80 to 100 cmof water, 5 to 10 cmof a solution of iron, 3 to 5 cmof hydrogen peroxide solution and heated to boiling.

Into the solution pour a solution of ammonia in such quantity that the copper passed into the ammonia complex, and from 5 to 10 cmof ammonia.

Stand the glass (the bulb) in a warm place plate to the coagulation of the precipitate. It is then filtered through a medium density filter «white ribbon» and washed three or four times with hot ammonia solution, diluted 1:19.

The filter cake is dissolved in 10−15 cmof hot nitric acid (hcl), diluted 1:1, and washed the filter with hot water until neutral wash water (test on universal indicator paper), collecting the filtrate and washings in a beaker (flask), which conducted the deposition. The solution after cooling was placed in a volumetric flask with a capacity of 100, 200 or 250 cmand top up with water to the mark.

For an amendment to the mass fraction of lead in the chemicals through all stages of the measurements carried out control experience.

The analyzed solution is injected into the flame of acetylene-air or propane-butane-air atomic absorption spectrometer, measure the absorbance of lead in the wavelength is 283.3 nm. The absorbance of the solution measured at least twice and for calculating take arithmetic mean value. When changing solutions, the spray system was washed with water to obtain the zero readings. The recommended maximum value of the measured absorbance of 0.5 units.

Measurement conditions selected in accordance with device used.

12.6.3 When the mass fraction of lead more than 0.01%

The weight of blister copper with a mass of 1 g was dissolved with heating in a volume of 10 to 15 cmof nitric acid, diluted 1:1, and evaporated up to wet salts. If, after the dissolution of the sample remained insoluble residue of dark color, then pour 1 to 2 cmof hydrochloric acid and evaporated to moist salts.

Allowed the use of other types of decomposition portion (for example, a mixture of hydrochloric and nitric acids, hydrochloric acids, etc.).

Poured to wet the rest of 10 cmof water, place the solution in a volumetric flask with a capacity of 250 or 500 cm, adjusted to the mark with nitric (muriatic) acid diluted 1:9 or 1:95 and stirred.

The obtained solution is sprayed in the flame of acetylene-air or propane-butane-air and measure the absorbance at the wavelength is 283.3 nm.

Measurement conditions selected in accordance with device used.

12.7 Processing of measurement results

12.7.1 Mass fraction of lead , %, is calculated by the formula

, (14)

where is the mass concentration of lead was found in the calibration schedule, mg/cm;

 — capacity volumetric flasks, cm;

 — the weight of the portion of blister copper, g;

 — a conversion factor of milligrams to grams.

12.7.2 For the measurement result taking the arithmetic mean of two parallel definitions, provided that the absolute difference between them in terms of repeatability does not exceed the values (with confidence probability of 0.95) limit of repeatability are given in table 11.

If the discrepancy between the results of parallel measurements exceeds the limit value of the frequency of occurrence, perform the procedure described in GOST R ISO 5725−6 (paragraph 5.2.2.1).

12.7.3 the Discrepancy between the results of measurements obtained in two laboratories, should not exceed the limit values for the reproducibility given in table 11. In this case, the final result may be decided to their arithmetic mean value. At default of this condition can be used the procedure described in GOST R ISO 5725−6.

13 Atomic emission spectral method of measuring a mass fraction of antimony, arsenic, tin, bismuth, Nickel, iron, lead, zinc, sulfur, selenium, tellurium, with spark excitation and photoelectric registration of spectrum

13.1 Scope

In this section, the set of atomic-emission spectral measuring method with spark excitation and photoelectric registration of spectrum a mass fraction of antimony, arsenic, tin, bismuth, Nickel, iron, lead, zinc, sulfur, selenium, tellurium into crude copper in the ranges given in table 12.


Table 12

Percentage

Component	The range of mass fraction of component
Antimony	From 0.010 to 0.30 incl.
Arsenic	From 0,0060 to 0.30 incl.
Lead	From 0.010 to 1.00 incl.
Bismuth	From 0.0005 to 0.020 incl.
Nickel	From 0.010 to 0.90 incl.
Sulfur	From 0,0030 to 0.30 incl.
Zinc	From 0,0030 to 0,030 incl.
Tin	From 0,0010 to 0,090 incl.
Iron	From 0,00060 to 0,060 incl.
Tellurium	From 0,0030 to 0.065 incl.
Selenium	From 0,0030 to 0.065 incl.

13.2 Requirements for measurement uncertainty

Characteristics of errors of measurements of mass fraction of antimony, arsenic, tin, bismuth, Nickel, iron, lead, zinc, sulfur, selenium, tellurium, limit values of repeatability and reproducibility for a confidence probability of 0.95 should conform to the values given in table 13.


Table 13

Percentage

The designated component	Measurement range of mass fraction of components	Characterization of the measurement error	Limit
			repeatability	reproducibility
Arsenic	From to 0,0090 0,0030 incl.	0,0012	0,0010	0,0017
	SV. 0,0090 «0,0300 «	0,0051	0,0040	0,0072
	«0,030» 0,090 «	0,018	0,010	0,025
	«0,090» 0,300 «	0,043	0,030	0,060
Bismuth	To from 0,0005 0,0010 incl.	0,0004	0,0002	0,0005
	SV. 0,0010 «0,0030 «	0,0007	0,0003	0,0008
	«0,0030» 0,0060 «	0,0011	0,0005	0,0015
	«0,0060» 0,0100 «	0,0015	0,0010	0,0020
	«0,010» 0,020 «	0,004	0,002	0,004
Nickel	From 0,010 to 0,030 incl.	0,005	0,005	0,006
	SV. 0,030 «0,100 «	0,017	0,010	0,024
	«To 0.10» to 0.30 «	0,04	0,03	0,06
	«0,30» 0,90 «	0,08	0,07	0,11
Lead	From. Of 0.010 to 0.050 incl.	0,005	0,005	0,007
	SV. 0,050 «0,150 «	0,035	0,020	0,050
	«0,15» 0,60 «	0,07	0,05	0,08
	«0,60» 1,00 «	0,08	0,07	0,09
Antimony	From 0,010 to 0,030 incl.	0,006	0,005	0,008
	SV. 0,030 «to 0,060 «	0,011	0,008	0,016
	«Of 0.06» to 0.10 «	0,02	0,01	0,03
	«To 0.10» to 0.30 «	0,04	0,03	0,06
Sulfur	From to 0,0030 0,0100 incl.	0,0010	0,0008	0,0012
	SV. 0,010 «0,030 «	0,005	0,005	0,007
	«0,030» 0,100 «	0,011	0,012	0,018
	«To 0.10» to 0.30 «	0,02	0,02	0,03
Selenium	From to 0,0030 0,0060 incl.	0,0008	0,0010	0,0011
	SV. 0,0060 «0,0100 «	0,0015	0,0020	0,0020
	«0,010» 0,030 «	0,004	0,003	0,005
	«0,030» to 0.065 «	0,009	0,005	0,010
Tellurium	From to 0,0030 0,0060 incl.	0,0008	0,0010	0,0011
	SV. 0,0060 «0,0100 «	0,0015	0,0020	0,0020
	«0,010» 0,030 «	0,004	0,003	0,005
	«0,030» to 0.065 «	0,009	0,005	0,010
Zinc	From to 0,0090 0,0030 incl.	0,0011	0,0010	0,0015
	SV. 0,009 «0,030 «	0,004	0,003	0,005
Iron	From about 0.0006 to 0,0020 incl.	0,0004	0,0003	0,0005
	SV. 0,0020 «0,0060 «	About 0.0006	About 0.0006	0,0009
	«0,006» 0,020 «	0,002	0,0020	0,003
	«0,020» 0,060 «	0,007	0,007	0,010
Tin	From to 0,0010 0,0030 incl.	0,0004	0,0004	About 0.0006
	SV. 0,0030 «0,0090 «	0,0011	0,0010	0,0015
	«0,009» 0,030 «	0,003	0,003	0,004
	«0,030» 0,090 «	0,011	0,010	0,015

13.3 measurement Means, auxiliary devices, materials, solutions

When performing measurements using the following measuring instruments and auxiliary devices:

spectrometer atomic emission «SPECTRO LAB S» or similar;

— laboratory scales with the greatest limit of weighing of 200 g of special accuracy class according to GOST R 53228 with a readability of 0.0001 g;

milling machine «HERZOG», «NC 80 F» or similar;

— the lathe table TN-150 or equivalent;

compressor model M 1−7 or similar;

— pressure gauge with measuring range from 0 to 10 MPa;

— high-frequency melting plant «Lifumat Met the 3.3 VAC» or similar;

oven cleaning argon «Rare Gas Purifier MP-2000» or similar;

— the mold copper or graphite;

— graphite crucible;

— ceramic crucibles;

— spout ceramic for crucibles.

