GOST 16274.1-77

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  ГОСТ 16274.1-77

GOST 16274.1−77 Bismuth. Method of chemical-spectral analysis (with Amendments No. 1, 2, 3)

GOST 16274.1−77

Group B59

STATE STANDARD OF THE USSR

BISMUTH

Method of chemical-spectral analysis

Bismuth. Spectrochemical analysis

AXTU 1709

Date of introduction 1978−01−01

INFORMATION DATA

1. DEVELOPED AND INTRODUCED by the Ministry of nonferrous metallurgy of the USSR

DEVELOPERS

PS Poklonsky, F. M. Manji, G. V. Khabarova

2. APPROVED AND promulgated by the DECREE of the State Committee of standards of Ministerial Council of the USSR from 25.01.77 N 172

3. The frequency of inspection 5 years

4. INTRODUCED FOR THE FIRST TIME

5. REFERENCE NORMATIVE AND TECHNICAL DOCUMENTS

6. Resolution of the state standard from 30.07.92 N 836 removed the limitation of the validity period

7. REPRINT (July 1997) with Amendments No. 1, 2, 3, approved in January 1983, June 1987, July 1992 (IUS 5−83, 11−87, 10−92)


This standard applies to the grades Vi00 bismuth, Ви000, Ви0000 and installs chemical-spectral method of determination of lead, zinc, iron, antimony, copper, silver, arsenic, cobalt, cadmium, manganese, molybdenum, Nickel, tin, chromium and India.

Chemical impurities concentrate for the determination of molybdenum and arsenic (from 5·10to 1·10%), tin (from 1·10to 1·10%) and antimony (from 3·10to 1·10%) is produced by separating the main mass of bismuth in the form of iodide of bismuth.

Chemical admixtures for concentrate for determination of iron, lead and zinc (from 5·10to 1·10%), cadmium, manganese, copper, Nickel and silver (from 3·10to 1·10%), India, cobalt and chromium (from 1·10to 1·10%) is produced by separating the main mass of the bismuth as basic nitrate of bismuth.

Chemical admixtures for concentrate for determination of iron, indium, cobalt, copper, manganese, Nickel, lead, chromium, zinc, tin and antimony (from 1·10to 1·10%) is obtained by pyrometallurgical slag processes based on the extraction of impurities in the slag at treatment of molten metal with a mixture of the gaseous reactants: air, water vapor, argon, and hydrochloric acid fumes.

(Changed edition, Rev. N 1, 2).

1. GENERAL REQUIREMENTS

1.1. General requirements for method of analysis according to GOST 16274.0.

2. APPARATUS, REAGENTS AND SOLUTIONS

The quartz type spectrograph ISP-30 (complete set).

Arc generator AC type IVS-28.

A constant current source to power the arc, providing a voltage of 200−400 V and the current to 15 A.

Microphotometer designed to measure pucherani spectral lines.

Electrodes, carbon, high purity 7−4 with a crater depth and diameter 4 mm and wall thickness of 0.5 mm, pre-baked in the arc of DC power 12 And for 15 S.

The machine tool for sharpening of electrodes.

Spectrographic plates size 9x12 cm types I, II and UFS.

Caps glass storage cleaned and loaded electrodes.

Tweezers and pads for electrodes of organic glass.

Graphite powder of high purity according to GOST 23463.

Tile electrical heating appliances according to GOST 14919 with a closed spiral.

Quartz conical flasks according to GOST 19908 capacity of 600−800 cm.

Quartz glasses according to GOST 19908 capacity 300−350, 600−800 cm.

The quartz crucible according to GOST 19908.

Sticks and pestles quartz.

Burette glass for NTD with a capacity of 50 cm, filled before use.

A quartz distillation apparatus.

Magnetic stirrer with heating.

Nitric acid of high purity according to GOST 11125, distilled in quartz apparatus, which does not contain nitrogen oxides (the nitrogen oxides are removed by boiling before work) and diluted 1:1, 1:2, 1:100, and solutions 1, 2 and 6 mol/DM.

Distilled water according to GOST 6709, distilled twice in a quartz distillation apparatus or demineralized on the cation exchanger KU-2 and anionite EDE-10P at a speed of 50−60 DM/h (the height of the columns of 500−600 mm, diameter 85 mm, the resistivity of water is not less than 11·10Ohm/cm).

