GOST 1652.11-77

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  ГОСТ 1652.11-77

GOST 1652.11−77 (ISO 4742−84) Alloys copper-zinc. Method for the determination of Nickel (with Amendments No. 1, 2, 3, 4)

GOST 1652.11−77
(ISO 4742−84)

Group B59

STATE STANDARD OF THE USSR

ALLOYS COPPER-ZINC

Methods for determination of Nickel

Copper-zinc alloys.
Methods for the determination of nickel

AXTU 1709

Date of introduction 1978−07−01

INFORMATION DATA

1. DEVELOPED AND INTRODUCED by the Ministry of non-ferrous industry of the USSR

DEVELOPERS

Y. F. Chuvakin, M. B. Taubkin, A. A. Nemodruk, N. V. Egiazarov (supervisor), I. A. Vorobyev

2. APPROVED AND promulgated by the Decree of the State Committee of standards of Ministerial Council of the USSR from 27.04.77 N 1062

3. INSTEAD, GOST 1652.11−71

4. The standard fully complies with ISO 4742−84*
________________
* Access to international and foreign documents referred to here and hereinafter, can be obtained by clicking on the link to the site shop.cntd.ru. — Note the manufacturer’s database.

5. REFERENCE NORMATIVE AND TECHNICAL DOCUMENTS

6. Resolution of the state standard from 28.12.92 N 1525 removed the limitation of the validity period

7. REPRINT (July 1997) with Amendments No. 1, 2, 3, 4, approved in October 1981 and November 1987, October 1989 (IUS 12−81, 2−88, 2−90, 3−93)


This standard specifies a gravimetric method for the determination of Nickel (at a mass fraction of Nickel from 0.5 to 7%) and extraction-photometric and atomic absorption methods for the determination of Nickel (at a mass fraction of Nickel from 0.01 to 7%) in copper-zinc alloys according to GOST 15527−70, GOST 17711−80* and GOST 1020−77.

________________
* Probably, the error of the original. Should read: GOST 17711−93. — Note the manufacturer’s database.


It is allowed to conduct determination of Nickel in copper-zinc alloys according to ISO 4742 (see Annex).

(Changed edition, Rev. N 2, 3, 4).

1. GENERAL REQUIREMENTS

1.1. General requirements for methods of analysis according to GOST 25086 with the addition in paragraph 1.1 of GOST 1652.1.

(Changed edition, Rev. N 2).

2. GRAVIMETRIC METHOD FOR THE DETERMINATION OF NICKEL

2.1. The essence of the method

The method is based on precipitation of Nickel in ammoniacal solution in the presence of tartaric or citric acid dimethylglyoxime in the form of insoluble chelation.

2.2. Reagents and solutions

Crucibles filter according to GOST 23932, type TF-3−20, TF-3−32.

Nitric acid according to GOST 4461 and diluted 1:1.

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

Hydrochloric acid according to GOST 3118, 9 mol/DMsolution.

Tartaric acid according to GOST 5817, a solution of 400 g/DM.

Ammonium nitrate solution 100 g/DM.

Citric acid according to GOST 3652, a solution of 400 g/DM.

Hydrofluoric acid according to GOST 10484.

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

The technical rectified ethyl alcohol according to GOST 18300.

Dimethylglyoxime according to GOST 5828, alcoholic solution of 10 g/DM.

(Changed edition, Rev. N 4).

2.3. Analysis

2.3.1. For alloys containing silicon

A sample of alloy weighing 1 g is placed in a platinum Cup, add 10 cmof nitric acid, diluted 1:1 and 1 cmhydrofluoric acid. The dissolution is carried out under heating. Then add 5 cmof sulphuric acid diluted 1:1, and the solution was evaporated prior to the allocation of white smoke of sulfuric acid. The residue is cooled, rinse the walls of the Cup with water and again evaporate until white smoke of sulfuric acid. Salt dissolved in water, the solution was transferred to a beaker with a capacity of 300 cm, dilute with water to 150 cm, 8 cm addboiled nitric acid, diluted 1:1, and produce copper by electrolysis according to GOST 1652.1.

