GOST 12645.4-77

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  ГОСТ 12645.4-77

GOST 12645.4−77 indium. Chemical-spectral method for the determination of aluminium, bismuth, cadmium, copper, manganese, Nickel, lead, silver and zinc (with Amendments No. 1, 2, 3, 4)

GOST 12645.4−77

Group B59

STATE STANDARD OF THE USSR

INDIUM

Chemical-spectral method for the determination of aluminium, bismuth,
cadmium, copper, magnesium, manganese, Nickel, lead, silver and zinc

Indium. Chemicospectral method for determination of aluminium, bismuth,
cadmium, copper, magnesium, manganese, nickel, lead, silver and zinc

AXTU 1709

Date of introduction 1978−07−01

INFORMATION DATA

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

DEVELOPERS

A. P. Sychev, L. K. Larina (supervisor), M. G. Saun (supervisor), V. N. Makarceva, N. With. References: E. V. Lisitsyn, N. Romanenko, V. A. Kolesnikov

2. APPROVED AND promulgated by the Decree of the State Committee of standards of Ministerial Council of the USSR from 08.07.77 N 1715

Change No. 3 adopted by the Interstate Council for standardization, Metrology and certification 15.03.94 (report of the Technical Secretariat N 1)

The adoption voted:

3. REFERENCE NORMATIVE AND TECHNICAL DOCUMENTS

4. Limitation of actions taken by Protocol No. 3−93 Interstate Council for standardization, Metrology and certification (ICS 3−6-93)

5. REPRINT (January 1998) with Amendments No. 1, 2, 3, approved in February 1983, December 1987-June 1996 (IUS 5−83, 3−88, 9−96)

The Change No. 4 adopted by the Interstate Council for standardization, Metrology and certification (minutes dated 28.05.99 N 15). The state developed by Russia. By the resolution of Gosstandart of Russia from 19.04.2001, N 184th St 01.01.2002

N 4 a change made by the manufacturer of the database in the text ICS N 7, 2001

This standard specifies the chemical-spectral method for the determination of aluminium, bismuth, cadmium, copper, magnesium, manganese, Nickel, lead, silver and zinc in India to mass fractions in percent:

There are two method

Method A is based on preliminary chemical concentration of the impurities by separation of the main quantity of India extraction -dichloroethylene with ether (hloreksa) in the form of bromide from solution bromatological acid concentration of 8 mol/DM. The solution containing the impurities, is evaporated on graphite powder containing 4% of sodium chloride.

Method B is based on a preliminary chemical concentration of the impurities by separation of the main quantity of indium extraction with diethyl ether in the form of a bromide of indium from solution bromatological acid concentration of 5 mol/DM. The solution containing the impurities, is evaporated on graphite powder containing 5% indium oxide.

Spectral determination of impurities in the concentrate based on the measurement of pochernenija lines of impurities and the background in the arc spectrum obtained by evaporation of samples from hole carbon electrode (anode) in the flame of the arc DC.

(Changed edition, Rev. N 1, 2, 3).

1. GENERAL REQUIREMENTS

1.1. General requirements for method of analysis and security requirements — according to GOST and GOST 12645.0 22306.

2. APPARATUS, REAGENTS AND MATERIALS

The quartz spectrograph medium dispersion of any type that allows for one exposure to a range of up to 225,0 400,0 nm, being equipped with an illumination system of the slit and the three-step and nine-the attenuators.

The diffraction type spectrograph DFS-8 (first order), being equipped with a lighting system or slit spectrograph STE-1.

A constant current source providing the voltage to 200 V and currents up to 20 A, type PN-145, 2ВН-20 etc.

The arc generator is activated to ignite types of PS-39, DG-2, IVS-28 with an external resistor for operation at power current 15 A.

Microphotometer designed to measure pucherani spectral lines.

Libra torsion bar type W with a weighing error of no more than 0.001 g.

Analytical scale with a weighing error of no more than 0,0002 g.

The infrared lamp of any type with laboratory auto-transformer type CTL-250−2.

Hot plate with thermostat.

Quartz instrument for the distillation of reagents (acids, dihloretilaminovogo ether, alcohol).

Mortar made of organic glass.

Quartz tableware (glasses, cups, crucibles, separating funnels) according to GOST 19908.

Boxes of organic glass.

