GOST 6689.17-92

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  ГОСТ 6689.17-92

GOST 6689.17−92 Nickel, alloys Nickel and copper-Nickel. Methods for determination of bismuth

GOST 6689.17−92

Group B59

STATE STANDARD OF THE USSR

NICKEL, ALLOYS NICKEL AND COPPER-NICKEL

Methods for determination of bismuth

Nickel, nickel and copper-nickel alloys. Methods for the determination of bismuth

AXTU 1709

Date of introduction 1993−01−01

INFORMATION DATA

1. DEVELOPED AND INTRODUCED by the Ministry of metallurgy of the USSR

DEVELOPERS

V. N. Fedorov, Y. M. Leybov, Boris Krasnov, A. N. Bulanova, L. V. Morea, A. I. Vorobyov

2. APPROVED AND ENTERED INTO force by the Decision of the Committee of standardization and Metrology of the USSR from 18.02.92 N 167

3. REPLACE GOST 6689.17−80

4. REFERENCE NORMATIVE AND TECHNICAL DOCUMENTS

This standard specifies the photometric (with a mass fraction of bismuth from 0.0005 to 0.003% and 0.001 to 0.02%) and atomic absorption (at a mass fraction of from 0.001 to 0.02%) methods for determination of bismuth in Nickel, Nickel and copper-Nickel alloys according to GOST 492* and GOST 19241.
________________
* On the territory of the Russian Federation GOST 492−2006. — Note the manufacturer’s database.

1. GENERAL REQUIREMENTS

General requirements for methods of analysis GOST 25086 with the addition of sec. 1 GOST 6689.1.

2. The PHOTOMETRIC METHOD for the DETERMINATION of BISMUTH (with bismuth mass fraction of from 0.0005 to 0.003%)

(when the mass fraction of bismuth from 0.0005 to 0.003%)

2.1. The essence of the method

The method is based on the isolation of bismuth by its coprecipitation with ferric hydroxide, the formation of a bismuth colored complex with selenology orange and measuring its optical density.

2.2. Apparatus, reagents and solutions

Photoelectrocolorimeter or spectrophotometer.

Nitric acid according to GOST 4461, diluted 1:1, solutions of 0.1 and 1 mol/DM.

Sulfuric acid according to GOST 4204, diluted 1:4.

Hydrochloric acid according to GOST 3118, diluted 1:1 and 1:2.

Hydrofluoric acid according to GOST 10484.

Ascorbic acid according to normative-technical documentation, solution 100 g/l, freshly prepared.

Ammonia water according to GOST 3760 and diluted 1:50.

Ammonium neccersarily according to GOST 20478, a solution of 250 g/DM.

Sodium fluoride according to GOST 4463, a solution of 5 g/DM.

Silver nitrate according to GOST 1277, a solution of 10 g/cm.

Iron chloride according to GOST 4147, a solution of 1 g/DM: 1 g of ferric chloride dissolved in 250 cmof hydrochloric acid (1:1) and top up with water to 1 DM.

Selenology orange, solution 1 g/lin 0.1 mol/DMnitric acid.

Hydrogen peroxide according to GOST 10929.

Bismuth GOST 10928, mark Vi00.

Standard solutions of bismuth

Solution a: 0.1 g of bismuth dissolved in 10 cmof nitric acid (1:1), the nitrogen oxides are removed by boiling and the solution is transferred into a measuring flask with volume capacity of 1000 cm, add 100 cmof nitric acid (1:1) and topped to the mark with water.

1 cmof the solution contains 0.0001 g of bismuth.

Solution B: 10 cmsolution And placed in a volumetric flask with a capacity of 100 cmand top up with water to the mark.

1 cmof solution B contains 0,00001

g of bismuth.

