GOST 15483.1-78
GOST 15483.1−78 Tin. Methods for determination of antimony (with Amendments No. 1, 2, 3)
GOST 15483.1−78
Group B59
INTERSTATE STANDARD
TIN
Methods for determination of antimony
Tin. Methods for determination of antimony
AXTU 1709
Date of introduction 1980−01−01
INFORMATION DATA
1. DEVELOPED AND INTRODUCED by the Ministry of nonferrous metallurgy of the USSR
DEVELOPERS
B. C. Bais, T. A. Almanova, G. M. Vlasov, C. B. Meshkova, L. V. Mishchenko, L. D. Savilov, R. D. Kresnicka
2. APPROVED AND put INTO EFFECT by Decision of the USSR State Committee for standards from
3. The standard complies ST SEV 4811−84 in part photometric (at a mass fraction of antimony from 0.003 to 0.35%) and atomic absorption methods
4. REPLACE GOST 15483.1−70
5. REFERENCE NORMATIVE AND TECHNICAL DOCUMENTS
| The designation of the reference document referenced |
Item number |
| GOST 83−79 |
3.2 |
| GOST 860−75 |
4.2 |
| GOST 1089−82 |
2.2; 3.2; 4.2 |
| GOST 2603−79 |
2.2 |
| GOST 3118−77 |
2.2; 4.2 |
| GOST 4197−74 |
2.2 |
| GOST 4204−77 |
2.2; 4.2 |
| GOST 4461−77 |
4.2 |
| GOST 4521−78 |
3.2 |
| GOST 5789−78 |
2.2 |
| GOST 6691−77 |
2.2 |
| GOST 6709−72 |
2.2 |
| GOST 6836−80 |
3.2 |
| GOST 10484−78 |
4.2 |
| GOST 11125−84 |
3.2 |
| GOST 14261−77 |
2.2; 3.2 |
| GOST 14262−78 |
2.2; 3.2 |
| GOST 15483.0−78 |
1.1 |
| GOST 17206−96 |
3.2 |
6. Limitation of actions taken by Protocol No. 4−93 of the Interstate Council for standardization, Metrology and certification (ICS 4−94)
7. REVISED (April 1999) with Amendments 1, 2, 3, approved in August 1984, October 1985, June 1989 (IUS 12−84, 1−86, 10−89)
This standard specifies the photometric (with a mass fraction of antimony from 0.00001 to 0.35%), atomic absorption (at a mass fraction of antimony from 0.02 to 0.35%) methods and the method of Stripping voltammetry with accumulation (when the mass fraction of antimony from to 0,00002 0,00005%).
The standard complies ST SEV 4811 in part photometric (at a mass fraction of antimony from 0.003 to 0.35%) and atomic absorption methods.
(Changed edition, Rev. N 2).
1. GENERAL REQUIREMENTS
1.1. General requirements for methods of analysis and security requirements — according to GOST 15483.0.
(Changed edition, Rev. N 1).
2. PHOTOMETRIC DETERMINATION OF ANTIMONY
2.1. The essence of the method
The method is based on dissolving the sample in sulfuric acid extraction of complex compounds of antimony with brilliant green layer of toluene and subsequent measurement of optical density of the organic phase on the spectrophotometer at a wavelength of 656 nm or photoelectrocolorimeter in the range of wavelengths of 640 to 670 nm.
(Changed edition, Rev. N 2).
2.2. Apparatus, reagents and solutions
Photoelectrocolorimeter or spectrophotometer.
Separating funnel with a capacity of 150 cm.
Volumetric flasks with a capacity of 25 cmwith ground stoppers.
Test tubes measuring up to 10 cmwith ground stoppers.
Distilled water according to GOST 6709, distilled twice: the first distillation to the water add 2−3 crystals of potassium permanganate.
Redistillate (stored in a plastic container, is used for analysis of tin in high purity).
Sulfuric acid according to GOST 4204.
Hydrochloric acid of high purity according to GOST 14261 and diluted 3:1.
Sodium atomistically according to GOST 4197, a solution with a mass fraction of 10%.
Urea according to GOST 6691, a saturated solution of 50 g of urea are dissolved in 50 cmof hot water.
Brilliant green aqueous solution with a mass fraction of 0.1%.
Tin dichloride, a freshly prepared solution with a mass fraction of 10% concentrated hydrochloric acid.
Toluene according to GOST 5789.
Acetone according to GOST 2603.
Antimony metal according to GOST 1089 brand su-00.
