GOST 13938.10-78
GOST 13938.10−78 Copper. Methods for determination of antimony (with Amendments No. 1, 2, 3, 4)
GOST 13938.10−78
Group B59
INTERSTATE STANDARD
COPPER
Methods for determination of antimony
Copper. Methods for determination of antimony
AXTU 1709
Date of introduction 1979−01−01
INFORMATION DATA
1. DEVELOPED AND INTRODUCED by the Ministry of nonferrous metallurgy of the USSR
DEVELOPERS
G. P. Giganov, E. M. Peneva, A. A. Blyahman, E. D. Shuvalov, A. N. Savelieva
2. APPROVED AND promulgated by the Decree of the State Committee of standards of Ministerial Council of the USSR from
3. REPLACE GOST 13938.10−68
4. The standard corresponds to the international standard ISO 5956−84
5. REFERENCE NORMATIVE AND TECHNICAL DOCUMENTS
The designation of the reference document referenced |
Section number, paragraph |
GOST 859−78 |
The introductory part; 2; 5.1 |
GOST 1089−82 |
2; 5.1 |
GOST 3118−77 |
2; 5.1 |
GOST 3760−79 |
5.1 |
GOST 4166−76 |
2 |
GOST 4204−77 |
2; 5.1 |
GOST 4461−77 |
5.1 |
GOST 5456−79 |
2 |
GOST 5457−75 |
5.1 |
GOST 5644−75 |
2 |
GOST 9849−86 |
5.1 |
GOST 10929−76 |
2 |
GOST 13938.1−78 |
1 |
GOST 20448−90 |
5.1 |
6. Limitation of actions taken by Protocol No. 3−93 Interstate Council for standardization, Metrology and certification (ICS 5−6-93)
7. REPRINT (November 1999) with Amendments No. 1, 2, 3, 4, approved in March 1979, April 1983, June 1985, April 1988 (IUS 5−79, 7 to 83, 8−85, 7−88)
This standard sets the photometric and atomic absorption (at a mass fraction of from 0.0005 to 0.1%) methods for determination of antimony in copper grades according to GOST 859*.
_______________
* On the territory of the Russian Federation GOST 859−2001, here and hereafter. — Note the manufacturer’s database.
Photometric method based on formation of colored compounds chlorocomplexes of antimony (V) with rhodamine C (In) in the organic phase after extraction of antimony chlorocomplexes isopropyl ether. The optical density of solutions of compounds of antimony with rhodamine C (In) measured at a wavelength of 550 mm*.
________________
* Consistent with the original. — Note the manufacturer’s database.
Atomic absorption method is based on measuring absorption lines of antimony in the flame acetylene-air or propane-butane-air at a wavelength of 217,6 nm. When the antimony content is 0.01% pre-allocate its coprecipitation on iron hydroxide and dissolving the precipitate in hydrochloric acid.
(Changed edition, Rev. N 4).
1. GENERAL REQUIREMENTS
General requirements for methods of analysis and safety requirements when performing tests according to GOST 13938.1.
Sec. 1. (Changed edition, Rev. N 4).
2. APPARATUS, REAGENTS AND SOLUTIONS
Photoelectrocolorimeter or spectrophotometer with all accessories.
Centrifuge with all accessories.
Hydrochloric acid according to GOST 3118, 1 mole/DMsolution and diluted 7:3.
Sulfuric acid according to GOST 4204.
Hydroxylamine hydrochloric acid according to GOST 5456, a solution of 10 g/lin 1 mol/DMhydrochloric acid (sustained for 3 days).
Copper according to GOST 859, solution: 25 g of copper was dissolved in 150 cmof hydrochloric acid, adding portions 100 cmof hydrogen peroxide. In order to avoid premature decomposition of the hydrogen peroxide solution is continuously cooled. The copper solution is transferred to a volumetric flask with a capacity of 500 cmand topped to the mark with hydrochloric acid diluted 7:3.
Sodium sulphate anhydrous according to GOST 4166.
Sanitarily anhydrous sodium GOST 5644, a freshly prepared solution of 10 g/DM.
Hydrogen peroxide according to GOST 10929.
Rhodamine ©, a solution of 0.4 g/lin 1 mol/DMhydrochloric acid.
Cerium (IV) sulphate, a solution of 42 g/DMis prepared as follows: 4.2 g of cerium sulfate is heated with 5 cmof sulphuric acid until sulphuric acid fumes. To the solution poured 50 cmof water, heated to dissolve the salts, cooled and transferred to a volumetric flask with a capacity of 100 cm. Topped up to the mark with water and mix.
The isopropyl ester.
Of antimony trioxide.
Antimony GOST 1089.
Solutions of antimony standard.
