GOST 6689.6-92

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  ГОСТ 6689.6-92

GOST 6689.6−92 Nickel, alloys Nickel and copper-Nickel. Methods for determination of manganese

GOST 6689.6−92

Group B59

STATE STANDARD OF THE USSR

NICKEL, ALLOYS NICKEL AND COPPER-NICKEL

Methods for determination of manganese

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

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, L. V. Morea, A. I. Vorobyov

2. APPROVED AND promulgated by the Decree of Committee of standardization and Metrology of the USSR from 18.02.92 N 167

3. REPLACE GOST 6689.6−80

4. REFERENCE NORMATIVE AND TECHNICAL DOCUMENTS

This standard specifies the titrimetric method for the determination of manganese (at a mass proportion of manganese from 0.5 to 15%), photometric (at a mass fraction of manganese from 0.001 to 1.5%) and atomic absorption (at a mass fraction of from 0.001 to 6%) methods for determination of manganese in 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. TITRIMETRIC METHOD FOR THE DETERMINATION OF MANGANESE

2.1. The essence of the method

The method is based on the oxidation of divalent manganese to pneumococcal neccersarily ammonium in an acidic medium in the presence of silver nitrate as a catalyst and titration with a solution of sodium servational to a bleaching solution or salt Mora with potentiometric or visual indication of the titration end.

2.2. Apparatus, reagents and solutions

Potentiometer pH-340 or other device of the same accuracy class.

The indicator electrode is a platinum electrode ETPL-01M.

The reference electrode — silver chloride electrode EVL-1M, filled with a saturated solution of nitrate of potassium.

Nitric acid according to GOST 4461, diluted 1:1.

Sulfuric acid according to GOST 4204, diluted 1:1 and 1:9.

Orthophosphoric acid according to GOST 6552.

Hydrofluoric acid according to GOST 10484.

Sodium carbonate crystal according to GOST 84 and a solution of 2 g/DM.

Acid N-phenylanthranilic, a solution of 4 g/DM; 0.4 g of reagent was dissolved in 100 cmof warm sodium carbonate solution, filtered and stored for not more than 10 days.

Ammonium neccersarily according to GOST 20478, a solution of 200 g/DM(solution store no more than 5 days).

Silver nitrate according to GOST 1277, a solution of 10 g/DM.

Potassium permanganate according to GOST 20490, 0.01 mol/DMsolution.

Salt of protoxide of iron and ammonium double sulfate (salt Mora) according to GOST 4208, solution 0,005 mol/DM; 19,608 g of Mohr salt dissolved in 100 cmof sulphuric acid (1:9) and the same acid diluted to 1000 cm.

Sodium carnavalito acid (sodium thiosulfate); 0,0025 mol/DMsolution: 1.3 g carnavalito acid sodium are dissolved in 1000 cm — freshly prepared and chilled water. To stabilize the mass concentration of the solution was added 0.05 g of sodium carbonate. The mass concentration of the solution establish a standard solution of manganese.

Manganese brand or Мр0 Мр00 according to GOST 6008.

Standard manganese solution: 0.1 g of manganese dissolved in 10 cmof sulphuric acid (1:1). The solution was cooled, transferred to a volumetric flask with a capacity of 100 cm, made up to the mark with water and mix.

1 cmof the solution contains 0.001 g m

organza.

2.2.1. The installation of the mass concentration of salt solution Mora for potentiometric titration: titrated to the sample solution (p.2.3.1) add a 10 cmsolution of potassium permanganate and titrated again with a solution of salt Mora to jump in the potential.

2.2.2. The installation of the mass concentration of salt solution Mora for visual titration with phenylanthranilic acid in the conical flask with a capacity of 250 cmis placed 10 cmsulfuric acid (1:1), 10 cmof phosphoric acid, 100 CCof water and 10 cmof a solution of potassium permanganate. The mixture is cooled and titrated with a solution of salt Mora to slightly pink coloring, then add 4−5 drops of solution phenylanthranilic acid and continue the titration until you move the crimson color of the solution yellow.

