GOST 1652.7-77
GOST 1652.7−77 Alloys copper-zinc. Methods for determination of bismuth (with Amendments No. 1, 2, 3)
GOST 1652.7−77
Group B59
STATE STANDARD OF THE USSR
ALLOYS COPPER-ZINC
Methods for determination of bismuth
Copper-zinc alloys.
Methods for the determination of bismuth
AXTU 1709
Date of introduction 1978−07−01
INFORMATION DATA
1. DEVELOPED AND INTRODUCED by the Ministry of nonferrous metallurgy of the USSR
DEVELOPERS
Y. F. Chuvakin, M. B. Taubkin, A. A. Nemodruk, N. In. 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
3. REPLACE GOST 1652.7−71
4. REFERENCE NORMATIVE AND TECHNICAL DOCUMENTS
| The designation of the reference document referenced |
The number of the paragraph, subparagraph |
| GOST 8.315−91 |
4.4, 5.4.4, 6.4.4 |
| GOST 435−77 |
5.2, 6.2 |
| GOST 859−78 |
Sec. 2 |
| GOST 1020−77 | Chapeau |
| GOST 1652.1−77 | 1.1 |
| GOST 2062−77 |
Sec. 2, 5.2, 6.2 |
| GOST 3118−77 |
Sec. 2, 5.2, 6.2 |
| GOST 3652−69 |
5.2 |
| GOST 3760−79 |
Sec. 2, 5.2, 6.2 |
| GOST 4109−79 |
Sec. 2, 5.2, 6.2 |
| GOST 4147−74 |
Sec. 2 |
| GOST 4204−77 |
5.2 |
| GOST 4461−77 |
Sec. 2, 5.2, 6.2 |
| GOST 6008−90 |
6.2 |
| GOST 6344−73 |
5.2 |
| GOST 4463−76 |
Sec. 2 |
| GOST 5457−75 |
6.2 |
| GOST 5817−77 |
5.2 |
| GOST 5841−74 |
5.2 |
| GOST 10928−90 |
Sec. 2, 5.2, 6.2 |
| GOST 10929−76 |
Sec. 2, 5.2, 6.2 |
| GOST 15527−70 |
Chapeau |
| GOST 17711−93 |
Chapeau |
| GOST 18300−87 |
5.2, 6.2 |
| GOST 20490−75 |
5.2, 6.2 |
| GOST 25086−87 |
1.1, 4.4, 5.4.4, 6.4.4 |
5. Resolution of the state standard from
6. REPRINT (July 1997) with Amendments No. 1, 2, 3, approved in October 1981, November 1987-December 1992 (IUS 12−81, 2−88, 3−93)
This standard sets the photometric and atomic absorption methods for the determination of bismuth (with bismuth mass fraction of from 0.0005 to 0.05%) in copper-zinc alloys according to GOST 15527, GOST and GOST 17711 1020.
(Changed edition, Rev. N 2).
1. GENERAL REQUIREMENTS
1.1. General requirements for method of analysis according to GOST 25086 with the Supplement according to claim 1.1 GOST 1652.1.
(Changed edition, Rev. N 2).
2A. PHOTOMETRIC METHOD WITH SELENOLOGY ORANGE
2A.1. The essence of the method
The method is based on the formation of bismuth colored complex with selenology orange and measuring the optical density of the colored complex.
2A, 2A.1. (Added, Rev. N 2).
2. APPARATUS, REAGENTS AND SOLUTIONS
Photoelectrocolorimeter or spectrophotometer.
Nitric acid according to GOST 4461 and 0.1 and 1 mol/DMsolution and diluted 1:1.
Hydrochloric acid according to GOST 3118, diluted 1:8, 1:5 and 1:1.
Bromatologia acid according to GOST 2062.
The acid chloride.
Bromine according to GOST 4109.
Ammonia water according to GOST 3760 and diluted 1:20.
Ascorbic acid, freshly prepared solution of 100 g/DM.
The mixture of acids to dissolve; prepared as follows: 180 cmbromatological acid is mixed with 20 cm
of bromine.
Iron chloride according to GOST 4147, solution 1 g/l; prepared as follows: 0.1 g of ferric chloride dissolved in 25 cm
of hydrochloric acid diluted 1:1 and top up with water to 100 cm
.
Sodium fluoride according to GOST 4463, a solution of 5 g/DM.
Hydrogen peroxide according to GOST 10929, a solution of 300 g/DM.
Selenology orange, solution 1 g/lin 0.1 mol/DM
nitric acid solution.
Copper grade M00k GOST 859.
