GOST 6689.19-92

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  ГОСТ 6689.19-92

GOST 6689.19−92 Nickel, alloys Nickel and copper-Nickel. Methods for determination of phosphorus

GOST 6689.19−92

Group B59

STATE STANDARD OF THE USSR

NICKEL, ALLOYS NICKEL AND COPPER-NICKEL

Methods for determination of phosphorus

Nickel, nickel and copper-nickel alloys. Methods for the determination of phosphorus

AXTU 1709

Date of introduction 1993−01−01

INFORMATION DATA

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

DEVELOPERS

V. N. Fedorov, Y. M. Leybov, Boris Krasnov, A. N. Bulanova, I. A. Vorobyev

2. APPROVED AND put INTO EFFECT by Decree of the Committee on standardization and Metrology of the USSR from 18.02.92 N 167

3. REPLACE GOST 6689.19−80

4. REFERENCE NORMATIVE AND TECHNICAL DOCUMENTS

This standard specifies the extraction-photometric (mass fraction in phosphorus from 0.0005 to 0.05%) and photometric (at a mass fraction of phosphorus from 0.005 to 0.05%) methods for determination of phosphorus in Nickel, Nickel and copper-Nickel alloys according to GOST 492* and GOST 19241.
_________________
* On the territory of the Russian Federation GOST 492−2006. — Note the manufacturer’s database.

1. GENERAL REQUIREMENTS

General requirements for methods of analysis GOST 25086 with the addition of sec. 1 GOST 6689.1.

2. EXTRACTION-PHOTOMETRIC METHOD FOR THE DETERMINATION OF PHOSPHORUS

2.1. The essence of the method

The method is based on measuring the optical density of the extract molybdophosphate after extraction with a mixture of butyl alcohol and chloroform, and the restoration of molybdophosphate dichloride tin to phosphorus molybdenum blue.

2.2. Apparatus, reagents and solutions

Photoelectrocolorimeter or spectrophotometer.

Nitric acid according to GOST 4461 and diluted 1:1 and 1:9.

Hydrochloric acid according to GOST 3118, diluted 1:1 and 1:9.

Sulfuric acid according to GOST 4204, a solution of 0.5 mol/DM.

Hydrofluoric acid according to GOST 10484.

Perchloric acid, 57% solution and diluted 1:9.

Ammonia water according to GOST 3760, diluted 1:50.

Sodium atomistically according to GOST 4197, a solution of 50 g/DM.

The technical rectified ethyl alcohol according to GOST 18300.

Alum salesonline according to GOST 4205, a solution of 100 g/DM.

10 g of alum was dissolved with heating in 70 cmwater and 5 cmof nitric acid, the solution was filtered and diluted with water to 100 cm.

Calcium nitrate cetarehwodie according to GOST 4142, a solution of 120 g/DM: 60 g of salt dissolved in 100 sm, filter the undissolved residue and the solution is diluted with water to 500 cm.

Potassium hydroxide according to GOST 9285, a solution of 30 and 100 g/DM.

Wash solution: 1 DMof potassium hydroxide solution (30 g/DM) was added 20 cmof a solution of nitrate of calcium, vigorously stirred, incubated 2 h, add another 8 cmof a solution of calcium nitrate and stirred. After 20 min the solution was filtered through a double filter of medium density.

Ammonium molybdate according to GOST 3765, recrystallized, solution 100 g/DM. The recrystallization of ammonium molybdate is carried out according to GOST 6689.7.

Tin dichloride according to GOST 36, a freshly prepared solution of 40 g/lin hydrochloric acid (1:9).

Tin dichloride, diluted solution: 1 cmof a solution of tin dichloride (40 g/lin hydrochloric acid (1:9) diluted with 50 cmof 0.5 mol/DMsolution of sulphuric acid. The solution is prepared before use.

Chloroform according to GOST 20015*.
_________________
* On the territory of the Russian Federation GOST 20015−88. — Note the manufacturer’s database.

-Butyl alcohol according to GOST 6006.

Extraction mixture: three parts of chloroform mixed with one part butyl alcohol.

The washing liquid for washing of the extract: to 80 cmof water add 10 cmto 57% strength solution of perchloric acid and 10 cmof a solution of molybdate of ammonium.