Mass concentration solution of salt Mora () is calculated by the formula

,

where is the mass of manganese, corresponding to 1 cmof 0.01 mol/DMsolution of manganese-sour potassium g;

 — the volume of 0.01 mol/DMsolution of manganese-sour potassium, taken for titration, cm;

 — the volume of salt solution Mora, used for titration, see

.

2.2.3. The installation of the mass concentration of the solution servational sodium: 5 cmstandard solution of manganese is placed in a conical flask with a capacity of 250 cm, add 10 cmsulphuric acid (1:1), 90 cmwater, 10 cmof phosphoric acid, 15 cmof a solution of silver nitrate and 20 cmof a solution of ammonium naternicola. The mixture was heated to boiling and boil until the destruction of excess ammonium naternicola. Painted purple solution is rapidly cooled and titrated manganese acid solution servational sodium to the disappearance of the pink color.

Mass concentration of solution carnavalito acid sodium () is calculated by the formula

,

where is the mass of manganese, was taken for titration, g;

the volume of the solution servational sodium, spent on titration, sm.

2.3. Analysis

2.3 1. For alloys containing less than 0.1% silicon

A portion of the alloy (tab.1) is placed in a beaker with a capacity of 250 cm, add 20 cmof nitric acid, cover with watch glass, glass or plastic plate and dissolved by heating.

Table 1

Glass or the plate and the wall of the beaker rinse with water, add 10 cmsulphuric acid (1:1) and the solution is evaporated until a white smoke of sulfuric acid. The residue is cooled, add water to a volume of 50−60 cmand heated to dissolve the salts. Then add 10 ml of phosphoric acid, 15 cmof a solution of silver nitrate, 20−25 cmnaternicola solution of ammonia, heated to boiling and boil until the destruction of excess ammonium naternicola (which are known by the termination of allocation of bubbles of oxygen).

2.3.1.1. Potentiometric titration with a solution of salt Mora

The hot solution is painted in violet color, quickly titrated with a solution of salt Mora to the jump in potential while stirring the solution with a magnetic stirrer.

2.3.1.2. The visual titration with a solution of salt Mora

The hot solution is painted in violet color, rapidly cooled, diluted with water to a volume of 150 cmand titrated with a solution of salt Mora to slightly pink coloring, then add 4−5 drops of solution phenylanthranilic acid and continue to titrate to the transition of the crimson colouring in yellow.

2.3.1.3. Titration with a solution of sodium servational

The hot solution is painted in violet color, rapidly cooled and titrated manganese acid solution servational sodium to the disappearance of the pink color.

2.3.2. For alloys containing more than 0.1% silicon

A portion of the alloy (see table.1) is placed in a platinum Cup, add 10 cmof nitric acid, 2−3 cmhydrofluoric acid and dissolved by heating. Rinse the walls of the Cup with water, add 10 cmsulphuric acid (1:1) and the solution is evaporated until a white smoke of sulfuric acid. The residue is cooled, add 30−40 cmof water, heated to dissolve the salts, the solution was transferred to a beaker with a capacity of 250 cm. Then add 10 cmof phosphoric acid and further analysis is carried out as specified in PP.2.3.1, 2.3.1.1, 2.3.1.2 and 2.3.1.3.

2.4. Processing of the results

2.4.1. Mass fraction of manganese () in percent is calculated by the formula

,

where  — the volume of salt solution Mora or chernovetskogo sodium consumed for titration, cm;

mass concentration of salt solution Mora or chernovetskogo sodium manganese, g/cm;

 — 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 Nickel and copper-Nickel alloys, approved under GOST 8.315*, or a comparison of the results obtained photometric or atomic absorption methods, in accordance with GOST 25086.
________________
* On the territory of the Russian Federation GOST 8.315−97, here and hereafter. — Note the manufacturer’s database.

3. THE PHOTOMETRIC METHOD FOR THE DETERMINATION OF MANGANESE

3.1. The essence of the method

The method is based on measuring the optical density of coloration of manganese acid after oxidation of divalent manganese to pneumococcal hodnoceni potassium.