Copper nitrate, solution 50 g/l; prepared as follows: 5 g of copper metal is dissolved in 50 cm
of nitric acid, diluted 1:1, boil to remove oxides of nitrogen, cooled, the solution was transferred to a volumetric flask with a capacity of 100 cm
and up to the mark and top up with water.
Bismuth brand Ви0 according to GOST 10928.
Standard solutions of bismuth
Solution A, prepared as follows: 0.1 g of bismuth dissolved in 20 cmof concentrated nitric acid. Nitrogen oxides are removed by boiling, poured the solution into a measuring flask with a capacity of 1 DM
, made up to the mark with water and mix.
1 cmof the solution contains 0.0001 g of bismuth.
Solution B is prepared as follows: 50 cmsolution And transferred to a volumetric flask with a capacity of 500 cm
, made up to the mark with water and mix.
1 cmof solution B contains 0,00001 g of bismuth.
3. ANALYSIS
3.1. For alloys not containing tin, antimony and lead
A sample of alloy weighing 1 g is placed in a beaker with a capacity of 300 cm, add 15 cm
of nitric acid, diluted 1:1, and heated to dissolution. The solution was then diluted with water to 150 cm
, add 10 cm
of a solution of ferric chloride and precipitated hydroxide a solution of ammonia until the formation of a soluble deep blue ammonia complex of copper. The mixture was incubated for 30 min at 50−60 °C.
The precipitate was filtered off on a medium density filter, washed 6−8 times with hot ammonia solution diluted 1:20, and dissolved in 20 cmof hot nitric acid diluted 1:1 in the Cup, which was held a deposition, the filter was washed 8−10 times with hot water. Reprecipitation was repeated once more.
The precipitate is dissolved on the filter in 20 cmof hot nitric acid diluted 1:1 in the Cup, which was held a deposition, the filter was washed with water 5−7 times, and the solution was evaporated to dryness. To the dry residue poured 3 cm
1 mol/DM
nitric acid solution, rinse the walls of the Cup 2−3 cm
of water, heat the solution to boiling and boil to dissolve the residue. Then add 4 cm
of ascorbic acid solution and cooled. Add 1 cm
of a solution of sodium fluoride, 1 cm
of solution kylinalove orange, transferred to a volumetric flask with a capacity of 50 cm
, made up to the mark with water, mix. When the mass fraction of bismuth of more than 0,008% to the dry residue add 1 mol/DM
nitric acid solution in a quantity according to table.1.
Table 1
| Mass fraction of bi, % |
The volume of 1 mol/DM |
Capacity volumetric flasks, cm |
The volume aliquote part of the solution, cm |
| From 0.008 to 0.02 incl. |
7,5 |
25 |
10 |
| SV. 0,02 «0,05 « |
30,0 |
50 |
5 |
Add a 3−5 cmwater, 10 cm
of a solution of ascorbic acid, heated to boiling and dissolution of the residue is cooled, transferred to a volumetric flask with a capacity of 25 or 50 cm
, made up to the mark with water and mix.
In a volumetric flask with a capacity of 50 cmis taken aliquot part of the solution according to the table.1 add 1 cm
of a solution of sodium fluoride, 1 cm
of solution kylinalove orange, made up to the mark with water and mix.
(Changed edition, Rev. N 3).
3.2. For alloys containing tin, antimony and mass fraction of up to 0.5% lead
Analysis of the alloy is carried out as specified in clause 3.3, except the selection of lead chloride.
3.3. For alloys containing tin, antimony and mass fraction more than 0.5% lead
A sample of alloy weighing 1 g is placed in a beaker with a capacity of 300 cmand dissolved in 15 cm
of the mixture of acids to dissolve. In case of incomplete dissolution, add dropwise bromine. Once dissolved, add 15−20 cm
of perchloric acid, evaporated the solution to lighten and the appearance of dense white fumes (the volume of the remaining solution should not exceed 5 cm
) and cooled. The walls of the glass should be rinsed with a small amount of water, the solution was diluted to 30 cm
and heated to dissolve the salts. The solution is poured 10 cm
of hydrochloric acid diluted 1:1, and cooled with ice water. The precipitate of chloride of lead is filtered off on a medium density filter, collecting the filtrate in a beaker with a capacity of 250 cm
. The filter with the precipitate and the glass is washed with a small amount (5−8 cm
) of hydrochloric acid diluted 1:8. The precipitate is discarded. To the filtrate add 10 cm
of a solution of ferric chloride, was diluted to a volume of 150 cm
and lead further analysis as described in Chapter 3.1.