Itestosterone acid according to GOST 4200, H. h, does not contain free iodine, and arsenic. Acid purified in the following manner: within 7−10 days insist acid with a small amount of red phosphorus powder to lighten it. Before operation the clarified acid is purified from arsenic by extraction with benzene. For this 50−60 cmacid 1 min. and extracted with three portions of benzene at 10.0 cmeach. Then acid is distilled in a distillation apparatus, collecting the fraction at 124−127 °C (take the average portion of 78−80% of the total number, but the first and last portion of the drop).

The concentration itestosterone acid set by titration with sodium hydroxide solution 1 mol/DMwith the indicator phenolphthalein.

Sodium hydroxide according to GOST 4328, solution 1 mol/DM.

Red phosphorus technical GOST 8655.

Phenolphthalein on the other 6−09−5360.

Ammonia water according to GOST 24147, solution 1 mol/DM.

Hydrochloric acid according to GOST 14261.

Antimony brand Su000 according to GOST 1089.

Manganese nitrate on the other 6−09−4011.

Potassium permanganate according to GOST 20490.

Silver nitrate according to GOST 1277.

Arsenious anhydride according to GOST 1973.

Tartaric acid according to GOST 5817.

Benzene according to GOST 5955.

Decison for NTD.

Carbon tetrachloride according to GOST 20288.

Potassium dichromate according to GOST 4220.

Ammonium molybdate according to GOST 3765.

Manganese GOST 6008.

Indium GOST 10297.

Tellurium on the other 6−04−65.

Lead according to GOST 22861.

Zinc GOST 3640.

Iron, the reduced hydrogen.

Copper according to GOST 859*.
_______________
* On the territory of the Russian Federation GOST 859−2001. — Note the manufacturer’s database.

Cobalt GOST 123*.
_______________
* On the territory of the Russian Federation GOST 123−2008. — Note the manufacturer’s database.

Nickel GOST 492*.
_______________
* On the territory of the Russian Federation GOST 492−2006. — Note the manufacturer’s database.

Gold GOST 6835*.
______________
* On the territory of the Russian Federation GOST 6835−2002. — Note the manufacturer’s database.

Standard solutions for sample preparation comparison and the composition of the samples of the comparison is given in the Appendix.

Installation for concentrating impurities by the method of «pyrometallurgical slagging», consisting of four blocks:

Unit 1 unit regulate the flow of gases; it consists of two rheometers, filled with water and adjusted to a flow rate of air and argon and the mixing of gases.

Unit 2 unit evaporation; consists of three vessels made of quartz glass, and two heaters (stove and oven). The vessel for the formation of water vapor with a capacity of 1000−1500 cmhas a cone with tubes for inlet and outlet gases. Vessel for partial condensation of the excess steam with a capacity of 100−200 cmhas a socket with two holes for inlet and outlet gas mixture. The container-dispenser of hydrochloric acid with a capacity of 20−25 cmwith a glass stopper for pouring acid and two taps for the inlet and outlet gas mixture.

Unit 3 — block a reaction vessel with condensate receivers. Consists of a reaction vessel, heating furnace, condensate receivers, which are equipped with refrigerators, running water.

Unit 4 — control unit; consists of a system of valves, pump type MK-1, two millivoltmeters of the M 4213, two ammeters type e 421, three autotransformers type CTL-250−2.

Tripods, holders, stands.

Argon in cylinders.

Note. Allowed the use of devices with photovoltaic spectra and other spectral instruments, other reagents, materials, photographic plates, generating accuracy metrics defined in this standard.


(Changed edition, Rev. N 1, 2, 3).

3. PREPARATION FOR ASSAY

3.1. Sample preparation comparison is given in the Appendix.

(Changed edition, Rev. N 2, 3).

3.2. The concentration of impurities of tin, arsenic, molybdenum, antimony, separation of the main mass of bismuth in the form of iodide.

For analysis take two sample of bismuth 20 g and placed in a quartz conical flask with a capacity of 600−800 cm, is added to 100 cmof solution nitric acid 6 mol/l, and dissolved by heating.

