GOST 13637.3-93

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  ГОСТ 13637.3-93

GOST 13637.3−93 Gallium. The chemical-atomic emission method for the determination of aluminium, bismuth, indium, cadmium, cobalt, silicon, magnesium, manganese, copper, Nickel, lead, silver, chromium, zinc and iron

GOST 13637.3−93

Group B59

INTERSTATE STANDARD

GALLIUM

The chemical-atomic emission method for the determination of aluminium, bismuth,
of indium, cadmium, cobalt, silicon, magnesium, manganese, copper, Nickel,
lead, silver, chromium, zinc and iron

Gallium. Chemical-atomic-emission method for the determination of aluminium,
bismuth, cobalt, silicon, magnesium, manganese, copper, nickel, lead,
silver, chromium, zinc and iron

AXTU 1709

Date of introduction 1995−01−01

Preface

1. DEVELOPED by the Interstate technical Committee 104 «of the Semiconductor and rare metals products. Especially pure metals», State Institute of rare metals (Giredmet)

INTRODUCED by Gosstandart of Russia

2. ADOPTED by the Interstate Council for standardization, Metrology and certification (Protocol No. 4−93 of 19 October 1993)

The adoption voted:

3. Resolution of the Committee of the Russian Federation for standardization, Metrology and certification from 02.06.94 N 160 inter-state standard GOST 13637.3−93 introduced directly as state standard of the Russian Federation from 01.01.95

4. REPLACE GOST 13637.3−77

INFORMATION DATA

REFERENCE NORMATIVE AND TECHNICAL DOCUMENTS

This standard specifies the chemical-atomic emission method for the determination of mass fractions of impurities in Gaul:

1) upon dissolution of the metal in a mixture of hydrochloric and nitric acids and the concentration of the impurities by the extraction of gallium butyl acetate or ethyl ether hydrochloric acid solution

2) upon dissolution of the metal vapors of bromine in the presence of carbon tetrachloride and hydrochloric acid and concentration by distillation of trihalogen gallium, followed by extraction of residual gallium ethyl ether

3) when extraction of the impurities in the form of diethyldithiocarbamate chloroform or carbon tetrachloride

Concentrate determined of impurities on the graphite powder with the addition of sodium chloride analyse atomic-emission method.

1. GENERAL REQUIREMENTS

General requirements for method of analysis and safety requirements according to GOST 13637.3.

2. APPARATUS, MATERIALS AND REAGENTS

The diffraction type spectrograph DFS-8 or similar type with the grating of 600 lines/mm and being light.

The arc generator type DG-2 with optional rheostat or similar type adapted to ignite the DC arc high frequency discharge.

Rectifier 250−300, 30−50 A.

Microphotometer type MF-2 or similar type.

Spectromancer of PS-18 or similar type.

Grinding machine graphite electrodes.

The shaped graphite electrodes for atomic-emission analysis of high purity 7−4, 6 mm in diameter, sharpened to a cone; or graphite electrodes, machined from high purity graphite rods 7−3, 6 mm in diameter, sharpened to a cone with an apex angle of 15 degrees and with a platform with a diameter of 1.5 mm at the tip, burnt in the arc of direct current at 15 And during 15 s.

The shaped graphite electrodes for atomic-emission analysis of high purity 7−4, 6 mm in diameter, with a channel depth of 6 mm and a diameter of 4 mm; or graphite electrodes of the same size, machined from high purity graphite rods 7−3, burned in the arc of direct current at 15 And during 15 s.

Cleaning firing is subjected to each pair of electrodes before measurement (electrode, sharpened to a cone — cathode, the electrode with the channel / anode).

Graphite powder of high purity according to GOST 23463.

Laboratory scales of the 1st class according to GOST 24104*.
_______________
* On the territory of the Russian Federation GOST 24104−2001. — Note the manufacturer’s database.

The infrared lamp of the type ikz-500 with voltage regulator type RNO-250−2 or regulator of a similar type.

Box of organic glass.

Mortar and pestle made of organic glass.

Installation for the distillation of the halides of gallium liquid shutter made of molybdenum glass (Fig.1).

