GOST 9853.4-96
GOST 9853.4−96 Titan spongy. Methods of determination of chlorine
GOST 9853.4−96
Group B59
INTERSTATE STANDARD
TITANIUM SPONGE
Methods of determination of chlorine
Sponge titanium. Methods for determination of chlorine
ISS 77.120*
AXTU 1709
_______________
* In the index «National standards» 2007
OKS
Date of introduction 2000−07−01
Preface
1 DEVELOPED by the Interstate technical Committee for standardization MTK 105, Ukrainian research and design Institute of titanium
SUBMITTED to the State Committee of Ukraine for standardization, Metrology and certification
2 ADOPTED by the Interstate Council for standardization, Metrology and certification (Protocol No. 9 dated April 12, 1996)
The adoption voted:
| The name of the state |
The name of the national authority standardization |
| The Republic Of Azerbaijan |
Azgosstandart |
| The Republic Of Belarus |
Gosstandart Of Belarus |
| The Republic Of Kazakhstan |
Gosstandart Of The Republic Of Kazakhstan |
| Russian Federation |
Gosstandart Of Russia |
| Turkmenistan |
The main state inspection of Turkmenistan |
| Ukraine |
Gosstandart Of Ukraine |
3 Resolution of the State Committee of the Russian Federation for standardization and Metrology dated 19 October 1999 No. 353-St inter-state standard GOST 9853.4−96 introduced directly as state standard of the Russian Federation from July 1, 2000.
4 REPLACE GOST 9853.4−79
1 Scope
This standard specifies the turbidimetric (mass fraction of chlorine at from 0.003% to 0.12%), coulometric (mass fraction of chlorine at from 0.01% to 0.4%) and mercurimetric (when the mass fraction of chlorine from 0.05% to 0.3%) methods for determining chlorine in the spongy titanium according to GOST 17746.
Turbidimetric method is based on the reaction of formation of the finely dispersed silver chloride in the sample solution without separation of the titanium and subsequent measurement of optical density.
Coulometric method is based on the coulometric titration of chloride ions in the presence of titanium and the formation of silver chloride. To reduce adsorption of the chloride ions precipitate administered polyvinyl alcohol.
Mercurimetric method based on the formation of multisoliton connection dichloride of mercury during the titration of a solution containing chlorine, solution of nitrate of mercury was used as an indicator nitroprusside sodium.
2 Normative references
The present standard features references to the following standards:
GOST 8.315−97 State system for ensuring the uniformity of measurements. The standard samples. The main provisions, the order of development, certification, approval, registration and application
GOST 1277−75 Silver nitrate. Specifications
GOST 3765−78 Ammonium molybdate. Specifications
GOST 4204−77 sulfuric Acid. Specifications
GOST 4232−74 Potassium iodide. Specifications
GOST 4233−77 Sodium chloride. Specifications
GOST 4461−77 nitric Acid. Specifications
GOST 4520−78 Mercury (II) nitrate 1-water. Specifications
GOST 9656−75 boric Acid. Specifications
GOST 10163−76 Starch soluble. Specifications
GOST 10484−78 hydrofluoric Acid. Specifications
GOST 10779−97 polyvinyl alcohols. Specifications*
_______________
* On the territory of the Russian Federation GOST 10779−78 polyvinyl alcohols. Specifications. (Index «National standards», 2007).- Note the manufacturer’s database.
GOST 10929−76 Hydrogen peroxide. Specifications
GOST 17746−96 spongy Titanium. Specifications
GOST 23780−96 spongy Titanium. Methods of sampling and sample preparation
GOST 25086−87 non-ferrous metals and their alloys. General requirements for methods of analysis
GOST 27068−86 Chernovetskiy Sodium (sodium thiosulfate) 5-water. Specifications
3 General requirements
3.1 General requirements for methods of analysis GOST 25086.
3.2 Selection and preparation of samples is carried out according to GOST 23780.
3.3 Mass fraction of chlorine determined for the two batches.
4 Turbidimetric method
4.1 measuring instruments and auxiliary devices
Spectrophotometer type SF-46 or photoelectric colorimeter concentration of type KLF-2, or similar device.
Hydrofluoric acid according to GOST 10484, diluted 1:5.
Nitric acid according to GOST 4461 and diluted 1:19.
Sodium chloride (sodium chloride) according to GOST 4233.
Boric acid according to GOST 9656.
Silver nitrate (silver nitrate) GOST 1277, solution mass concentration of 2 g/DM.
State standard samples according to GOST 8.315.
Standard solutions of sodium chloride.
Solution a: 1,649 g of sodium chloride, dried at a temperature of 383 K To a constant mass, dissolved in water, transferred to a measuring flask with volume capacity of 1000 cm, made up to the mark with water and mix.
