GOST 23859.8-79

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  ГОСТ 23859.8-79

GOST 23859.8−79 heat-resistant Bronze. Methods for determination of zirconium (with Amendments No. 1, 2)

GOST 23859.8−79

Group B59

INTERSTATE STANDARD

BRONZE HIGH-TEMPERATURE

Method for the determination of zirconium

Bronze fire-resistance. Methods for the determination of zirconium

AXTU 1709

Date of introduction 1981−01−01

Resolution of the USSR State Committee for standards, dated 16 October 1979, N 3937 time of the introduction set with 01.01.81

Limitation of actions taken by Protocol No. 5−94 of the Interstate Council for standardization, Metrology and certification (ICS 11−12−94)

EDITION with Amendments No. 1, 2 approved in June 1985, March 1990 (IUS 9−85, 7−90).


This standard establishes photometric methods for determination of zirconium (at a mass fraction of zirconium from 0.005 to 0.3%) in high-temperature copper alloys.

(Changed edition, Rev. N 1, 2).

1. GENERAL REQUIREMENTS

1.1. General requirements for method of analysis according to GOST 25086−87 with the addition of a GOST 23859.1−79, sec. 1.

(Changed edition, Rev. N 2).

2. The PHOTOMETRIC METHOD for the DETERMINATION of ZIRCONIUM using ARSENAZO III IN 8 M HYDROCHLORIC ACID CONTAINING 20% of ACETONE (at a mass fraction of zirconium from 0.005 to 0.3%)

2.1. The essence of the method

The method is based on the formation of Zirconia colored complex with arsenazo III in 8 M hydrochloric acid containing 25% of acetone and measuring the optical density of the solution.

2.2. Apparatus, reagents and solutions

Photoelectrocolorimeter or spectrophotometer.

Nitric acid GOST 4461−77.

Hydrochloric acid by the GOST 3118−77 and 2 and 8 M solutions.

Sulfuric acid GOST 4204−77 and diluted 1:1.

Hydrofluoric acid (hydrofluoric acid) according to GOST 10484−78.

Arsenazo, III, an aqueous solution of 4 g/DM.

Acetone according to GOST 2603−79.

Zirconium metal (ideny).

Zirconium oxychloride.

Standard solutions of zirconium.

A. solution of 0.1 g of metallic zirconium is placed in a platinum Cup, pour 10 cmof concentrated sulfuric acid, 1 cmhydrofluoric acid and heated until dissolved. The solution is evaporated prior to the appearance of a white smoke of sulfuric acid. After cooling, the walls of the Cup then rinsed with water, the solution was stirred and evaporated again prior to the allocation of white smoke of sulfuric acid. After cooling, to the residue add 25 cmof water, heated to obtain clear solution, the solution transferred to a volumetric flask with a capacity of 100 cm, made up to the mark with water and mix.

1 cmof the solution contains 0.001 g of zirconium.

Solution B. 5 cmof the solution And placed in a volumetric flask with a capacity of 100 cm, made up to the mark with 2 M hydrochloric acid and stirred. Solution B is prepared on the day of application. 1 cmof the solution contains of 0.00005 g of zirconium.

Standard solutions of zirconium oxychloride zirconium.

Solution A. 3.5 g of zirconium oxychloride ZrOCl·8HO is placed in a volumetric flask with a capacity of 1 DM, dissolved in 2 M hydrochloric acid, was adjusted to the mark with the same acid. The content of zirconium in the solution set of a gravimetric method to form zirconium dioxide.

Solution B. 5 cmof the solution And placed in a volumetric flask with a capacity of 100 cm, made up to the mark with 2 M hydrochloric acid and stirred. 1 cmof solution B contains 0,00005 g

zirconium.

2.3. Analysis

2.3.1. The weight of bronze weighing 0.1 g was placed in a platinum or PTFE Cup, add 1 cmhydrofluoric acid and 5 cmof nitric acid. After the termination of reaction, the reaction mixture was heated until complete dissolution of the sample. To the resulting solution was added 2 cmof sulphuric acid diluted 1:1, and is evaporated prior to the allocation of white smoke of sulfuric acid. After cooling, rinse the walls of the Cup with water and again evaporated to release white smoke of sulfuric acid.