1 — quartz vessel with cone, stand for crucibles; 2 — a support for the crucibles;
3 — quartz tube vessel with cone; 4 — crucible; 5 — tubular furnace;
6 — connecting tube of rubber; 7 — water shutter
filled with a solution of potassium hydroxide

Damn.1

The unit capacity of 300 watts covered with a quartz cuvette and plate of glassy carbon.

Thermocouple chromel — alumel with a millivoltmeter MP-64−02 GOST 9736.

Vessel with Teflon screw cap with a capacity of 1000 cm(Fig.2).

1 — Teflon vessel; 2 — cover of PTFE; 3 — crucible; 4 — stand made of PTFE.

Damn.2

The quartz Cup with a capacity of 10 cmand 100 cm.

The quartz or glassy carbon crucibles with a capacity of 30 cm.

Pipette with divisions 1 and 5 cm.

Measuring cylinders with divisions in 10 cm.

Funnel separating from transparent quartz glass with a capacity of 30 cm.

Primary aluminium GOST 11069*, grade A 99 or higher.
_______________
* On the territory of the Russian Federation GOST 11069−2001. — Note the manufacturer’s database.

Bismuth or oxide of bismuth GOST 10216.

Radio engineering carbonyl iron according to GOST 13610 brand SS or iron oxide.

Indium GOST 10297−75* brand Ying 000 or higher or an oxide of indium (indium trioxide) OS. h-9−3.
_______________
* On the territory of the Russian Federation GOST 10297−94. — Note the manufacturer’s database.

Cadmium GOST 1467 brand CD-2 or higher or cadmium oxide according to GOST 11120.

Cobalt GOST 123* stamps K1 or higher or nitrous oxide of cobalt GOST 4467.
_______________
* On the territory of the Russian Federation GOST 123−98 (01.07.2009 valid GOST 123−2008). — Note the manufacturer’s database.

Silicon dioxide according to GOST 9428.

Magnesium primary GOST-804 brand MG-90 or higher or magnesium oxide according to GOST 4526.

Manganese metal according to GOST 6008 brand Мр0 or Мр00 or manganese dioxide, anhydrous high purity-9−2.

Copper according to GOST 859* brand M3 or higher or copper oxide according to GOST 16539порошкообразная.
_______________
* On the territory of the Russian Federation GOST 859−2001. — Note the manufacturer’s database.

Nickel GOST 849* brand N-2 or higher or the black oxide of Nickel GOST 4331.
_______________
* On the territory of the Russian Federation GOST 849−97 (01.07.2009 standards 849−2008). — Note the manufacturer’s database.

Lead according to GOST 3778 brand S3 or higher or a lead oxide.

Silver GOST 6836* stamps CP or 999,0 999,9 or silver nitrate according to GOST 1277.
_______________
* On the territory of the Russian Federation GOST 6836−2002. — Note the manufacturer’s database.

Chrome according to GOST 5905* stamps X 00.
_______________
* On the territory of the Russian Federation GOST 5905−2004. — Note the manufacturer’s database.

Zinc GOST 3640* stamps C1 or higher or zinc oxide according to GOST 10262.
_______________
* On the territory of the Russian Federation GOST 3640−94. — Note the manufacturer’s database.

The main solutions of concentrations 1 mg/cmdetermined by the impurities of aluminum, bismuth, iron, indium, cadmium, cobalt, magnesium, manganese, copper, Nickel, lead, silver, chromium and zinc prepared as follows:

The main solutions of bismuth, iron, indium, cadmium, cobalt, magnesium, manganese, copper, Nickel, lead and silver is prepared by dissolving 100 mg of metallic bismuth, iron, indium, cadmium, cobalt, magnesium, manganese, copper, Nickel, lead and silver, respectively, or 117,7 mg of bismuth oxide, 143,0 mg of iron oxide, 120,9 mg oxide India, only 114.2 mg of cadmium oxide, 140,7 mg nitrous-oxide of cobalt, 165,8 mg of magnesium oxide, 158,3 mg of manganese dioxide, 125,2 mg of copper oxide, 140,9 mg oxide black Nickel 107,7 mg of lead oxide, 157,5 mg of silver nitrate in a minimum amount of nitric acid. The solutions were transferred to volumetric flasks with a capacity of 100 cm, adjusted to the mark with deionized water, and stirred.