Column organic glass or fluoroplastic ion exchange water purification.

The knife of tantalum.

Electrodes of graphite rods of high purity with a diameter of 6 mm with the size of the crater 4x3 mm and grade C-3 with crater size 4x4 mm.

Graphite powder of high purity according to GOST 23463 or derived from graphite rods of high purity.

Sodium chloride of high purity.

Distilled water according to GOST 6709, thrice distilled or purified on a column of ionization.

The air -dialogically (hloreksa), cleaned as follows: in a separating funnel hloreksa washed three times with hydrochloric acid (Hcl)=3 mol/DM, then twice with water. After the last wash is left in the funnel overnight for delamination. Then distilled twice in a quartz apparatus (collected fraction, boiling at 175−178 °C. glycerol Bath).

Bromatologia acid according to GOST 2062, three times distilled, the solution (NVG)=8 mol/DM. The concentration bromatological acid set titration with a solution of hydrate of sodium oxide.

The technical rectified ethyl alcohol according to GOST 18300.

Sodium hydroxide according to GOST 4328.

Bromine according to GOST 4109, distilled in a quartz apparatus in a water bath at a water temperature of (60±5) °C (collecting bromine under water in a quartz cones).

Hydrochloric acid according to GOST 3118, solution (Hcl)=3 mol/DM.

Photographic plates spectrographic types SFC-02, the SFC-03, PFS-04, NT-2SV and slide.

Samples comparison to method A. the basis for the preparation of samples comparisons and collector impurities is graphite powder with the addition of 4% sodium chloride (in the determination of zinc and cadmium, and 0.1% of sodium chloride).

Samples comparison to method B. the Basis for the preparation of samples comparisons and collector impurities is graphite powder with the addition of 5% indium oxide.

The purity of the prepared bases check by the spectral method under specified conditions of analysis.

The main sample is prepared by introducing 10 g of the basis of the calculated amount of solutions of metals (table.1A), prepared according to Appendix 1.

Table 1a

The sample was dried under a heat lamp and carefully grind in a mortar made of organic glass by diluting the primary and the newly prepared samples of comparisons a-based get series of working samples of the comparison in accordance with the table.1B.

Table 1B

The basis and references stored in buksh or tightly closed jars.

Diethyl ether (medical).

India oxide of high purity.

Note. Allowed the use of plasma with inductive coupling as a source of excitation spectra, and the use of devices with photovoltaic spectra and other spectral instruments, other reagents and materials, providing the accuracy that rivals regulated in this standard.


Sec. 2. (Changed edition, Rev. N 2, 3).

3. ANALYSIS

3.1. The chemical concentration of the impurities by the method And

The weight India weight 0,500−1,000 g (in the determination of cadmium and zinc in India brand Ин000 weight of 2,000 g) was placed in a quartz Cup with a capacity of 20−50 cm, pour 5 cm(for hanging of India 2,000 g — 10 cm) solution bromatological acid concentration of 8 mol/DMand dissolve the metal when heated on a hot plate with thermostatic control (temperature must not exceed 90 °C). The resulting solution was evaporated to dryness, the residue is dissolved in 7 cmof solution bromatological acid concentration of 8 mol/DM, translate the solution into a separating funnel and wash the remaining solution from the walls of the Cup 3 cmof a solution bromatological acid. There add 10 cm(for hanging of India 2,000 g — 20 cm) -dihloretilaminovogo ether and gently shake the funnel for 1−2 minutes After standing until complete disappearance of the air bubbles and the aqueous layer drained into another separating funnel and repeat twice extraction India 10 cm-dihloretilaminovogo ether. For obtaining colored organic layer before each extraction with a separating funnel, add 1−2 drops of bromine. Acidic solution was transferred to a quartz Cup, add 40 mg of carbon powder, evaporated the solution under an infrared lamp to dryness, wash the dry residue from the walls of the Cup a small amount (1.5 cm) of water, and again evaporated to dryness. The dry residue is mixed with 10 mg of graphite powder containing 20% of sodium chloride, and transferred to a spectral analysis. Enrichment of lead from three, in the determination of cadmium and zinc in six parallel batches. In the determination of zinc and cadmium, two concentrate of impurities are combined and evaporated to 100 mg of carbon powder containing 0.1% of sodium chloride. Simultaneously with the preparation of samples through all stages of the analysis carried out control and experience on all the reagents in the presence of pre-cleaned bromide India.