After complete dissolution of the metal is obtained a solution of nitrate of bismuth is boiled for several minutes to remove loose oxides of nitrogen that interfere with the precipitation of iodide of bismuth.

Chilled solutions was diluted to 300 cmnitric acid, diluted 1:100 do not contain free nitrogen oxides, and pour the calculated stoichiometric amount of a solution of freshly prepared acid itestosterone 6−8 mol/land 0.2−0.5 cmit in excess for complete precipitation of bismuth.

During the deposition of iodide of bismuth should the walls of the flasks to be washed with water acidified with nitric acid (3 drops by 100 cm), after each added portion (2−3 cm) itestosterone acid. The total amount of water used for washing the walls of the flasks, 60−70 cm.

The cessation of deposition of black sludge when adding the next drop itestosterone acid indicates the complete precipitation of bismuth. Add itestosterone acid in excess of more than 1 cmis not recommended, as the precipitate of bismuth iodide dissolves in excess itestosterone acid with formation of soluble complex.

The volume of the solutions in the flasks was adjusted with water to 500 cm, mix and leave in a dark place for 3 h. Then gently, without affecting the sediment, the solutions from the flasks is poured into quartz glasses, which are inscribed with the marks of volume, and measure their volumes (480 cm). The solutions were evaporated in a preheated and weighed quartz bowls. Dry residues nitrate of bismuth is weighed and converted to the spectral-pure oxide of bismuth, by multiplying by the conversion factor equal to 0.6. Enrichment of lead from two parallel batches.

For spectral analysis it is necessary to 130−150 mg of spectral pure bismuth oxide. If the balance is less than this value, then it is corrected cleared spectral-pure bismuth oxide or residue from a flask as follows: to the dry residue pour 2−3 cmof nitric acid, add the desired number of spectral-pure bismuth oxide, stirred, evaporated and carefully dried. The resulting concentrate is calcined at a temperature of 500−550 °C for 30 min. Calcined concentrates are weighed and ground quartz with the pestle in the same cups. Then add the sample spectral pure graphite powder, taken in the ratio from spectral-pure oxide of bismuth, 5:1 (by weight). The mixture was thoroughly stirred and transferred to a spectral analysis.

The enrichment coefficient of the impurity () is calculated by the formula

,

where  — the weight of the portion of the sample of bismuth taken for analysis, g;

0,96 — conversion factor mass of sample of bismuth taken for analysis, including 20 cmof solution remaining inside the precipitate of iodide of bismuth (500 cm — 480 cm=20 cm);

 — the weight of the portion of the obtained concentrate, g;

0,897 — the ratio of bismuth oxide to bismuth.

Simultaneously prepare a control sample. In a quartz Cup with a capacity of 300−350 cmis added (with a uniform evaporation) all the reagents in the quantities added to the samples. The solution was evaporated to small volume, add 140 mg of spectral bismuth oxide, dried and calcined at 500−550 °C for 30 min. Calcined mixture of bismuth is mixed with spectral pure graphite powder in the same proportions and in the same manner as the sample.

For the quantitative determination of a control sample to calculate the enrichment coefficient () by the formula

,

where the amount of bismuth taken for enrichment, g;

 — the number of spectral-pure oxide of bismuth introduced in the test sample, g;

0,897 — ratio spectral-pure bismuth oxide to bismuth.

Notes:

1. Before the deposition of bismuth in the form of iodide solution test should be completely transparent and should not contain the free oxides of nitrogen. The appearance of turbidity of the basic nitrate of bismuth is necessary to add 0.5−1 cmof concentrated nitric acid.

2. (Deleted, Rev. N 2).

3. To withstand precipitate of iodide of bismuth in a period of 4−5 h is required for recrystallization of the precipitate. To leave a residue the next day is not recommended due to possible oxidation.

4−6. (Deleted, Rev. N 2).


(Changed edition, Rev. N 1, 2, 3).

3.3. The concentration of impurities of copper, silver, lead, Nickel, manganese, cadmium, zinc, chromium, cobalt, indium and iron. The separation of the main mass of the bismuth as basic nitrate.