1 cmof the solution contains 0.001 g of chlorine.
Solution B: 2 cmof solution A is placed in a volumetric flask with a capacity of 100 cm
, made up to the mark with water and mix.
1 cmof solution B contains 0,00002 g of chlorine.
4.2 procedures for measuring
4.2.1 Sample the sample weight of 0.3−1.0 g according to table 1 was placed in a polyethylene beaker with a capacity of 100 cm, moistened with 1.5−2.0 cm
of water. The beaker was placed in a crystallizer with cold distilled water at a temperature not above (288±2) K and gradually in small portions poured 10 cm
hydrofluoric acid (1:5); cover the beaker with a lid. The sample was dissolved with constant stirring. After complete dissolution of the sample flow 3 cm
of concentrated nitric acid to the bleaching solution, the Cup is served until termination of the reaction, add 1.5 g of boric acid, stirred to dissolve the boric acid and the solution transferred to a volumetric flask with a capacity of 50 cm
. The solution from the cap and walls of plastic glass, washed with nitric acid, diluted 1:19, it poured the solution in the flask up to the mark and mix.
Table 1
| Mass fraction of chlorine, % |
The mass of charge, g |
Aliquota part of the solution, see |
| From 0.003 to 0.01 incl. |
1,0 |
25 |
| SV. The 0.01 «to 0.08 « |
0,5 |
15 |
| «0,08» to 0,12 « |
0,3 |
5 |
Aliquot part of the solution is 5−25 cm, according to table 1 was placed in a volumetric flask with a capacity of 50 cm
, pour nitric acid, diluted 1:19, to a volume of approximately 35 cm
, mix and add 3 cm
of silver nitrate solution. Without mixing, the solutions were left in dark place for 10 min, then poured nitric acid, diluted 1:19, to the mark, mix and measure the optical density of the solution at a wavelength of 400 nm thick absorbing layer of 50 mm. Solution comparison the solution serves as the reference experiment.
Mass fraction of chlorine in the sample is calculated according to the calibration schedule.
4.2.2 For constructing the calibration curve in seven of the eight volumetric flasks with a capacity of 50 cmplaced 0,5; 1,0; 2,0; 3,0; 4,0; 5,0; 6,0 cm
standard solution B, which corresponds to 0,00001; 0,00002; 0,00004; 0,00006; 0,00008; 0,00010; 0,00012 g of chlorine.
The eighth solution of the flask is a solution of the reference experiment.
The solutions in all flasks was diluted nitric acid, diluted 1:19, to a volume of approximately 35 cm, mix, add 3 cm
of silver nitrate solution. Don’t stir, leave in a dark place for 10 min and then do as specified
According to the obtained values of optical density and corresponding mass of chlorine build calibration curve.
4.3 the Processing of the measurement results
Mass fraction of chlorine , %, is calculated by the formula
where is the mass of chlorine in the sample solution found by the calibration schedule g;
— total volume of sample solution, cm
;
— the mass of sample, g;
— aliquotes volume of the sample, cm
.
4.4 Permissible error of measurement
4.4.1 the Difference between the two measurements and the results of the analysis (with confidence 
Table 2
Percentage
| Mass fraction of chlorine |
Permitted the discrepancy between the results of the parallel measurements |
Permitted the discrepancy between the results of the analysis |
The margin of error of measurement |
| From to 0,0030 0,0100 incl. |
0,0015 |
0,0020 |
0.0016 inch |
| SV. 0,010 «0,030 « | 0,007 |
0,008 |
0,006 |
| «0,030» 0,080 « | 0,010 |
0,015 |
0,012 |
| «0,080» 0,120 « | 0,015 |
0,020 |
0,016 |
4.4.2 Control the accuracy of the results of the analysis carried out according to standard sample in accordance with GOST 25086.
Allowed to monitor the accuracy of analysis results by the method of additives in accordance with GOST 25086.
Additives is a standard solution A.
5 Coulometric method
5.1 measuring instruments and auxiliary devices
The laboratory coulometric titrator with silver electrodes (silver, high-purity microwave 10 with a diameter of 2−3 mm) type T-201 or similar device.
Hydrofluoric acid according to GOST 10484, diluted 1:5.
Hydrogen peroxide according to GOST 10929, 3% solution.
Sodium chloride (sodium chloride) according to GOST 4233.
The polyvinyl alcohol according to GOST 10779, solution mass concentration 10 g/DM.
Spongy titanium with a mass fraction of chlorine from 0.02% to 0.04%.
Ammonium molybdate (ammonium molybdate) according to GOST 3765, solution mass concentration of 300 g/DM.
Sulfuric acid according to GOST 4204, solution molar concentration of 2 mol/DM.
Potassium iodide (potassium iodide) according to GOST 4232.
