GOST 1367.11-83
STATE STANDARD OF THE USSR
ANTIMONY
CHEMICAL-SPECTRAL METHOD OF ANALYSIS
Antimony. Chemical-spectral method of analysis
GOST 1367.11−83
Group B59
AXTU 1709
Valid from January 1, 1985
before January 1, 1990
This standard specifies the chemical-spectral method of determination of lead, iron, zinc, bismuth, Nickel, copper, cadmium, magnesium, manganese and silver in antimony.
Chemical-spectral method allows to determine the mass fraction of impurities in the antimony, %:
lead from before ;
iron from to ;
zinc from ;
of bismuth from up to ;
Nickel from before ;
copper from to ;
cadmium from before ;
of magnesium from before ;
manganese from before ;
silver from to .
The method is based on the preconcetration of Stripping impurities of antimony in the form of bromides, the evaporation residue of a solution of graphite powder and subsequent spectral analysis of the obtained concentrate.
1. GENERAL REQUIREMENTS
1.1. General requirements for method of analysis and safety requirements according to GOST 1367.0−83.
2. APPARATUS, MATERIALS AND REAGENTS
The diffraction type spectrograph DFS-8 with grille 600 strokes at 1 mm or another similar device.
The quartz spectrograph medium dispersion type of ISP-30 or other similar device.
Microphotometer geregistreerde type MF-2 or another similar device.
A constant current source providing a voltage of at least 200 In and designed for a current of 20 A.
Generator activated arc type DG-2, DG-1, PS-39 for ionization of the interelectrode gap at the time of switching arc DC.
Grinding machine graphite electrodes with a speed of up to 1420 rpm.
(as amended by Change No. 1, approved. By the decree of Gosstandart of the USSR from
Graphite electrodes with a diameter of 6 mm marks-2 or high purity-7−4 with a crater diameter of 4 mm and a depth of 8 mm.
Contradictory of graphite rods stamps-2 or high purity-7−4 with a diameter of 6 mm, length 30 — 50 mm, one end of which is sharpened to a cone.
The graphite powder of high purity according to GOST 23463−79 or obtained from graphite electrodes high purity-7−4.
(as amended by Change No. 1, approved. By the decree of Gosstandart of the USSR from
Photographic plates of the spectral type II sensitivity 15 standard units according to GOST 2817−50 or photographic plates of the same type, providing a normal blackening of analytical lines and the background in the spectrum.
Photographic plates UFS-3 sensitivity of at least 16 units according to GOST 2817−50 or photographic plates of the same type, providing a normal blackening of analytical lines and the background in the spectrum.
The developer according to GOST 10691.1−84.
(as amended by Change No. 1, approved. By the decree of Gosstandart of the USSR from
Fixer: 300 g chernovetskogo sodium (GOST 27068−86) and 20 g of ammonium chloride (GOST 3773−72) was dissolved in 700 and 200 cm3 of water respectively, the resulting solutions merge together and adjusted with water to 1 dm3.
(as amended by Change No. 1, approved. By the decree of Gosstandart of the USSR from
The weighing error of 0.1 g. photoreactive
Analytical scale.
The infrared lamp of SCP-500 with voltage regulator type RNO-250−0,5 GOST 13874−83 or controller of the same type.
(as amended by Change No. 1, approved. By the decree of Gosstandart of the USSR from
Boxes of organic glass.
Mortar, agate, Jasper organic glass pestle of the same material.
(as amended by Change No. 1, approved. By the decree of Gosstandart of the USSR from
Spatulas made of organic glass.
Jars-plastic or plastic with lids with capacity of 50 — 100 cm3 sample storage comparison.
The quartz glasses with a capacity of 50 cm3.
Lead according to GOST 22861−77 or lead oxide according to GOST 9199−77.
Iron metal, reduced hydrogen, GOST 9849−86 or iron oxide on the other 6−09−5346−87.
(as amended by Change No. 1, approved. By the decree of Gosstandart of the USSR from
Zinc GOST 3640−79 or zinc oxide according to GOST 10262−73.
Bismuth GOST 10928−75 or oxide of bismuth GOST 10216−75.
Nickel GOST 849−70 or oxide of Nickel GOST 4331−78.
Copper GOST 859−78 or copper oxide under GOST 16539−79.
Cadmium GOST 22860−77 or oxide of cadmium GOST 11120−75.