Solutions of antimony standard.
Solution a: 0,1000 g of metallic antimony is dissolved by heating in 5 cmof concentrated sulfuric acid, then cooled and diluted with 20 cm
of hydrochloric acid, diluted 3:1, again cooled, transferred to a volumetric flask with a capacity of 1 DM
, adjusted to the mark with hydrochloric acid, diluted 3:1, and stirred.
1 cmof the solution contains 1·10
g of antimony.
Solution B is prepared on the day of application: 10 cmsolution And transferred to a volumetric flask with a capacity of 100 cm
, is diluted to the mark with hydrochloric acid, diluted 3:1, and stirred.
1 cmof a solution contains 1·10
g of antimony.
Solution prepared on the day of application: 10,0 cmof solution B is transferred to a volumetric flask with a capacity of 100 cm
, made up to the mark with hydrochloric acid, diluted 3:1, and stirred.
1 cmof the solution contains 1·10
g of antimony.
Hydrochloric acid according to GOST 3118.
Sulfuric acid of high purity according to GOST 14262.
(Redrafted From
M. N 1, 3).
2.3. Analysis
2.3.1. When the mass fraction of antimony from 0.003 to 0.35%
A portion of tin mass of 0.5 g was placed in a conical flask with a capacity of 100 cm, pour 5 cm
of sulphuric acid and evaporated to release vapors of sulphuric anhydride. Heating was continued on a hot plate to remove sulfur from the walls of the flask. Sulfuric acid solution was cooled, poured 20 cm
of hydrochloric acid, diluted 3:1, slightly heated to dissolve the salts, again cooled, transferred to a volumetric flask with a capacity of 100 cm
, adjusted to the mark with hydrochloric acid, diluted 3:1, and stirred.
Depending on the mass fraction of antimony taken aliquot part of the solution in accordance with the table.1 and transferred to a beaker with a capacity of 100 cm.
Table 1
| Mass fraction of SB, % |
Aliquota part of the solution, see | |||
| To | 0,05 |
10,0 | ||
| SV. | 0,05 | « | 0,12 |
5,0 |
| « | 0,12 | « | 0,35 |
2,0 |
To selected parts of a solution (if selected 2.0 cmof the solution, add 3.0 cm
of hydrochloric acid, diluted 3:1) with stirring dropwise poured tin dichloride to a bleaching solution, 1 cm
of a solution of sodium attestatio and leave for 5 mins then Pour an equal volume of water, 1 cm
of a solution of urea and stirred until complete termination of allocation of bubbles. The solution was then transferred to a separatory funnel, dilute with water to 100 cm
(if you had selected aliquota part 10.0 cm
) or up to 50 cm
(if you had selected aliquota part 5.0 cm
).
To the solution in the funnel pour 1 cmof solution of brilliant green and 10 cm
of toluene and extracted antimony within 1 min. After liquid-liquid separation, the aqueous layer is separated, add to it 1 cm
of solution of brilliant green, 5 cm
of toluene and repeat the extraction.
The extracts decanted into a dry volumetric flask with a capacity of 25 cm, which was pre-poured 10 cm
of acetone, adjusted to the mark with toluene and mixed.
After 10 minutes measure the optical density of the organic solution on the spectrophotometer at a wavelength of 656 nm or photocolorimeter, using the filter with the area of light transmission in the range of waves from 640 to 670 nm and a cuvette with an optimum thickness of the layer. The comparison solution is a mixture of toluene and acetone in the ratio 3:2.
From the readings of the optical density of the analyzed solution subtract the readings of the optical density of the solution in the reference experiment, carried out through all stages of the analysis.
The mass of antimony in solution is determined by the calibration schedule.
(Changed edition, Rev. N 1
, 2, 3).
2.3.2. To build a calibration curve in eight of the nine cups with a capacity of 100 cmmeasured 0,15; 0,25; 0,5; 1,0; 1,5; 2,0; 2,5 and 4.0 cm
standard solution B, which corresponds to 0,0015; 0,0025; 0,005; 0,01; 0,015; 0,020; 0,025 and 0,040 mg of antimony. All the glasses are poured at 5 cm
of hydrochloric acid, while stirring, poured dropwise a solution of tin dichloride to a bleaching solution. Then continue as described in section
(Changed edition, Rev. N 2).