Weighed sample of bismuth 10 grams are placed in a quartz flask with a capacity of 500 cm, 45 cm pournitric acid, diluted 1:2, dissolved under low heat, evaporated to syrupy state and poured 100 cmof hot water. Thus fall a white precipitate. The precipitation of the basic nitrate produces in a solution of ammonia of 1.2 mol/DM. For this, the flask with the solution set on the magnetic stirrer, the heating is switched, the flow from the burette drop by drop ammonia and the precipitated basic nitrate with good stirring. At pH 2−3, the deposition is stopped.

The residue should be crystalline and easy to settle. Solution and the precipitate was allowed to stand for 25−30 min, then the solution was poured in a suspended myprivatekey Cup, and the residue washed with water, acidified with nitric acid to pH 2−3. After settling for 20−25 min. drained wash solution in the same Cup. The solution is carefully evaporated under low heat to a volume of 10−20 cm, Cup close watch glass and evaporate the solution to dryness. Watch glass is removed from the cups, using quartz blades scraped him in a Cup of the bulk of the condensed salts. Glass and the walls of the Cup is washed with 3−4 cmof nitric acid and again evaporated to dryness. The residue is calcined on a hot stove, and then in a muffle at a temperature of 500−550 °C for 45 min and weighed.

Through all stages of the analysis spend control experience. As the basis for it is used the oxide of bismuth in an amount of 100 mg.

The enrichment coefficient of the impurity () is calculated by the formula

,

where  — the weight of the portion of the sample of bismuth taken for analysis, g;

0,897 — ratio spectral-pure bismuth oxide to bismuth.

Concentrates are analyzed and control samples are mixed with graphite powder in a ratio of 5:1 (by weight) and transferred to a spectral analysis.

Enrichment of lead from the four parallel batches.

(Changed edition, Rev. N 1, 2).

3.3. The concentration of impurities of iron, indium, cobalt, copper, manganese, Nickel, lead, chromium, zinc, antimony and tin pyrometallurgical method of slagging. A sample of bismuth with a mass of 100 g is placed in a reaction vessel. Steam generator and vessel for mixing gases is filled with water. In the container-dispenser pour 3−5 cmof hydrochloric acid. The reaction vessel attached receivers condensate impurities, which poured 20 cmof nitric acid solution 1:1. Connect all the blocks. Installation in 10−15 minutes rinsed with argon with a speed of 10−20 cm/ min. Water in the steam generator is heated to the boil and include a furnace heating the reaction vessel. Connect the compressor and delivers air at a speed of 2 cm/min Flow of argon and air are strictly controlled by rheometer. Treatment of molten metal with a gas mixture (argon, water vapor, air) is carried out at a temperature (430±10) °C for 90−100 min, Then the furnace temperature is reduced to (300±10) °C, connect the oven to preheat hydrochloric acid and treated molten metal with a gas mixture another 90−100 min. Compressor off, disconnect the receivers condensate impurities and a pipette from the reaction vessel and stop the flow of argon. The reaction vessel with the sample is removed from the oven, open the lid and pour 5−6 cmof glycerin. For better separation of slag from the surface of the metal vessel is gently shaken. The vessel is then set at an angle to the solidification of the metal in the form of long sticks. After complete solidification of the metal and the vessel is washed with 10 cmof hot water, which is then together with the glycerin is drained into the beaker for evaporation. Cleaning the slag from the metal vessel and repeat the hot water from prominance and condensates 1 and 2. All the washing solutions were poured into the same beaker. The solution was evaporated on a hotplate to a volume of 20−25 cm, transferred quantitatively in a suspended quartz Cup and evaporated to dryness. The sediment and the Cup is treated with two portions of 7−10 cmof nitric acid solution 1:1 to clarification of the precipitate, the solution was evaporated to dryness, calcined on a hot plate and in a muffle furnace at a temperature (530±20) °C for 15 min.

The resulting concentrate of impurities is weighed and calculated the enrichment coefficient () by the formula

,

where is the mass of a bismuth sample taken for analysis, g;

the weight of the concentrate, g;

0,897 — the ratio of bismuth oxide to bismuth.

Enrichment of lead from two parallel batches.