3.4. Construction of calibration curve
In glasses with a capacity of 300 cmis placed 10 cm
solution of copper nitrate, injected 0; 0,5; 1,0; 2,0; 4,0; 5,0; 6,0 and 8.0 cm
of a standard solution of bismuth (solution B), 10 cm
of a solution of ferric chloride, dilute with water to 150 cm
and lead further analysis as described in Chapter 3.1.
Solution comparison is the solution not containing bismuth.
On the found values of optical densities build the calibration graph.
4. PROCESSING OF THE RESULTS
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 of alloy,
4.2. The absolute discrepancies in the results of parallel measurements ( — convergence) must not exceed the permissible values given in table.2.
Table 2
| Mass fraction of bi, % |
|
|
| From 0.0005 to 0.001 incl. |
0,0002 |
0,0003 |
| SV. 0,001 «0,003 « |
0,0003 |
0,0004 |
| «Of 0.003» to 0.005 « |
0,0005 |
0,0007 |
| «0,005» 0,01 « |
0,001 |
0,0014 |
| «Is 0.01» to 0.03 « |
0,002 |
0,003 |
| «To 0.03» to 0.05 « |
0,003 |
0,004 |
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.
4.2, 4.3. (Changed edition, Rev. N 2, 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 under GOST 8.315, or by additives or by comparing the results obtained by another method in accordance with GOST 25086.
(Changed edition, Rev. N 3).
4.4.1−4.4.3. (Deleted, Rev. N 3).
5. THE PHOTOMETRIC METHOD FOR THE DETERMINATION OF BISMUTH WITH THIOUREA
5.1. The essence of the method
The method is based on the formation of a bismuth colored complex with thiourea in the environment of 1 mol/DMnitric acid solution and measuring its optical density at a wavelength of 470 nm.
(Changed edition, Rev. N 3).
5.2. Apparatus, reagents and solutions
Photoelectrocolorimeter or spectrophotometer.
Nitric acid according to GOST 4461 and diluted 2:5, 1:2, 1:100.
Hydrochloric acid according to GOST 3118, diluted 2:1 and 1:9.
The acid chloride.
Bromatologia acid according to GOST 2062.
Sulfuric acid according to GOST 4204, diluted 1:3.
Bromine according to GOST 4109.
Mix to dissolve, freshly prepared: bromatologia acid and bromine in a ratio of 9:1.
Ammonia water according to GOST 3760.
Manganese sulfate according to GOST 435, a solution of 80 g/DM.
Potassium permanganate according to GOST 20490, a solution of 30 g/DM.
Hydrogen peroxide according to GOST 10929.
Citric acid according to GOST 3652.
Hydrazine sulfate according to GOST 5841, solution 20 g/DM.
Tartaric acid according to GOST 5817.
A solution mixture of citric and tartaric acids; prepared as follows: 300 g of tartaric acid and 200 g of citric acid dissolved in 500 cmof water.
Thiourea according to GOST 6344, a freshly prepared solution of 100 g/DM.
Bismuth brand Ви0 according to GOST 10928.
Standard solutions of bismuth
Solution a: 1.0 g dissolved in 50 cmof concentrated nitric acid, the solution was cooled, transferred to a measuring flask with volume capacity of 1000 cm
, add 50 cm
of concentrated nitric acid, made up to the mark with water.
1 cmof the solution contains 0.001 g of bismuth.
Solution B: 50 cmsolution And transferred to a volumetric flask with a capacity of 500 cm
, add 30 cm
of concentrated nitric acid, made up to the mark with water and mix.
1 cmof a solution contains 0.0001 g of bismuth.
5.3. Analysis
5.3.1. Weighed samples of ground mounted depending on the expected content of bismuth in accordance with the table.3, is placed in a beaker with a capacity of 250 cm, add the mixture to dissolve and gently heat.
Table 3
| Mass fraction of bi, % |
The mass of charge, g |
The volume of the mixture for dissolution, cm |
| From 0.001 to 0.005 incl. |
5 |
70 |
| SV. Of 0.005 «to 0.02 « | 2 | 30 |
| «0,02» 0,05 « | 1 | 15 |
In case of incomplete dissolution, add dropwise bromine. The solution was boiled down to 5−7 cm, and then add 40, 20 or 10 cm
, respectively, perchloric acid and evaporated the solution to lighten and the appearance of a white smoke of perchloric acid. The residue is diluted with water up to 30−100 cm
and is heated to dissolve the salts. In the presence of lead add 10−20 cm
of hydrochloric acid, diluted 2:1, and the solution was cooled with ice water. The remainder of the chloride of lead is filtered off on a medium density filter, collecting the filtrate in a tall glass with a capacity of 400−600 cm
. The filter residue is washed with 5−10 cm
of hydrochloric acid, diluted 1:9. The filtrate was diluted to 100−200 cm
, neutralized with ammonia before the advent of unfading during the mixing of the precipitate, dissolve it in a minimal amount of nitric acid, diluted 1:2, and the solution is diluted with water up to 200−300 cm
(pH 2−3).