When taking measurements, use the following products and solutions:

standard samples (CO) composition of copper;

standard samples (CO) composition of blister copper for spectral analysis;

— argon according to GOST 10157;

— air compressed under a pressure of 4 to 6 MPa;

— silicone grease;

— ethyl alcohol according to GOST 18300.

13.4 Method of measurement

The method is based on measuring the intensity of emission spectral lines of the designated components in a metal test specimen and the metal samples compare with the use of atomic-emission spectrometer «SPECTRO LAB S» or other type of optical spectrometer with an arc or spark excitation source and the photoelectric registration of spectrum.

13.5 Preparations for measurements

13.5.1 preparation of the device

The unit measurement is carried out in accordance with the requirements of the operating instructions of the mass spectrometer. The spectrometer will graduate when you create a method using a standard sample of composition of copper and build the dependence of the intensity of the analytical line from the mass fraction of each component you define. In future work adjust calibration parameters in accordance with the manual of the spectrometer.

Analytical lines components (channels) and the measurement modes determined by the components installed in accordance with the method of measurement.

13.5.2 Requirements for samples

Samples for measurement must come in the form of chips or solid sample having at least one flat surface with a diameter of 20 mm.

13.5.3 Preparation of samples for measurement

Shavings of blister copper pre-atminciai. Then the weighed chip of blister copper weight from 30,00 to 50,00 g is placed in a ceramic crucible or a ceramic crucible with graphite insert, and fused by high-frequency melting plant of 3.3 units for 2 minutes until «green eyes» in accordance with the manual «Lifumat Met 3.3 VAC». The sample is obtained in the form of a monolithic sample. The surface of the sample directly before the measurement process on a milling or turning machine in accordance with a manual milling or lathe. Similarly treat the surface of control samples and standard samples for spectral analysis. Surface treatment of samples is carried out in accordance with the working manual milling machine. On the treated surface should be free of holes, scratches, cracks, and slag inclusions.

13.5.4 performance measurement

The measurements are carried out in accordance with the manual of the device. Mass fraction of the components are determined in two parallel samples.

13.5.5 the Processing of the measurement results

Processing of results of measurements carried out on a computer program and present them in the form of values of the mass fraction of the designated component. For the outcome measurements take the average of results of two parallel measurements, provided that the difference between their values at confidence probability of 0.95 does not exceed the limit values of the recurrence given in table 13.

If the discrepancy between the results of parallel measurements exceeds the limit value of the frequency of occurrence, perform the procedure described in GOST R ISO 5725−6 (paragraph 5.2.2.1).

Discrepancies between measurements obtained in two laboratories, should not exceed the reproducibility limit given in table 13. In this case, the final result may be decided to their arithmetic mean value. At default of this condition can be used the procedure described in GOST R ISO 5725−6.

14 Atomic emission spectral method with inductively coupled plasma measurements of the mass fraction of platinum and palladium

14.1 Scope

In this section, the set of atomic emission spectral method with inductively coupled plasma measurements of the mass fraction of platinum and palladium in the range from 0.25 to 50.0 g/t assay after pre-concentration.

14.2 Requirements for measurement uncertainty

The error of measurement of mass fraction of platinum and palladium, the values for the limits of repeatability and reproducibility for a confidence probability of 0.95 should conform to the values given in table 14.


Table 14

In grams per ton

The designated component	Measurement range of mass fraction of component	Characterization of the measurement error	Limit
			repeatability	reproducibility
Platinum, palladium	From 0.25 to 0.50 incl.	0,11	0,11	0,15
	SV. 0,50 «1,00 «	0,22	0,23	0,31
	«Of 1.0» to 2.5 «	0,4	0,4	0,5
	«With 2.5» and 5.0 «	0,5	0,6	0,7
	«5,0» 10,0 «	1,4	1,1	1,9
	«10,0» 25,0 «	2,7	3,1	3,8
	«25,0» 50,0 «	4,3	5,3	6,1

14.3 measurement Means, auxiliary devices, materials, solutions

When performing measurements using the following measuring instruments and auxiliary devices:

spectrometer of atomic emission with inductively coupled plasma «Spectrо CIROS» or similar;

— muffle furnace (melting) temperature of heating up to 1000 °C;

— the stove is electric with a closed heating element for temperature up to 350 °C;

oven cooperational with the heating temperature up to 1000 °C;

— a mold of cast iron or steel;

— special laboratory scales of accuracy class according to GOST R 53228 increments of 0.0001, 0,00001, 0,000001 g;

— hammer and anvil steel working lead alloy;

— hammer and anvil steel polished to raskopki Korolkov;

— Curling of serburov;

— tongs for anything;

— surbery an inner diameter of from 50 to 60 mm, height from 23 to 35 mm (if necessary, pre-glazed);

— Cappel magnesite, prepared from a mixture consisting of 85% of periclase powder according to GOST 10360 brands of PPI 8891 PPI, PPTI 92 or magnesite powder according to GOST 4689 and 15% of Portland cement according to GOST 10178 grade not lower than 400 (crushed to a particle size passing through a sieve 0,071 according to GOST 6613) with the addition of 10% water. Before use, the drops should be dried.

Note — it is possible to produce anything of a different composition, providing measurements with a set accuracy;


— flasks KN-2−100−18 TCS, KN-2−750−29/32 TCS GOST 25336;

— volumetric flasks 2−25−2, 2−100−2 according GOST 1770;

— funnel In-100−150 MS, In-150−230 TC GOST 25336;

— funnel In-36−80 TC GOST 25336;

pipettes according to GOST 29227;

— glazed porcelain crucible according to GOST 9147.

When taking measurements, use the following products and solutions:

— hydrochloric acid according to GOST 3118, diluted 1:1, 1:5, 1:6, 1:100;

— nitric acid according to GOST 4461, diluted 1:3;

— sulfuric acid according to GOST 4204;

— thiourea according to GOST 6344;

— lead according to GOST 3778 or other regulatory documents;

— lead foil with a thickness of 0.1 to 0.3 mm, is made of lead according to GOST 3778 (or other regulatory documents);

— mercury (II) nitrate 1-water according to GOST 4520, solution mass concentration of 26 g/DM;

sodium chloride according to GOST 4233 and solution mass concentration of 20 g/DM;

— borax according to GOST 8429 (calcined);

— distilled water according to GOST 6709;

— quartz or crushed glass;

— the charge for Sherburne bottoms, consisting of two parts by weight of calcined borax and one part by weight of soda. 10 kg of the mixture is added 3 kg of quartz or crushed glass. One sample of the sample spend between 6 to 8 g of the charge;

the filter paper according to GOST 12026, brands, f, FS;

— sulfur according to the normative documents;

— argon according to GOST 10157;

— platinum according to GOST 31290;

— palladium according to GOST 31291;

filters obestochennye [2] or similar;

— the state standard samples for composition of ion solution of platinum and palladium with a mass fraction of 1 g/DM.

14.4 Method of measuring

The method is based on obtaining a ruled optical emission spectra of atoms and ions of the analyte sample when spraying the sample solution in inductively connected plasma. The relationship of radiation intensity and the mass concentration of a component in solution is established by means of calibration curve.