3.2. Apparatus, reagents and solutions

Photoelectrocolorimeter or spectrophotometer.

Nitric acid according to GOST 4461, diluted 1:1 and 1:100.

Sulfuric acid according to GOST 4204, diluted 1:1.

Orthophosphoric acid according to GOST 6552.

Hydrofluoric acid according to GOST 10484.

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

Potassium cognately.

Potassium permanganate according to GOST 20490, 0,02 mol/DMsolution.

Manganese brand or Мр0 Мр00 according to GOST 6008.

Standard solutions of manganese

Solution a: 0.1 g of manganese dissolved in 10 cmof nitric acid, diluted 1:1, and boil to remove oxides of nitrogen. The dissolution can be carried out in 10 cmof sulphuric acid (1:1). The solution is transferred into a measuring flask with volume capacity of 1000 cm, made up to the mark with water.

Standard solution And manganese can also be prepared from 0.02 mol/DMsolution of potassium permanganate: 9.1 cmof 0.02 mol/DMsolution of potassium permanganate is placed in a volumetric flask with a capacity of 100 cmand then filled to the mark with water.

1 cmof the solution contains 0.0001 g of manganese.

Solution B: 25 cmsolution And placed in a volumetric flask with a capacity of 250 cm, and topped to the mark with water.

1 cmof solution B contains 0,00001 g mA

Lanza.

3.3. Analysis

3.3.1. For alloys containing less than 0.1% of silicon and chromium and tungsten

A portion of the alloy (tab.3) is placed in a beaker with a capacity of 250 cm, add 20 cmof nitric acid (1:1), 10 cmof phosphoric acid and dissolved by heating. After cooling, rinse walls of beaker with water and the mass fraction of manganese is less than 0.05% use entire solution, and for the mass concentration of over 0.05% the resulting solution was transferred to a volumetric flask with a capacity of 100 cmand top up with water to the mark.

Table 3

Aliquot part of the solution (see table.3) is placed in a beaker with a capacity of 100 cm, is diluted with water to a volume of 50 cmand add 0.3 g of potassium jednolitego. If the photometry using the entire solution, ignominy potassium is added directly into the glass, which made the dissolution. The solution is heated nearly to boiling and allowed to stand in a water bath at 90 °C for about 20 min Then the solution was cooled, transferred to a volumetric flask with a capacity of 100 cm, made up to the mark with water and measure the optical density of the solution on a photoelectrocolorimeter with a green optical filter in a cuvette with a thickness of the light absorbing layer 2 or 5 cm (depending on the mass fraction of manganese), or on the spectrophotometer at 528 nm in a cuvette with the thickness of the light absorbing layer 1 cm.

As a solution comparison, using part of the sample solution, in which manganese acid reduced to divalent manganese by the addition dropwise of a solution of sodium attestatio.

3.3.2. For alloys containing tungsten

A portion of the alloy (see table.3) is placed in a beaker with a capacity of 250 cm, add 20 cmof nitric acid (1:1), cover with watch glass, glass or plastic plate and dissolved by heating. Glass or plate and the side of the Cup then rinsed with water and the solution is evaporated to a syrupy condition. Then add 100 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, a glass and a precipitate was washed 6−8 times with hot nitric acid (1:100), collecting the filtrate and washings in a beaker with a capacity of 250 cm. Filter the precipitate discarded, and the filtrate is evaporated to a volume of about 50 cm. To the solution was added 10 cmof phosphoric acid and 0.3 g jednolitego potassium is heated nearly to boiling and allowed to stand in a water bath at 90 °C for 20 min and further analysis is carried out as specified in clause 3.3.1.

3.3.3. For alloys containing more than 0,1% of chromium and silicon

A portion of the alloy (see table.3) is placed in a platinum Cup, add 20 cmof nitric acid (1:1), 1−2 cmhydrofluoric acid and dissolved by heating. The cooled solution was added 20 cmof sulphuric acid and is evaporated prior to the allocation of white smoke of sulfuric acid. A Cup of cooled, rinse the walls of the Cup with water and repeat the evaporation to start the selection of a white smoke of sulfuric acid. To the cooled residue add 30 cmof water and dissolved by heating.

