GOST 13047.14-2002
NICKEL. COBALT
METHODS FOR DETERMINATION OF BISMUTH
THE INTER-STATE COUNCIL
FOR STANDARDIZATION, METROLOGY AND CERTIFICATION
Minsk
Preface
1 DEVELOPED by Interstate technical committees for standardization MTK 501 Nickel and MTC 502 «Cobalt», JSC «Gipronikel ' Institute»
INTRODUCED by Gosstandart of Russia
2 ADOPTED by the Interstate Council for standardization, Metrology and certification (Protocol № 21 dated may 30, 2002)
The adoption voted:
| The name of the state | The name of the national authority for standardization |
| The Republic Of Azerbaijan | Azgosstandart |
| The Republic Of Armenia | Armastajad |
| The Republic Of Belarus | Gosstandart Of The Republic Of Belarus |
| Georgia | Gosstandart |
| The Kyrgyz Republic | Kyrgyzstandard |
| The Republic Of Moldova | Moldovastandart |
| Russian Federation | Gosstandart Of Russia |
| The Republic Of Tajikistan | Tajikstandart |
| Turkmenistan | The MDCSU «Turkmenstandartlary» |
| The Republic Of Uzbekistan | Standards |
| Ukraine | Gosstandart Of Ukraine |
3 Resolution of the State Committee of the Russian Federation for standardization and Metrology dated 17 September 2002 No. 334-St inter-state standard GOST 13047.14−2002 introduced directly as state standard of the Russian Federation from July 1, 2003
4 REPLACE GOST 13047.11−81, GOST 741.17−80
GOST 13047.14−2002
INTERSTATE STANDARD
NICKEL. COBALT
Methods for determination of bismuth
Nickel. Cobalt.
Methods for determination of bismuth
Date of introduction 2003−07−01
1 Scope
This standard specifies the spectrophotometric and atomic absorption methods for the determination of bismuth at a mass fraction of from 0.0001% to 0,010% in the primary Nickel GOST 849, Nickel powder according to GOST 9722 and GOST cobalt 123 on.
2 Normative references
The present standard features references to the following standards:
GOST 123−98 Cobalt. Specifications
GOST 849−97 Nickel primary. Specifications
GOST 4232−74 Potassium iodide. Specifications
GOST 4461−77 nitric Acid. Specifications
GOST 5457−75 Acetylene, dissolved and gaseous. Specifications
GOST 9722−97 Nickel Powder. Specifications
GOST 10157−79 Argon gaseous and liquid. Specifications
GOST 10928−90 Bismuth. Specifications
GOST 11125−84 nitric Acid of high purity. Specifications
GOST 13047.1−2002 Nickel. Cobalt. General requirements for methods of analysis
3 General requirements and safety requirements
General requirements for methods of analysis and safety requirements when performing work — according to GOST 13047.1.
4 a spectrophotometric method (mass fraction of bismuth from of 0.0002% to 0.001%)
4.1 Method of analysis
The method is based on measuring light absorption at a wavelength of 540 nm of a solution of complex compounds of bismuth with selenology orange after pre-extraction of bismuth in the form of godenovo complex compounds with isoamyl acetate.
4.2 measuring instruments, auxiliary devices, materials, reagents, solutions
Spectrophotometer or photoelectrocolorimeter, which provides measurements in the wavelength range 500 — 560 nm.
pH meter (ion meter) for measurements in the pH range of 1.4 to 1.5.
Nitric acid according to GOST 4461, if necessary, purified by distillation, or according to GOST 11125 diluted 1:1, molar concentration of solutions 1 mole/DM3 and 0.03 mol/DM3.
The solution for Stripping: the solution of nitric acid molar concentration of 0.03 mol/DM3 is added dropwise a solution of nitric acid molar concentration of 1 mol/DM3 to achieve a pH in the range from 1.4 to 1.5 at a pH-meter.
Ascorbic acid of the Pharmacopoeia [1], the solution of the mass concentration of 0.05 g/cm3.
Potassium iodide according to GOST 4232, solution mass concentration of 0.02 g/cm3.
Bismuth GOST 10928.
Selenology orange, solution mass concentration of 0.001 g/cm3.
Isoamyl ether acetic acid (isoamyl acetate) at [2].
Bismuth solutions of known concentration.
The solution And the mass concentration of bismuth of 0.001 g/cm3: in a glass with a capacity of 250 cm3 was placed a suspension of bismuth with a mass of 0.5 g, flow 30 — 40 cm3 of nitric acid, diluted 1:1, dissolved by heating, boil 2 — 3 minutes, cooled, the solution was transferred to volumetric flask with a capacity of 500 cm3, flow of 50 cm3 of nitric acid, diluted 1:1, made up to the mark with water.