Solution A, prepared as follows: 0,120 g of antimony trioxide are heated with 200 cmof hydrochloric acid diluted 7:3, in the conical flask with a capacity of 1 DMwith cone and deflegmatora until dissolved. The solution was transferred to a volumetric flask with a capacity of 1 DMand topped to the mark with hydrochloric acid diluted 7:3. The same solution may be prepared of antimony: tankomaster 0,100 g of antimony is placed in a beaker with a capacity of 400 cmand dissolved with strong heating in 20 cmof sulfuric acid. The solution was evaporated to a volume of 5 cm, cool, add 200 cmof hydrochloric acid diluted 7:3. The solution was transferred to a volumetric flask with a capacity of 1 DM, rinse the beaker with hydrochloric acid of the same concentration and added to the solution in a volumetric flask. The solution was topped to the mark with hydrochloric acid diluted 7:3, and mixed.
1 cmof the solution contains 0.1 mg of antimony.
Solution B is prepared as follows: a pipette, take 25 cmof solution A in a volumetric flask with a capacity of 100 cm, made up to the mark with hydrochloric acid diluted 7:3, and mixed.
1 cmof the solution contains 0.025 mg of antimony.
Solution; prepared as follows: pipette select 20 cmof solution B in a volumetric flask with a capacity of 100 cm, made up to the mark with hydrochloric acid diluted 7:3, and mixed.
1 cmof the solution contains 0.005 mg of antimony.
Solutions B and C sustained for 8 hours
(Changed edition, Rev. N 4).
3. ANALYSIS
3.1. A sample of copper with a mass given in table.1, is placed in a beaker with a capacity of 400 cmand dissolved in 50 cmof hydrochloric acid diluted 7:3, adding small amounts of 15 cmof hydrogen peroxide. The excess of hydrogen peroxide and the liberated chlorine is removed by boiling the solution.
Table 1
Mass fraction of SB, % |
The weight of the portion of copper, g |
Volume volumetric flasks, cm |
Aliquota part of the solution, see |
The volume of isopropyl ether, see |
From 0.0005 to 0.0025 incl. |
5,0 |
100 |
10 |
10 |
SV. 0,0025 «0,006 « |
2,0 |
100 |
10 |
10 |
«0,006» 0,025 « |
2,5 |
100 |
10 |
50 |
«0,025» 0,06 « |
2,5 |
250 |
10 |
50 |
«Of 0.06» to 0.1 « |
1,0 |
200 |
10 |
50 |
The solution was cooled, transferred to a volumetric flask and topped to the mark with hydrochloric acid diluted 7:3.
Measure with a pipette 10 cmof the solution in a beaker with a capacity of 100−150 cm, pour 1 cmof a solution of sodium semitecolo and 5 cmof hydrochloric acid diluted 7:3, closing a glass watch glass and heated to boiling. The solution is immediately cooled with cold water (below 20 °C) and add 4 cmof sulfate solution of cerium (IV). After 1 min pour 10 drops of hydroxylamine hydrochloride solution, mix well and transfer the contents of the Cup 50 cmof water in a separating funnel with a capacity of 100−150 cm. Measure with a burette isopropyl ether (see table.1) and extracted antimony for 1 min. Aqueous solution is discarded, the extract is washed with 2 cmof hydrochloric acid hydroxylamine solution for 30 s. After separation of the aqueous extract is washed with 5 cm1 mol/DMhydrochloric acid solution. The aqueous solution is separated and the organic layer was added 4 cmof a solution of rhodamine and stirred the contents of the funnel for 30 s. the Excess solution of rhodamine was separated, the extract is decanted into a glass centrifuge and tsentrifugirujut for 2 min.
In the absence of a centrifuge extract is poured into a glass with a capacity of 100−150 cm, dehydrate with 0.5 g of sodium sulfate and placed in a cylinder with a glass stopper. The optical density of the extract is measured at a wavelength of 550 nm in a cuvette with an optimum thickness of the layer.
Solution comparison in the measurement of optical density is isopropyl ether.
At the same time carried out two test experience with all the applied reagents. The average value of optical density in the reference experiment is subtracted from the value of the optical density of the analyzed solution.
The mass of antimony in the solution set for the calibration schedule.
3.2. Construction of calibration graphs
The calibration graphs built accordingly to the contents of antimony, given in table.2. To do this, in glasses with a capacity of 100−150 cmselect 0; 0,5; 1,0; 1,5; 2,0 and 3,5 cmof a standard solution of antimony B or C and the volume of the copper solution corresponding table.2.
Table 2
Mass fraction of SB, % |
The volume of copper solution |
The volume of a standard solution of antimony |
Weight of antimony, ág |
The volume of isopropyl ether, see |
cm |
||||
Solution | ||||
From 0.0005 to 0,006 |
4 |
0,5 |
2,5 |
10 |
4 |
1,0 |
5,0 |
10 | |
4 |
1,5 |
7,5 |
10 | |
4 |
2,0 |
10,0 |
10 | |
4 |
2,5 |
12,5 |
10 | |
Solution B | ||||
SV. Of 0.006 to 0.1 |
2 |
0,5 |
12,5 |
50 |
2 |
1,0 |
25,0 |
50 | |
2 |
1,5 |
37,5 |
50 | |
2 |
2,0 |
50,0 |
50 | |
2 |
2,5 |
62,5 |
50 |
Solutions of diluted hydrochloric acid, diluted 7:3, to a volume of 15 cm, add 1 cmof a solution of sodium semitecolo, cover with a watch glass and heated to boiling. Next, carry out analysis as specified in paragraph 3.1.