14.5 Preparation for measurements

14.5.1 Preparation of solutions from pure metals

For preparation of a solution of platinum mass concentration of 1.0 mg/cmweighed platinum mass 0,1000 g is placed in a conical flask with a capacity of 100 cmand dissolved by heating in 30 cmmixture of nitric and hydrochloric acids (1:3), evaporated to wet salts. The residue is dissolved in 10 cmof hydrochloric acid, bring to the boil, pour 50 cmof hydrochloric acid diluted 1:6 and is boiled to dissolve the salts, and cooled. The resulting solution was placed in a volumetric flask with a capacity of 100 cm, made up to the mark with hydrochloric acid, diluted 1:6, and stirred. The solution is stable for one year.

For preparation of a solution of platinum mass concentration of 0.1 mg/cmin a volumetric flask with a capacity of 100 cmis placed 10 cmsolution of platinum mass concentration of 1.0 mg/cm, made up to the mark with hydrochloric acid, diluted 1:6, and stirred. The solution is stable for three months.

For preparation of a solution of palladium mass concentration of 1.0 mg/cma sample of palladium weighing 0,1000 g is placed in a conical flask with a capacity of 100 cmand dissolved by heating in 30 cmmixture of nitric and hydrochloric acids (1:3), evaporated to wet salts. The residue is dissolved in 10 cmof hydrochloric acid, bring to the boil, pour 50 cmof hydrochloric acid diluted 1:6 and is boiled to dissolve the salts, and cooled. The resulting solution was placed in a volumetric flask with a capacity of 100 cm, made up to the mark with hydrochloric acid, diluted 1:6, and stirred. The solution is stable for one year.

For preparation of a solution of palladium mass concentration of 0.1 mg/cmin a volumetric flask with a capacity of 100 cmis placed 10 cmsolution of palladium mass concentration of 1.0 mg/cm, made up to the mark with hydrochloric acid, diluted 1:6, and stirred. The solution is stable for three months.

14.5.2 For the construction of calibration curve prepare solutions of platinum and palladium concentration.

In preparing the solution And the mass concentration of platinum and palladium 100 µg/cmin a volumetric flask with a capacity of 100 cmplaced at 10 cmof solutions of platinum and palladium with a mass fraction 1 mg/cm, made up to the mark with hydrochloric acid diluted 1:5, and stirred.

The solution is stable for three months.

In the preparation of a solution of mass concentration of platinum and palladium of 10 µg/cmin a volumetric flask with a capacity of 100 cmis placed 10 cmsolution A, made up to the mark with hydrochloric acid diluted 1:5, and stirred. The solution is stable for one month.

14.5.3 Preparation of the calibration solutions

In a series of volumetric flasks with a capacity of 100 cmeach placed successively an aliquot of solution B, solution A and solution ions of platinum and palladium mass concentration of 1 mg/cmin accordance with table 15. Topped up to the mark with hydrochloric acid diluted 1:5, and stirred. Solutions are stable for seven days.


Table 15

The index of the calibration solution	Mass concentration of the basic solution , mg/cm	The name of the basic solution	The volume of the aliquot of solution, cm	Mass concentration of platinum (palladium) in a solution of comparison , µg/cm
RM 17−0	0	-	0	0
RM 17−1	10	Solution B	1,5	0,15
RM 17−2	10	Solution B	3,0	0,30
RM 17−3	100	Solution A	1,0	1,0
RM 17−4	100	Solution A	5,0	5,0
RM 17−5	1000	Certified reference material of composition of the solution ions of platinum and palladium	1,0	10,0
RM 17−6	1000	Certified reference material of composition of the solution ions of platinum and palladium	2,5	25,0
Notes 1 as the calibration solution M17−0 using hydrochloric acid, diluted 1:5. 2 these Data are for guidance only and can be changed depending on the sensitivity of emission spectrometry with inductively coupled plasma, etc. 3 For the preparation of the calibration solutions can be used solutions prepared from pure metals.

14.5.4 preparation of the device

In accordance with the manual of the spectrometer launch a work program and perform at least two measurements of the analytical signal of the zero solution, then the corresponding calibration solution.

Expect calibration characteristics.

Note — the determination of the calibration parameters, processing and storage of the results of the calibration carried out using standard software supplied with the spectrometer.


Stability control calibration parameters is carried out with the use of calibration mixtures RM RM 17−3 or 17−4. The calibration characteristics are recognized as stable if the deviation of the result from the set value of the mass concentration of the component in the calibration solution does not exceed 10% Rel.

14.5.5 sample Preparation to measurement

14.5.5.1 Pre-concentrate of platinum and palladium in gold and silver Wren

The weight of blister copper mass of 25.00 to 50.00 g was placed in a conical flask with a capacity of 750 cm, flow from 30 to 35 cmof water, from 10 to 40 cmof solution of nitrate of mercury is added and stirred until complete amalgamation of the chip. Then go from 100 to 150 cmof sulphuric acid and place the flask on a hot stove. The dissolution is conducted at a heating and occasional stirring until complete dissolution of the sample of blister copper. A sign of dissolution is the change in the solution colour from dark green to light gray-blue. At the end of the process is introduced 4 g of sulfur and add 3 to 4 g of thiourea.

Note — the verification of quality control measurements by the method of additions is not allowed to add sulphur and thiourea in the presence of a low mass fraction of platinum group metals and the high mass fraction of silver in the composition of the sample.


After cooling, pour water to a volume of 500 cm, the solution is heated to boiling, poured 30 cmof sodium chloride solution and boiled to coagulate the precipitate, then the solution is cooled to a temperature of from 70 °C to 80 °C and filtered through a double filter of «white» or «blue ribbon» in the cone which is enclosed a little filtrowanie mass. Wash walls with water, remove the sediment remains damp piece of filter and attach this piece to the main precipitate on the filter. The filter is washed two or three times with hot water to remove copper sulphate from the filter.

The filter with the precipitate is transferred in server, placed in a muffle furnace, was dried and burned at a temperature of from 400 °C to 500 °C, for blister copper grades МЧ3-МЧ6 with a high content of impurities of the above-mentioned operation must be performed at a temperature of 600 °C. Then, server add 30 g of lead, the charge for Sherburne bottoms, placed in a muffle furnace, heated to a temperature of from 950 °C to 1000 °C. Melting the original lead with the door closed (the damper) muffle furnace until complete melting of the sample and the appearance of the «eye» of lead. Then the door (flap) muffle furnace if necessary, open and continue the process of oxidation and slagging at temperatures below 950 °C till the complete closing lead of a highlight (eyes) slag.

Server removed from the furnace, the contents poured into the mold, separate the alloy from the slag and alloy to give the shape of a cube. Then spend cupellation.

Cupellation of the lead alloy is carried out at a temperature from 950 °C to 980 °C for anything that is preheated to furnace temperature. After melting of the lead door (flap) muffle furnaces open and when the masses of lead will remain slightly, the door (flap) closed. At the end of cupellation is the flare, then darkening and hardening of gold-silver bead. Then drops removed from a muffle furnace, cooled, clean the bead from adhering particles of drops and weighed. If the mass is less than 200 mg, the silver is adjusted to the desired weight, wrapped in a lead foil and fuse into drops at a temperature of from 950 °C to 980 °C for 10−11 min. the Bead is cooled, cleaned, washed with water, dried at a temperature of from 400 °C to 500 °C.

14.5.5.2 Preparation of solution for measurement

The gold-silver bead is placed in a conical flask with a capacity of 100 cmand dissolved by heating in 20 cmof nitric acid, diluted 1:1, the insoluble precipitate is filtered through filter «blue ribbon». The filter cake is washed with nitric acid, diluted 1:4, then hot water. To give a solution B.

The filter with sediment was dried and incinerated in a porcelain crucible at a temperature from 600 °C to 900 °C for 30 min. To the residue after ashing poured 15 cmmixture of nitric and hydrochloric acids (1:3), washing the walls of the crucible, leave it for 20 (30) min on the stove at moderate heat. The contents of the crucible cooled and filtered through filter «blue ribbon». The filter cake was washed with hydrochloric acid solution, diluted 1:5. Get solution G.