1 cmeach of the solutions contains 1 mg of the corresponding element.

For preparing basic solutions of aluminium, chromium and zinc take 100 mg of each of these metals (instead of zinc metal can I take 124,4 mg zinc oxide), dissolve in a minimum quantity of hydrochloric acid (1:1). The solutions were transferred to volumetric flasks with a capacity of 100 cm, adjusted to the mark with deionized water, and stirred.

1 cmeach of the solutions contains 1 mg of the corresponding element.

Photographic plates of type SFC-04 or equivalent, providing normal blackening of analytical lines and the background in the spectrum.

Developer:

Hydrochloric acid H. h according to GOST 3118, a concentrated.

Hydrochloric acid of high purity according to GOST 14261 concentrated and distilled twice in a quartz apparatus with a concentration of 6 mol/DM.

Nitric acid according to GOST 11125 or nitric acid according to GOST 4461 double-distilled in quartz apparatus.

Orthophosphoric acid according to GOST 6552.

Bromine according to GOST 4109, h.d. a.

Potassium hydroxide according to GOST 24363 H. h, solution concentration of 400 g/DM.

Universal indicator paper.

Chloroform medical.

Carbon tetrachloride according to GOST 20288.

Water deionized with a specific resistivity of 10−20 Mω·cm.

The ethyl ether medical purified three times by extraction with a hydrochloric acid concentration of 6 mol/DM, each time for 5 min when the ratio of the volumes of acid and ether 1:10.

Butyl ether of acetic acid (butyl acetate) according to GOST 22300 or ethyl ether medical purified three times by extraction with hydrochloric acid concentration is 6 mol/DM, each time for 5 min when the ratio of the volumes of acid and ether 1:10.

The aqueous ammonia of high purity according to GOST 24174.

Sodium , -diethyldithiocarbamate according to GOST 8864, solution concentration of 20 g/DM, freshly prepared and purified; 100 cmof solution was placed in a separatory funnel, pour 3 cmof chloroform or carbon tetrachloride and vigorously stirred for 3 min. After separation the organic layer discarded. The extraction is repeated three more times with the same amount of chloroform or carbon tetrachloride. The solution for the working day keep in a cool place.

Tartaric acid according to GOST 5817.

Solution Vinokurova ammonium: 200 cmaqueous solution of tartaric acid concentration of 500 g/DMin a glass with a capacity of 500 cmof water is neutralized with ammonia solution on the indicator paper until a pH of 8, placing the glass in the mold with ice, the solution was transferred to a separatory funnel, add 20 cmof a solution of sodium diethyldithiocarbamate, 60 cmof chloroform or carbon tetrachloride and shaken for one minute. After separation the organic layer discarded and the extraction repeated four more times with the same amount of reagents. Vinokurova ammonium solution stored in a plastic jar.

Sodium chloride high purity 10−3.

The technical rectified ethyl alcohol according to GOST 18300, nederevyannyy and double-distilled in quartz apparatus.

3. PREPARATION FOR ASSAY

3.1. Sample preparation comparison (OS)

3.1.1. The main reference sample A (OOSA) with mass fractions of 0.1% of aluminum, bismuth, indium, cadmium, cobalt, silicon, magnesium, manganese, copper, Nickel, lead, chromium, zinc, and silver in a quartz Cup with a capacity of 100 cmis placed 9,860 grams of powdered graphite. Then it added one at 10 cmfundamental solutions of these impurities in the order listed. After each addition of the basic solution mixture is dried on the tile. After adding the basic silver solution and drying the mixture it is stirred. About 1 g of the mixture powder of graphite with a defined impurities fray with 21.5 mg of silicon dioxide in the presence of ethyl alcohol in a mortar made of organic glass for 40 min. in a mortar Then add the remaining (weighing about 9 g) graphite powder with impurities and 30 cmof ethanol. The mixture was mulled for 60 min, and then dried under an infrared lamp.

3.1.2. The main reference sample B (ODSS) with a mass fraction of 0.1% aluminium in quartz Cup is placed 9,990 g of powdered graphite and pour 10 cmof the basic solution of aluminium concentration of 1 mg/cm. The mixture is stirred and dried, first in a quartz Cup and then in a mortar made of organic glass, with the addition of ethanol to maintain the mixture in a pasty condition for 60 min. the resulting mixture was dried under an infrared lamp.