On the found values of optical density and relative content of antimony building a calibration curve.
(Changed edition, Rev. N 2).
4. PROCESSING OF THE RESULTS
4.1. Mass fraction of antimony in percent is calculated by the formula
,
where is the mass of the copper sample, g;
— the weight of antimony was found in the calibration schedule, mcg;
— the volume of the analyzed solution, cm;
— volume aliquote part of the analyzed solution, cm.
4.2. Discrepancies in the results of two parallel measurements and the two tests should not exceed the values given in table.3.
Table 3
Mass fraction of SB, % |
The absolute maximum discrepancy, %, results | |
parallel definitions |
tests | |
To from 0,0005 0,0010 incl. |
0,0002 |
0,0003 |
SV. 0,0010 «0,0030 « |
0,0004 |
About 0.0006 |
«0,003» 0,010 « |
0,001 |
0,002 |
«0,010» 0,030 « |
0,002 |
0,004 |
«0,030» 0,100 « |
0,004 |
0,007 |
(Changed edition, Rev. N 4).
4.3. Allowed determination of antimony extraction-photometric method with the use of crystal violet or brilliant green.
(Added, Rev. N 4).
5. ATOMIC ABSORPTION METHOD
5.1. Equipment, reagents, solutions
Spectrophotometer atomic absorption of any type.
A radiation source for antimony.
Acetylene according to GOST 5457.
Propane-butane according to GOST 20448.
Air compressor.
Nitric acid according to GOST 4461 solution (1:1), 1 mol/DM.
Hydrochloric acid according to GOST 3118 solution (1:1).
Sulfuric acid according to GOST 4204.
Ammonia water according to GOST 3760 and a solution of 1:99.
Iron according to GOST 9849, solution 25 g/lin nitric acid 1 mol/DM.
Copper according to the GOST 859.
Antimony GOST 1089.
Antimony trioxide.
Standard solutions of antimony in sec. 2.
5.2. Analysis
5.2.1. A sample of copper with a mass of 5.0 g (when the antimony content is 0.01%) were placed in a glass with a capacity of 400 cmand dissolved by heating in 25 cmof a solution of nitric acid (1:1). After removal of the nitrogen oxides flow of 250 cmwater and 5 cmof a solution of iron, heated to 60−70 °C. ammonia is Added in such quantity that the whole of the copper passed into the ammonia complex and 5 cm.
Leave at 60 °C to coagulate the precipitate, and then filtered through a filter of medium density. The precipitate is washed on the filter 2−3 times with hot ammonia solution (1:99).
Dissolve the residue in 10 cmof hydrochloric acid (1:1), collecting the filtrate in a volumetric flask with a capacity of 25 cm, and the filter was washed 2−3 times with hot water. After cooling, dilute to the mark with water and mix.
Measure the absorption of the test solution at a wavelength 217,7 nm simultaneously with the solution of the control experience and solutions to build the calibration curve.
Mass of antimony is determined according to the calibration schedule.
It allowed the determination in the analyzed solution of bismuth (from 0.0005 to 0.005%), tin (0.01 to 0.06%) and lead (from 0.0005 to 0.005%).
5.2.2. A sample of copper with a mass of 1.0 g (when the antimony content is above 0.01%) were placed in a glass with a capacity of 100 cmand dissolved in 10−15 cmof nitric acid (1:1). After dissolution, the sample flow 10 cmof hydrochloric acid (1:1), transferred to a volumetric flask with a capacity of 50 cm, is diluted to the mark with hydrochloric acid 1 mol/land stirred.
Measure the absorption as described in section
5.2.3. To build a calibration curve of seven glasses with a capacity of up to 400 cmis placed 1.0 or 5.0 g of copper (depending on the antimony content) and dissolve in accordance with the PP.5.2.1 and
According to the obtained values of optical density and corresponding concentrations of antimony in building the calibration curve.
When plotting the signal value of the background solution is subtracted from the signal values of each standard solution and carry out the schedule from the origin.
5.3. Processing of the results
5.3.1. Mass fraction of antimony in percent is calculated by the formula
,
where is the mass of antimony in a solution of the sample, was found in the calibration graphics mg;
— the weight of antimony in the solution in the reference experiment, mg;
— the weight of the portion of copper, g;
— capacity volumetric flasks, cm.
5.3.2. Discrepancies in the results of two parallel measurements and the two tests should not exceed the values given in table.3.
Sec. 5. (Added, Rev. N 4).
APP. (Deleted, Rev. N 4).