2.3.3. When the mass fraction of antimony 0.00001 to 0.00005% of the
A portion of tin weighing 1 g is placed in a beaker with a capacity of 100 cm, pour 5 cm
of sulphuric acid (hos.CH.), heated to dissolve the sample tin, the removal of sulfur from the walls of the glass and evaporation of the excess acid to slightly wet salts.
To the cooled residue poured 7 cmof hydrochloric acid, diluted 3:1, slightly warmed (not above 50 °C) to dissolve the salts, add while stirring 1 cm
of a solution of nitrous acid sodium and leave for 5 min Then with shaking poured 8 cm
water, 1 cm
of a saturated solution of urea was stirred until the termination of allocation of bubbles and transfer the solution into the separatory funnel with a capacity of 150 cm
. The glass is washed with 53 cm
of water, add 1 cm
of a solution of brilliant green, 6 cm
of toluene and extracted for 1 min. the Organic layer decanted into a dry measuring beaker with a capacity of 10 cm
, which was pre-poured 4 cm
of acetone, adjusted to the mark with toluene and mixed.
After 10 minutes measure the optical density of a solution as in claim 2.3.1 using a cuvette, the optimal thickness of the layer.
(Changed edition, Rev. N
1, 3).
2.3.4. To build a calibration curve in glasses with a capacity of 100 cmmeasure off 0,1; 0,3; 0,5; 0,7 and 1,0 cm
standard solution, made up to 5 cm
of hydrochloric acid, diluted 3:1, and conduct analysis as indicated in claim
According to the obtained values of optical density and known concentration of antimony building a calibration curve.
(Changed edition, Rev. N 3).
2.4. Processing of the results
2.4.1. Mass fraction of antimony in percent is calculated by the formula
where is the mass of antimony, was found in the calibration schedule g;
— weight of tin, corresponding aliquote part of the solution,
(Changed edition, Rev. N 1).
2.4.2. Allowable absolute discrepancies in the results of parallel measurements at a confidence level 
Table 2
| Mass fraction of SB, % |
The absolute allowable difference, % | ||||||||
| To | 0,005 |
0,002 | |||||||
| SV. | 0,005 | « | 0,01 |
0,003 | |||||
| « | 0,01 | « | 0,015 |
0,004 | |||||
| « | 0,015 | « | 0,03 |
0,006 | |||||
| « | 0,03 | « | 0,05 |
0,01 | |||||
| « | 0,05 | « | 0,15 |
0,02 | |||||
| « | 0,15 | « | 0,2 |
0,03 | |||||
| « | 0,2 | « | 0,35 |
0,04 | |||||
Table 3
| Mass fraction of antimony in tin high frequency, % |
The absolute allowable difference, % | ||||
| From |
0,00001 | to | 0,00002 |
0,000006 | |
| SV. |
0,00002 | « | 0,00004 |
0,000012 | |
| « | 0,00004 | « | 0,00005 |
0,000015 | |
(Changed edition, Rev. N 2).
3. THE METHOD OF STRIPPING VOLTAMMETRY WITH ACCUMULATION
3.1. The essence of the method
The method is based on the determination of antimony by Stripping voltammetry method with the use of accumulation at the mercury film electrode. The sample was transferred to a solution of hydrochloric acid in the presence of cobalt chloride as a catalyst.
3.2. Apparatus, reagents and solutions
Hydrochloric acid of high purity according to GOST 14261.
Cobalt dichloride 6-aqueous, OS.h.
Blend for reconstitution to 250 cmof concentrated hydrochloric acid is added 0.1−0.15 g of cobalt dichloride. The resulting solution was stored in a quartz flask with a glass stopper to full use.
Sulfuric acid of high purity according to GOST 14262 and diluted 1:1.
Nitric acid of high purity according to GOST 11125 and diluted 1:1.
Mercury ferrous nitrate according to GOST 4521.
Mercury odnoklasnica.
Silver metal according to GOST 6836* wire diameter 0.3−0.6 mm.
______________
* On the territory of the Russian Federation GOST 6836−2002. — Note the manufacturer’s database.
Resin epoxy EDG.
Potassium chloride, OS.CH., crystal and in solution saturated at room temperature and a saturated solution diluted by half.
Agar microbiological GOST 17206, a solution with a mass fraction of 3% in a saturated solution of potassium chloride.
The solution for the amalgamation: to 50 cmof water, acidified with 1−2 drops of concentrated nitric acid, crystals add to the ferrous nitrate of mercury to full saturation.
Copper metal in the form of chopped chips.
The anhydrous sodium carbonate according to GOST 83.
Antimony metal according to GOST 1089.