Sodium sulfate according to GOST 4166.

Potassium phosphate according to GOST odnosemjannyj 4198.

The standard solutions of phosphorus

Solution a: 0,4394 g of single potassium phosphate is dissolved in water, transferred into a measuring flask with volume capacity of 1000 cmand topped to the mark with water.

1 cmof the solution contains 0.0001 g of phosphorus.

Solution B: 10 cmsolution And placed in a volumetric flask with a capacity of 100 cm, made up to the mark perchloric acid (1:9).

1 cmof a solution of sod

refer to 0,00001 g of phosphorus.

2.3. Analysis

2.3.1. For alloys not containing chromium and tungsten

A portion of the alloy (see table.1) is placed in a platinum Cup, add 20−30 cmof nitric acid (1:1), 1−3 cmhydrofluoric acid and dissolved by heating.

Table 1

The walls of the Cup then rinsed with water, the solution was evaporated to dryness, the dry residue add 10 cmof nitric acid (1:1) and again evaporated to dryness.

To the dry residue add 20 cmof nitric acid (1:1) and heated to dissolve the salts. The solution was transferred to a beaker with a capacity of 250 cm, rinse the Cup 10 cmof nitric acid (1:1) and a small amount of water.

For alloys containing manganese, the hot solution was added dropwise with stirring a solution of sodium attestatio to dissolve the precipitated manganese dioxide. To the solution was added 10 cm57% perchloric acid, evaporated to stop the allocation of thick white smoke and cool.

To the residue add 30 cmof water, the beaker cover watch glass, glass or plastic plate, heated to dissolve the salts (if the salt is fully dissolved, add dropwise with stirring with 57% perchloric acid, boiled for 2 min and cooled).

The resulting solution was placed in a separating funnel with a capacity of 150 cm, rinse a glass or a plate and a glass of 5 cmof perchloric acid (1:9), add 3 cmof a solution of ammonium molybdate and incubated for 10 min before the formation of molybdophosphate.

Add 5 cm-butyl alcohol, shake vigorously to saturate the aqueous solution of -butyl alcohol, add 10 cmof the extraction mixture, gently stirred for 1 min, inverting the funnel 20 to 25 times and give fluids to flake. The organic layer placed in a second separatory funnel with a capacity of 150 cm, and to the water layer add 10 cmof the extraction mixture and repeat the extraction. Combine the extracts in a second separating funnel and washed with wash liquid. After the bundle is placed the organic layer into the dry glass with a capacity of 50 cm, the funnel rinsed 4−5 cmof the extraction mixture. Heat the solution on a water bath until complete removal of chloroform, after cooling, the solution was placed in a separating funnel with a capacity of 100−150 cm, add 15 cm-butyl alcohol and stirred. In the funnel add 5 cmof dilute solution of dichloride of tin, vigorously stirred for 30 s and after separation of the phases and remove the aqueous layer and the organic layer transferred into a dry volumetric flask with a capacity of 50 cm, which had previously placed 0.2−0.3 g sodium sulphate, or filtered through a dry filter, rinse the separatory funnel -butyl alcohol, adding it to the same flask, topped up to the mark -butyl alcohol and the optical density is measured on a photoelectrocolorimeter with a red light filter in a cuvette with a thickness of the light absorbing layer 2 cm or on the spectrophotometer at 780 nm in a cuvette with the thickness of the light absorbing layer 1 cm.

Solution comparison is the solution of the control experiment conducted using the whole analysis.

The phosphorus content find first gradua

rosacea schedule.

2.3.2. For alloys containing tungsten

A portion of the alloy (see table.1) placed in a glass of 250−300 cm, add 40−60 cmof nitric acid (1:1), cover with watch glass, glass or plastic plate and dissolved by heating. After the dissolution of a glass or plate and the side of the Cup then rinsed with water, the solution is evaporated to a syrupy state, add 10 cmof water and the solution to precipitate tungsten acid, incubated in a hot bath for 5−10 min. the Precipitate was filtered off on a double thick filter glass, and the precipitate is washed 4−5 times with hot solution of nitric acid (1:100). The filtrate and the wash solution collected in a beaker with a capacity of 300 cmand save, and the residue washed from the filter with hot water into a glass, which carried out the dissolution of the alloy is dissolved in 70−75 cm,a boiling solution of potassium hydroxide (100 g/DM) and the filter washed with hot water.