If the mass fraction of Zirconia in bronze above 0.02%, the residue is dissolved in 8 M hydrochloric acid, the solution transferred to a volumetric flask with a capacity of 50 cm, made up to the mark with the same acid and mix. Aliquot part (see table) is placed in a volumetric flask with a capacity of 50 cm, which is pre-concentrated acid is added in the amount indicated in the table. The addition of concentrated hydrochloric acid is needed to the total concentration of hydrochloric acid (including contained in aliquotes taken part) in the final volume was equal to 8 M. Then add 10 cmof acetone, 1 cmof the solution, arsenazo III, made up to the mark with water, mix and measure the optical density on the spectrophotometer at 665 nm or photoelectrocolorimeter FEK-N-57 with red filter (656−700 nm) in a cuvette with a thickness of absorbing layer 1 cm.

________________
* The amount specified for hydrochloric acid with a concentration of 11.5−12.0 M; when using hydrochloric acid of different concentration is carried out corresponding conversion.


A solution of comparison, using the same solution, but without addition of arsenazo III. From the obtained optical density is subtracted optical density of the solution, arsenazo III, prepared as follows: into a measuring flask with a capacity of 50 cm35.5 cm makeof concentrated hydrochloric acid, 10 cmof acetone, 1 cmof the solution, arsenazo III, to the mark and top up with water, stirred and measured relative to water. Found the difference of optical density using a calibration chart, find the content of zirconium in the analyzed solution.

If the mass fraction of Zirconia in bronze below 0.02%, residue after evaporation is dissolved in 15 cmof concentrated hydrochloric acid and the solution is placed in a volumetric flask with a capacity of 50 cm, rinse the walls of the Cup 20.5 cmof concentrated hydrochloric acid, add 10 cmof acetone and then do as stated your

E.

2.3.2. Construction of calibration curve

In a volumetric flask with a capacity of 50 cmis administered at 35.5 cmof concentrated hydrochloric acid, make 0; 0,1; 0,2; 0,3; 0,4 and 0,5 cmstandard solution B, zirconium, added to 10 cmof acetone and then do as described in claim 2.3.1. Solution comparison is the solution not containing zirconium.

2.4. Processing of the results

2.4.1. Mass fraction of zirconium () in percent is calculated by the formula

,

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

 — the weight of the portion corresponding to aliquote part,

2.1−2.4.1. (Changed edition, Rev. N 1).

2.4.2. Discrepancies in the results of three parallel definitions should not exceed the values permitted by the divergence (the rate of convergence), calculated according to the formula

,

where  — mass fraction of zirconium in the alloy, %.

(Changed edition, Rev. N 2).

2.4.3. Discrepancies in the results analysis, obtained in two different laboratories or two of the results of analysis obtained in the same laboratory but under different conditions (a measure of reproducibility) shall not exceed the values calculated according to the formula

,

where  — mass fraction of zirconium in the alloy, %.

2.4.4. Control of accuracy of analysis results is carried out according to State standard samples of heat-resistant (CR) bronze or by a method of additives in accordance with GOST 25086−87.

2.4.5. Method is used when the differences in quality assessment of high-temperature bronzes.

2.4.3−2.4.5. (Added, Rev. N 2).

3. The PHOTOMETRIC METHOD for the DETERMINATION of ZIRCONIUM using ARSENAZO III 2 MOL/DM HYDROCHLORIC ACID (with a mass fraction of zirconium from 0.01 to 0.3%)

3.1. The essence of the method

The method is based on the formation of Zirconia colored complex with arsenazo III 2 mol/DMhydrochloric acid and measuring the optical density of the solution.

3.2. Apparatus, reagents and solutions

Photoelectrocolorimeter or spectrophotometer.

Nitric acid GOST 4461−77.

Hydrochloric acid by the GOST 3118−77, 2 mol/DMsolution.

Sulfuric acid GOST 4204−77 and diluted 1:1.

Hydrofluoric acid according to GOST 10484−78.

Zirconium metal (ideny).

Zirconium oxychloride.