Solution antimony standard, substitute: dissolve 0,1000 g of metallic antimony in 10−15 cmof concentrated sulfuric acid at high temperatures. The solution was cooled, transferred to a volumetric flask with a capacity of 100 cm
and dilute to the mark with the same acid.
1 cmfallback solution contains 1 mg of antimony.
Solution a: 5 cmbackup solution is transferred to a volumetric flask with a capacity of 100 cm
, diluted sulfuric acid, diluted 1:1, up to the mark and mix. 1 cm
of solution A contains 0.05 mg.
Solution B: 1 cmsolution And transferred to a volumetric flask with a capacity of 100 cm
, where a pre-poured 20 cm
of concentrated hydrochloric acid, made up to the mark with water and mix.
1 cmof a solution contains 0.0005 mg of antimony.
Polarograph recording that allows automatic recording in forward and backward directions, with all accessories, type LP-7, Czechoslovakia.
The container with inert gas (nitrogen, argon, helium).
The furnace is tubular with inserted in it a quartz tube containing chopped copper shavings for inert gas purification from oxygen at 250−300 °C.
V-shaped water manometer.
The cell with interchangeable quartz glass cups or cups made of glass «Pyrex» (hell.1) consists of a glass vessel, the bottom base which is tightly connected to the base of the PTFE 11. In the hole on top is placed a mercury film electrode 8, is used as the cathode. In one of the side openings of the cell is introduced an agar-agar bridge 7connecting the vessel to polarographically 10 with a saturated calomel electrode 6 isused as the anode. Another side opening is introduced, the glass tube 9 and drawn with a curved lower end that serves to purge the solution with inert gas. The upper end of the tube with a rubber hose connected to the pressure gauge through which an inert gas is. All of these parts of the cell collected on the sections.
Damn.1
The saturated calomel electrode consists of a vessel (with a diameter in the widest part of 20 mm), with soldered to it a platinum wire 1, the bottom of which poured mercury 2 so that the platinum wire was completely immersed in it. On top of the mercury layer thickness of 2−3 mm put the calomel paste 3, prepared by grinding 1 g of calomel, pre-moistened with a saturated solution of potassium chloride with a few drops of metallic mercury until a homogeneous mass. Over pasta placed crystals of potassium chloride 4 and the remaining capacity is filled with saturated solution of potassium chloride 5. You need to ensure that the layers did not mix. Prepared calomel electrode aged for 24 h and then used in the work.
Mercury film silver electrode: silver wire cut a length of 1−1,5 cm is brazed with copper wire. Silver wire with an epoxy resin glued to a glass capillary with a drawn end so that the outside remained the end of the wire length of 0.5−0.7 cm After solidification of the resin the outer end of the silver wire is cleaned of resin.
Installation for the amalgamation of the electrode (Fig.2) contains: rechargeable battery or dry battery 2, resistance 1, milliammeter 3, a vessel for amalgamation 4. Vessel for amalgamation (Fig.3) contains as electrolyte a saturated solution of ferrous nitrate of mercury 1, acidified with nitric acid. In the side wall of the receptacle is soldered a platinum wire 4, is used as the anode. Contact is through mercury metal, filled in the side tube 3. In the top opening of the vessel is inserted amalgamiles electrode 2, is used as the cathode.
Damn.2
Damn.3
The silver electrode is placed in a vessel for amalgamation and electrolysis is carried out for 2.5 min at a current of 15 mA. The amalgamated electrode was washed with water, gently rubbed with a piece of tracing paper and again washed with water. The resulting electrode is stored in water.
(Changed edition, Rev. N 1, 3).
3.3. Analysis
3.3.1. A portion of the sample weighing 2 g was placed in a quartz glass with a capacity of 100 cm, 10 cm, pour the
mixture to dissolve and are dissolving at 40−50 °C in a water bath. The resulting solution was cooled, transferred to a measuring cylinder with a capacity of 10 cm
, adjusted to the mark with the mixture to dissolve and stirred. Aliquot part of the solution in an amount of 1 cm
placed in a clean quartz glass, add 4 cm
of water and transferred into a cell for polarography. Film electrode must be completely immersed in the solution. Include current of inert gas for mixing of the solution and removal of oxygen (3 min). The flow of gas is controlled by a manometer. Set the voltage of 0.40 V at the normal calomel electrode and connect the cell to polarography, after putting the shunt sensitivity to the position providing the minimum amperage. Spend electrolytic concentration on the electrode for 5−10 minutes depending on the content of antimony in the sample (electrolysis is conducted while stirring the solution by a current of inert gas). At the end of the time turned off the gas, reduce the potential of up to minus 0.33 In, switch shunt to the desired polarograph «sensitivity» and remove polarogram the reverse movement of the drum at a rate of 200 mA/min in the interval of potentials from minus 0.33 and minus 0,009 Pieck of antimony lies at a potential of minus 0,18 V. the Determination of antimony is carried out by additives, by measuring the peak height for the sample without additive and with the additive of 0.1, 0.15 and 0.2 cm
standard solution B.