When the mass fraction of manganese in the alloy is less than 0.05% the solution was transferred to a beaker with a capacity of 100 cm, dilute with water to 50 cm, add 10 cmof phosphoric acid, 0.3 g of potassium jednolitego and further analysis is carried out as specified in clause 3.3.1.

In the case of analysis of alloys containing chromium, the optical density of the solution measured at 545−565 nm and using a calibration graph constructed under the same wavelength

.

3.3.4. Construction of calibration curve

3.3.4.1. Standard manganese solution prepared from metallic manganese

In glasses with a capacity of 100 cmare placed sequentially 1,0; 2,0; 3,0; 4,0; 6,0 and 7.0 cmAnd a standard solution of manganese (nitric acid solution for analysis by PP.3.3.1 and 3.3.2 or sulphate solution for analysis according to claim 3.3.3 in the determination of manganese from 0.001 to 0.01%) or 2,0; 4,0; 6,0; 8,0; 10,0; 12,0 cmstandard solution B of manganese (nitric acid solution for analysis by PP.3.3.1 and 3.3.2 and sulfuric acid solution for analysis according to claim 3.3.3 when the mass fraction of manganese from 0.01 to 0.5%), is added to 15 cmof nitric acid (1:1) and boil to remove oxides of nitrogen or add 10 cmsulphuric acid. To the solutions was added 5 cmof phosphoric acid, 0.3 g of potassium jednolitego and further analysis is carried out as specified in clause 3.3.1. For alloys containing chrome, optical density of the solution measured at 545−565 nm. When applying a standard solution And manganese absorbance calibration curve is measured on a photoelectrocolorimeter in a ditch with the thickness of the light absorbing layer 2 cm and when using a standard solution of B — 5 see

3.3.4.2. Standard manganese solution prepared from a solution of potassium permanganate

In a volumetric flask with a capacity of 100 cmconsistently placed: 1,0; 2,0; 3,0; 4,0; 5,0; 6,0; 7,0 cmstandard solution And manganese or 2,0; 4,0; 6,0; 8,0; 10,0; 12,0 cmstandard solution B of manganese, made up to the mark with water, mix and measure the optical density as indicated in the claims.3.3.1 and 3.3.4.1.

3.4. Processing of the results

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

,

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

 — weight of alloy, suitable aliquote part of the solution,

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 a comparison of the results obtained by atomic absorption method, in accordance with GOST 25086.

4. ATOMIC ABSORPTION METHOD FOR THE DETERMINATION OF MANGANESE

4.1. The essence of the method

The method is based on measuring the absorption of light by atoms of manganese formed during the introduction of the analyzed solution in the flame acetylene-air.

4.2. Apparatus, reagents and solutions

Atomic absorption spectrometer with a radiation source for manganese.

Nitric acid according to GOST 4461 and diluted 1:1 and 1:100.

Hydrochloric acid according to GOST 3118 and 1 and 2 mol/DMsolutions.

A mixture of acid: mix one volume of nitric acid with three volumes of hydrochloric acid.

Hydrofluoric acid according to GOST 10484.

Sulfuric acid according to GOST 4204, diluted 1:1.

Manganese GOST 6008.

Standard manganese solution: 0.1 g of manganese dissolved by heating in 10 cmof nitric acid (1:1). The solution was transferred to a volumetric flask with a capacity of 1 DMand topped to the mark with water.

1 cmof the solution contains 0.0001 g of manganese.

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

Standard copper solution: 10 g of copper was dissolved with heating in 80 cmof nitric acid (1:1). The solution was transferred to a volumetric flask with a capacity of 100 cmand top up with water to the mark.

1 cmof the solution contains 0.1 g of copper.

Nickel GOST 849*.
________________
* On the territory of the Russian Federation GOST 849−2008. — Note the manufacturer’s database.