The electrolyte was transferred to a beaker with a capacity of 600 cm, dilute with water to 200 cmand then carry out the analysis as described in section 2.3.2.

2.3.2. For copper zinc alloys other brands

A sample of alloy weighing 0.5 g were placed in a glass with a capacity of 300 cmand dissolved in 10 cmof nitric acid, diluted 1:1, when heated. After complete dissolution of the sample rinse the walls of the glass with water and remove the oxides of nitrogen by boiling. The solution was then diluted to a volume of 150 cmof water, add 7 cmof sulphuric acid, diluted 1:4, and produce copper by electrolysis according to GOST 1652.1. The electrolyte was transferred to a beaker with a capacity of 600 cmand dilute with water to 200 cm.

The solution is heated to 70 °C, add 20 cmof a solution of tartaric or citric acid, neutralized with ammonia to slightly acid reaction (pH 4−5) on universal indicator paper and with vigorous stirring, 20−25 cmalcohol solution dimethylglyoxime and 2−3 cmof ammonia to slightly alkaline environment. Solution and the precipitate is kept in a warm place for 40−60 minutes and then the precipitate was filtered off on a filter of medium density. The glass and the precipitate washed with hot water. The filter cake is dissolved in 30 cm9 mol/DMhydrochloric acid solution in a beaker which carried out the deposition. The filter is washed with hot water. The solution is diluted with hot water up to 200 cm. The Nickel deposition is repeated, adding 10 cmof a solution of tartaric or citric acid, neutralized with ammonia to a pH of 4−5, add a 10 cmalcohol solution dimethylglyoxime and 2−3 cmof ammonia. Solution and the precipitate is kept in a warm place for 40−60 minutes (can leave overnight).

The precipitate was filtered on a previously weighed filter crucible under suction. The precipitate is washed three times with aqueous ammonia, diluted 1:50, and then five times with hot water and finally twice with ethanol, diluted 1:3. The crucible with the precipitate is dried in a drying Cabinet at 105−110 °C to constant mass and weighed.

(Changed edition, Rev. N 4).

2.4. Processing of the results

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

,

where is the mass of dimethylglyoximato Nickel, g;

0,2032 — conversion factor dimethylglyoximate of Nickel to Nickel;

 — the weight of the portion,

2.4.2. The absolute discrepancies in the results of parallel measurements ( — convergence) must not exceed the permissible values given in table.1.

Table 1

2.4.3. The absolute discrepancies of the analysis results obtained in two different laboratories or two of the results of analysis obtained in the same laboratory but under different conditions (the reproducibility) shall not exceed the values specified in table.1.

2.4.2, 2.4.3. (Changed edition, Rev. N 2, 4).

2.4.4. The control accuracy of the analysis carried out according to State standard samples (GSO) or industry standard sample (CCA), or by standard samples of the enterprise (SOP) copper-zinc alloys, approved according to GOST 8 .315, or by additives or by comparing the results obtained by another method in accordance with GOST 25086.

(Changed edition, Rev. N 4).

2.4.4.1, 2.4.4.2. (Deleted, Rev. N 4).

3. EXTRACTION-PHOTOMETRIC METHOD FOR THE DETERMINATION OF NICKEL

3.1. The essence of the method

The method is based on extraction of Nickel in the form of dimethylglyoximate chloroform, re-extraction of Nickel in the aqueous phase, the formation in the aqueous phase of a complex of Nickel with dimethylglyoxime in the presence of an oxidant and measuring the optical density of colored solution.

3.2. Apparatus, reagents and solutions

Photoelectrocolorimeter or spectrophotometer.

Nitric acid according to GOST 4461, diluted 1:1.

Hydrochloric acid according to GOST 3118, diluted 1:1 and 5 mol/DMsolution.

Ammonia water according to GOST 3760 and diluted 1:100.