Standard solutions of zirconium

A. solution of 0.1 g of metallic zirconium is placed in a platinum Cup, pour 10 cmof concentrated sulfuric acid, 1 cmhydrofluoric acid and heated until dissolved. The solution is evaporated prior to the appearance of a white smoke of sulfuric acid. After cooling, the walls of the Cup then rinsed with water, the solution was stirred and evaporated again prior to the allocation of white smoke of sulfuric acid. After cooling, to the residue add 25 cmof water, heated to obtain clear solution, the solution transferred to a volumetric flask with a capacity of 100 cm, made up to the mark with water and mix. 1 cmof the solution contains 0.001 g of zirconium.

Solution B. 5 cmof the solution And placed in a volumetric flask and mix. Solution B is prepared on the day of application. 1 cmof a solution of 0.00005 g contains zirconium.

Standard solutions of zirconium oxychloride zirconium.

Solution A. 3.5 g of zirconium oxychloride ZrOCl·8HO is placed in a volumetric flask with a capacity of 1 DM, is dissolved in 2 mol/DMhydrochloric acid and bring to mark with the same acid.

The content of zirconium in the solution set of a gravimetric method to form zirconium dioxide.

Solution B. 5 cmof the solution And placed in a volumetric flask with a capacity of 10 cm, made up to the mark with 2 mol/DMhydrochloric acid and stirred. 1 cmof a solution of 0.00005 g contains zirconium.

Arsenazo III, solution 1 g/l: 0.1 g, arsenazo III are dissolved in 60 cmof water when heated (not boiling), the resulting solution is settled and carefully poured in a measuring flask with volume capacity of 100 cm. The undissolved portion of the reagent is rubbed with a glass rod, add 10−15 cmof water and again heated, the solution is settled and decanted into a volumetric flask. The cooled solution was added 15 cmof the solution, 2 mol/DMof hydrochloric acid, made up to the mark with water. Solution defend 48 hours, stirring occasionally. Then filtered through a thick layer of cotton wool, discarding the first 10 cmof the filtrate. Such a solution maintain 5−7

day.

3.1, 3.2. (Changed edition, Rev. N 1, 2).

3.3. Analysis

3.3.1. The weight of bronze weighing 0.1 g was placed in a platinum or PTFE Cup, add 1 cmhydrofluoric acid and 5 cmof nitric acid. After termination of the reaction the mixture was heated until complete dissolution of the sample. The solution was cooled, added to 2 cmof sulphuric acid diluted 1:1, and is evaporated prior to the allocation of white smoke of sulfuric acid. After cooling, rinse the walls of the Cup with water and again evaporated to release white smoke of sulfuric acid.

The residue is dissolved in 2 mol/DMhydrochloric acid, the solution transferred to a volumetric flask with a capacity of 50 cm, made up to the mark with the same acid and mix. Aliquot part (see table) is placed in a volumetric flask with a capacity of 50 cm, 10 cm was added2 mol/DMof hydrochloric acid, boil 1 min, cool, add 1 cmof a solution of arsenazo III, adjusted to the mark with 2 mol/DMhydrochloric acid, stirred and after 5 min, but not later than 30 min, the optical density is measured on photoelectrocolorimeter FEK-N-57 or FEK-M with red filter in a cuvette with a thickness of the absorbing layer 2 cm or on the spectrophotometer at 665 nm in a cuvette with a thickness of absorbing layer 1 cm.

A solution of comparison, using the same solution, but without addition of arsenazo III. From the obtained optical density is subtracted optical density of the solution, arsenazo III, prepared as follows: into a measuring flask with a capacity of 50 cmmake 1 cmof the solution, arsenazo III, mark topped up with 2 mol/DMhydrochloric acid, stirred and measured relative to water. Found the difference of optical density using a calibration chart, find the content of zirconium in solution.

(Changed edition, Rev. N 1, 2).

3.3.2. Construction of calibration curve.

In a volumetric flask with a capacity of 50 cmmake 0; 0,1; 0,2; 0,3; 0,4 and 0,5 cmstandard solution B, zirconium, add 10 cmof 2 mol/DMof hydrochloric acid and then act as described in paragraph 3.3.1.

(Changed edition, Rev. N 1).

3.4. Processing of the results

3.4.1. Mass fraction of zirconium () in percent is calculated by the formula

,

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

 — the weight of the portion corresponding to aliquote part,

3.4.2. Discrepancies in the results of three parallel definitions should not exceed the values permitted by the divergence (the rate of convergence), calculated according to the formula

,

where  — mass fraction of zirconium in the alloy, %.