Sodium thiosulfate (sodium Chernovetskiy) (fixanal) according to GOST 27068, solution of molar concentration 0.05 mol/DM.
The soluble starch according to GOST 10163, 0,1% solution.
State standard samples according to GOST 8.315.
Standard solutions of sodium chloride.
Solution a: 1,649 g of sodium chloride (pre-dried at a temperature of 383 K) is dissolved in water, transferred into a measuring flask with volume capacity of 1000 cm, adjusted to the mark with water and mix.
1 cmof the solution contains 0.001 g of chlorine.
Solution B: 10 cmsolution And placed in a volumetric flask with a capacity of 100 cm
, adjusted to the mark with water and mix.
1 cmof a solution contains 0.0001 g of chlorine.
5.2 preparation for measurement
Before taking measurements for 40−60 minutes includes an electrical network of display units and current regulator titrator T-201.
Generator set current equal to 20 mA. The dial of the titration end point set to 15 µa. The electrode surface should be shiny.
Before measurements accurately establish the concentration of 3% hydrogen peroxide solution. This 100 cmof concentrated hydrogen peroxide are placed in a measuring flask with volume capacity of 1000 cm
, adjusted to the mark with water and mix. Aliquot part of the solution is 3 cm
is placed in a volumetric flask with a capacity of 250 cm
, made up to the mark with water and mix.
To aliquote parts of a solution of 25 cmadd 10 cm
sulphuric acid 1 g of potassium iodide, 3 drops of ammonium molybdate solution, 2−3 drops of starch solution and titrated with sodium thiosulfate until the disappearance of blue color.
The hydrogen peroxide concentration set once after cooking.
Mass fraction of hydrogen peroxide , %, is calculated by the formula
where is the volume of sodium thiosulfate consumed in the titration, cm
;
— mass concentration of sodium thiosulfate by hydrogen peroxide, equal 0,00085 g/cm
;
— total dilution of hydrogen peroxide, cm
.
5.3 procedures for measuring
5.3.1 a sample weighing 0.3 g was placed in a polyethylene beaker with a capacity of 35−40 cm, add 15 cm
hydrofluoric acid and close the lid. After complete dissolution of the sample solution with the cap flush to Cup 2−3 cm
of water. The solution was cooled to room temperature. From the buret add 5 cm
of hydrogen peroxide solution and injected 1 cm
solution of polyvinyl alcohol. The total volume of the solution in the beaker was adjusted to 30 cm
.
The titration in the following manner: a glass solution is placed in the titration table and immerse the electrodes in it with a stirrer. The switch kind of work included in the position «Training», at the same time turn the agitator. Handle reset counter set the stopwatch to zero. After the needle of microammeter is set for divisions 5−7 µa, the switch knob sort of works include to «Titration». At the same time include a stopwatch. After you stop the titration (with indicator is an indicator lamp is illuminated «End»), record meter readings. Next, the counter is reset, the electrodes and the stirrer is washed with water.
Before measuring the concentration of chloride ion in the sample solution is carried out the calibration of an instrument and the construction of calibration curve.
5.3.2 For the construction of calibration curve seven plastic cups placed sample weight of 0.3 g titanium sponge with the established chlorine content less than 0.04%, is dissolved in hydrofluoric acid, add a solution of hydrogen peroxide and polyvinyl alcohol as described standard solution B, which corresponds to 0,0001; 0,0002; 0,0003; 0,0004; 0,0005; 0,0006 g of chlorine. The solution of the seventh glass is a solution in the reference experiment. The volume of solution in the beakers was adjusted with water to 30 cm
. The titration as specified
According to the obtained counter values and their corresponding masses of chlorine, expressed in percent, build a calibration curve. Without changing the slope of the graph, carry the calibration straight line parallel to the ordinate axis at the value of the mass fraction of chlorine in percent in the sample of titanium sponge used to build a calibration chart.
5.4 the Processing of the measurement results
Mass fraction of chlorine found by the calibration schedule.
5.5 Permissible error of measurement
5.5.1 the Difference between the two measurements and the results of the analysis (with confidence 
Table 3
Percentage
| Mass fraction of chlorine |
The permissible discrepancy between the results of the parallel measurements |
The permissible discrepancy between the results of the analysis |
The margin of error of measurement |
| From 0,010 to 0,030 incl. |
0,008 |
0,010 |
0,008 |
| SV. 0,030 «to 0,060 « | 0,010 |
0,025 |
0,020 |
| «0,060» 0,080 « | 0,012 |
0,030 |
0,024 |
| «0,080» 0,100 « | 0,016 |
0,040 |
0,032 |
| «0,100» 0,120 « | 0,018 |
0,045 |
0,036 |
| «Of 0.12» to 0.30 « | 0,02 |
0,05 |
0,04 |
| «To 0.30» and 0.40 « | 0,03 |
0,06 |
0,05 |
5.5.2 accuracy Control of the results of the analysis carried out according to standard sample in accordance with GOST 25086.