To the solution In dropwise poured hydrochloric acid diluted 1:1, to complete the deposition of silver, avoiding excess of hydrochloric acid is kept on the stove at moderate heat (not allowing to boil) until coagulation of the precipitate to be filtered. The precipitate of silver chloride washed with hydrochloric acid, diluted 1:100. Get solution D.

The resulting solutions D and e are combined in a conical flask with a capacity of 100 cm, is evaporated to a volume 5 (10) cm, transferred into a volumetric flask with a capacity of 25 cm, adjusted to the mark with hydrochloric acid diluted 1:5, and stirred.

14.5.6 measurements

The setting of the spectrometer, the measurement parameters are set in accordance with the manual of the device. To achieve the optimal values for sensitivity and precision components, measuring the intensity of analytical spectral lines of defined components is carried out at wavelengths specified in table 16.


Table 16

The designated component	Wavelength, nm
Platinum	265,945
Palladium	340,458
Note — allowed the use of other wavelengths, provided that the required metrological characteristics.

The measurement should be started after 20 to 30 min after the ignition of plasma for stabilization of the measurements conditions.

When performing measurements sequentially injected into the plasma solutions in the reference experiment, the calibration solutions analyte from the sample solution. For each solution perform three measurements of the intensity of analytical lines of each component and calculate the average value.

Using the calibration dependences find the value of the mass concentration of a specific component in the solution.

The results of measurements of mass concentration of a specific component in the sample is automatically displayed on the monitor screen.

14.5.7 processing of the results

14.5.7.1 Mass fraction of the designated component , g/t, calculated by the formula

, (15)

where is the mass concentration of the determined component in a sample, µg/cm;

 — the volume of the sample solution, cm;

 — the weight of the portion of the sample,

14.5.7.2 For the measurement result taking the arithmetic mean of two parallel definitions, provided that the absolute difference between them in terms of repeatability does not exceed the values (with confidence probability of 0.95) limit of repeatability are given in table 14.

If the discrepancy between the results of parallel measurements exceeds the limit value of the frequency of occurrence, perform the procedure described in GOST R ISO 5725−6 (paragraph 5.2.2.1).

Discrepancies between measurements obtained in two laboratories, should not exceed the limit values for the reproducibility given in table 14. In this case, the final result may be decided to their arithmetic mean value. At default of this condition can be used the procedure described in GOST R ISO 5725−6.

15 Atomic absorption method of measuring the mass fraction of palladium

15.1 Scope

In this section, the set of atomic absortsionnym method of measuring the mass fraction of palladium in the range from 0.10 to 10.0 g/t.

15.2 Requirements of the measurement error

The measurement error of the mass fraction of palladium, the values for the limits of repeatability and reproducibility for a confidence probability of 0.95 should conform to the values given in table 17.


Table 17

In grams per ton

Measurement range of mass fraction of palladium	Characterization of the measurement error	Limit
		repeatability (2)	reproducibility
From 0.10 to 0.25 incl.	0,08	0,08	0,12
SV. 0,25 «0,50 «	0,11	0,11	0,18
«0,50» 1,00 «	0,22	0,22	0,36
«Of 1.0» to 2.5 «	0,4	0,4	0,6
«With 2.5» and 5.0 «	0,5	0,6	0,8
«5,0» 10,0 «	1,4	1,1	2,3

15.3 measurement Means, auxiliary devices, materials, solutions

When performing measurements using the following measuring instruments and auxiliary devices:

spectrometer of atomic absorption with flame atomizer and a radiation source for palladium;

— air compressor;

— the stove is electric with a closed heating element for temperature up to 350 °C;

— special laboratory scales of accuracy class according to GOST R 53228 with a readability of 0.0001 g;

— volumetric flasks 2−100−2 according GOST 1770;

— glasses-1−250 TCS according to GOST 25336;

— flasks KN-2−250−19/26 TCS GOST 25336;

pipettes not lower than 2nd accuracy class according to GOST and GOST 29169 29227;

tube P-2−20−13/23 according to GOST 1770;

— separating funnel VD-1−100 TC GOST 25336.

When taking measurements, use the following products and solutions:

— air compressed under a pressure of from 2·10to 6·10PA;

— acetylene according to GOST 5457;

— propane-butane according to GOST 20448;

— distilled water according to GOST 6709;

— hydrochloric acid according to GOST 3118, diluted 1:3 and 1:10, and the solution molar concentration of 2 mol/DM;

— nitric acid according to GOST 4461;

— palladium according to GOST 31291;

— the state standard samples (GSO) of the composition of the solution of palladium ions;

— alkilany (AA) for technical documentation;

— toluene according to GOST 5789;

filters obestochennye [2] or similar;

the filter paper according to GOST 12026, brands f, FS.

15.4 Method of measurement

The method is based on measuring absorption of atomic resonance lines of palladium after the introduction of the analyzed solution in the flame acetylene-air or propane-butane-air.

15.5 Preparation for measurements

15.5.1 Preparation of solutions

15.5.1.1 the Preparation of the solution alkylamine (AA) in toluene

One volume part of AA and two volume parts of toluene were mixed and placed in a separatory funnel, pour an equal volume of hydrochloric acid and shake for 5 min. the Bottom layer is separated, poured a fresh portion of hydrochloric acid. The operation is repeated four or five times to obtain a slightly colored bottom layer. The organic phase is washed with hydrochloric acid molar concentration of 2 mol/DMand allowed to stand for one day. The AA solution in toluene is separated, poured into a bottle made of dark glass and store in the fridge.

15.5.1.2 Preparation of solution for extraction

In a volumetric flask with a capacity of 100 cmis placed 40 cmof the AA solution, made up to the mark with toluene and mixed.

15.5.1.3 Preparation of solutions of known concentration

In preparing the solution And the mass concentration of palladium of 0.1 mg/cma sample of palladium weighing 0,1000 g dissolved in 10 cmof a mixture of hydrochloric and nitric acids (3:1) under heating. The resulting solution is evaporated to wet salts and transferred into a measuring flask with volume capacity of 1000 cm, made up to the mark with hydrochloric acid diluted 1:3 and stirred.

A solution of known concentration is allowed to use a certified reference material of composition of the solution of palladium ions with the mass concentration of palladium of 0.1 mg/cm.

Solution And stored for not more than six months.

15.5.1.4 the Preparation of the calibration solutions

In the preparation of a solution of palladium Pd is 20 mass concentration of 20 micrograms/cmin a volumetric flask with a capacity of 100 cmis placed 5 cmmortar And poured 20 cmof hydrochloric acid diluted 1:3, and 25 cmof a solution for extraction. Perform the extraction for 14−20 min. the Extract was separated with a separating funnel.

In the preparation of a solution of palladium Pd of 0.4 of the mass concentration of 0.4 ág/cmin the tube was placed 0.2 cmof a solution of Pd 20 and 9.8 cmof toluene and stirred.

In the preparation of a solution of palladium Pd 1 mass concentration of 1.0 g/cmin the tube was placed 0.5 cmof the solution Pd 20 and 9.5 cmof toluene and stirred.

In the preparation of a solution of palladium Pd 2 mass concentration of 2.0 ág/cmin a test-tube place 1 cmof a solution of Pd 20 and 9.0 cmof toluene and stirred.

In the preparation of a solution of palladium Pd 5 mass concentration of 5.0 ág/cmin the tube was placed 2.5 cmof a solution of Pd 20 and 7.5 cmof toluene and stirred.

In the preparation of a solution of palladium Pd 10 mass concentration of 10.0 µg/cmin the test tube is placed 5 cmsolution, 20 Pd and 5 cmof toluene and stirred.

Solutions to keep no more than three months.

15.5.1.5 Construction of calibration curve

For construction of calibration curve the prepared solutions were sprayed into the flame of acetylene-air or propane-butane-air.

The abscissa shows the delay of the mass concentration of determined component in solution in micrograms per cubic centimeter, and the y — axis the corresponding values of the analytical signals.

15.6 performance measurement

15.6.1 General requirements for methods of measurements and safety requirements when performing measurements in accordance with section 4.