3.4. Processing of the results
3.4.1. Mass fraction of antimony in percent is calculated by the formula
where is the height of the peak of antimony to the sample without additives, mm;
— the concentration of the added standard solution antimony, ág/cm
;
— the volume of added standard solution antimony, cm
;
— the height of the peak of antimony for the sample with additive, mm;
— weight of tin, g
.
3.4.2. Allowable absolute discrepancies in the results of parallel measurements at a confidence probabilityof 0.95 should not exceed 1.5·10
%.
4. ATOMIC ABSORPTION METHOD
4.1. The essence of the method
The method is based on dissolving the sample in a mixture of hydrofluoric and nitric acids with water and the measurement of atomic absorption of antimony in the flame acetylene-air at a wavelength of the amount of 231.1 nm.
4.2. Apparatus, reagents and solutions
Atomic absorption spectrometer with all accessories.
A radiation source for antimony.
The PTFE beakers with a capacity of 50 cmor Cup platinum with a capacity of not less than 50 cm
.
The polyethylene flask with a capacity of 50 cm.
Nitric acid according to GOST 4461.
Sulfuric acid according to GOST 4204.
Hydrofluoric acid according to GOST 10484.
Hydrochloric acid according to GOST 3118.
Mix to dissolve: hydrofluoric and nitric acid is mixed with water in the ratio 2:3:5 respectively; stored in a plastic container.
Tin of high purity according to GOST 860.
Antimony metal according to GOST 1089.
Standard solution of antimony: 0,1000 g of antimony is dissolved by heating in 10 cmsulfuric acid, cooled, diluted with 20 cm
of a hydrochloric acid solution, again cooled, translating into volumetric flask 1 DM
, adjusted to the mark with hydrochloric acid and stirred.
1 cmof the solution contains 10
g www
s.
4.3. Analysis
4.3.1. A portion of tin by weight, are given in table.4, is placed in a beaker made of PTFE and dissolved in 10 cmof the mixture to dissolve, adding it in small portions in order to avoid violent reaction. After dissolving the contents of the beaker heated for 1−2 minutes, without boiling, and cooled. The solution was transferred to a volumetric flask with a capacity of 50 cm
, adjusted to the mark with water and mix.
Table 4
| Mass fraction of SB, % |
The mass of charge, g | |||
| From |
0,02 | to | 0,1 | 1 |
| SV. |
0,1 | « | 0,35 | 0,5 |
Measure the atomic absorption of antimony in the flame acetylene-air at a wavelength of the amount of 231.1 nm in parallel with solutions for constructing the calibration curve and the reference experiment.
The concentration of antimony in the solution found by the calibration schedule.
4.3.2. To build a calibration curve in eight glasses of PTFE or platinum Cup is placed a portion of tin of high purity by mass in accordance with table.4 and dissolved in 10 cmof the mixture to dissolve, adding it in small portions in order to avoid violent reaction. After dissolving the contents of the beaker heated for 1−2 minutes, without boiling, and cooled. The solution is transferred to volumetric flasks with a capacity of 50 cm
and seven of them measure 2,0; 4,0; 6,0; 8,0; 10,0; 15,0 20.0 cm
standard solution of antimony, which corresponds to 0,2; 0,4; 0,6; 0,8; 1,0; 1,5 and 2.0 mg of antimony, adjusted to the mark with water and mix. Measure the atomic absorption of antimony as described in section
4.4. Processing of the results
4.4.1. Mass fraction of antimony in percent is calculated by the formula
where is the concentration of antimony was found in the calibration schedule, g/cm
;
— the concentration of antimony in solution in the reference experiment, was found in the calibration schedule, g/cm
;
— the volume of the sample solution, cm
;
— weight of tin, g
.
4.4.2. Allowable absolute discrepancies in the results of parallel measurements at p = 0.95 does not exceed the values given in table.2.
Sec. 4. (Added, Rev. N 2).