To carry out control experience in a quartz Cup poured 5 cmbromatological acid (HBR)=8 mol/DMand evaporated to a volume of 0.5−1 cm. Add another 10 cmof the same solution bromatological acid and transfer the solution into the separatory funnel, which add 10 cm-dihloretilaminovogo of ether and the extraction is carried out three times. After the third extraction the aqueous phase is decanted into a quartz Cup, podparyvajut under the lamp to remove vapors of bromine and makes 50 mg of graphite powder. The solution was evaporated to dryness, add 1 cmof water and again evaporated. The dry residue is dried under an infrared lamp for 30 min and transferred to a spectral analysis.

The same hloreksa can be used for extraction India five times, each time conducting a regeneration according to the method given in Appendix 2.

(Changed edition, Rev. N 2, 3, 4).

3.2. Spectral analysis of the concentrate of impurities

3.2.1. The source excitation spectrum is an arc of DC power between 15 And vertically set with graphite electrodes. The electrodes are pre-anneal for 15 s in the arc of a DC power of 15 A.

(Changed edition, Rev. N 1).

3.2.2. Terms of spectrographically in the determination of aluminium, bismuth, copper, magnesium, manganese, Nickel, lead and silver

From each concentrate sample, reference experiment and reference sample taken at the two sample mass of 20 mg and placed in the crater of the lower electrode (anode) with a depth of 4 and a diameter of 4 mm. the Upper electrode sharpened to a truncated cone with the diameter of the pad is 2 mm.

The spectra photographed with a quartz spectrograph medium dispersion being a condenser and a slit width of 0.015 mm using a three-step attenuator. The exposure time of 20 s. an Analytical range from 2.5 to 3.0 mm.

In the spectral region from 200 to 230 nm, using photographic plates types SFC-03, PFS-04, NT-2SV, in the spectral region from 230 to 310 nm — photographic plates of type SFC-02, the SFC-03, NT-2SV, in the spectral region from 310 to 400 nm — photographic plates of type SFC-01.

3.2.3. Terms of spectrographically in the determination of zinc and cadmium

From each concentrate sample, reference experiment and reference sample taken at the two sample mass of 45 mg and placed in the crater of the lower electrode (anode) depth and diameter of 4 mm. the Upper electrode is a truncated cone. The spectra photographed using a diffraction spectrograph DFS type-8 (first order) or spectrograph STE-1 being the illumination system of the slit. The width of the slit of a spectrograph 0.020 mm, exposure time 8−10 s. photographic Plates types SFC-02, the SFC-03, NT-2SV.

3.2.2, 3.2.3. (Changed edition, Rev. N 2, 3).

3.3. The chemical concentration of the impurities by the method B

Weighed India (before weighing the sample India is washed with hydrochloric acid concentration of 6 mol/l, washed with deionized water) weighing 1,000 g was placed in a quartz Cup with a capacity of 20−50 cm, 5 cm pour thesolution bromatological acid concentration of 8.5 mol/DM, cover the quartz Cup with a lid and dissolve by heating on a hot plate with thermostatic control (temperature must not exceed 90 °C). The resulting solution was evaporated to dryness, the residue is dissolved in 3 cmof a solution bromatological acid concentration of 5 mol/DM.

The cooled solution was transferred to a separating funnel, washing the Cup with 2−3 cmof this solution bromatological acid. For the extraction of indium in the separatory funnel add 5 cmof diethyl ether and vigorously shaken for one minute. After separation of the liquids, the aqueous layer drained into another separating funnel and repeat the extraction two more times the same amount of diethyl ether.

Acidic solution was transferred to a quartz Cup, add 40 mg of graphite powder, evaporated to dryness at a temperature of about 100 °C under an infrared lamp. The obtained dry residue is mixed with 10 mg of graphite powder containing 25% indium oxide, and is transmitted to spectral analysis.

At the same time through all stages of the analysis carried out control experience for an amendment to the pollution of the reagents in the presence of pre-cleaned bromide India. For this purpose, resulting in the analysis of the ether extract of bromide India, which for the complete removal of the ether was transferred to a quartz Cup and evaporated in a water bath with hot water (without heating).