Sodium hydroxide according to GOST 4328, 1 mole/DMsolution.

Hydroxylamine hydrochloric acid according to GOST 5456, solution 100 g/DM.

Sodium Chernovetskiy.

Sodium acetate according to GOST 199, a solution of 400 g/DM.

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

Phenolphthalein according to GOST 5851, solution 100 g/lin ethanol.

Deacetyltaxol (dimethylglyoxime) according GOST 5828, a solution of 35 g/land 1 mol/DMsolution of sodium hydroxide.

Dimethylglyoxime, alcoholic solution of 10 g/DM.

Sodium vinocity.

The technical rectified ethyl alcohol according to GOST 18300.

Hydrogen peroxide according to GOST 10928.

Ammonium neccersarily according to GOST 20478, a solution of 100 g/DM.

Chloroform.

Nickel brand H0.

A standard solution of Nickel.

Solution a: prepared as follows: 0.1 g of Nickel were placed in a glass with a capacity of 250 cm, and dissolved in 20 cmof hydrochloric acid diluted 1:1, and 10 cmof hydrogen peroxide, which is added gradually. The dry residue is dissolved in 100 cmof hydrochloric acid diluted 1:1, and transferred to a volumetric flask with a capacity of 1 DM, then topped to the mark with water and mix.

1 cmof the solution contains 0.0001 g of Nickel.

(Changed edition, Rev. N 4).

3.3. Analysis

3.3.1. A sample weighing 1 g is placed in a beaker with a capacity of 250−300 cmand dissolved in 15 cm.of nitric acid diluted 1:1. To the solution was added 20 cmof sulphuric acid diluted 1:1, and evaporated almost to dryness. The residue is dissolved in hot water with the addition of 2−3 cmof hydrochloric acid diluted 1:1, transfer the solution into a volumetric flask with a capacity of 100 cm, made up to the mark with water and mix. Aliquot part of 10 cmwhen the mass fraction of Nickel up to 0.2% and 2 cmfor the mass concentration of Nickel of more than 0.2% was placed in a separating funnel with a capacity of 250 cm, dilute with water to 25 cmand basified with ammonia and then again acidified with hydrochloric acid diluted 1:1. Then add 0.5 g of sodium Vinokurova 10 cmof a solution of sodium acetate and 10 cmof a solution of sodium servational and set the pH of the solution is 6.5±0.3 mm, adding a solution of sodium acetate. Add 1 cmof a solution of hydroxylamine hydrochloric acid to pH 6.5 on the indicator paper. Then add 5 g chernovetskogo sodium, 0.5 g of sodium Vinokurova 10 cmof a solution of sodium acetate, 1 cmof a solution of hydroxylamine hydrochloric acid, shaking after each addition of the reagent. Then add 4 cmethanol solution and extracted dimethylglyoxime 20 cmof chloroform for 3 min. After phase separation, painted in yellow color chloroform extract is transferred to another separatory funnel, and the remaining aqueous solution repeat the extraction with 10 cmof chloroform.

The extracts are combined and extravert Nickel 30 cm5 mol/DMhydrochloric acid solution. The organic layer is discarded and the aqueous solution neutralized with ammonia to phenolphthalein and consistently add 2.5 g chernovetskogo sodium, 0.25 g of sodium Vinokurova 10 cmof a solution of sodium acetate, 1 cmof a solution of hydrochloric acid hydroxylamine, 2 cmof mortar dimethylglyoxime in ethanol and extracted for 3 min 20 cmof chloroform. The extract is drained into another separatory funnel, and the remaining aqueous solution repeat the extraction with 10 cmof chloroform. The combined extracts are washed with 15 cmof ammonia, diluted 1:100 for 2 min. Rinsing of the extract again. To the washed chloroform extract in a separating funnel add 5 cmof the alkaline solution dimethylglyoxime, 4 cmnaternicola solution of ammonia and stirred for 5 min. After separation of the layers the organic layer removed and the aqueous phase was transferred to volumetric flask with a capacity of 50 cm, made up to the mark with water and after 5 minutes measure the optical density in a cuvette with a layer thickness of 1 cm on the spectrophotometer at a wavelength of 445 nm or photoelectrocolorimeter with a blue filter. As a solution comparison solution is used in the reference experiment.