The solution was heated, diluted with water to 250 cmand cooled to room temperature. Add 5 cmof a solution of nitrate of calcium, vigorously stirred and left for 2 h. Add 2 cmof a solution of nitrate of calcium and after 20 min the precipitate is filtered off on a tight filter. The glass in which the deposition was performed, and the filter cake washed 8−10 times flushing solution. The filter cake is dissolved in 30 cmof hot nitric acid (1:1) in glass, which conducted the deposition, the filter was washed 2−3 times with hot nitric acid (1:100) and water.

The solution was boiled down to 20−25 cm, attached to the filtrate obtained after separation of tungsten acid, and evaporated to 20−25 cm. After cooling, to the solution was added 10 cm57% perchloric acid and evaporated until the termination of allocation of dense white smoke. The residue was cooled, added to 50 cmof water, 2 cm57% perchloric acid, the beaker cover watch glass, glass or plastic plate, heated to dissolve the salts and boil 2 min. After cooling, the solution was placed in a separating funnel with a capacity of 150 cm, a glass should be rinsed with 5 cmof perchloric acid (1:9) and further analysis are as shown

in p.2.3.1.

2.3.3. For alloys containing chromium

A portion of the alloy (see table.1) is placed in a platinum Cup, add 20−30 cmof nitric acid (1:1), 1−3 cmhydrofluoric acid and dissolved by heating. Then the solution was evaporated to dryness, the residue is cooled, add 10 cmof nitric acid (1:1) and again evaporated to dryness. This operation is repeated three more times. To the dry residue add 20 cmof nitric acid (1:1) and heated to dissolve the salts. The solution is placed in a beaker with a capacity of 250−300 cm, rinse the Cup 10 cmof nitric acid (1:1) and water. To the obtained solution add 15−20 cm57% perchloric acid, is evaporated before the termination of allocation of dense white smoke and cool. To the residue add 30 cmof water, the beaker cover watch glass, glass or plastic plate, heated to dissolve the salts (if the salt is fully dissolved, add dropwise with stirring with 57% perchloric acid and boil for 2 min). After cooling, the solution is diluted with water to 150−180 cm, add 1 cmgentoomaniac alum solution, heated to 60−70 °C and precipitated ferric hydroxide with ammonia, carefully adding the last to the formation of the soluble ammonia complex of Nickel and beyond that another 5−6 cmin excess.

The solution is incubated 30 min at 60−70 °C for coagulation of the precipitate of iron hydroxide. The precipitate was filtered off on a filter of medium density. The glass and the filter cake is washed 6−8 times with a hot solution of ammonia (1:50), and dissolve the filter cake in 20 cmof hot hydrochloric acid (1:1) in glass, which conducted the deposition, rinsing the filter 5−7 times in hot water. Sedimentation, filtering and washing the precipitate again. The precipitate of iron hydroxide on the filter was dissolved in 35 cmhot perchloric acid, diluted 1:9 in the glass, which made the deposition, and the filter was washed 5−7 times in hot water. The resulting solution is evaporated to 25−30 cm, after cooling, placed in a separatory funnel with a capacity of 150 cmand rinse the glass with water so that the total solution volume was 35 cm. Add 3 cmof a solution of molybdate of ammonium, kept for 10 min for the formation of molybdophosphate and further analysis are as indicated in claim 2.3.1.

The phosphorus content find the second graduirovannam

mu schedule.

2.3.4. Construction of calibration graphs

2.3.4.1. The construction of the first calibration curve

In a separating funnel with a capacity of 150 cmis placed 1,0; 2,0; 3,0; 4,0; 5,0; 6,0; 7,0 and 10.0 cmstandard solution B phosphorus, dilute perchloric acid (1:9) to 35 cm, add 3 cmof a solution of molybdate of ammonium and further analysis are as indicated in claim 2.3.1.

2.3.4.2. The construction of the second calibration curve

In glasses with a capacity of 250 cmis placed 0,5; 1,0; 2,0; 3,0; 4,0; 5,0; 6,0; 7,0 and 10.0 cmstandard solution B, add 10 cmto 57% perchloric acid, dilute with water to 150−180 cm, add 1 cmgentoomaniac alum solution, heated to 60−70 °C, precipitated ferric hydroxide with ammonia and further analysis are as indicated in claim 2.3.3.