2.3. Analysis

2.3.1. For alloys with a mass fraction of silicon not more than 0.1%, not containing chromium and tungsten

A sample of alloy weighing 3 g when the mass fraction of bismuth from 0.0005 to 0.001% or 2 g when the mass fraction of bismuth from 0.001 to 0.003% is placed in a beaker with a capacity of 300 cm, add 30−40 cmof nitric acid (1:1), cover with watch glass, glass or plastic plate and dissolved by heating. Glass or plate and the side of the Cup then rinsed with water and the solution was boiled to remove oxides of nitrogen. The solution is diluted with water to a volume of 150 cm, add 10 cmof a solution of ferric chloride, heated to 50−60 °C, ammonia is added to complete transfer of Nickel and copper into soluble ammonia complexes and beyond that another 5 cmof ammonia. Solution and the precipitate was aged 45−50 min at 60 °C for coagulation of the precipitate of iron hydroxide. The precipitate was filtered off on a filter of medium density. The precipitate on the filter and the glass is washed 6−8 times with a hot solution of ammonia (1:50).

The precipitate is washed with hot water, filter and dissolve in 20 cmhot sulphuric acid (1:4) (if present in the alloy of manganese, by dissolving the precipitate add a few drops of hydrogen peroxide) in a beaker, which was carried out the precipitation of the hydroxide, the filter was washed 5−7 times in hot water. Deposition, filtering, washing the precipitate hydroxides and dissolution repeat. The solution after re-dissolution was evaporated to dryness. To the dry residue add 5 cm1 mol/DMnitric acid, the side of the Cup and rinse 3−5 cmof water and the solution was heated to dissolve the residue. Add 4 cmof ascorbic acid solution, cooled, added with 1 cmof a solution of sodium fluoride, 1 cmkylinalove orange solution, the mixture is transferred into a measuring flask with a capacity of 50 cmand then filled to the mark with water. After 15 min measure the optical density of the solution on a photoelectrocolorimeter with a green optical filter in a cuvette with a thickness of the light absorbing layer 5 cm or spectrophotometer at 540 nm in a cuvette with the thickness of the light absorbing layer 1 cm relative to the solution in the reference experiment, carried through all the stages and

analysis.

2.3.2. For alloys containing chromium and more than 0.1% silicon

A portion of the alloy specified in paragraph 2.3.1, is placed in a platinum Cup, add 30 cmof nitric acid (1:1), 2−3 cmhydrofluoric acid and dissolved by heating. To the cooled solution add 10 cmsulphuric acid and is evaporated prior to the allocation of white smoke of sulfuric acid. The residue is cooled, rinse the walls of the Cup with water and re-evaporated prior to the allocation of white smoke of sulfuric acid. After cooling, to the residue add 30−40 cmof water and dissolved by heating. The solution was transferred to a beaker with a capacity of 300 cm, add water up to 100 cm, 5 cmsolution of silver nitrate, 40 cmof a solution naternicola ammonium, the mixture was heated and boiled to complete dissolution naternicola ammonium (until the complete cessation of release of air bubbles).

The solution was cooled to 60−70 °C, add 10 cmof a solution of ferric chloride and then analysis is carried out as specified in clause 2.3

.1.

2.3.3. For alloys containing tungsten

A portion of the alloy specified in paragraph 2.3.1, is placed in a platinum Cup, add 30 cmof nitric acid (1:1), 2−3 cmhydrofluoric acid and dissolved by heating. To the cooled solution add 10 cmsulphuric acid and is evaporated prior to the allocation of white smoke of sulfuric acid. The residue is cooled, rinse the walls of the Cup with water and re-evaporated prior to the allocation of white smoke of sulfuric acid. After cooling, to the residue add 30−40 cmof water and dissolved by heating. The solution was transferred to a beaker with a capacity of 300 cm. The platinum Cup add 3−4 cmof concentrated ammonia solution for dissolving tungsten acid, adhering to the Petri dish, and the resulting solution was attached to the main solution in the beaker. To the solution was added 10 cmof a solution of ferric chloride and then analysis of the result as specified in item 2.3.1

.