The Nickel content is calculated according to the calibration schedule.

(Changed edition, Rev. N 4).

3.3.2. Construction of calibration curve

In a separating funnel contribute 0; 0,5; 1; 2; 3; 4; 5 and 6 cmstandard Nickel solution, add ammonia to alkaline reaction, again acidified with hydrochloric acid diluted 1:1, to pH 6.5 and then transferred as described in section 3.3.1.

Solution comparison is the solution obtained in a similar manner without the addition of a standard solution of Nickel.

3.4. Processing of the results

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

,

where is the mass of Nickel was found in the calibration schedule g;

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

3.4.2. The absolute discrepancies in the results of parallel measurements ( — convergence) must not exceed the permissible values given in table.2.

Table 2

3.4.3. The absolute discrepancies of the analysis results obtained in two different laboratories or two of the results of analysis obtained in the same laboratory but under different conditions (the reproducibility) shall not exceed the values specified in table.2.

3.4.2, 3.4.3. (Changed edition, Rev. N 2, 4).

3.4.4. The control accuracy of the analysis carried out according to State standard samples (GSO) or industry standard sample (CCA), or by standard samples of the enterprise (SOP) copper-zinc alloys, approved according to GOST 8.315, or by additives or by comparing the results obtained by another method in accordance with GOST 25086.

3.4.4.1−3.4.4.3. (Deleted, Rev. N 4).

4. ATOMIC ABSORPTION METHOD

4.1. The essence of the method

The method is based on dissolving the sample in a mixture of hydrochloric and nitric acids and measuring the absorbance of Nickel in the flame acetylene-air, using radiation with a wavelength of 232 nm or 341,5.

4.2. Apparatus, reagents and solutions

The atomic absorption spectrometer.

Lamp with hollow cathode for Nickel.

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

Nitric acid according to GOST 4461, diluted 1:1.

A mixture of hydrochloric and nitric acids in the ratio 1:1.

Nickel brand H0 according to GOST 849.

Standard solutions of Nickel.

Solution a: 1 g of Nickel is dissolved in 20 cmof a mixture of acids. The solution was cooled and transferred into a measuring flask with volume capacity of 1000 cm, made up to the mark with water and mix.

1 cmof the solution contains 1 mg of Nickel.

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

1 cmof a solution contains 0.1 mg of Nickel.

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

Hydrofluoric acid according to GOST 10484.

4.3. Analysis

4.3.1. For alloys containing silicon up to 0.05%

A sample of alloy weighing 0.1 or 0.5 g, according to table.3, is placed in a beaker with a capacity of 250 cmand dissolved by heating at 10−20 cmof the mixture of acids. The solution was transferred to a volumetric flask with a capacity of 100 or 250 cm,and topped to the mark with water.

Table 3

4.3.2. For alloys containing silicon in excess of 0.05%

A sample of alloy weighing 0.1 or 0.5 g is placed in a platinum Cup and dissolve by heating in 10−20 cmof nitric acid (1:1) and 2 cmhydrofluoric acid. Then add 10 cmsulphuric acid (1:1) and the solution is evaporated prior to the allocation of thick white smoke of sulfuric acid. After cooling, add 30 cmof water, the residue is dissolved, the solution transferred to a volumetric flask with a capacity of 100 or 250 cm,and topped to the mark with water.

4.3.3. Construction of calibration graphs

When the mass fraction of Nickel from 0.01 to 0.5% in seven of the eight volumetric flasks with a capacity of 100 cmplaced 0,5; 1,0; 2,0; 4,0; 6,0; 8,0 and 10.0 cmstandard solution B of Nickel, which corresponds to 0,05; 0,1; 0,2; 0,4; 0,6; 0,8 and 1.0 mg of Nickel. All flasks is poured 10 cmof the mixture of acids and add water to the mark.