A standard solution of Nickel: 10 g of Nickel is dissolved by heating in 80 cmof nitric acid (1:1). The solution was transferred to a volumetric flask with a capacity of 100 cmand top up with water to the mark.

1 cmof the solution contains 0.1 g nick

Yale.

4.3. Analysis

4.3.1. For alloys not containing tin, silicon, chromium, tungsten and titanium

A portion of the alloy by weight (table.4) was dissolved with heating in 10−20 cmof nitric acid (1:1). The solution was transferred to a volumetric flask with a capacity of 100 cmand top up with water to the mark. When the mass fraction of manganese of more than 0.5% 10 cmof the sample solution transferred to a volumetric flask with a capacity of 100 cm, add 10 cmof 2 mol/DMhydrochloric acid solution and add water to the mark.

Table 4

Measure the atomic absorption of manganese in the flame acetylene-air at a wavelength of 279.5 nm parallel to the calibration solutions.

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

A portion of the alloy (see table.4) was dissolved with heating in 10 cmof a mixture of acids. The solution was transferred to a volumetric flask with a capacity of 100 cmand topped to the mark of 1 mol/DMhydrochloric acid solution With mass fraction of manganese of more than 0.5% 10 cmof the sample solution transferred to a volumetric flask with a capacity of 100 cmand topped to the mark of 1 mol/DMhydrochloric acid solution. Measure the atomic absorption of manganese, as specified in clause 4.3.1.

4.3.3. For alloys containing silicon, titanium and chromium

A portion of the alloy (see table.4) is placed in a platinum Cup and dissolve by heating in 10−20 cmof nitric acid (1:1) and 2 cmhydrofluoric acid. Then add 10 cmsulphuric acid (1:1) and evaporated until a white smoke of sulfuric acid. Cup cooled and the residue is dissolved in 50 cmof water when heated. The solution was transferred to a volumetric flask with a capacity of 100 cmand top up with water to the mark. When the mass fraction of manganese of more than 0.5% 10 cmof the sample solution transferred to a volumetric flask with a capacity of 100 cm, add 10 cmof 2 mol/DMhydrochloric acid solution and add water to the mark. Measure the atomic absorption of manganese, as specified in clause 4.3

.1.

4.3.4. For alloys containing tungsten

A portion of the alloy (see table.4) was dissolved with heating in 10−20 cmof nitric acid (1:1), then add 30 cmof hot water, the precipitate tungsten acid is filtered off on a tight filter and washed with hot nitric acid (1:100). The filtrate is transferred to a volumetric flask with a capacity of 100 cmand top up with water to the mark. When the mass fraction of manganese of more than 0.5% 10 cmof the sample solution transferred to a volumetric flask with a capacity of 100 cm, add 10 cmof 2 mol/DMhydrochloric acid solution and add water to the mark. Measure the atomic absorption of manganese, as specified in clause 4.3.1

.

4.3.5. Construction of calibration curve

In seven of the eight volumetric flasks with a capacity of 100 cmplaced 0,2; 2,0; 3,0; 4,0; 5,0; 6,0 cmstandard solution of manganese, which corresponds to 0,02; 0,1; 0,2; 0,3; 0,4; 0,5 and 0.6 mg of manganese. To all flasks add 10 cmof 2 mol/DMhydrochloric acid solution. For the mass concentration of manganese less than 0.05% aliquote add volumes of standard solutions (see table.4) copper (if copper is the basis of alloy) or Nickel (if Nickel is a base alloy) and topped to the mark with water. Measure the atomic absorption of manganese, as specified in clause 4.3.1. According to the obtained results build a calibration curve.

4.4. Processing of the results

4.4.1. Mass fraction of manganese () in percent is calculated by the formula

,

where is the concentration of manganese was found in the calibration schedule, g/cm;

 — the volume of the sample solution, cm;

 — the weight of the portion of the sample,

4.4.2. 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.

4.4.3. 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 additives or by comparison of the results obtained photometric or titrimetric methods, in accordance with GOST 25086.