2.4. Processing of the results

2.4.1. Mass fraction of phosphorus in percent is calculated by the formula

,

where is the mass of phosphorus was found in the calibration schedule,

 — the weight of the portion,

2.4.2. Discrepancies in the results of three parallel measurements (rate of convergence) and the results of the two tests (index of reproducibility) shall not exceed the values of permissible differences given in table.2.

Table 2

2.4.3. Control of accuracy of analysis results is carried out according to State standard samples (GSO) or industry standard sample (CCA), or by standard samples of the enterprise (SOP) of Nickel, Nickel and copper-Nickel alloys, approved under GOST 8.315*, or method of additions or by comparison of the results obtained by the photometric method according to GOST 25086.
________________
* On the territory of the Russian Federation GOST 8.315−97. Here and further. — Note the manufacturer’s database.

3. THE PHOTOMETRIC METHOD FOR THE DETERMINATION OF PHOSPHORUS

3.1. The essence of the method

The method is based on formation of yellow phosphomolybdenum complex and the measurement of its optical density.

3.2. Apparatus, reagents and solutions

Photoelectrocolorimeter or spectrophotometer.

Nitric acid according to GOST 4461 and diluted 1:1 and 2:3.

Hydrochloric acid according to GOST 3118.

The mixture of acids to dissolve: to mix 120 cmof hydrochloric acid, 320 cmof concentrated nitric acid and 560 cmof water.

Hydrofluoric acid according to GOST 10484.

Boric acid according to GOST 18704, a solution of 40 g/DM.

Ammonium undeviatingly meta GOST 9336, a solution of 2.5 g/DM: 2.5 g dissolved in 500−700 cmof hot water in a volumetric flask with a capacity of 1000 cm, add 10 cmof concentrated nitric acid, made up to the mark with water, mixed and filtered.

Ammonium molybdate according to GOST 3765, recrystallized from alcoholic solution, a freshly prepared solution of 100 g/DM. The recrystallization of ammonium molybdate is carried out as specified in clause 3.2 GOST 6689.7.

Potassium permanganate according to GOST 20490, a solution of 10 g/DM.

Ammonia water according to GOST 3760.

The technical rectified ethyl alcohol according to GOST 18300.

Hydrogen peroxide according to GOST 10929, 3% solution.

High purity copper with a mass fraction of phosphorus not more than 0,0002%.

Sodium phosphate disodium GOST 4172.

Potassium phosphate according to GOST odnosemjannyj 4198.

Standard solution of phosphorus: 0,4395 g of single phosphate or potassium 0,4586 g twosemester sodium phosphate (previously dried at 105 °C to constant weight) was placed in a measuring flask with volume capacity of 1000 cm, dissolved in water, made up to the mark with water and mix.

1 cmof the solution contains 0.0001 g fo

store.

3.3. Analysis

3.3.1. For alloys with a mass fraction of tin and silicon is less than 0.05%

A sample of alloy weighing 1 g is placed in a beaker with a capacity of 100 cm, add 10 cmof nitric acid (2:3). After reconstitution, the solution boiled for 1 min to remove oxides of nitrogen. Add 1 cmof solution of potassium permanganate, and heated nearly to boiling. Add 2 cmof hydrogen peroxide solution and mix the solution until the destruction of the excess of potassium permanganate and enlightenment solution. Add 5 cmof the solution vadeevaloo ammonium and gently boil for 1 min. the solution was Then cooled to room temperature, transferred to a flask with a capacity of 50 cm, add 5 cmof ammonium molybdate solution, dilute to the mark with water and mix. After 5 min measure the optical density on a photoelectrocolorimeter with a blue filter or on a spectrophotometer at 440 nm in a cuvette with the thickness of the light absorbing layer 1 see Solution comparison is the solution to which is added a solution of molybdate of ammonium. The obtained values of optical density calculate the value of optical density in the reference experiment.

The solution in the reference experiment was prepared as follows: 10 cmof nitric acid (2:3) were placed in a glass with a capacity of 100 cmand boil the solution 1 min to remove oxides of nitrogen. Add 1 cmof a solution of potassium permanganate, and then do as above. Solution comparison is the solution to which is not added to the solution of molybdate of ammo

niya.