The solution was added 2.5 cmof a solution of sulphate of manganese, heated to boiling, add 3 cm
of a solution of potassium permanganate, and boil for 1 min. after 30 min the precipitate was filtered off on a medium density filter and washed 5 times with nitric acid, diluted 1:100.
The precipitate is washed with water in a glass, which conducted the deposition, and the residue on the filter is dissolved in 20 cmhot sulphuric acid, at the same time add 5−6 drops of hydrogen peroxide. The filter is washed several times with hot water and discarded.
The solution was evaporated until a white smoke. After cooling, add 10 cmof water and a solution of hydrazine sulfate and boiled for 3 min until discoloration of the solution. The solution was cooled, transferred to a volumetric flask with a capacity of 100 cm
, the side of the Cup should be rinsed with 20 cm
solution of a mixture of tartaric and citric acid and add 20 cm
of nitric acid, diluted 2:5, and 20 cm
of a solution of thiourea. The solution was topped to the mark with water, mix and measure optical density of solution on a photoelectrocolorimeter with a blue filter or on a spectrophotometer at a wavelength of 470 nm. Solution comparison is the solution of the reference experiment.
5.3.2. Construction of calibration curve
In six of the seven volumetric flasks with a capacity of up to 100 cmis placed 0,5; 1,0; 2,0; 3,0; 4,0 and 5,0 cm
standard solution B, which corresponds to 0,05; 0,1; 0,2; 0,3; 0,4 and 0,5 mg of bismuth. All flasks is poured 20 cm
of a solution of a mixture of tartaric and citric acids, 20 cm
of nitric acid, diluted 2:5, 20 cm
of a solution of thiourea and then do as specified in clause
5.4. Processing of the results
5.4.1. 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,
5.4.2. The absolute discrepancies in the results of parallel measurements ( — convergence) must not exceed the permissible values given in table.2.
5.4.3. 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.
5.4.2,
5.4.4. 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 under GOST 8.315, or by additives or by comparing the results obtained by another method in accordance with GOST 25086.
(Changed edition, Rev. N 3).
5.4.4.1−5.4.4.3. (Deleted, Rev. N 3).
6. ATOMIC ABSORPTION METHOD FOR THE DETERMINATION OF BISMUTH
6.1. The essence of the method
The method is based on dissolving the sample in nitric acid or mixtures bromatological acid and bromine and the measurement of atomic absorption of bismuth in solution of organic solvents (after pre-gidratirovannogo coprecipitation on manganese dioxide) in a flame acetylene-air at a wavelength of 223,1 nm.
6.2. Apparatus, reagents and solutions
The atomic absorption spectrometer.
Lamp hollow cathode or electrodeless lamp for bismuth.
Hydrochloric acid according to GOST 3118 and diluted 2:1, 1:5 and 1:9.
Nitric acid according to GOST 4461 and diluted 1:1, 1:2 and 1:100.
The acid chloride.
Bromatologia acid according to GOST 2062.
Bromine according to GOST 4109.
Mix to dissolve the acid and bromine bromatologica 9:1.
Ammonia water according to GOST 3760.
Acetylene according to GOST 5457.
Potassium permanganate according to GOST 20490, a solution of 30 g/DM.
Manganese sanitarily according to GOST 435, a solution of 80 g/DM.
Hydrogen peroxide according to GOST 10929.
The technical rectified ethyl alcohol according to GOST 18300.
Methyl isobutyl ketone.
A mixture of ethanol and methyl isobutyl ketone in the ratio of 1:1.
A mixture of ethyl alcohol, methyl isobutyl ketone and concentrated hydrochloric acid in the ratio 4,5:4; 5:1.
Manganese metal according to GOST 6008 with a mass fraction of bismuth less than 0.0005%.
The solution of manganese: 10 g of manganese metal is dissolved in 40 cmof concentrated nitric acid removed the oxides of nitrogen by boiling, adding 250 cm.
of concentrated hydrochloric acid, add water to 1 DM
and stirred.
1 cmof the solution contains 0.01 g of manganese.