15.6.2 Preparation of samples for measurement

The weight of blister copper in accordance with table 18 were placed in a glass (or conical flask) with a capacity of 250 cm, flow 25 to 30 cmof a mixture of hydrochloric and nitric acids (3:1) and evaporated with moderate heat to dryness without calcination. For a more complete removal of nitric acid to the dry residue poured 10 cmof hydrochloric acid and the evaporation repeated.


Table 18

Estimated mass fraction of palladium, g/t	The weight of the portion of blister copper, g
From 0.1 to 2.0 incl.	5
SV. 2.0−5.0 incl.	2
SV. 5.0 to 10.0 incl.	1

For a more complete removal of nitric acid to the dry residue poured 10 cmof hydrochloric acid and the evaporation repeated. To the dry residue poured 10 cmof hydrochloric acid diluted 1:3 and heated to dissolve the salts. The solution is filtered. The filtrate volume should not exceed 100−110 cmtogether with flushing solution hydrochloric acid, diluted 1:10. The filtrate is poured into 2cmof solution for extraction, extracted for 14−20 min. Extract after the full bundle is directed to the measurements.

15.6.3 measurements

Preparation for work and inclusion of atomic absorption spectrometer is performed in accordance with the operating instructions of the device.

The extract obtained in 15.6.2, injected into the flame of acetylene-air or propane-butane-air atomic absorption spectrometer, measure the absorbance of palladium. The absorbance of the extract measured at least twice and for calculating take arithmetic mean value. When changing solutions, the spray system was washed with water to obtain the zero readings.

The measurement is performed simultaneously with the control solutions and the solutions for constructing the calibration curve.

Measurement conditions selected in accordance with device used.

15.7 Processing of measurement results

15.7.1 bag dropping Mass fraction of palladium , g/t, calculated by the formula

, (16)

where is the mass concentration of palladium in the extract, was found in the calibration schedule, µg/cm;

the volume of the solution for extraction, cm;

 — the weight of the portion of blister copper,

15.7.2 For the measurement result taking the arithmetic mean of two parallel definitions, provided that the absolute difference between them in terms of repeatability does not exceed the values (with confidence probability of 0.95) limit of repeatabilityare given in table 17.

If the discrepancy between the results of parallel measurements exceeds the limit value of the frequency of occurrence, perform the procedure described in GOST R ISO 5725−6 (paragraph 5.2.2.1).

15.7.3 Differences between measurements obtained in two laboratories, should not exceed the limit values repeatability, are given in table 17. In this case, the final result may be decided to their arithmetic mean value. At default of this condition can be used the procedure described in GOST R ISO 5725−6.

16 Atomic emission spectral method with inductively coupled plasma measurements of the mass fraction of arsenic, bismuth, iron, Nickel, lead, antimony, tin and zinc

16.1 Scope

In this section, the set of atomic emission spectral method with inductively coupled plasma measurements of the mass fraction of arsenic, bismuth, iron, Nickel, lead, antimony, tin and zinc blister copper in the ranges given in table 19.


Таблица19

Percentage

The designated component	The range of mass fraction of component
Arsenic	From 0,0050 to 0.40 incl.
Bismuth	From 0.0020 to 0.050 incl.
Iron	From 0,0025 up to 0,080 incl.
Nickel	From 0.020 to 1.50 incl.
Lead	From 0.050 to 0.60 incl.
Antimony	From 0.010 to 0.40 incl.
Tin	From 0,080 to 0,0030 incl.
Zinc	From 0.0020 to 0,030 incl.

16.2 Requirements to measurement error

The error of measurement of mass fraction of arsenic, bismuth, iron, antimony, lead, Nickel, tin, zinc, values for the limits of repeatability and reproducibility for a confidence probability of 0.95 should conform to the values given in table 20.


Table 20

Percentage

The designated component	Measurement range of mass fraction of component	Characterization of the measurement error	Limit
			repeatability (2)	reproducibility
Arsenic	From 0,0050 0,0100 to incl.	0,0020	0,0020	0,0028
	SV. Of 0.010 «to 0.025 «	0,004	0,004	0,005
	«0,025» 0,050 «	0,009	0,009	0,012
	«0,050» 0,100 «	0,015	0,013	0,018
Arsenic	SV. 0.10 to 0.20 incl.	0,03	0,03	0,04
	«To 0.20» and 0.40 «	0,05	0,05	0,07
Bismuth	From 0,0020 0,0050 to incl.	0,0009	0,0008	0,001
	SV. 0,0050 «0,0100 «	0,0017	0.0016 inch	0,0022
	«Of 0.010» to 0.025 «	0,003	0,003	0,004
	«0,025» 0,050 «	0,006	0,006	0,008
Iron	From 0,0025 0,0050 to incl.	0,0010	0,0009	0,0013
	SV. 0,0050 «0,0100 «	0,0017	0,0013	0,0019
	«0,010» 0,030 «	0,003	0,003	0,004
	«0,030» 0,080 «	0,008	0,007	0,010
Nickel	From 0.020 to 0.050 incl.	0,008	0,008	0,011
	SV. 0,050 «0,100 «	0,017	0,014	0,019
	«To 0.10» to 0.25 «	0,03	0,03	0,04
	«Of 0.25» to 0.60 «	0,07	0,06	0,08
	«0,60» 1,50 «	0,1	0,09	0,13
Lead	From 0.050 to 0.100 incl.	0,019	0,018	0,025
	SV. Of 0.10 «to 0.30 «	0,03	0,03	0,04
	«Of 0.30» to 0.60 «	0,06	0,06	0,09
Antimony	From 0.010 to 0.025 incl.	0,005	0,005	0,007
	SV. 0,025 «0,050 «	0,010	0,010	0,014
	«0,050» 0,100 «	0,017	0,018	0,025
	«To 0.10» to 0.20 «	0,03	0,04	0,05
	«To 0.20» and 0.40 «	0,04	0,05	0,07
Tin	From to 0,0030 0,0050 incl.	0,0012	0,0012	0,0017
	SV. 0,0050 «0,0100 «	0,0014	0,0013	0,0018
	«0,010» 0,030 «	0,003	0,003	0,004
	«0,030» 0,080 «	0,006	0,005	0,007
Zinc	From 0,0020 0,0050 to incl.	0,0009	0,0008	0,0011
	SV. 0,0050 «0,0100 «	0,0015	0,0014	0,0020
	«0,010» 0,030 «	0,003	0,003	0,004

16.3 measurement Means, auxiliary devices, materials, solutions

When performing measurements using the following measuring instruments and auxiliary devices:

emission spectrometer with inductively coupled plasma as the excitation source with all accessories;

— special laboratory scales of accuracy class according to GOST R 53228 with a readability of 0.0001 g;

— volumetric flasks 2−100−2, according GOST 1770;

— flasks KN-2−100−13/23 TCS GOST 25336;

pipettes not lower than 2nd accuracy class according to GOST and GOST 29169 29227;

cylinders 3−25−2 according GOST 1770;

— beakers 50 according to GOST 1770;

cover of porcelain by GOST 9147.

When taking measurements, use the following products and solutions:

— distilled water according to GOST 6709;

— nitric acid according to GOST 4461 or diluted 1:1;

— hydrochloric acid according to GOST 3118 or diluted 1:1 and 1:5;

— argon gas according to GOST 10157;

— the state standard samples (GSO) of the composition of the solution arsenic ions with a mass concentration of 0.1 mg/cm;

— the state standard samples (GSO) of the composition of the solution of bismuth, iron, Nickel, lead, antimony, tin, zinc mass concentrations of 1.0 mg/cm;

filters obestochennye [2] or similar.

16.4 Method of measurement

The method is based on excitation of atoms of the sample solution in inductively coupled plasma and measuring the intensity of radiation emission detectable component, when spraying of the solution of the sample into the plasma. The relationship of radiation intensity and the mass concentration of a component in solution is established by means of calibration curve.

16.5 Preparation for measurements

16.5.1 Prepare instrument for measurement

Preparing the spectrometer to the measurements carried out in accordance with the manual.