(Changed edition, Rev. N 2).

3.4.3. Discrepancies in the results analysis, obtained in two different laboratories or two of the results of analysis obtained in the same laboratory but under different conditions (a measure of reproducibility) shall not exceed the values calculated according to the formula

,

where  — mass fraction of zirconium in the alloy, %.

3.4.4. Control of accuracy of analysis results is carried out according to State standard samples of heat-resistant (CR) bronze or by a method of additives in accordance with GOST 25086−87.

3.4.3, 3.4.4. (Added, Rev. N 2).

4. The PHOTOMETRIC METHOD for the DETERMINATION of ZIRCONIUM WITH the USE of PETROMIN-EPSILON (with a mass fraction of zirconium from 0.005 to 0.3%)

4.1. The essence of the method

The method is based on the formation of complex compounds of zirconium with pikramenos-Epsilon in the solution of 0.9 to 1.2 mol/DMof hydrochloric acid and measuring the optical density of the solution.

4.2. Apparatus, reagents and solutions

Photoelectrocolorimeter or spectrophotometer.

Nitric acid GOST 4461−77 diluted 1:1.

Sulfuric acid GOST 4204−77 and diluted 1:1.

Hydrochloric acid by the GOST 3118−77, a solution of 2 mol/land diluted 1:1.

Hydrofluoric acid according to GOST 10484−78.

Ascorbic acid, a solution of 10 g/DM.

The aqueous ammonia solution according to GOST 3760−79.

Thiourea according to GOST 6344−73, a solution of 100 g/DM.

Ammonium chloride according to GOST 3773−72, a solution of 20 g/DM.

Salt is the disodium Ethylenediamine — N, N, N', N'-tetraoxane acid 2-water (Trilon B) according to GOST 10652−73, a solution of 20 g/DM.

Rectified ethyl alcohol GOST 18300−87.

Petromin-Epsilon, an aqueous solution of 20 g/DM.

Iron chloride according to GOST 4147−74, a solution of 10 g/DM.

Zirconium metal (ideny).

Zirconium oxychloride.

Standard solutions of zirconium.

Solution a: 0.1 g of metallic zirconium is placed in a platinum Cup, add 10 cmof concentrated sulfuric acid and 1 cm ofhydrofluoric acid and dissolved by heating. Upon dissolution the solution is evaporated prior to the appearance of a white smoke of sulfuric acid. After cooling, the walls of the Cup then rinsed with water, the solution was stirred and re-evaporated prior to the allocation of white smoke of sulfuric acid. After cooling, to the residue add 25 cmof water, heated to obtain clear solution, the solution transferred to a volumetric flask with a capacity of 100 cm, made up to the mark with water and mix.

1 cmof the solution contains 0.001 g of zirconium.

Solution B: 5 cmsolution And placed in a volumetric flask with a capacity of 100 cm, made up to the mark with a solution of 2 mol/DMhydrochloric acid and stirred. Solution B is prepared on the day of application.

1 cmof a solution of 0.00005 g contains zirconium.

Solution: 10 cmof solution B is placed in a volumetric flask with a capacity of 100 cm, made up to the mark with a solution of 2 mol/DMhydrochloric acid and stirred. Solution prepared on the day of application.

1 cmof the solution contains 0,000005 g of zirconium.

Standard solutions of zirconium oxychloride zirconium

Solution: 3.5 g of zirconium oxychloride (ZrOCl·8HO) was placed in a flask with volume capacity of 1000 cm, is dissolved in a solution of 2 mol/DMhydrochloric acid is poured to the mark with the same acid. Mass fraction of zirconium in the solution set of a gravimetric method to form zirconium dioxide.

Solution B: 5 cmsolution And placed in a volumetric flask with a capacity of 100 cm, is poured a solution of 2 mol/DMhydrochloric acid and stirred. Solution B is prepared on the day of application.

1 cmof a solution of 0.00005 g contains zirconium.

Solution: 10 cmof solution B is placed in a volumetric flask with a capacity of 100 cm, made up to the mark with a solution of 2 mol/DMhydrochloric acid and stirred. Solution prepared on the day of application.

1 cmof solution with

keeps 0,000005 g of zirconium.