Solution B mass concentration of bismuth 0.0001 g/cm3: in a volumetric flask with a capacity of 100 cm3 is taken 10 cm3 of solution A, pour 10 cm3 of nitric acid, diluted 1:1, made up to the mark with water.
Solution of the mass concentration of bismuth 0,000005 g/DM3: in a volumetric flask with a capacity of 100 cm3 is taken 5 cm3 of a solution and topped up to the mark solution of nitric acid 1 mol/DM3.
4.3 Preparation for analysis
For calibration curve in a separating funnel with a capacity of 100 cm3 is taken 0,5; 1,0; 2,0; 4,0; 6,0 cm3 of solution, made up to 40 cm3 solution of nitric acid 1 mol/DM3, pour 1.0 cm3 of a solution of potassium iodide and then do as specified in 4.4.
The mass of bismuth in solutions for the calibration curve is 0,0000025; 0,0000050; 0,0000100; 0,0000200; 0,0000300 G.
The light absorption values of solutions and their corresponding masses of bismuth build a calibration curve based on the value of absorption solution, prepared without the introduction of a solution of bismuth.
4.4 analysis
In a glass with a capacity of 250 cm3 place the weighed sample mass of 3,000 g, pour 30 — 40 cm3 of nitric acid, diluted 1:1, dissolve while heating, evaporate to a volume of 5 — 10 cm3, add 15 cm3 of water and transferred the solution in a separating funnel with a capacity of 100 cm3. Pour water up to 40 cm3, add 1.0 cm3 of potassium iodide solution, 10 cm3 of isoamyl acetate and shake the funnel for 1 min. the Aqueous lower phase is transferred into another separatory funnel with a capacity of 100 cm3, pour 5 cm3 of isoamyl acetate and repeating the extraction 1 min. the Aqueous phase is discarded and the organic phases combined.
The joint solution pour 20 cm3 of nitric acid of 1 mol/cm3, 0.5 cm3 of a solution of ascorbic acid, 0.5 cm3 of a solution of potassium iodide and, gently turning funnel 5 to 6 times, washed the organic phase. The aqueous phase is discarded, the washing of the organic phase repeated. To the washed organic phase flow of 15 cm3 of the solution for Stripping, 0.2 cm3 kylinalove orange funnel and shake for 1 min. Aqueous phase was transferred to volumetric flask with a capacity of 25 cm3, filtering it through a funnel with a cotton swab, pre-washed with a solution for Stripping. After filtration, the swab is washed with Stripping solution and pour into the flask to the mark with this same solution.
Measure the light absorption of the solution after 20 minutes on the spectrophotometer at a wavelength of 540 nm or photoelectrocolorimeter in the wavelength range 500 — 560 nm, using a solution of comparison, the water and the cuvette with the thickness of the absorbing layer of 5 cm.
The mass of bismuth in the sample solution found by the calibration schedule.
4.5 Processing the analysis results
Mass fraction of bismuth in the sample of X %, is calculated by the formula
(1)
where Mx is the mass of bismuth in the sample solution, g;
MK — mass of bismuth in the solution in the reference experiment, g;
M — the weight of the portion of the sample,
4.6 accuracy Control analysis
Control of metrological characteristics of the results of the analysis carried out according to GOST 13047.1. Standards monitoring and error analysis method are given in table 1.
Table 1 — Standards for monitoring and error analysis method
Percentage
| Mass fraction of bismuth | The permissible discrepancy between two parallel definitions d2 |
Permissible discrepancies in the results of three parallel measurements d3 |
The allowable discrepancy of the two results of analysis D | The error analysis method D |
| 0,00020 | Of 0.00006 | 0,00007 | 0,00012 | 0,00008 |
| 0,00030 | 0,00008 | 0,00010 | 0,00015 | 0,00010 |
| 0,00050 | 0,00010 | 0,00012 | 0,00020 | 0,00015 |
| 0,00100 | 0,00020 | 0,00024 | 0,00040 | 0,00030 |
5 Atomic absorption method with electrothermal atomization (mass fraction of bismuth from 0.0001% to 0.001%)
5.1 Method of analysis
The method is based on measuring absorption at a wavelength of 223,1 nm resonance radiation by atoms of bismuth resulting from the electrothermal atomization of the sample solution.
5.2 measurement Means, auxiliary devices, materials, reagents, solutions
Atomic absorption spectrophotometer measurements with electrothermal atomization, the correction non-selective absorption and the automated flow of the solution into the atomizer.
Lamp with hollow cathode for the excitation of spectral lines of bismuth.
Argon gas according to GOST 10157.
Filters obestochennye in [3] or other medium density.
Nitric acid according to GOST 4461, if necessary, purified by distillation, or according to GOST 11125, diluted 1:1, 1:9.