Allowed to monitor the accuracy of analysis results by the method of additives in accordance with GOST 25086.
Additives is a standard solution A.
6 Mercurimetric method
6.1 measuring instruments and auxiliary devices
Hydrofluoric acid according to GOST 10484, diluted 1:5.
Nitric acid according to GOST 4461 concentrated (
) and diluted 1:4 and 1:10.
Boric acid according to GOST 9656.
Sodium nitroprusside, according to existing normative document, solution mass concentration of 100 g/DM.
Mercury nitrate (mercury nitrate) GOST 4520, solution of molar concentration 0.05 mol/DM.
Sodium chloride (sodium chloride) according to GOST 4233.
State standard samples according to GOST 8.315.
The sodium chloride solution of molar concentration 0.1 mol/DMprepared from standard-titer according to the current normative document.
Standard solutions of sodium chloride.
Solution a: 1,649 g of sodium chloride, dried at a temperature of (383±10) K, dissolved in water, transferred to a measuring flask with volume capacity of 1000 cm, made up to the mark with water and mix.
1 cmof the solution contains 0.001 g of chlorine.
Solution B: 10 cmsolution And transferred to a volumetric flask with a capacity of 100 cm
, made up to the mark with water and mix.
1 cmof a solution contains 0.0001 g of chlorine.
6.2 preparation for measurement
6.2.1 preparation of the solution of mercurous nitrate: 17.0 g of mercurous nitrate is dissolved in 150 cmof water with the addition of 20 cm
of nitric acid (
). The solution is transferred into a measuring flask with volume capacity of 1000 cm
, made up to the mark with water and mix.
6.2.2 determination of the correction factor molar concentration of a mercurous nitrate solution: in a conical flask with a capacity of 250 cmtaken 25 cm
of sodium chloride molar concentration of 0.1 mol/DM
, add 6 cm
of nitric acid (1:4), 2 cm
of sodium nitropruside solution and titrated with a solution of nitrate of mercury until the appearance does not disappear while stirring the dregs.
The correction factor molar concentration of a solution of nitrate of mercury is calculated by the formula
where 25 is the volume of sodium chloride solution taken for titration, cm;
— the volume of mercurous nitrate solution consumed for titration, sm
.
The results calculated with an accuracy to the fourth decimal place. The result of taking the average value of three parallel measurements. The correction factor molar concentration should be within 0,9500−1,0500. The correction factor molar concentration check once per month.
6.3 procedures for measuring
A sample weighing 2 g was placed in a polyethylene beaker with a capacity of 100−200 cmand moistened with 2 cm
of water. Glass put in a mold with cold distilled water at a temperature of not higher (288±2) K and gradually, in small portions pour the 40 cm
of a solution of hydrofluoric acid (1:5), cover with a glass lid. The sample was dissolved with constant stirring. After complete dissolution of the sample poured 4−5 cm
of concentrated nitric acid to the bleaching solution, the Cup is served until the termination of the reaction, the solution was cooled to room temperature.
The solution was transferred to a conical flask with a capacity of 250 cm, where previously introduced 2 g of boric acid and 50 cm
of water, the solution was stirred until complete dissolution, poured 10 cm
of nitric acid (1:10), add 1−2 cm
of sodium nitropruside solution and titrated from microburette solution of nitrate of mercury until the appearance does not disappear with careful stirring of the dregs.
Simultaneously conduct control experience through all stages of the analysis.
6.4 Processing of results of measurements
Mass fraction of chlorine , %, is calculated by the formula
where is the volume of mercurous nitrate solution consumed for titration, cm
;
— the volume of mercurous nitrate solution consumed for titration of the control experience, cm
;
— correction factor for molar concentration of a solution of nitrate of mercury;
0,00355 — mass concentration of nitrate of mercury, g/cmchlorine;
— the weight of the portion,
6.5 Permissible error of measurement
6.5.1 Difference between the two measurements and the results of the analysis (with confidence 
Table 4
Percentage
| Mass fraction of chlorine |
The permissible discrepancy between the results of the parallel measurements |
The permissible discrepancy between the results of the analysis |
The margin of error of measurement |
| From 0,050 to 0,150 incl. |
0,013 |
0,020 |
0,016 |
| SV. 0,150 «0,300 « |
0,028 |
0,040 |
0,030 |
6.5.2 Control the accuracy of the results of the analysis carried out according to standard sample in accordance with GOST 25086.
Allowed to monitor the accuracy of analysis results by the method of additives in accordance with GOST 25086.
Additives is a standard solution A.
7 qualifications
To perform analysis allowed the analyst qualification not less than 4th level.