3.1.3. The main reference sample (OOSW) with a mass fraction of 0.1% of iron in quartz Cup is placed 9,990 g of powdered graphite and pour 10 cmof the main solution of iron iron concentration of 1 mg/cm. The mixture is stirred and dried, first in a quartz Cup and then in a mortar made of organic glass, with the addition of ethanol to maintain the mixture in a pasty condition for 60 min. the resulting mixture was dried under an infrared lamp.

3.1.4. References OS: ОСА1-ОСА7 prepare a serial dilution of OOSA powdered graphite. The mass fraction of each of the designated impurities in ОСА1-ОСА7 and added to the mixture of sample powder of graphite and diluted sample, mixing for this sample are given in table.1.

Table 1

3.1.5. References OS: ОСБ1-ОСБ6 and ОСВ1-ОСВ4 prepare a serial dilution, respectively ODSS and OOSV powdered graphite. The mass fraction of each impurity determined in ОСБ1-ОСБ6 and ОСВ1-ОСВ4 and added to the mixture of sample powder of graphite and diluted sample, mixing for this sample are given in table.2.

Table 2

Are given in table.1 and 2 samples of powdered graphite and dilute the reference sample is placed in a mortar made of organic glass, carefully fray OC1-ОС3 with ethyl alcohol, and ОС4-ОС7 — with double-distilled ethanol, for 50 min and dried under an infrared lamp in a box made of organic glass.

Note. OOSA, ODSS and OOV also allowed to cook by introducing the designated elements in the form of oxides (see 13637.1 or GOST GOST 13637.2).


In order to avoid introducing dirt 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 aluminium, bismuth, indium, cadmium, cobalt, silicon, magnesium, manganese, copper, Nickel, lead, silver, chromium, zinc.

A portion of gallium by mass of 1 g were placed in Teflon Cup, pour 10 cmof a mixture of hydrochloric acid concentration of 6 mol/land nitric acid in ratio 3:1, the PTFE Cup closed with a lid and dissolve 50−60 min on a hotplate, covered with a quartz cuvette, under low heat. The resulting solution is evaporated to a syrupy condition. Then it poured 5cmof hydrochloric acid concentration is 6 mol/DMand slightly heated. The cooled solution was transferred to a separatory funnel, washing out the Cup another 5 cmof hydrochloric acid solution with a concentration of 6 mol/DM.

The extraction of gallium can be done in two almost equal extractants: butyl acetate or ethyl ether. When working with ethyl ether should be considered his explosiveness. When extraction is necessary to periodically release from the separating funnel formed of a pair of ether.

For the extraction of gallium in the separatory funnel add 10 cmbutyl acetate or ethyl ether, and shake the funnel vigorously for 2 min. After stratifying liquids of the lower aqueous phase was transferred to another separating funnel and repeat the extraction two more times with the same amount of butyl acetate or ethyl ether.

Hydrochloric acid solution, obtained after extraction of gallium, transferred to clean Teflon Cup, add 50 mg of powdered graphite and the solution is evaporated to dryness at a temperature of about 100 °C on a hotplate, covered with a quartz cuvette. The obtained dry residue is a concentrate of impurities, is subjected to atomic-emission analysis.

At the same time through all stages of the analysis carried out three control experience and get three dry residue concentrate

.

4.2. The concentration of aluminium

4.2.1. Preparation of dishes

With mounting set for distillation, gallium, two vessels PTFE (for bromination and saturation with hydrochloric acid), three separating funnels and quartz cups are repeatedly carried out control experiments on p. 4.2.3, until the amendment of the control experience does not satisfy the requirements of section 5.2.

Note. When working with a new crucible of glassy carbon for determination of the 2·10% aluminum number of control experiments required for the preparation of dishes, bychno is at least 5.

4.2.2. Storage quartz separating funnels and cups

Quartz separating funnel and Cup after analysis, rinse with water and stored filled with deionized water immersed in deionized water in containers made of PTFE or glassy carbon.