Nickel powder according to GOST 9722 or standard sample of Nickel with the prescribed mass fraction of bismuth is not more than 0.0001%.
Cobalt GOST 123 or standard sample of cobalt with a prescribed proportion of bismuth is not more than 0.0001%.
Bismuth GOST 10928.
Bismuth solutions of known concentration.
The solution And the mass concentration of bismuth of 0.001 g/cm3 prepared as described in 4.2.
Solution B mass concentration of bismuth 0.0001 g/cm3 prepared as described in 4.2.
Solution of the mass concentration of bismuth 0,00001 g/cm3: in a volumetric flask with a capacity of 100 cm3 is taken 10 cm3 of a solution, pour 10 cm3 of nitric acid, diluted 1:1, made up to the mark with water.
The solution G of the mass concentration of bismuth 0,000001 g/cm3: in a volumetric flask with a capacity of 100 cm3 is taken 10 cm3 of solution, pour 10 cm3 nitric acid, diluted 1:1, made up to the mark with water.
5.3 Preparation for assay
For calibration curve into beakers or flasks with a capacity of 250 cm3 place the sample weighing 0,500 g sample of Nickel powder or cobalt, or a standard sample of Nickel or cobalt with the prescribed mass fraction of bismuth. The number of batches matches the number of points of calibration curve, including Supervisory experience.
The sample flow 15 — 20 cm3 of nitric acid, diluted 1:1 and dissolved by heating. When using the Nickel powder in the solutions were filtered through filters (red or white ribbon), washed 2 — 3 times with nitric acid, diluted 1:9, the filters are washed 2 — 3 times with hot water. The solutions were evaporated to a volume of 10 — 15 cm3, flow 40 — 50 cm3 of water, heated to boiling, cooled, transferred to volumetric flasks with a capacity of 100 cm3.
In the flask is taken 0,5; 1,0; 2,0; 3,0; 4,0; 5,0 cm3 of solution G in the flask with the solution in the reference experiment, a solution of bismuth is not administered, made up to the mark with water and then measure the absorbance as indicated in 5.4.
The mass of bismuth in solutions for constructing the calibration curve is 0,0000005; 0,0000010; 0,0000020; 0,0000030; 0,0000040; 0,0000050 G.
5.4 analysis
In a glass or flask with a capacity of 250 cm3 is placed a portion of the sample weighing 0,500 g, pour 15 — 20 cm3 of nitric acid, diluted 1:1, dissolve while heating, evaporate to a volume of 5 — 7 cm3, was transferred to a volumetric flask with a capacity of 100 cm3, cooled and topped to the mark with water.
Measure the absorbance of the sample solution and solutions for calibration at a wavelength of 223,1 nm, slit width less than 0.5 nm with the correction non-selective absorption in the current of argon at least two times, sequentially inserting them into the atomizer. Depending on the type of spectrophotometer select the optimal amount of solution injected into the atomizer, from 0.010 to 0.050 cm3 or the optimal time of an aerosol spray from 5 to 20 s. wash the system with water, check the zero point and the stability of the calibration curve. To check the zero point solution is used, the appropriate control experience, prepared as described in 5.3.
Selection of optimal temperature regimes for the atomizer is carried out individually for the used spectrophotometer on solutions for calibration.
Recommended operating conditions of the atomizer shown in table 2.
Table 2 — operating conditions of the atomizer
| The name of the stage | Temperature, °C | Time |
| Drying | 120 — 150 | 2 — 20 |
| Ashing | 700 — 900 | 10 — 20 |
| Atomization | 2000 — 2400 | 4 — 5 |
The values of absorption solutions for the calibration and corresponding masses of bismuth build the calibration graph.
The mass of bismuth in the sample solution found by the calibration schedule.
5.5 Processing of analysis results
Mass fraction of bismuth in the alloy, X %, is calculated by the formula
(2)
where Mx is the mass of bismuth in the sample solution, g;
M — the weight of the portion of the sample,
5.6 Control of accuracy of analysis
Control of metrological characteristics of the results of the analysis carried out according to GOST 13047.1. Standards monitoring and error analysis method are given in table 3.