4.3. Analysis

4.3.1. When the mass fraction of zirconium of more than 0,015%

Weighed bronze (see table.2) is placed in a platinum or Teflon, or glass-carbon Cup, add 1 cmhydrofluoric acid and 10 cmof nitric acid (1:1). After the termination of reaction, the reaction mixture was heated until complete dissolution of the sample. To the obtained solution add 1 cmof sulfuric acid (1:1) and removed prior to the allocation of white smoke of sulfuric acid. After cooling, rinse the walls of the Cup with water and again evaporated to release white smoke of sulfuric acid. The residue is dissolved in 5 cmof water when heated, cooled, the solution was transferred to a volumetric flask with a capacity of 100 cmwith a solution of 2 mol/DMhydrochloric acid, topped up to the mark with the same acid and mix.

Table 2

Aliquot part of the solution (see table.2) is placed in a volumetric flask with a capacity of 50 cm, is diluted with water to 20 cm, heated to boiling and boil for 1−2 min. Then solution was cooled, added hydrochloric acid (see table.2), 2 cmof ascorbic acid solution, a solution of thiourea (see table.2) and incubated for 10 min, Then add ethyl alcohol (see table.2), water up to ~40 cm, 2 cmof mortar petromin-Epsilon, made up to the mark with water and mix. After 20 minutes, measure the optical density of the solution on the spectrophotometer at 566 nm in a cuvette with a thickness of absorbing layer 1 cm or photoelectrocolorimeter with a yellow filter in a cuvette with a thickness of the absorbing layer 2 or 3 cm relative to the comparison solution.

Reference solution: in a volumetric flask with a capacity of 50 cmis placed aliquot part of the solution (see table.2), was added a solution of thiourea (see table.2), 2 cmof ascorbic acid solution, 1 cmof solution Trilon B and incubated for 10 min. Then add 2cmof a solution petromin-Epsilon, to label top up with water and paramashiva

yut.

4.3.2. For the mass concentration of zirconium to 0.015%.

Dissolution of the sample (see table.2) and evaporation until white smoke of sulfuric acid is carried out as indicated in paragraph 4.3.1. The residue is dissolved in water, the solution was transferred to a beaker with a capacity of 250 cm, dilute with water to 100 cm. Then add 1 cmof solution of ferric chloride and ammonia solution before the formation of a soluble blue complex of copper. The solution is kept at 50−60 °C for coagulation of the precipitate of iron hydroxide and zirconium. The separated precipitate was filtered off on a medium density filter, a glass and the precipitate washed with hot solution of ammonium chloride 7−8 times. The precipitate is dissolved in solution of 2 mol/DMhydrochloric acid into the beaker, which conducted the deposition, the solution transferred to a volumetric flask with a capacity of 100 cm, made up to the mark with the same acid and mix. Aliquot part of the solution (see table.2) is placed in a volumetric flask with a capacity of 50 cm, was boiled down to 20 cmand further analysis is carried out as specified in clause 4.3.1

.

4.3.3. Construction of calibration curve

In six volumetric flasks with a capacity of up to 50 cmare added successively 0; 1,0; 2,0; 3,0; 4,0 and 5,0 cmstandard solution In Zirconia, dilute with water to 20 cm, heated to boiling and boil for 1−2 min. the Solution was cooled, added in 8.5 cmof a hydrochloric acid solution (1:1) and then do as specified in clause 4.3.1.

Solution comparison is the solution not containing zirconium.

4.4. Processing of the results

4.4.1. Mass fraction of zirconium () in percent is calculated by the formula

,

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

 — the weight of the portion corresponding to aliquote part,

4.4.2. Discrepancies in the results of three parallel definitions should not exceed the values permitted by the divergence (the rate of convergence), calculated according to the formula

,

where  — mass fraction of zirconium in the alloy, %.

4.4.3. Discrepancies in the results analysis, obtained in two different laboratories or two of the results of analysis obtained in the same laboratory but under different conditions (a measure of reproducibility) shall not exceed the values calculated according to the formula

,

where  — mass fraction of zirconium in the alloy, %.

4.4.4. Control of accuracy of analysis results is carried out according to State standard samples or by the method of additives in accordance with GOST 25086−87.

Sec. 4. (Added, Rev. N 2).