Bismuth brand Ви0 according to GOST 10928.
Standard solutions of bismuth
Solution a: 1.0 g of bismuth dissolved in 50 cmof nitric acid. After removal of oxides of nitrogen by boiling the solution was cooled, transferred to a measuring flask with volume capacity of 1000 cm
, made up of 50 cm
of concentrated nitric acid, made up to the mark with water and mix.
1 cmof the solution contains 0.001 g of bismuth.
Solution B: 50 cm solution And transferred into a measuring flask with volume capacity of 1000 cm, made up with hydrochloric acid diluted 1:5, up to the mark and mix.
1 cmof a solution of 0.00005 g contains bismuth.
6.3. Analysis
6.3.1. For alloys containing up to 0.1% tin, antimony and lead
A portion of the sample weighing 3 g (when the mass fraction of bismuth and 0.005%) or 1 g (in mass fraction in excess of 0.005%) were placed in a glass with a capacity of 600 cmand a dissolved in 10 or 30 cm
of nitric acid, diluted 1:1. After dissolution the solution is diluted with water to 100 cm
, neutralized with ammonia before the advent of unfading during mixing of the sediment, dissolve in the desired amount of nitric acid, diluted 1:2 and diluted with water to 200 or 300 cm
. Add 2.5 cm
of a solution of sulphate of manganese, the solution is heated to boiling, add 3 cm
of a solution of potassium permanganate, and boil for 1 min.
After 30 min the precipitate was filtered off on a medium density filter and washed on the filter with hot nitric acid, diluted 1:100.
The precipitate is washed with hot water into a glass, which conducted the deposition, and the residue on the filter was dissolved 30 cmhot hydrochloric acid, diluted 1:5, and the solution was evaporated almost to dryness. To the residue add 5 cm
of concentrated hydrochloric acid, heated to dissolve, cooled and transferred to a volumetric flask with a capacity of 50 cm
, the side of the Cup rinse with a mixture of ethanol and methyl isobutyl ketone, made up to the mark with the same mixture and stirred. Measure the atomic absorption of bismuth in the sample solution in parallel with the solutions to construct the calibration curve and the solution in the reference experiment in the flame acetylene-air at a wavelength of 223,1 nm. The instrument zero set of a mixture of hydrochloric acid, ethanol and methyl isobutyl ketone.
6.3.2. For alloys containing more than 0.1 percent of tin, antimony and lead
A portion of the sample weighing 3 g (when the mass fraction of bismuth and 0.005%) or 1 g (in mass fraction of bismuth of more than 0,005%) were placed in a glass with a capacity of 250 cmand dissolved in 45 or 15 cm
of the mixture for dissolution. In case of incomplete dissolution, add dropwise bromine. The solution was boiled down to 10 or 5 cm
, then add 25 or 10 cm
of perchloric acid and evaporated to lighten and the appearance of a white smoke of perchloric acid. After cooling, the residue is dissolved in 50−70 cm
of water when heated. In the presence of lead added 10−15 cm
of hydrochloric acid, diluted 2:1, and the solution was cooled with ice water. The precipitate of chloride of lead is filtered off on a medium density filter, collecting in a glass with a capacity of 400−600 cm
. The filter residue is washed with 5−10 cm
of hydrochloric acid, diluted 1:9. The filtrate is diluted with water to 150 cm
, neutralized with ammonia and then do as specified in clause
6.3.3. Construction of calibration curve
In seven of eight glasses with a capacity of 100 cmplaced 0,5; 1,0; 2,0; 4,0; 6,0; 8,0 and 10.0 cm
standard solution B. In all the glasses added to 10 cm
of a solution of manganese and evaporated almost to dryness. To the residue add 5 cm
of concentrated hydrochloric acid and then act as indicated in item
6.4. Processing of the results
6.4.1. Mass fraction of bismuth in percent is calculated by the formula
where is the concentration of bismuth in the analyzed solution samples, was found in the calibration schedule, g/cm
;
— the concentration of bismuth 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
.
6.4.2. The absolute discrepancies in the results of parallel measurements ( — convergence) must not exceed the permissible values given in table.2.
6.4.3. The absolute discrepancies of the analysis results obtained in two different laboratories or two analyses in the same laboratory but under different conditions (the reproducibility) shall not exceed the values specified in table.2.
6.4.2,
6.4.4. 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 under GOST 8.315, or by additives or by comparing the results obtained by another method in accordance with GOST 25086.
(Changed edition, Rev. N 3).
6.4.4.1−6.4.4.3. (Deleted, Rev. N 3).