Analysis of each sample India carried out from 3 parallel batches.

(Added, Rev. N 3. Changed the wording, Rev. N 4).

3.3.1. Spectral analysis of the concentrate of impurities

The concentrates obtained from the analyzed samples, concentrates in the reference experiment, 50 mg of each of the samples of the comparison is placed in channels of a graphite electrode with a diameter of 4 mm and a depth of 6 mm, previously annealed in the arc of a DC power of 15 And during 15 s.

The excitation source is an arc spectra DC power of 15 A. the Spectra are photographed on the type of spectrograph DFS-8. Exposure 45 C.

(Added, Rev. N 3).

4. PROCESSING OF THE RESULTS

4.1. Spectra of each sample and control experience photographing in the concentration method And six times, while concentrating on the method Used, and sample comparison — three times on one record. On spectrograms using microphotometry measure of the blackening of the lines defined elements and the surrounding background. On the measured values and using the characteristic curve of photographic plates, to determine the logarithms of the intensity of the line and background and the logarithm of the background intensity . Find . Calibration graphs constructed in the coordinates: where is the logarithm of the mass fraction of impurities in the calibration samples.

Mass fraction of impurities () in percent is calculated by the formula

,

where is the mass of the concentrate, mg;

 — mass fraction of impurities in the concentrate was found in the calibration schedule, %;

 — mass fraction of impurities in a control experiment, was found in the calibration schedule, %;

 — the weight of the portion of the original sample, mg.

(Changed edition, Rev. N 2, 3).

4.2. For the determination of impurities use the analytical lines given in table.1.

Table 1

(Changed edition, Rev. N 2).

4.3. For the results analysis be the arithmetic mean of results of three parallel measurements obtained on the same photographic plate (each simultaneous determination of the two spectrograms in the concentration of method A, from one spectrogram — method B).

The difference between the smallest of the three results of parallel measurements with a confidence probability of 0.95 does not exceed the value of permissible differences calculated by the formulae:

1. Method A:

in the determination of copper (from 5·10to 1·10%), silver (from 5·10to 1·10%) and zinc (from 1·10to 5·10%);

in the determination of aluminium, bismuth, cadmium, magnesium, manganese, and silver (from 8·10to 5·10%), zinc (1·10to 1·10%); Nickel and lead.

2. Method B:

 — when determining bismuth, Nickel, silver and zinc;

in the determination of magnesium, cadmium, manganese, lead and aluminum;

where is the arithmetic mean of the three results of parallel measurements.

The difference between the results of two analyses of the same sample with a confidence level of 0.95 does not exceed the value of permissible differences calculated by the formulae:

1. Method A:

in the determination of copper (from 5·10to 1·10%), zinc (1·10to 5·10%), silver (from 5·10to 1·10%);

in the determination of aluminium, bismuth, cadmium, manganese, silver (from 8·10to 5·10%), zinc (1·10to 1·10%); Nickel and

of wine.

2. Method B:

 — when determining bismuth, Nickel, silver and zinc;

in the determination of copper, magnesium, cadmium, manganese, lead and aluminum,

where  — the average of the two results of the analysis.

(Changed edition, Rev. N 2, 3).

4.4. (Deleted, Rev. N 1).

ANNEX 1 (mandatory). SOLUTIONS OF METALS USED FOR SAMPLE PREPARATION COMPARISON

ANNEX 1
Mandatory

1. For the preparation of solutions of metals used

1.1. Metals, with a mass fraction of main substance not less than 99.99%:

aluminium GOST 11069* foil or aluminum according to GOST 618;
______________
* On the territory of the Russian Federation GOST 11069−2001. — Note the manufacturer’s database.

bismuth GOST 10928;

gallium GOST 12797;

iron, the reduced hydrogen;

cadmium GOST 22860;

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

lead according to GOST 22861;

zinc GOST 3640;

manganese GOST 6008;

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

silver GOST 6836*;
______________
* On the territory of the Russian Federation GOST 6836−2002. — Note the manufacturer’s database.

thallium GOST 18337*;
______________
* On the territory of the Russian Federation GOST 18337−95. — Note the manufacturer’s database.

tin GOST 860;

magnesium GOST 804.