4.2.3. To obtain a concentrate of aluminium

Six crucibles made of quartz or glassy carbon with a capacity of 30 cmis introduced to 15 cmof carbon tetrachloride and 3 cm, double-distilled hydrochloric acid. Three of the crucible is placed a portion of the crushed gallium weighing 3 g. Then all six crucibles set on the base fluoropolymer of the vessel 1 (Fig.2). At the bottom of the vessel ftoroplastov pre-poured 40 cmof bromine, the vessel is sealed with a screw cap 2 and left for 24 h in a fume hood. The next day Teflon vessel open, three of the crucible in the reference experiment and three of the crucible dissolved with the breakdown of alternately placed on the stand 2 (Fig.1) quartz vessel. In a vessel pre-pour a solution of potassium hydroxide at 1/3 of its height. The vessel 1 connect the rubber tube 6 with the liquid valve 7, which is filled with a solution of potassium hydroxide. After the installation of the crucible 4 on a support (Fig.1) the vessel 1 is closed with a stopper 3, pre-lubricated phosphoric acid, and the tube is put on the furnace 5. The furnace is heated gradually by adjusting the voltage of its power supply regulator type RNO-250−2 so that first, from the solutions in the crucibles was tognella bromine, and then the remaining liquid to obtain a dry residue. Then the furnace is removed. After cooling, the crucibles with dry residues transferred from the quartz vessel 1 (Fig.1) on a support made of PTFE 4 (Fig.2) on the bottom of Teflon vessel 1 (Fig.2) pre-pour 200 cmof concentrated hydrochloric acid to neutralize the dry residue and leave for 1 h. Then in each of the crucibles poured 5 cmdouble-distilled hydrochloric acid. After dissolution of the residue and the solution transferred to a separatory funnel with a capacity of 30 cm, poured to 10 cmof ethyl ether saturated with hydrochloric acid, and shaken for 2 min. After separation, the acid layer is transferred into another separatory funnel with a capacity of 30 cm, and the ether layer discarded. The extraction with ether repeated two more times. Then the acid layer is transferred to a quartz Cup with a capacity of 10 cm, is evaporated to a volume of 1−1,5 cm, add 50 mg of powdered graphite and evaporated to dryness on a hotplate, covered with a quartz cuvette and plate of glassy carbon.

The obtained dry residue is a concentrate of aluminium subjected to atomic-emission analysis. Analysis of each sample of gallium is carried out from three parallel batches.

At the same time through all stages of the analysis carried out three control experience and get three dry residue — the concentration

rata.

4.3. The concentration of iron

A portion of gallium by mass of 1 g was placed in a quartz Cup with a capacity of 40−50 cm. In a Cup pour 4 cmof nitric acid. Cup cover, quartz lid, and heated on a hotplate weak intensity. After the beginning of the dissolution, the Cup is removed from the tiles after 1 hour in a Cup add 2 cmof hydrochloric acid concentration is 6 mol/DM, and heated a Cup until dissolved gallium, avoiding violent boiling of the solution. The resulting solution is evaporated to a thick syrup, then add 10 cmof a solution of ammonium Vinokurova. The solution is neutralized with ammonia to pH 8 by universal indicator paper and transferred to a quartz separating funnel with a capacity of 50 cm. Add 1 cmof a solution of sodium diethyldithiocarbamate and 3 cmof chloroform or carbon tetrachloride. The funnel vigorously shaken for 3 min. After separation of phases the organic phase was transferred to another separatory funnel and repeat extraction under the same conditions another time. The combined extract (organic phase) was washed with 5 cmdeionized water in a quartz separating funnel with a capacity of 30 cmthree times and transferred to a clean quartz Cup with a capacity of 30 cm. The Cup adds 50 mg of graphite powder collector and carefully evaporated the solution on a hotplate, covered with a quartz cuvette at a temperature of 50−60 °C. the resulting dry residue is a concentrate of iron, subjected to atomic-emission analysis.

At the same time through all stages of the analysis carried out three follow-up experience for contamination of reagents and get three dry residue concentrate.

Analysis of each sample of gallium according to claim.4.1, 4.2, 4.3 conduct of three parallel naves

esok.