3.3.2. For alloys with a mass fraction of silicon in excess of 0.05%

A sample of alloy weighing 1 g is placed in a platinum Cup or Teflon beaker with a capacity of 100 cmand dissolved in a mixture of 15 cmof boric acid solution, 1 cmhydrofluoric acid and 10 cmof concentrated nitric acid. After reconstitution, the solution kept for 1 h at 90 °C. the Solution was transferred to a glass beaker with a capacity of 100 cm, rinse the Cup or glass 5 cmof water, add 1 cmof solution of potassium permanganate and heated until boiling, add 2 cmof hydrogen peroxide solution and stirred until the destruction of the excess of potassium permanganate and enlightenment solution. The solution is neutralized with ammonia to a pH of 3, add 5 cmof nitric acid (1:1), 5 cmsolution vadeevaloo ammonium and boil for 1 min. Further analysis is carried out as specified in clause 3.3.1. Reference solution and the solution prepared in the reference experiment, as indicated in paragraph 3.

3.1.

3.3.3. For alloys with a mass fraction of tin in excess of 0.05%

A sample of alloy weighing 1 g is placed in a beaker with a capacity of 100 cm, add exactly 15 cmof the mixture of acids to dissolve and dissolve with a moderate heat. Add 1 cmof hydrogen peroxide solution and gently boil for 3−5 minutes, avoiding loud and prolonged boiling. Then the solution was added 5 cmof the solution vadeevaloo ammonium, cooled to room temperature and transferred to a volumetric flask with a capacity of 50 cm. Add 5 cmof ammonium molybdate solution, dilute to the mark with water and mix. Further analysis is carried out as specified in clause 3.3.1. Reference solution and the solution prepared in the reference experiment, as indicated in paragraph 3.3.1.

3.3.4. Construction of calibration curve for alloys with a mass fraction of tin and silicon is less than 0.05%

In eight glasses with a capacity of 100 cmplaced 1 g of copper, and seven of them added 0,5; 1,0; 2,5; 5,0; 7,5; 10,0 and 12.0 cmstandard solution of phosphorus.

In all the glasses added to 10 cmof nitric acid (2:3) and then do as described in claim 3.3.1. Solution comparison is the solution not containing phosphorus. According to the obtained results build a calibration curve.

3.3.5. Construction of calibration curve for alloys with a mass fraction of silicon in excess of 0.05%.

Eight Cup platinum or PTFE beakers with a capacity of 100 cmplaced 1 g of copper, and seven of them added 0,5; 1,0; 2,5; 5,0; 7,5; 10,0 and 12.0 cmstandard solution of phosphorus. All glasses add 15 cmof boric acid solution, 1 cmhydrofluoric acid and 10 cmof concentrated nitric acid, then act as described in section 3.3.2. Solution comparison is the solution not containing phosphorus.

According to the obtained results build a calibration curve.

3.3.6. Construction of calibration curve for alloys with a mass fraction of tin in excess of 0.05%

In eight glasses with a capacity of 100 cmplaced 1 g of copper, and seven of them placed 0,5; 1,0; 2,5; 5,0; 7,5; 10,0 and 12.0 cmstandard solution of phosphorus. All glasses are placed at 15.0 cmof the mixture of acids to dissolve, then do as stated in claim 3.3.3. Solution comparison is the solution not containing phosphorus. According to the obtained results build a calibration curve.

3.4. Processing of the results

3.4.1. Mass fraction of phosphorus in percent is calculated by the formula

,

where is the mass of phosphorus was found in the calibration schedule g;

 — the weight of the portion of alloy,

3.4.2. Discrepancies in the results of three parallel measurements (rate of convergence) and the results of the two tests (index of reproducibility) shall not exceed the values of permissible differences given in table.2.

3.4.3. Control of accuracy of analysis results is carried out according to State standard samples (GSO) or industry standard sample (CCA), or by standard samples of the enterprise (SOP) of Nickel, Nickel and copper-Nickel alloys, approved under GOST 8.315, or by a method of additives, or a comparison of the results obtained for extraction-photometric method according to GOST 25086.