1.2. Reagents high purity or qualifications not lower than H. h or h.d. a.

1.3. Measuring bowl 1st or 2nd class of accuracy.

1.4. Analytical balance with a weighing error of no more than 0,0002 g.

2. Preparation of solutions

2.1. A solution of aluminium: 0.1 g of aluminum foil is placed in a beaker with a capacity of 50 cm. Pour 20 cmof nitric acid solution 1:3 and dissolved aluminium by heating on a hot plate. The dissolution is slow. Keep adding nitric acid until complete dissolution of the metal. The solution was boiled to remove oxides of nitrogen, cooled, transferred to a volumetric flask with a capacity of 100 cm, adjusted to the mark with water and mix.

1 cmof the solution contains 1 mg of aluminium.

2.2. The solution of bismuth: 0.1 g of bismuth metal were placed in a glass with a capacity of 50 cmand dissolved by heating in 5 cmof nitric acid solution 1:1. The solution is brought to a boil to remove oxides of nitrogen, cooled and transferred to a volumetric flask with a capacity of 100 cm, in which pre-add 5 cmof nitric acid was adjusted to the mark with water and mix.

1 cmof the solution contains 1 mg of bismuth.

2.3. The gallium solution: 0.1 g of gallium metal is placed in a beaker with a capacity of 50 cmand is dissolved in 7 cm.of a mixture of nitric and hydrochloric acids is 1:3. Transferred to a volumetric flask with a capacity of 100 cm, adjusted to the mark with water and mix.

1 cmof the solution contains 1 mg of gallium.

2.4. The solution of iron: 0.1 g of iron, reduced hydrogen, placed in a beaker with a capacity of 50 cmand dissolve in low heat in 5−6 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 and mix.

1 cmof the solution contains 1 mg of iron.

2.5. Solutions of cadmium, copper, lead, zinc, manganese, Nickel, silver, thallium is prepared by placing a weighed 0.1 g of one of these metals in a beaker with a capacity of 50 cm, and dissolve in low heat and in 5−6 cmof nitric acid solution 1:1. After complete dissolution of the metal 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 and mix.

1 cmthus obtained solution contains 1 mg of taken metal.

2.6. A solution of magnesium: 0.1 g of magnesium metal is placed in a beaker with a capacity of 50 cmand dissolved in 5−6 cmof a solution of nitric acid 1:2. The dissolution is carried out under the lid, adding a solution of nitric acid in portions of 2 cm(the reaction takes place rapidly, with much heat!). After cooling, the solution is transferred to a volumetric flask with a capacity of 100 cm, adjusted to the mark with water and mix.

1 cmof the solution contains 1 mg of magnesium.

2.7. The solution of tin: 0.1 g of finely chopped tin metal placed in a beaker with a capacity of 50 cm, add 4 g of oxalic acid and 2−3 cmof nitric acid. Dissolution is in the cold, then with a small heating. After complete dissolution of the tin add 10 cmof water and the solution transferred to a volumetric flask with a capacity of 100 cm, adjusted to the mark with water and mix.

1 cmof the solution contains 1 mg of tin.

Solutions to keep in a pot, closed tubes not more than 1 year.

APPENDIX 2 (recommended). The METHOD of REGENERATION of SPENT -DIHLORETILAMINOVOGO ETHER (hloreksa)

ANNEX 2
Recommended

The method is extended to -dialogically ether (hloreksa), purified and distilled before work under this standard, reglementary the conditions for its regeneration and allows for the determination of impurities in India high purity to use five times the same hloreksa passed every time three-time regeneration.

The method is based on washing the ether with water. Regenerated the hloreksa should be transparent and should not contain water, indium and metal impurities determined in India brands Ин00, Ин000.

The regeneration performance: 120−150 cmwaste -dihloretilaminovogo ether is transferred to a separatory funnel with a capacity of 500 cm(volume of air should not exceed the volume of the funnel), add 120−150 cmdouble-distilled water and vigorously stirred for 5 min. After separation of the phases (20−30 min) the aqueous phase and the suspension of oxybromide India poured into a glass. The ether is transferred into another separatory funnel with a capacity of 500 cmand washed twice with water.

Washed thus the hloreksa can be used for the extraction of indium.

Allowed the same hloreksa to be used for extraction five times, holding each time, three times washing it with water.


ANNEXES 1, 2. (Added, Rev. N 2