4.4. Atomic emission analysis concentrates

To each concentrate obtained from a sample of the sample and control experiments, and 50 mg each of samples of the comparison is added 2 mg of sodium chloride and gently mix with a spatula on a piece of tracing paper.

Each mixture with a spatula is placed in the channel of the graphite electrode with a diameter of 4 mm and a depth of 6 mm and compacted using nabuaki of organic glass. The spatula and kick ball after each sample is carefully rubbed with pieces of calico, soaked with ethanol, and dried in air.

The electrode with the concentrate of impurities (or the reference) 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.

Spectra photographed with the intermediate aperture 5 mm, gap width 15 µm, the scale of the wavelength set at 280 nm, and exposure time of about 45 (to complete combustion of sodium chloride).

During exposure the distance between the electrodes is maintained at 3 mm.

On the same photographic plate in the same conditions photographed three times the range of concentrates of the analyzed samples, the range of concentrates obtained from control experiments, and the range of each of the samples of the comparison.

Exposed photographic exhibit, washed with water, fixed, washed in running water for 15 min and dried.

5. PROCESSING OF THE RESULTS

5.1. In each spectrogram photometric blackening of analytical lines of the designated element (see table.3) and nearby background (minimum blackening near the analytical line of the element on either side, but with the same side in all the spectra taken on one disc) and calculate the difference pucherani .

On three values , , obtained three spectrograms taken for each sample, find the arithmetic mean . From the obtained average values are transferred to corresponding values of the logarithms of relative intensity using the table provided in mandatory Appendix GOST 13637.1.

Values and comparison of samples for build calibration curve in the coordinates , . According to this calibration graph and the value for concentrates control experiments determine the average value of the mass fraction of the designated impurities in the concentrates control experiments. Accordingly, the value for concentrates of the sample find the schedule for the calibration the mean value of the mass fraction of the designated impurities in the concentrate to analizira

Amoy sample.

5.2. Mass fraction of impurity in the sample (result of analysis) in percent is calculated by the formula

,

where  — weight of powdered graphite that is used as a header, g,

 — the weight of the portion of the sample of gallium, g,

 — average mass fraction of impurities in the concentrates of the sample, %,

 — average mass fraction of impurities in the concentrates in the reference experiment, %.

Table 3

Note. When the mass fraction of titanium in the concentrate of the sample of gallium 3·10% or more of zinc is determined according to GOST 13637.2 as prevents the imposition of the line titanium 328,23 nm for the analytical line of zinc.


The value should not exceed 0.8 . If this condition is not ensured, you must perform a phased cleaning, jobs, used equipment, reagents and materials.

Found by the formula the value of the mass fraction of impurity in the sample (in %) is the result of the analysis, the average of the three results of parallel measurements, each made from a separate sample of the sample of gallium.

While monitoring convergence results of parallel measurements of the three values , , obtained three spectrograms for the three concentrates of the sample, select the largest and smallest values are transferred from them to the tables contained in mandatory Appendix GOST 13637.1, to the corresponding values and find the corresponding values of the mass fraction of impurities in the sample

and .

5.3. Permissible discrepancies in the results of three parallel measurements (the ratio of largest to smallest) and two results of the analysis (the ratio of largest to smallest), are given in table.4.

Table 4

Allowable differences for intermediate values of mass fraction are calculated by using linear interpolation.

5.4. Control of the correctness analysis is carried out by additives. To do this, from one of the previously analyzed samples, we take three sample of gallium weighing 1 g each, enter the additives of the identified elements, and transferred into a solution according to claim.4.1 and 4.2. Additives are added in such amount to the calculated value of the mass fraction of each impurity in the sample of gallium with the addition of percentage is not less than 3and not more than 10or upper limits of detectable concentrations of this impurity.

calculated by the formula

,

where is the result of the analysis of the previously analysed sample mass fraction of the corresponding impurity, %;

 — the mass of impurity in the additive, mg.

The obtained solutions with additives analyzed in the same way as the solutions of sample batches with no additives, receiving the values as the geometric mean of results of three parallel measurements.

The analysis considered correct if the ratio of the greater to the lesser of the two values to not exceed the values permitted by the variances of the two test results for samples with a mass fraction determined by the impurities is equal .