Table 3 — Standards for monitoring and error analysis method
Percentage
| Mass fraction of bismuth | The permissible discrepancy between two parallel definitions d2 |
Permissible discrepancies in the results of three parallel measurements d3 |
The allowable discrepancy of the two results of analysis D | The error analysis method D |
| 0,00010 | 0,00003 | 0,00004 | Of 0.00006 | 0,00004 |
| 0,00020 | 0,00004 | 0,00005 | 0,00008 | 0,00008 |
| 0,00030 | 0,00005 | Of 0.00006 | 0,00010 | 0,00007 |
| 0,00040 | Of 0.00006 | 0,00007 | 0,00012 | 0,00008 |
| 0,00050 | 0,00007 | 0,00009 | 0,00014 | 0,00010 |
| 0,00060 | 0,00008 | 0,00010 | 0,00017 | 0,00012 |
| 0,00100 | 0,00015 | 0,00020 | 0,00030 | 0,00020 |
6 Atomic absorption method with flame atomization (mass fraction of bismuth from 0.002% to 0,010%)
6.1 Method of analysis
The method is based on measuring absorption at a wavelength of 223,1 nm resonance radiation by atoms of bismuth, generated as a result of atomization upon introduction of the sample solution into the flame acetylene-air.
6.2 measurement Means, auxiliary devices, materials, reagents, solutions
Atomic absorption spectrophotometer measurements in the flame acetylene-air.
Lamp with hollow cathode for the excitation of spectral lines of bismuth.
Acetylene gas according to GOST 5457.
Filters obestochennye in [3] or other medium density.
Nitric acid according to GOST 4461, if necessary, purified by distillation, or according to GOST 11125, diluted 1:1, 1:9.
Nickel powder according to GOST 9722 or standard sample of Nickel with the prescribed mass fraction of bismuth is not more than 0,002%.
Cobalt GOST 123 or standard sample of cobalt with the prescribed mass fraction of bismuth is not more than 0,002%.
Bismuth GOST 10928.
Bismuth solutions of known concentration.
The solution And the mass concentration of bismuth of 0.001 g/cm3 prepared as described in 4.2.
Solution B mass concentration of bismuth 0.0001 g/cm3 prepared as described in 4.2.
6.3 Preparation for analysis
For calibration curve into beakers or flasks with a capacity of 250 cm3 place hitch weight 3,000 g sample of Nickel powder or cobalt, or a standard sample of Nickel or cobalt with the prescribed mass fraction of bismuth. The number of batches must match the number of points of calibration curve, including Supervisory experience.
Sample poured to 25 — 30 cm3 of nitric acid, diluted 1:1 and dissolved by heating. When using the Nickel powder in the solutions were filtered through filters (red or white ribbon), washed 2 — 3 times with nitric acid, diluted 1:9, the filters are washed 2 — 3 times with hot water. The solutions were evaporated to a volume of 10 — 15 cm3, flow 40 — 50 cm3 of water, heated to boiling, cooled, transferred to volumetric flasks with a capacity of 100 cm3.
In the flask is taken 0,5; 1,0; 2,0; 3,0; 4,0 cm3 of solution B in the flask with the solution in the reference experiment, a solution of bismuth is not administered, made up to the mark with water and then measure the absorbance as indicated in 6.4. The mass of bismuth in solutions for the calibration is 0,00005; 0,00010; 0,00020; 0,00030; 0,00040 G.
6.4 analysis
In a glass or flask with a capacity of 250 cm3 place the weighed sample mass of 3,000 g, pour 25 — 30 cm3 of nitric acid, diluted 1:1, dissolved by heating, boil for 2 — 3 min, evaporated to a volume of 10 — 15 cm3, flow 40 — 50 cm3 of water, heated to boiling, cooled, transferred to volumetric flasks with a capacity of 100 cm3.
Measure the absorbance of the sample solution and solutions for calibration at a wavelength of 223,1 nm, slit width of 0.3 nm at least two times, sequentially inserting them into a flame, wash the system with water, check the zero point and the stability of the calibration curve. To check the zero point of the solution is used in the reference experiment, prepared as specified in 6.3.
The values of absorption solutions for the calibration and corresponding masses of bismuth build the calibration graph.
The mass of bismuth in the sample solution found by the calibration schedule.
6.5 Processing of analysis results
Mass fraction of bismuth in the sample of X %, is calculated by the formula
(3)
where Mx is the mass of bismuth in the sample solution, g;
M — the weight of the portion of the sample,
6.6 accuracy Control analysis
Control of metrological characteristics of the results of the analysis carried out according to GOST 13047.1. Standards monitoring and error analysis method are given in table 4.
Table 4 — Standards for monitoring and error analysis method
Percentage
| Mass fraction of bismuth | The permissible discrepancy between two parallel definitions d2 |
Permissible discrepancies in the results of three parallel measurements d3 |
The allowable discrepancy of the two results of analysis D | The error analysis method D |
| 0,0020 | 0,0002 | 0,0003 | 0,0004 | 0,0003 |
| 0,0030 | 0,0004 | 0,0005 | 0,0007 | 0,0005 |
| 0,0050 | About 0.0006 | 0,0007 | 0,0012 | 0,0008 |
| 0,0100 | 0,0010 | 0,0012 | 0,0020 | 0,0015 |