16.5.2 For the construction of calibration curve prepare solutions of known concentration.

In preparing the solution And the mass concentration of bismuth, iron, Nickel, lead, antimony, tin, zinc 0,100 mg/cmin a volumetric flask with a capacity of 100 cmplaced at 10 cmof solutions of bismuth, iron, Nickel, lead, antimony, tin, zinc mass concentrations of 1.0 mg/cm. The solution was adjusted to the mark with hydrochloric acid diluted 1:5, and stirred. Solution And sustainable for three months.

In the preparation of a solution of mass concentration of arsenic, bismuth, iron, Nickel, lead, antimony, tin, zinc 0.01 mg/cmin a volumetric flask with a capacity of 100 cmis placed 10 cmsolution A and 10 cmof a solution of the ion of arsenic mass concentration of 0.1 mg/cm. The solution was adjusted to the mark with hydrochloric acid diluted 1:5, and stirred. Solution B is stable for seven days.

When cooking solution To the mass concentration of copper of 100 mg/cma sample of copper weighing 10,0000 g is placed in a conical flask with a capacity of 100 cm, is dissolved in 30 cmof nitric acid, diluted 1:1, kept under the porcelain lid until completely dissolved when heated, the lid and the wall of the flask is washed with water. The resulting solution was cooled, transferred to a volumetric flask with a capacity of 100 cm, the volume of the solution made up to mark with distilled water and mix. The solution is stable for one year.

Note — the use of other techniques for preparing solutions of known component concentrations, and the use of certified blends, subject to receipt of the accuracy rate that rivals those in table 22.

16.5.3 the Construction of calibration graphs

16.5.3.1 the Preparation of the calibration solutions

For the preparation of the calibration solutions, an aliquot of solutions of known concentration in accordance with table 21 is placed in a volumetric flask with a capacity of 100 cmeach, poured 10 cmof the solution, the solution volume adjusted to the mark with hydrochloric acid diluted 1:5, and stirred.


Table 21

The component name	Mass concentration of the calibration solutions mass concentration and volume of solutions of known concentration
	Solution 1			Solution 2			Solution 3			A solution of 4			A solution of 5
Arsenic	0,01	2,0	0,2	0,01	5,0	0,5	0,1	1,0	1,0	0,1	3,0	3,0	0,1	10,0	10,0
Bismuth	0,01	2,0	0,2	0,01	5,0	0,5	0,1	1,0	1,0	0,1	3,0	3,0	0,1	10,0	10,0
Iron	0,01	2,0	0,2	0,01	5,0	0,5	0,1	1,0	1,0	0,1	3,0	3,0	0,1	10,0	10,0
Nickel	0,01	2,0	0,2	0,01	5,0	0,5	0,1	1,0	1,0	0,1	3,0	3,0	0,1	10,0	10,0
Lead	0,01	2,0	0,2	0,01	5,0	0,5	0,1	1,0	1,0	0,1	3,0	3,0	0,1	10,0	10,0
Antimony	0,01	2,0	0,2	0,01	5,0	0,5	0,1	1,0	1,0	0,1	3,0	3,0	0,1	10,0	10,0
Tin	0,01	2,0	0,2	0,01	5,0	0,5	0,1	1,0	1,0	0,1	3,0	3,0	0,1	10,0	10,0
Zinc	0,01	2,0	0,2	0,01	5,0	0,5	0,1	1,0	1,0	0,1	3,0	3,0	0,1	10,0	10,0
Copper	10, 10, 10000
Notes 1  — mass concentration of a solution of known concentration, mg/cm,  — volume aliquots of a solution of known concentration, cm;  — mass concentration of the determined component, µg/cm. 2 these Data are for guidance only and can be changed depending on the sensitivity of emission spectrometry with inductively coupled plasma, uniformity of the analyte, etc.

16.5.3.2 In accordance with the manual of the spectrometer, launch a work program and perform at least two measurements of the analytical signal of the zero solution, then the corresponding calibration solution.

Expect calibration characteristics.

Note — the determination of the calibration parameters, processing and storage of the results of the calibration carried out using standard software supplied with the spectrometer.

16.6 measurements

16.6.1 General requirements for methods of measurements and safety requirements when performing measurements in accordance with section 4.

At the same time through all stages of sample preparation to the measurement carried out control and experience on the purity of the reagents.

16.6.2 the weight of blister copper of mass 1 g is placed in a conical flask with a capacity of 100 cm, flow 20 cmof a mixture of nitric and hydrochloric acids (3:1), dissolve under the porcelain lid for 30−40 min, the cover washed with distilled water over the flask, then the solution is evaporated to wet salts. Pour 5 cmof hydrochloric acid and evaporated to remove the nitrogen oxides. Salt is dissolved in 10 cmof hydrochloric acid diluted 1:1. The solution was cooled, transferred to a volumetric flask with a capacity of 100 cm, adjusted to the mark with hydrochloric acid diluted 1:5, and stirred.

If the mass fraction of the designated component in the sample solution exceeds the calibration range, the sample solution is diluted. Depending on the mass fraction of the designated component values of the dilutions analyzed solutions are given in table 22.


Table 22

Range of determined concentrations, %	The volume of the aliquot of solution, cm	The volume of the bulb, cm
From 0.10 to 0.50 incl.	10	50
SV. 0,50 «1,00 «	5	50
«1,00» 1,50 «	2	50

16.6.3 Setting of the spectrometer, generator power, argon flow, the height of the recorded zone of the plasma, the stabilizing time of plasma and other parameters set according to the operating instructions of the device. To achieve the optimal values for sensitivity and precision components, measuring the intensity of analytical spectral lines of defined components is carried out at wavelengths specified in table 23.


Table 23

The designated component	Wavelength, nm
Arsenic	193,759
Bismuth	190,24
Iron	259,94
Nickel	231,604; 341,476; 220,670
Lead	283,307; 405,783
Antimony	206,833
Tin	189,991
Zinc	334,502
Note — allowed the use of other wavelengths, provided that the required metrological characteristics.

16.6.4 Measurement should be started after 20 to 30 min after the ignition of plasma for stabilization of the measurements conditions.

16.6.5 When performing measurements sequentially injected into the plasma solutions in the reference experiment, the calibration solutions analyte from the sample solution. For each solution perform three measurements of the intensity of analytical lines of each component and calculate the average value.

Using the calibration dependences find the value of the mass concentration of a specific component in the solution.

The results of measurements of mass concentration of a specific component in the sample is automatically displayed on the monitor screen.

16.7 Processing of measurement results

16.7.1 Mass fraction of the designated component , %, is calculated by the formula

, (17)

where is the mass concentration of the component obtained according to the schedule in the sample, µg/cm;

 — volume of the volumetric flask, cm;

 — volume of the volumetric flask to an aliquot of solution, cm;

 — volume aliquot of the solution, cm;

 — weight of sample, g;

 — conversion factor from micrograms to grams.

16.7.2 For the measurement result taking the arithmetic mean of two parallel definitions, provided that the absolute difference between them in terms of repeatability does not exceed the values (with confidence probability of 0.95) limit of repeatability are given in table 20.

If the discrepancy between the results of parallel measurements exceeds the limit value of the frequency of occurrence, perform the procedure described in GOST R ISO 5725−6 (paragraph 5.2.2.1).

16.7.3 the Discrepancy between the results of measurements obtained in two laboratories, should not exceed the limit values repeatability, are given in table 20. In this case, the final result may be decided to their arithmetic mean value. At default of this condition can be used the procedure described in GOST R ISO 5725−6.

17 Atomic emission spectral method of measuring a mass fraction of arsenic, Nickel, antimony, bismuth, lead with an arc excitation source

17.1 Scope

In this section, the set method of measurements of mass fraction of arsenic, Nickel, antimony, bismuth, lead in the ranges shown in table 24, using atomic emission spectrometry with the arc excitation source.


Table 24

The designated component	The range of mass fraction of component %
Arsenic	From 0.010 to 0.10 incl.
Nickel	From 0.010 to 0.90 incl.
Antimony	From 0.010 to 0.30 incl.
Bismuth	From to 0,0002 0,0140 incl.
Lead	From 0.010 to 0.40 incl.