Magnesium GOST 804−72 or magnesium oxide according to GOST 4526−75.
Manganese GOST 6008−82 brand Mr0 or Мр00 or manganese peroxide according to GOST 4470−79.
(as amended by Change No. 1, approved. By the decree of Gosstandart of the USSR from
Silver GOST 6836−80 or silver nitrate according to GOST 1277−75.
Hydrochloric acid of high purity according to GOST 14261−77 and diluted 1:5.
Nitric acid of high purity according to GOST 11125−84 and diluted 1:1.
(as amended by Change No. 1, approved. By the decree of Gosstandart of the USSR from
Ethyl alcohol GOST 18300−87.
(as amended by Change No. 1, approved. By the decree of Gosstandart of the USSR from
Hydrogen peroxide according to GOST 177−77.
Bromine according to GOST 4109−79 nederevyannyy and double-distilled in quartz apparatus.
Water bidistilled; prepared by distillation of distilled water in a quartz distillation apparatus.
Standard solutions.
The solution of bismuth, lead, manganese; the weight of bismuth, lead, manganese with a mass of 0.1 g was placed in a beaker with a capacity of 100 cm3, poured 20 cm3 of nitric acid (1:1) heat. Once dissolved, pour 20 — 30 cm3 of water, boiled, cooled, transferred to a volumetric flask with a capacity of 100 cm3, made up to the mark with water and mix.
1 cm3 of solution contains 1 mg of bismuth, 1 mg lead 1 mg of manganese.
The solution of cadmium, copper, Nickel; a portion of the cadmium, copper, Nickel with a mass of 0.1 g was placed in a beaker with a capacity of 100 cm3, poured 10 to 15 cm3 of a mixture of concentrated hydrochloric and nitric acids (3:1) and evaporated almost to dryness. The residue is moistened with hydrochloric acid and again evaporated to moist salts. Treatment with hydrochloric acid is repeated twice more. Then the contents of the glass moistened with hydrochloric acid, poured 20 — 30 cm3 of water, boiled, cooled, transferred to a volumetric flask with a capacity of 100 cm3, made up to the mark with water and mix.
1 cm3 of solution contains 1 mg of cadmium, 1 mg copper, 1 mg Nickel.
Solution of magnesium, zinc, iron; magnesium first washed with hydrochloric acid (1:5) (removal from the surface of magnesium oxide). Then washed 2 — 3 times with water and dried at 100 — 105 °C.
A portion of the magnesium, zinc weighing 0.1 g was placed in a beaker with a capacity of 100 cm3, poured in 10 to 15 cm3 of hydrochloric acid (1:1) and slightly heated to dissolve.
A sample of iron with a mass of 0.1 g and placed in a beaker with a capacity of 100 cm3 and dissolved by heating and stirring in 10 cm3 of concentrated hydrochloric acid with addition of hydrogen peroxide.
After dissolution in both glasses poured with 20 cm3 of water, heated, cooled, and the beaker contents are transferred in one volumetric flask with a capacity of 100 cm3, made up to the mark with water and mix.
1 cm3 of solution contains 1 mg of magnesium, 1 mg of zinc and 1 mg of iron.
Silver solution: a portion of silver with a mass of 0.1 g was placed in a beaker with a capacity of 100 cm3, poured 20 cm3 of nitric acid (1:1) heat. After dissolution, add 20 — 30 cm3 of water, boiled, cooled, transferred to a volumetric flask with a capacity of 100 cm3, made up to the mark with water and mix.
1 cm3 of solution contains 1 mg of silver.
3. PREPARATION FOR ASSAY
3.1. Sample preparation comparison
3.1.1. The main reference sample (OOS) contains 0.1% of each of the designated impurities.
In quartz Cup is placed 9,000 g of graphite powder, pour 10 cm3 of a standard solution of bismuth, lead, manganese concentration of 1 mg/cm3, 10 cm3 of a standard solution of cadmium, copper, Nickel concentration of 1 mg/cm3 and 10 cm3 of a standard solution of magnesium, zinc, iron concentration of 1 mg/cm3. The mixture is dried under a heat lamp and thoroughly mixed. Add 10 cm3 of a standard solution of silver concentration of 1 mg/cm3 and again dried under a heat lamp. Mixed with ethyl alcohol, first in a quartz Cup and then in a mortar made of organic glass, for 60 minutes dried and Again stirred for 20 min.