2.3.4. Construction of calibration curve

In glasses with a capacity of 250 cmis placed 1,0; 2,0; 4,0; 6,0 and 8,0 cmstandard solution B of bismuth, add 30 cmof nitric acid (1:1), 10 cmof a solution of ferric chloride, diluted with water to a volume of 150 cm, is heated to 50−60 °C and then act as described in section 2.3.1.

2.4. Processing of the results

2.4.1. Mass fraction of bismuth in percent is calculated by the formula

,

where  — weight of bismuth, was found in the calibration schedule g;

 — the weight of the portion,

2.4.2. Discrepancies in the results of three parallel measurements (rate of convergence) and the results of the two tests (index of reproducibility) shall not exceed the values of permissible differences given in table.1.

Table 1

2.4.3. Control of accuracy of analysis results is carried out according to State standard samples (GSO) or industry standard sample (CCA) or by standard samples of the enterprise (SOP) of Nickel, Nickel and copper-Nickel alloys, approved under GOST 8.315*, or method of additions or by comparison of the results obtained by atomic absorption method, in accordance with GOST 25086.
________________
* On the territory of the Russian Federation GOST 8.315−97, here and hereafter. — Note the manufacturer’s database.

2.4.4. The photometric method is used in case of disagreement in assessing the quality of Nickel, Nickel and copper-Nickel alloys.

3. The PHOTOMETRIC METHOD for the DETERMINATION of BISMUTH (in mass fraction of bismuth from 0.001 to 0.02%)

(when the mass fraction of bismuth from 0.001 to 0.02%)

3.1.The essence of the method.

The method is based on the formation of bismuth with selenology orange coloured complex and the measurement of its optical density after preliminary isolation of bismuth by coprecipitation with manganese dioxide 1.5 mol/DMnitric acid. The interfering influence of iron is removed with ascorbic acid, and traces of tin — sodium fluoride.

3.2. Apparatus, reagents and solutions

Photoelectrocolorimeter or spectrophotometer.

Nitric acid according to GOST 4461 and diluted 1:1, 1:8, and the solutions of 1.5, 1 and 0.1 mol/DM.

The acid chloride.

Bromatologia acid according to GOST 2062.

Ascorbic acid according to normative-technical documentation, solution 100 g/DM.

Ammonia water according to GOST 3760.

Manganese nitrate according to GOST 6203, a solution of 50 g/DM.

Bromine according to GOST 4109.

The mixture for dissolution, fresh: 9 parts bromatological acid is mixed with 1 part of bromine.

Hydrochloric acid according to GOST 3118, diluted 1:1 and 1:8.

Sodium fluoride according to GOST 4463, a solution of 5 g/DM.

Potassium permanganate according to GOST 20490, a solution of 6 g/DM.

Hydrogen peroxide according to GOST 10929.

Selenology orange, solution 1 g/lin 0.1 mol/DMsolution of nitric acid.

Copper with a mass fraction of bismuth less than 0.0005%.

Copper nitrate, a solution of 20 g/DM: 2 g of copper is dissolved in 20 cmof nitric acid (1:1), and remove the oxides of nitrogen by boiling, the solution cooled and top up with water to 100 cm.

Bismuth GOST 10928 with a mass fraction of bismuth is not less than 99.9%.

Standard solutions of bismuth

Solution a: 0.1 g of bismuth dissolved in 20 cmof concentrated nitric acid removed the oxides of nitrogen by boiling, the solution was cooled, transferred to a measuring flask with volume capacity of 1000 cm, made up to the mark with water and mix.

1 cmof the solution contains 0.0001 g of bismuth.

Solution B: 25 cmsolution And placed in a volumetric flask with a capacity of 250 cm, add 20 cmof concentrated nitric acid, made up to the mark with water and mix.

1 cmof solution B contains 0,00001

g of bismuth.