17.2 Requirements for measurement uncertainty

The error of measurement of mass fraction of arsenic, Nickel, antimony, bismuth, lead, limit values of repeatability and reproducibility for a confidence probability of 0.95 should conform to the values given in table 25.


Table 25

Percentage

The designated component	Measurement range of mass fraction of component	Characterization of the measurement error	Limit
			repeatability (2)	reproducibility
Arsenic	From 0,010 to 0,030 incl.	0,004	0,003	0,006
	SV. Of 0.03 «to 0.10 «	0,01	0,01	0,02
Nickel	From 0,010 to 0,030 incl.	0,005	0,006	0,008
	SV. Of 0.03 «to 0.10 «	0,01	0,01	0,02
	«To 0.10» to 0.30 «	0,04	0,03	0,06
	«0,30» 0,90 «	0,05	0,06	0,08
Antimony	From 0,010 to 0,030 incl.	0,005	0,006	0,007
	SV. Of 0.03 «to 0.10 «	0,01	0,01	0,02
	«To 0.10» to 0.30 «	0,04	0,03	0,06
Bismuth	From to from 0.0002 to 0.0005 incl.	0,0001	0,0001	0,0002
	SV. Of 0.0005 «0,0010 «	0,0003	0,0002	0,0005
	«0,0010» 0,0030 «	0,0004	0,0003	About 0.0006
	«0,0030» 0,0060 «	About 0.0006	About 0.0006	0,0008
	«0,0060» 0,0140 «	0.0016 inch	0,0012	0,0022
Lead	From 0,010 to 0,014 incl.	0,0017	0,0012	0,0027
	SV. 0,014 «0,030 «	0,004	0,003	0,006
	«To 0.03» to 0.10 «	0,01	0,01	0,02
	«To 0.10» to 0.40 «	0,03	0,04	0,05

17.3 measurement Means, auxiliary devices, materials, solutions

When performing measurements using the following measuring instruments and auxiliary devices:

optical emission spectrometry with arc excitation source spectrum;

— the stove is electric with a closed heating element for temperature up to 350 °C;

oven muffle with heating temperature up to 600 °C;

— laboratory scales with the greatest limit of weighing of 200 g of special accuracy class according to GOST R 53228 with a readability of 0.0001 g;

the graphite spectral electrodes;

the spectral graphite powder;

— cups varicellae;

— a mortar of agate or organic glass with pestle (use a porcelain mortar according to GOST 9147).

When taking measurements, use the following products and solutions:

— distilled water according to GOST 6709;

— nitric acid according to GOST 4461, diluted 1:1;

standard samples (CO) composition of blister copper.

17.4 Method of measurement

The method is based on measuring the intensity of spectral lines is determined by the components in the analyzed sample and comparison samples using atomic emission spectrometry with the arc excitation source and the photoelectric registration of spectrum.

17.5 Preparing for measurement

17.5.1 preparation of the device

The unit measurement is carried out in accordance with the requirements of the user’s manual.

The spectrometer will graduate when you create a method using the composition of the blister copper and build the dependence of the intensity of the analytical line from the mass fraction of the designated component. When further work is done by the adjustment of calibration parameters.

Graphite electrodes sharpen on the machine tool for sharpening of electrodes according to the instruction manual. The upper electrode with a truncated cone, the lower with a crater depth of 3.5 to 5.0 mm and a diameter of from 3.0 to 3.5 mm.

17.6 measurements

17.6.1 General requirements for methods of measurements and safety requirements when performing measurements in accordance with section 4.

17.6.2 Preparation of samples for measurement

The weight of blister copper of mass 1 g is placed in vipiteno Cup, poured from 5 to 10 cmof nitric acid, diluted 1:1, evaporated to dryness on a steam bath. A Cup of dry salt is placed in a muffle furnace and calcined at 550 °C for 30 min. After cooling, the resulting copper oxide is ground in a mortar and the resulting powder of the oxide of copper selected a sample mass of 0.50 g, stirred her with 0.50 g spectral (graphite) powder. The prepared sample was Packed in a graphite crater electrode.

17.6.3 measurements

The electrodes are set in a tripod spectrometer at a distance of 1 mm from each other.

The setting of the spectrograph, generator power and other parameters set according to the operating instructions of the devices.

Measurement conditions selected in accordance with device used.

17.7 Processing of measurement results

17.7.1 the Processing of the measurement results is carried out for a given program and present them in the form of a mass fraction of the designated component.

17.7.2 For the measurement result taking the arithmetic mean of two parallel definitions, provided that the absolute difference between them in terms of repeatability does not exceed the values (with confidence probability of 0.95) limit of repeatability are given in table 25.

If the discrepancy between the results of parallel measurements exceeds the limit value of the frequency of occurrence, perform the procedure described in GOST R ISO 5725−6 (paragraph 5.2.2.1).

17.7.3 Differences between measurements obtained in two laboratories, should not exceed the limit values repeatability, are given in table 25. In this case, the final result may be decided to their arithmetic mean value. At default of this condition can be used the procedure described in GOST R ISO 5725−6.

18 Atomic absorption method of measuring a mass fraction of Nickel, antimony, and lead

18.1 Scope

In this section, the set of atomic-absorption method of measuring the mass fraction of Nickel, antimony, and lead in ranges in accordance with table 26.


Table 26

The designated component	The range of mass fraction of component %
Nickel	From 0.01 to 1.0 incl.
Antimony	From 0.01 to 0.50 incl.
Lead	From 0.01 to 0.50 incl.

18.2 Requirements for measurement uncertainty

The error of measurement of mass fraction of Nickel, antimony, and lead, limit values of repeatability and reproducibility for a confidence probability of 0.95 should conform to the values given in table 27.


Table 27

Percentage

The designated component	Measurement range of mass fraction of component	Characterization of the measurement error	Limit
			repeatability (2)	reproducibility
Nickel	From 0.010 to 0.020 incl.	0,003	0,003	0,005
	SV. 0,02 «0,050 «	0,007	0,007	0,013
	«0,05» 0,10 «	0,016	0,015	0,027
	«To 0.10» to 0.20 «	0,03	0,03	0,05
	«To 0.20» to 0.50 «	0,07	0,07	0,13
	«0,50» 1,00 «	0,16	0,15	0,27
Antimony	From 0,010 to 0,030 incl.	0,004	0,004	0,007
	SV. 0,030 «0,050 «	0,008	0,008	0,014
	«0,050» 0,100 «	0,016	0,016	0,027
	«To 0.10» to 0.30 «	0,04	0,04	0,07
	«To 0.30» to 0.50 «	0,08	0,08	0,14
Lead	From 0,010 to 0,030 incl.	0,004	0,003	0,006
	SV. 0,030 «0,050 «	0,007	0,007	0,012
	«0,050» 0,100 «	0,014	0,013	0,023
	«To 0.10» to 0.30 «	0,04	0,03	0,06
	«To 0.30» to 0.50 «	0,07	0,07	0,12

18.3 measurement Means, auxiliary devices, materials, solutions

When performing measurements using the following measuring instruments and auxiliary devices:

spectrometer of atomic absorption with flame atomizer and a source of radiation on Nickel, antimony, lead;

— air compressor;

— the stove is electric with a closed heating element for temperature up to 350 °C;

— special laboratory scales of accuracy class according to GOST R 53228 with a readability of 0.0001 g;

— volumetric flasks 2−50−2, 2−100−2 according GOST 1770;

— glasses-1−100 TCS-1−250 TCS according to GOST 25336;

— flasks KN-2−100−19/26 TCS, KN-2−250−19/26 TCS GOST 25336;

pipettes not lower than 2nd accuracy class according to GOST and GOST 29169 29227.