Conduct control experience for inclusion in the analysis result of the amendments, taking into account the purity of the used reagents and testing conditions. To do this, in the reaction vessel instead of 100 g of bismuth load of 1.0 g bismuth oxide used for preparation of samples comparison, all the operations carried out as described above using the same reagents.

The enrichment coefficient in the reference experiment () is calculated by the formula

,

where is the mass of a bismuth sample taken for analysis, g;

1,0 — its weight of oxide of bismuth, taken for the reference experiment,

(Changed edition, Rev. N 2, 3).

4. ANALYSIS

Carbon electrodes are pre-fired in an arc, the DC power of 12 And for 15 s. Samples comparison, concentrates analyte and the reference sample loaded into the crater of the carbon electrode. From each concentrate sample and in the reference experiment prepare two electrodes. Survey spectra to produce the spectrograph of the ISP-30 under the following conditions: slit width of 0.010 mm, the illumination slits being. The sample is burned in the arc DC to full burning power 12−13 A.

For optimum analytical lines pucherani photographing is carried out simultaneously on the plate of three types: type I (region 440,0−390,0 nm), type II (for the area 390,0: 270.0 cm nm) and UFS-3 (for area: 270.0 cm-of 210.0 nm).

(Changed edition, Rev. N 1, 2, 3).

5. PROCESSING OF THE RESULTS

5.1. Processing of the results is produced according to GOST 16274.8.

Obtained according to the calibration schedule results divided by a factor of enrichment of the sample.

The analytical lines of the determined elements are shown in table.2.

Table 2*

________________
* Table.1 excluded.

Discrepancies in the results of two parallel measurements () and the results of two tests () at a confidence probability of 0.95, should not exceed the permissible differences given in table 3.

Table 3

Permitted discrepancies for the intermediate mass fraction of impurities calculated using linear interpolation or according to the formulas:

1. The separation of the iodide of bismuth:

2. The separation of the basic nitrate of bismuth:

in the determination of Nickel and cobalt;

when you define India, manganese, lead, silver and zinc;

in the determination of iron, cadmium, copper and chromium.

3. In the pyrometallurgical slagging:

in the determination of iron, cobalt, manganese, lead and zinc;

in determining copper, Nickel, tin, antimony, and chromium;

when you define India,

where is the arithmetic mean of the results of the two analyses.

 — the arithmetic mean of the results of parallel measurements.

The analysis result should be the arithmetic mean of two parallel definitions for the two spectrograms each received on the same photographic plate.

(Changed edition, Rev. N 3).

APP (mandatory). PREPARATION OF STANDARD SOLUTIONS AND SAMPLES FOR CONSTRUCTING THE CALIBRATION GRAPHS

APP
Mandatory

1. Standard solutions

To prepare the standard solutions using a metal-containing basic substance is not less than 99.99%, or metal salts of a qualifying OS.h. or H. h

Standard iron solution

Solution a: 0,5000 g of iron, reduced hydrogen, transferred to a beaker with a capacity of 50−100 cmand dissolve in low heat in 20 cmof nitric acid solution 1:1. After complete dissolution of the iron solution is brought to a boil to remove oxides of nitrogen, cooled, transferred to a volumetric flask with a capacity of 100 cm, adjusted to the mark with water, mix.

1 cmof the solution contains 5 mg of iron.

Solution B: 20 cmiron mortar And transferred to a volumetric flask with a capacity of 100 cm, adjusted to the mark with water, mix.

1 cmof the solution contains 1 mg of iron.

Standard solutions of indium, cadmium, cobalt, manganese, copper, Nickel, silver, lead, tellurium, and zinc is prepared in the same way as the solution of iron.

1 cmof each of these solutions And contains 5 mg of the metal.

20 cmeach of the solutions And transferred to a volumetric flask with a capacity of 100 cm, adjusted to the mark with water, mix.

1 cmeach of the solutions B contains 1 mg of metal.

A standard solution of molybdenum

0,2251 g of ammonium molybdate (NH)MoOis transferred to a beaker with a capacity of 50−100 cmand dissolved in 10 cmof water, bring to the mark with water, mix.

1 cmof the solution contains 1 mg of molybdenum.