In order to avoid introducing dirt grinding in a mortar, and drying under a heat lamp are in the box of organic glass.
OOS can also be prepared by introducing the designated impurities in the form of oxides or nitrates.
In this case, in an agate or a Jasper mortar placed 9865,2 g of a graphite powder, is added 10.8 mg of lead oxide and 14.3 mg of iron oxide, 12.5 mg of zinc oxide, 11.1 mg of bismuth oxide, 14,1 mg of Nickel oxide, 12.5 mg of copper oxide, 11.4 mg of cadmium oxide, 16,6 mg of magnesium oxide, 15.8 mg of peroxide of manganese, and 15.7 mg of silver nitrate and triturated with ethyl alcohol for 60 min, dried under an infrared lamp, and again triturated for 20 min.
In order to avoid introducing dirt grinding in a mortar, and drying under a heat lamp are in the box of organic glass.
3.1.2. Samples OC1 — ОС10 prepare a serial dilution of OOS, and then each subsequent sample graphite powder.
The mass fraction of each of the designated impurities in samples OS1 — ОС10 and added to the mixture of sample graphite powder and diluted sample, mixing to obtain a further sample comparisons presented in table. 1.
Table 1
───────────┬────────────────┬─────────────────────────────────────
Designation│ Mass fraction │ Mass of test portions, g
end │ defined├─────────────┬───────────────────────
│ impurities, % │ graphite │ dilute sample
│ │ powder │ (in parentheses
│ │ │ symbol)
───────────┼────────────────┼─────────────┼───────────────────────
│ -2 │ │
OS1 │ 1 x 10 │ 1,800 │ 0,200 (EP)
│ -3 │ │
OS2 │ 3 x 10 │ 1,400 │ 0,600 (OC1)
│ -3 │ │
ОС3 │ 1 x 10 │ 1,200 │ 0,600 (OS2)
│ -4 │ │
OS4 │ 3 x 10 │ 1,400 │ 0,600 (ОС3)
│ -4 │ │
ОС5 │ 1 x 10 │ 1,200 │ 0,600 (OS4)
│ -5 │ │
OS6 │ 3 x 10 │ 1,400 │ 0,600 (ОС5)
│ -5 │ │
OS7 │ 1 x 10 │ 1,200 │ 0,600 (ОС6)
│ -6 │ │
ОС8 │ 3 x 10 │ 1,400 │ 0,600 (OS7)
│ -6 │ │
OS9 │ 1 x 10 │ 1,200 │ 0,600 (ОС8)
│ -7 │ │
ОС10 │ 3 x 10 │ 1,400 │ 0,600 (OS9)
Are given in table. 1 sample of the graphite powder and the diluted sample was placed in a mortar made of organic glass, carefully triturated with ethyl alcohol (ОС5 — ОС10 with ethanol, double-distilled in quartz apparatus) for 30 min and dried under an infrared lamp. Grinding in a mortar, and drying under a heat lamp are in the box of organic glass.
The samples of the comparison is stored in tightly closed cans of organic glass.
4. ANALYSIS
4.1. The concentration of impurities
1.0 g concreteras of antimony is placed in a quartz glass with a capacity of 50 cm3 and pour 3 cm3 of hydrochloric acid. Then carefully (the reaction takes place rapidly) with continuous stirring and cooling dropwise pour 2 cm3 of bromine. For cooling the beaker is placed in a vessel with cold water. At the end of the reaction the beaker cover watch glass, and moderately heated until complete dissolution of the metal. Then the watch glass is removed, washed for 0.5 — 1 cm3 with bidistilled water. The resulting solution is evaporated to a volume of 1 cm3, is added 50 mg of graphite powder and evaporated the solution to dryness. For a more complete removal of antimony in the residue moistened with 1 cm3 of hydrochloric acid, washing its walls of glass, add 1 cm3 of bromine and evaporated to dryness again. Then the glass is placed in a hotter place (the plate temperature 300 °C — 350 °C) and heated until the termination of allocation of white vapour of antimony trichloride. The analyzed sample is cooled. The obtained dry residue is a concentrate of impurities, is subjected to spectral analysis.