When the mass fraction of Nickel from 0.5 to 7% in eight volumetric flasks with a capacity of 100 cmplaced 0,5; 1,0; 2,0; 3,0; 4,0; 5,0; 6,0 and 7.0 cmstandard solution, And Nickel, which corresponds to 0,5; 1,0; 2,0; 3,0; 4,0; 5,0; 6,0 and 7.0 mg of Nickel. All flasks is poured 10 cmof the mixture of acids and add water to the mark.

4.2−4.3.3. (Changed edition, Rev. N 3).

4.3.4. Measure the atomic absorption of Nickel in solutions of the analyzed alloys and in the calibration solutions, recording the analytical signals. Using the flame of acetylene-air and analytical lines 232,0 nm (when the mass fraction of Nickel from 0.01 to 0.5% and the mass fraction of Nickel from 0.5 to 7.0% for solutions of alloys, diluted 10 times) and 341,5 nm (when the mass fraction of Nickel from 0.5 to 7.0%). According to the obtained values build the calibration graph.

(Added, Rev. N 3).

4.4. Processing of the results

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

,

where is the concentration of Nickel in the analyzed solution samples, was found in the calibration schedule, g/cm;

 — Nickel concentration in solution in the reference experiment, was found in the calibration schedule, g/cm;

 — volume of the volumetric flask for solution preparation of sample, cm;

 — weight of sample, g .

4.4.2. The absolute discrepancies in the results of parallel measurements ( — convergence) must not exceed the permissible values given in table.1 and 2.

(Changed edition, Rev. N 2, 3, 4).

4.4.3. The absolute discrepancies of the analysis results obtained in two different laboratories or two of the results of analysis obtained in the same laboratory but under different conditions (the reproducibility) shall not exceed the values specified in table.1 and 2.

(Changed edition, Rev. N 3, 4).

4.4.4. The control accuracy of the analysis carried out according to State standard samples (GSO) or industry standard sample (CCA), or by standard samples of the enterprise (SOP) copper-zinc alloys, approved according to GOST 8.315, or by additives or by comparing the results obtained by another method in accordance with GOST 25086.

(Changed edition, Rev. N 4).

4.4.4.1−4.4.4.3. (Deleted, Rev. N 4).

APPLICATION (recommended). ISO 4742−84 Copper alloys. The determination of Nickel. Gravimetric method

APP
Recommended

1. Scope

This international standard specifies a gravimetric method for the determination of the mass fraction of Nickel in all types of copper alloys are available in international standards.

The method is applicable when the mass fraction of Nickel from 2 to 50%.

2. Warning! Working under this standard, observe the normal precautions when working with perchloric acid.

3. The essence of the method

The method is based on dissolving the samples in nitric acid and the removal of tin and silicon, if present. The separation of copper by electrolysis and the deposition of Nickel from an electrolyte with dimethylglyoxime in the presence of citric acid.

4. Reagents

The analysis used reagents qualifications h. d. a. and distilled water or deionized water.

4.1. Nitric acid (g/cm).

4.2. Perchloric acid (g/cm).

4.3. Bromatologia acid (g/cm).

4.4. A solution of ammonia (g/cm).

4.5. A solution of nitric acid (1:1).

Mixed 100 cmof nitric acid (g/DM) and 100 cmof water.

4.6. Sulfamic acid, solution 100 g/DM.

4.7. Citric acid, a solution of 250 g/DM.

4.8. Dimethylglyoximate, sodium, solution of 25.9 g/DM.

5. Equipment

Ordinary laboratory apparatus, with the Supplement.