3.3. Analysis

3.3.1. For alloys with a mass fraction of tin up to 0.05%

A sample weighing 1 g is placed in a beaker with a capacity of 250 cm, and dissolved in 10 cmof nitric acid (1:1) under heating. Nitrogen oxides are removed by boiling and the solution diluted with water to 50 cm. Add 5 cmof a solution of nitrate of manganese, the solution is neutralized with ammonia until the appearance of the precipitate copper hydroxide, add 18 cmof nitric acid (1:1) and water to a volume of 90 cm. The solution is heated nearly to boiling, add 10 cmof a solution of potassium permanganate, and boil for 2 min. After 30 min the precipitate was filtered on a tight filter and washed the beaker and the precipitate 8−10 times hot of 1.5 mol/DMnitric acid until the disappearance of the blue color formed of copper nitrate. The deployed filter is washed with water in a glass, which conducted the selection, the filter is washed with 10 cmof hot nitric acid (1:1) containing a few drops of hydrogen peroxide solution and then with water. The washed filter is discarded, the solution was evaporated to a volume of about 5 cm, and then to dryness in a water bath.

To the cooled residue was added 1 mol/DMnitric acid (see table.2) rinse the walls of the Cup 2−3 cmof water and gently boil. Add ascorbic acid solution (see table.2), is heated and after dissolution of the precipitate is cooled. Then, when the mass fraction of bismuth in the alloy to 0.008% solution transferred to a volumetric flask with a capacity of 25 cm, while the mass fraction of bismuth in the alloy more than 0,008% solution transferred to a volumetric flask with a capacity of 25 cm, top up to the mark with water, mix and take aliquot part of the solution (see table.2) in a volumetric flask with a capacity of 25 cm.

Table 2

Add 1 cmof a solution of sodium fluoride, 1 cmof solution kylinalove orange, made up to the mark with water and mix. After 10 minutes measure the optical density of the solution on the spectrophotometer at a wavelength of 540 nm in a cuvette with the thickness of the light absorbing layer 1 cm or photoelectrocolorimeter with a green optical filter in a cuvette with a thickness of the light absorbing layer 5, see Solution comparison is the solution of the reference experiment. Mass fraction of bismuth is calculated according to the calibration schedule.

3.3.2. For alloys with a mass fraction of tin in excess of 0.05%

A sample weighing 1 g is placed in a wide glass with a capacity of 250 cmand dissolved in 15 cmof the mixture to dissolve first in cold and then when heated. In case of incomplete dissolution of the sample add a few drops of bromine.

Then add 10 cmof perchloric acid and evaporated to moist residue. The residue is cooled, the side of the Cup then rinsed with water and topped up to a volume of 50 cm, add 5 cmof a solution of manganese nitrate and further analysis is carried out as specified in clause 3.3.1.

3.3.3. Construction of calibration curve

In five of the six flasks with a capacity of 250 cm, containing 10 cmof copper solution, introduce 1,0; 2,0; 4,0; 6,0 and 8,0 cmstandard solution B of bismuth. The solutions were diluted with water to 50 cm, add 5 cmof a solution of manganese nitrate and further analysis is carried out as specified in clause 3.3.1. To the cooled residue add 3 cm1 mol/DMnitric acid solution, rinse the walls of the Cup 2−3 cmof water and gently boil. Then add 4 cmof ascorbic acid solution, heated and after dissolution of the precipitate is cooled, the solution was transferred to a volumetric flask with a capacity of 25 cmand then do as described in claim 3.3.1. Solution comparison is the solution not containing bismuth. According to the obtained results build a calibration gra

FIC.

3.4. Processing of the results

3.4.1. Mass fraction of bismuth in percent is calculated by the formula

,

where  — weight of bismuth, was found in the calibration schedule g;

 — the weight of the portion corresponding to aliquote part of the solution,

3.4.2. Discrepancies in the results of three parallel measurements (rate of convergence) and the results of the two tests (index of reproducibility) shall not exceed the values of permissible differences given in table.1.

3.4.3. Control of accuracy of analysis results is carried out as specified in clause 2.4.3

4. ATOMIC ABSORPTION METHOD FOR THE DETERMINATION OF BISMUTH

4.1. The essence of the method

The method is based on measuring the absorption of light by atoms of bismuth, formed by the introduction of the analyzed solution in the flame acetylene-air, after pre-allocation of bismuth to manganese dioxide.