From each analyzed sample of antimony take the six and get six batches of concentrates for the determination of zinc and cadmium. The operation is repeated and get six concentrates for the determination of lead, iron, bismuth, Nickel, copper, magnesium, manganese and silver.
At the same time through all stages of analysis performed control experiments (three for each photographic plates) for contamination of reagents.
4.2. Spectral analysis of concentrates
To each concentrate obtained from a test sample and the reference experiment, and 50 mg each of samples comparison of OS1 — ОС10 added 2 mg of sodium chloride and stirred. Each mixture was placed into the canal of the graphite electrode with a diameter of 4 mm and a depth of 8 mm. the Electrode with the sample (or reference sample) serves as the anode (lower electrode). The upper electrode is a graphite electrode, sharpened to a cone. Between the electrodes ignite the arc DC power of 15 A. Determination of lead, iron, bismuth, Nickel, copper, magnesium, manganese, and silver is carried out on the spectrograph DFS-8 with a grating of 600 lines/mm operating in the first order. Used being the lighting system. Intermediate diaphragm 5 mm. Scale wavelengths set at 280 nm. The width of the slit of a spectrograph 20 microns. Exposure time 45 s. the Arc gap is 3 mm. the Spectra of the concentrates obtained from a test sample and control experiments, and the spectrum of each of samples comparison of OS1 — ОС10 photographed on two photographic plates, getting on each photographic plate in the spectrum of each of the three above-mentioned concentrates and samples of comparison.
Determination of zinc and cadmium is carried out by spectrograph ISP-30 when the width of the slit of a spectrograph 15 microns. The light slit to produce a three-lens Achromat condenser (first condenser f = 75 mm is not aromatizirovannaya), the intermediate diaphragm is round. For photographing use records UFS, wavelengths 210 to 240 nm. The exposure time of 45 s, the arc gap is 3 mm.
The spectra of the concentrates obtained from a test sample and control experiments, and the spectra of each of the comparison samples OS1 — ОС10 photographed on two photographic plates, getting on each photographic plate in the spectrum of each of the three above-mentioned concentrates and samples of comparison.
Photographic plates showing, washed with water, fixed, washed in running water and dried.
5. PROCESSING OF THE RESULTS
5.1. In each spectrogram, the resulting photographic plates photometric blackening of the analyzed lines determined by impurities (tab. 2) and the surrounding background and calculate the difference of pochernenija .
Table 2
──────────────────────────┬───────────────────────────────────────
The designated item │ of the wavelengths of the analytical lines, nm
──────────────────────────┼───────────────────────────────────────
Lead │ 283,30
Iron │ 248,32 or 302,10
Zinc │ of 213.85
Bismuth │ 306,77
Nickel │ 300,24
Copper │ 327,29
Cadmium │ 228,80
Magnesium │ 277,98
Manganese │ 279,48
Silver │ 328,06
5.2. From the received values are transferred to corresponding values of the logarithms of relative intensity using the data provided in the application GOST 13637.1−77.
5.3. Values and comparison of samples for build calibration graphs in the coordinate and for each impurity.
5.4. For the calibration graphs and the values of the corresponding determine for each spectrogram on the plate mass fraction of impurities () in concentrate excluding control experiments without regard to the degree of concentration and mass fraction of impurities in the concentrate a control of the experience.
5.5. Calculated is the arithmetic mean of the results of the three definitions on each photographic plate.
5.6. Mass fraction of impurities With the interest calculated according to the photometry data of the same spectrogram on the plate (the result of one definition) is calculated according to the formula
,
where is the mass of the sample graphite powder collector is equal to 0.050 g;
— the weight of antimony, g;
and — mass fraction of impurities, determined by PP. 5.4 and 5.5.
The result of the analysis is defined as the arithmetic mean of the results of the six individual definitions from two photographic plates.
The difference between the largest and smallest results of six parallel measurements obtained at the two photos at confidence probability P = 0,95, shall not exceed the allowable absolute differences calculated by the formula:
,
where is the arithmetic mean of the six results of parallel measurements obtained on two photographic plates.
(as amended by Change No. 1, approved. By the decree of Gosstandart of the USSR from
The difference between two results of analysis of the same samples at a confidence probability P = 0.95 does not exceed the allowable absolute differences calculated by the formula:
,
where — the average of the two results of the analysis.
(paragraph as amended by Change No. 1, approved. By the decree of Gosstandart of the USSR from