A standard solution of tin

0,1000 g of finely chopped tin metal was transferred to a beaker with a capacity of 50−100 cm, add 4 g of oxalic acid and 2−3 cmof nitric acid. Dissolution is cold, then with a small heating. After complete dissolution add 10 cmof water and transferred to a volumetric flask with a capacity of 100 cm, adjusted to the mark with water, mix.

1 cmof the solution contains 1 mg of tin.

Standard solutions of antimony

0,5000 g finely ground antimony is transferred to a beaker with a capacity of 50−100 cmand add 20 cmof nitric acid. The glass is heated to complete the transfer of all of the antimony in measuremenu acid. Not stopping heating, add 30 cmof water and 15 g of tartaric acid. The obtained clear solution is transferred to a volumetric flask with a capacity of 100 cm, adjusted to the mark with water, mix.

1 cmof the solution contains 5 mg of antimony.

20 cmof a solution of antimony And transferred to a volumetric flask with a capacity of 100 cm, adjusted to the mark with water, mix.

1 cmof the solution contains 1 mg of antimony.

Standard solution chromium

0,2923 g chromological ammonium (NH)SGOntransferred to a beaker with a capacity of 50−100 cmand dissolved in 10−15 cmof water, the solution transferred to a volumetric flask with a capacity of 100 cm, adjusted to the mark with water, mix.

1 cmof the solution contains 1 mg of chromium.

Standard solution of arsenic

0,1320 g arsenic trioxide AsOwas transferred to a beaker with a capacity of 50−100 cmand dissolved in 15−20 cmof water with a few drops of ammonia in low heat. The solution was transferred to a volumetric flask with a capacity of 100 cm, adjusted to the mark with water, mix.

1 cmof the solution contains 1 mg of arsenic.

A standard solution of gold

0,1000 g of metallic gold was transferred to a beaker with a capacity of 50−100 cmand dissolved in 10 cmmixture of nitric and hydrochloric acids is 1:3. The solution was evaporated almost to dryness, pour 1−2 cmof hydrochloric acid and again evaporated on a water bath almost to dryness. Add 15−20 cmof hydrochloric acid diluted 1:1, transferred to a volumetric flask with a capacity of 100 cm, adjusted to the mark with water, mix.

1 cmof the solution contains 1 mg of gold. Store the solution in dark place.

2. References

The basis for the preparation of samples of comparison is the oxide of bismuth derived from bismuth brands Ви0000 or Ви000 as follows: finely powdered bismuth is dissolved in nitric acid solution 1:1. The resulting solution of nitrate of bismuth is evaporated to a syrupy condition and poured in small portions (5−10 cm) with careful stirring in a conical flask with a capacity of 1 DMcontaining 600−700 cmof boiling water. In a precipitate of the basic nitrate of bismuth. For better crystallization of the contents of the flask again, bring to the boil and leave for 2−3 h. the Solution is decanted. The precipitate is washed with water, acidified with nitric acid and transferred to a quartz Cup. Dried and calcined in a muffle furnace at a temperature of 500−550 °C. the resulting oxide of bismuth to be stored in a closed jar.

Sample comparison N 1: a quartz Cup with a capacity of 100 cmwill prevent 11,1482 g bismuth oxide, and adding the standard solutions of the designated impurities except a standard solution of arsenic, in amounts specified in table.1.

Table 1

Solutions of impurities are introduced gradually, after drying the previous batch. The mixture was evaporated under a lamp, dry it on the hotplate, and calcined in a muffle furnace at a temperature of 500−550 °C for 30−40 minutes, carefully grind in a mortar made of Plexiglas.

Sample comparison N 1 M for the determination of arsenic is prepared as follows: in a quartz Cup with a capacity of 100 cmis placed 11,1482 g of bismuth oxide and add 10 cmof a standard solution of arsenic. The mixture is dried and ground in a mortar. Mass fraction of arsenic in sample, N 1 M is about 0.1%, based on bismuth metal.

The method of successive dilution of the samples compare the NN 1 and 1 M and each of the subsequent basis of 2−3 times getting two series of work samples comparison with a mass fraction of impurities, given in table.2.

Table 2

Each of the prepared samples comparison, is mixed with powder graphite in a ratio of 5:1 (by weight). Samples stored for comparison in buksh or in cans with lids for 1 year.

App. (Changed edition, Rev. N 2, 3).