4.2. Apparatus, reagents and solutions

Atomic absorption spectrometer with a radiation source for bismuth.

Nitric acid according to GOST 4461 diluted 1:1, solution 2 and 1.5 mol/DM.

Sulfuric acid according to GOST 4204, diluted 1:4.

Hydrochloric acid by the GOST 3118−77, solution 1 mol/DM.

Ammonia water according to GOST 3760.

Manganese nitrate according to GOST 6203, a solution of 20 g/DM.

Potassium permanganate according to GOST 20490, a solution of 6 g/DM.

Hydrogen peroxide according to GOST 10929.

Bismuth GOST 10928 with a mass fraction of bismuth is not less than 99.9%.

Standard solutions of bismuth

Solution a: 0.25 g of bismuth was dissolved with heating in 20 cmof nitric acid (1:1), the solution was cooled, transferred to a volumetric flask with a capacity of 500 cmand top up with water to the mark.

1 cmof the solution contains 0.0005 g of bismuth.

Solution B: 10 cmsolution And placed in a volumetric flask with a capacity of 100 cm, add 10 cmof 2 mol/DMnitric acid and add water to the mark.

1 cmof a solution of 0.00005 g contains bismuth.

Solution In 20 cmof solution B is placed in a volumetric flask with a capacity of 100 cm, add 10 cmof 2 mol/DMnitric acid and add water to the mark.

1 cmof the solution contains 0,00001

g of bismuth.

4.3. Analysis

4.3.1. A sample of alloy weighing 2 g were placed in a glass with a capacity of 250 cmand dissolved by heating in 20 cmof nitric acid (1:1). Nitrogen oxides are removed by boiling and the solution diluted with water to a volume of 50 cm. Add 5 cmof a solution of nitrate of manganese, the solution is neutralized with ammonia until the appearance of the precipitate copper hydroxide, add 18 cmof nitric acid (1:1) and water to a volume of 90 cm. The solution is heated to boiling, add 10 cmof a solution of potassium permanganate, and boil for 2 min. after 30 min the precipitate was filtered off on a tight filter and washed the beaker and the precipitate 4−5 times a hot 1.5 mol/DMsolution of nitric acid. The deployed filter is washed with water in a glass, which conducted the deposition. The filter is washed with 10 cmof hot sulfuric acid solution (1:4) containing few drops of hydrogen peroxide solution and then with water. The washed filter is discarded and the solution was evaporated to wet salts. After cooling, add 8 cm1 mol/DMhydrochloric acid solution, transferred to a volumetric flask with a capacity of 100 cmand topped to the mark of 1 mol/DMhydrochloric acid solution.

Measure the atomic absorption of bismuth in the flame acetylene-air at a wavelength of 223,1 nm parallel calibration Rast

thieves.

4.3.2. Construction of calibration curve

In eight of the nine cups with a capacity of 250 cmis placed 1,0; 2,5; 5,0; 10,0 cmstandard solution Into and 4,0; 6,0; 8,0 and 10,0 cmstandard solution B. In all the cups add water to a volume of 50 cm, 5 cmsolution of manganese nitrate and further analysis is carried out as specified in clause 4.3.1. According to the obtained results build a calibration curve.

4.4. Processing of the results

4.4.1. Mass fraction of bismuth in percent is calculated by the formula

,

where is the concentration of bismuth was found in the calibration schedule, g/cm;

 — the volume of the final solution, cm;

 — the weight of the portion of alloy,

4.4.2. Discrepancies in the results of three parallel measurements (rate of convergence) and the results of the two tests (index of reproducibility) shall not exceed the values of permissible differences given in table.1.

4.4.3. Control of accuracy of analysis results is carried out according to State standard samples (GSO) or industry standard sample (CCA), or by standard samples of the enterprise (SOP) of Nickel, Nickel and copper-Nickel alloys, approved under GOST 8.315, or by additives or by comparison of the results obtained photometric methods in accordance with GOST 25086.