5.1. Glasses with a capacity from 300 to 400 cm.

5.2. Electrolysis installation with source current and platinum electrodes.

5.3. Filter crucible with a pore size of 16−40 mm.

6. Analysis

6.1. Linkage samples

6.1.1. When the mass fraction of Nickel from 2% to 4.25%

To weigh to the nearest 0.0001 g, about 2 g of the sample so that the mass fraction of Nickel in the sample was from 40 to 85 mg.

6.1.2. When the mass fraction of Nickel from 4 to 8.5%

To weigh to the nearest 0.0001 g to about 1 g of the sample so that the mass fraction of Nickel in the sample was from 40 to 85 mg.

6.1.3. When the mass fraction of Nickel from 8 to 50%

To weigh to the nearest 0.0001 g from 0.25 to 1 g of the sample so that the mass fraction of Nickel in the sample was from 80 to 125 mg.

6.2. Dissolution samples

6.2.1. For alloys not containing tin and silicon

Weighed samples were placed in a glass with a capacity of 300−400 cm, adding 25 cmof a solution of nitric acid and dissolved first in cold and then when heated.

After complete dissolution of the sample solution was boiled to remove oxides of nitrogen. Then add 50 cmof water, and further, if the solution is clear, continue with the analysis in section 6.3.

6.2.2. For alloys containing tin and silicon

After dissolution of sample of sample of alloy that contains tin, the solution will be turbid. In this case, you must allow the solution to stand for 1 h at 80 °C for the deposition of metalbands acid. The precipitate was filtered off on a tight filter with filtrowanie mass and several times washed the residue with warm nitric acid (1:99).

The filter with precipitate was placed in a beaker, which was performed dissolving the sample, add 15−20 cmof nitric acid and 10−15 cmof perchloric acid, covered with glass and heated until copious white fumes. Heating was continued until the destruction of all organic matter. The residue is cooled, rinsed the glass and walls of beaker with water, add 15 cmbromatological acid and heated to release abundant white vapour for the evaporation of tin. The operation is repeated by adding bromide-hydrogen acid to release vapors and clarification of the solution. The solution was then evaporated to dryness. The residue is cooled, dissolved in a small volume of water and add the solution to the filtrate.

6.3. Electrolysis

Add 5 cmof sulfamic acid to the solution and approximately 200 cmof water and carry out the electrolysis.

6.4. Deposition of Nickel

6.4.1. Added to the electrolyte 5 cmof nitric acid and 10 cmof perchloric acid and evaporate the solution until copious white fumes selection. Cool and add 100 cmof water. Transfer the solution into a glass with a capacity of 800 cm, if necessary, filtered. Add 10 cmof a solution of citric acid and ammonia solution until until the solution turns blue. Add an additional 1 cmand diluted with water to a volume of 400 cmand heated to 60−70 °C .

6.4.2. When the mass fraction of Nickel from 40 to 85 mg added 44 cmdimethylglyoximate solution of sodium to the solution with vigorous stirring. The solution was cooled to room temperature, stirring occasionally.

6.4.3. When the mass fraction of Nickel from 80 to 125 mg add 60 cmof a solution of sodium dimethylglyoximate to the solution with vigorous stirring. The solution was cooled to room temperature, stirring occasionally.

6.5. Filtering

Filter out the precipitate in the weighed filtering crucible, previously dried for 1 h at a temperature of 150 °C. the precipitate was Washed 10−12 times with a little water, allowing the filter to drain completely between washes. Then dry the precipitate for 1 h at a temperature of 150 °C, cooled and weighed.

7. Processing of the results

Mass fraction of Nickel in percent is calculated by the formula

,

where is the mass of sediment dimethylglyoximate Nickel, g;

0,2032 — conversion factor dimethylglyoximate of Nickel to Nickel;

 — the weight of the portion of the sample,

8. Analysis report

Report on the analysis shall contain:

a) the method of sampling;

b) apply analysis method;

C) the results obtained and the method of their calculation;

d) all of the characteristic features observed in the analysis;

d) all of the done operations not covered by this standard, or considered adverse.

APP. (Added, Rev. N 4).