When taking measurements, use the following products and solutions:

— air compressed under a pressure of from 2·10to 6·10PA;

— acetylene according to GOST 5457;

— propane-butane according to GOST 20448;

— distilled water according to GOST 6709;

— hydrochloric acid according to GOST 3118, diluted 1:1, 1:10;

— nitric acid according to GOST 4461, diluted 1:1, and the solution molar concentration of 1.0 mol/DM;

— the state standard samples (GSO) copper grade WSMO;

— the state standard samples (GSO) of the composition of the solution of Nickel ions;

— the state standard samples (GSO) of the composition of the solution of antimony ions;

— the state standard samples (GSO) of the composition of the solution of lead ions;

filters obestochennye [2] or similar.

18.4 Method of measuring

The method is based on measuring the atomic absorption of the resonance lines of Nickel at a wavelength of 232,0 nm, antimony at a wavelength of 217,9 nm, lead at the wavelength is 283.3 nm after the introduction of the analyzed solution in the flame acetylene-air or propane-butane-air. Placing the sample into solution is carried out acid treatment of the sample of blister copper.

18.5 Preparation for measurements

18.5.1 For the construction of calibration curve prepare solutions of Nickel, antimony, and lead, a known concentration.

In preparing the solution And the mass concentration of 0.1 mg/cmin a volumetric flask with a capacity of 50 cmis placed 5 cm insolutions of Nickel, antimony, and lead, with mass concentration of 1.0 mg/cm. The solution was topped to the mark with nitric acid molar concentration of 1.0 mol/land stirred.

In the preparation of a solution of mass concentration 0.01 mg/cm10.0 cmsolution And placed in a volumetric flask with a capacity of 100 cm, made up to the mark with distilled water and mix.

Solutions are stable for six months.

For the preparation of solutions with known concentrations of metals use metals and their compounds, containing at least 99.9% of the basic substance.

18.5.2 the Preparation of the solution of copper mass concentration of 100 g/DM

In preparing the solution of copper mass concentration of 100 g/DMa sample of copper with a mass of 10.0 g is dissolved in 70−80 cmof nitric acid, diluted 1:1, the resulting solution was placed in a volumetric flask with a capacity of 100 cm, made up to the mark with water and mix. The solution stability is not more than six months.

18.5.3 Construction of calibration curve

For construction of calibration curve prepare a series of calibration solutions. To do this in a volumetric flask with a capacity of 100 cmor 50 cmwas placed an aliquot of solutions of defined components of known concentration according to table 28. Into the flask pour 2 cmof a solution of copper mass concentration of 100 g/DM, made up to the mark with hydrochloric acid diluted 1:10, and stirred.


Table 28

Component	Room solution	The starting solution	An aliquot of the solution component, see	The volume of the bulb	Component mass concentration, µg/cm
Nickel	1	B	2	100	0,200
	2	And	1	100	1,000
	3	And	5	100	5,000
Nickel	4	And	10	100	10,000
	5	And	10	50	20,000
Antimony	1	B	2	100	0,21
	2	And	1	100	1,01
	3	And	2	100	2,01
	4	And	5	100	Of 5.01
	5	And	5	50	Of 10.01
Lead	1	B	2	100	0,21
	2	And	1	100	1,01
	3	And	2	100	2,01
	4	And	5	100	Of 5.01
	5	And	5	50	Of 10.01
Notes 1 Concentrations of the calibration solutions of Nickel, antimony, lead are Advisory in nature and depend on the characteristics of the used atomic absorption apparatus, the interval defined concentrations. For constructing a calibration curve allowed to use 3−7 calibration mixtures, but not less than 3. 2 Mass concentration of the calibration solutions are computed without accounting for impurities in the standard sample of copper.

For construction of calibration curve the calibration solutions injected into the flame of acetylene-air at 18.6.

The abscissa shows the delay of the mass concentration of the component determined in the calibration solutions, expressed in micrograms per cubic centimeter, and the y — axis the corresponding values of the analytical signals.

18.6 performance measurement

18.6.1 General requirements for methods of measurements and safety requirements when performing measurements in accordance with section 4.

18.6.2 the weight of blister copper with a mass of 0.5 g were placed in a glass or flask with a capacity of 250 cm, 20−25 cm pournitric acid, diluted 1:1, under low heat. If the dissolution in nitric acid does not occur, flow is from 2 to 5 cmof hydrochloric acid diluted 1:1, and heating was continued to dissolve the sample. Then transfer the solution into volumetric flask with a capacity of 100 cm, cooled, made up to the mark with hydrochloric acid diluted 1:1, and stirred.

For an amendment to the mass fraction of Nickel, antimony, and lead in the chemicals through all stages of the measurements carried out control experience.

18.6.3 the Analyzed solution is injected into the flame of acetylene-air or propane-butane-air atomic absorption spectrophotometer and measure the absorbance: Nickel — at a wavelength of 232,0 nm of antimony is at a wavelength of 217,6 nm; lead — when the wavelength is 283.3 nm. The absorbance of each solution is measured at least twice and for calculating take arithmetic mean value. When changing solutions, the spray system was washed with water to obtain the zero readings. The recommended maximum value of the measured absorbance of approximately 0.5 units. If necessary to reduce its value is allowed to carry out measurements at less sensitive wavelengths or deploy the burner.

The found value of the absorbance of the analyzed solution minus the absorbance of the solution in the reference experiment find a content-defined component for the calibration schedule.

18.7 Processing of measurement results

18.7.1 Mass fraction of Nickel, antimony or lead , %, is calculated by the formula

, (18)

where is the mass concentration of the component was found in the calibration schedule, taking into account the value of control experience, µg/cm;

 — the volume of the analyzed solution, cm;

 — weight of sample, g;

 — a conversion factor of milligrams to grams.

18.7.2 the measurement result taking the arithmetic mean of two parallel definitions, provided that the absolute difference between them in terms of repeatability does not exceed the values (with confidence probability of 0.95) limit of repeatability are given in table 27.

If the discrepancy between the results of parallel measurements exceeds the limit value of the frequency of occurrence, perform the procedure described in GOST R ISO 5725−6 (paragraph 5.2.2.1).

18.7.3 the Discrepancy between the results of measurements obtained in two laboratories, should not exceed the reproducibility limit given in table 27. In this case, the final result may be decided to their arithmetic mean value. At default of this condition can be used the procedure described in GOST R ISO 5725−6.

Bibliography

[1]	Specifications THAT 6−09−3901−75*	Diethyldithiocarbamate, lead (II)
________________ * The one referred to here and hereinafter, not shown. For additional information, please refer to the link. — Note the manufacturer’s database.
[2]	Specifications THAT 264221−001−05015242−07	Obestochennye filters (white, red, blue tape)
[3]	Specifications THAT 6−09−1181−89	Universal indicator paper to determine the pH and 1−10 7−13
[4]	Specifications THAT 6−09−4119−75	Crystal violet («N, N, N, N, N, N"-hexadecylpyridinium chloride), qualifications pure for analysis
[5]	Specifications THAT 6−09−5393−88	Tin (II) chloride 2-water (tin dichloride)
[6]	Pharmacopoeia article FS 42−2668−95*	Ascorbic acid USP
________________ * The document is not given. For additional information, please refer to the link. — Note the manufacturer’s database.
[7]	Specifications THAT 6−09−4711−81	Calcium chloride anhydrous (calcium chloride)
[8]	Specifications THAT 6−09−3880−75	Magnesium rate (anhydro)
[9]	Specifications THAT 48−19−30−91	Tungsten rods welded to the OS.h.
[10]	Specifications THAT 48−4-523−90	Oxides of rare earth metals: lanthanum, cerium, praseodymium, neodymium, samarium, europium
[11]	Specifications THAT 6−09−4773−84	The chlorides of yttrium and rare earth elements (lanthanum, praseodymium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, neodymium, samarium)
[12]	Specifications THAT 6−09−4770−79	Carbonates of yttrium and rare earth elements (salt carbonate of yttrium and rare earth elements), chemically pure, pure

__________________________________________________________________________
UDC 669.3:546.56.06:006.354 OKS 77.120.30

Keywords: blister copper, impurities, methods of analysis, method of measurement, General requirements, solution, standard sample, atomic absorption method, mass concentration, a solution of known concentration, a calibration chart