GOST 16273.1-2014

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  ГОСТ 16273.1-2014

GOST 16273.1−2014 Selenium technical. Method of spectral analysis

GOST 16273.1−2014

INTERSTATE STANDARD

SELENIUM TECHNICAL

Method of spectral analysis

Selenium technical. Method of spectral analysis

ISS 77.120.99

Date of introduction 2015−09−01

Preface

Goals, basic principles and main procedure of works on interstate standardization have been established in GOST 1.0−92 «interstate standardization system. Basic provisions» and GOST 1.2−2009 «interstate standardization system. Interstate standards, rules and recommendations on interstate standardization. Rules of development, adoption, application, renewal and cancellation»

Data on standard

1 DEVELOPED by the Technical Committee for standardization TC 368 «Copper"

2 recorded by the Interstate technical Committee for standardization MTK 503 «Copper"

3 ACCEPTED by the Interstate Council for standardization, Metrology and certification (Protocol dated 30 may 2014 No. 67-P)

The adoption voted:

4 by Order of the Federal Agency for technical regulation and Metrology from November 26, 2014 # 1775-St inter-state standard GOST 16273.1−2014 introduced as the national standard of the Russian Federation from September 1, 2015.

5 REPLACE GOST 16273.1−85


Information about the changes to this standard is published in the annual reference index «National standards», and the text changes and amendments — in monthly information index «National standards». In case of revision (replacement) or cancellation of this standard a notification will be published in the monthly information index «National standards». Relevant information, notification and lyrics are also posted in the information system of General use — on the official website of the Federal Agency for technical regulation and Metrology on the Internet

1 Scope

This standard specifies the spectral emission measurement methods the mass fraction of copper, iron, lead, tellurium, arsenic, mercury, aluminum, sodium, antimony, calcium, magnesium, potassium, sulphur, cadmium, Nickel and selenium in the technical ranges of mass fraction, are presented in table 1.

General requirements to methods of measurement, safety requirements, verification of the accuracy of measurements in accordance with GOST 25086, GOST 16273.0.

2 Normative references

This standard uses the regulatory references to the following international standards:

GOST 1770−74 laboratory Glassware measuring glass. Cylinders, beakers, flasks, test tubes. General specifications

GOST 4233−77 Reagents. Sodium chloride. Specifications

GOST 6709−72 distilled Water. Specifications

GOST 9147−80 Glassware and equipment lab porcelain. Specifications

GOST 10157−79 Argon gaseous and liquid. Specifications

GOST 11125−84 nitric Acid of high purity. Specifications

GOST 14261−77 hydrochloric Acid of high purity. Specifications

GOST 16273.0−85 Selenium technical. General requirements for method of spectral analysis

GOST 18300−87 ethyl rectified technical. Specifications

GOST 23463−79 Graphite powder of high purity. Specifications

GOST 24104−2001* laboratory Scales. General technical requirements
________________
* On the territory of the Russian Federation GOST R 53228−2008 Scales non-automatic actions. Part 1. Metrological and technical requirements. Test.


GOST 25086−2011 non-ferrous metals and their alloys. General requirements for methods of analysis

GOST 25336−82 Glassware and equipment laboratory glass. The types, basic parameters and dimensions

GOST 29227−91 (ISO 835−1-81) oils. Pipettes are graduated. Part 1. General requirements

GOST ISO 5725−6-2002* Accuracy (trueness and precision) of methods and measurement results. Part 6. The use of precision values in practice
________________
* On the territory of the Russian Federation GOST R ISO 5725−6-2002 Accuracy (correctness and precision) of methods and measurement results. Part 6. The use of precision values in practice.


Note — When using this standard appropriate to test the effect of reference standards for the sign «National standards» drawn up as of January 1 of the current year and related information signs, published in the current year. If the reference standard is replaced (changed), when using this standard should be guided by replacing (amended) standard. If the reference standard is cancelled without replacement, then the situation in which the given link applies to the extent that does not affect this link.

3 emission Spectral method with photovoltaic spectra

3.1 Scope

In this section, the set of spectral emission method of measurement with photoelectric registration of spectrum of the mass fraction of copper, iron, lead, tellurium, arsenic, mercury and aluminum within the ranges presented in table 1.

3.2 characteristics of the indicators of measurement accuracy

The accuracy of the measurements the mass fraction of copper, iron, lead, mercury, tellurium, arsenic, aluminum, corresponds to the characteristics given in table 2 (with R=0,95).

Limit values of repeatability and reproducibility of measurements for a confidence probability P=0.95 is shown in table 2.


Table 2 — Values of the measure of the accuracy, limits of repeatability and reproducibility of measurements of mass fraction of copper, iron, lead, tellurium, arsenic, mercury, aluminum, at confidence probability P=0,95

Percentage

3.3 measurement Means, auxiliary devices, materials, solutions

When performing measurements using the following measuring instruments and auxiliary devices:

— diffraction spectrometer type IFS with the analyzer Maes;

— drying Cabinet, providing a heating temperature of from 100 °C to 105 °C;

— special laboratory scales of accuracy class according to GOST 24104;

— device for sharpening carbon electrodes, for example, the machine model CP-35, CCS-6;

box of organic glass;

— a mortar made of organic glass;

electrodes graphite high purity [1], grade not below the EU 12, with a diameter of 6 mm, a length of 35−55 mm, with a crater diameter of 4 mm, depth 4 mm and sharpened to a cone;
________________
* POS. [1]-[3], see Bibliography. — Note the manufacturer’s database.


— stainless steel tweezers;

— volumetric flasks 2−50−2 according GOST 1770;

— flasks KN-2−100−13/23ТХС according to GOST 25336;

pipettes 1−2-2−1, 1−2-2−2, 1−2-2−5, 1−2-2−10 according to GOST 29227.

When performing measurements, use the following materials, solutions:

— distilled water according to GOST 6709;

— ethyl alcohol according to GOST 18300;

sodium chloride according to GOST 4233;

— graphite powder of high purity according to GOST 23463;

— aluminum metal with a mass fraction of the basic substance of 99.9%;

iron metal with a mass fraction of the basic substance of 99.9%;

— copper oxide with a mass fraction of the basic substance of 99.9%;

— arsenic (III) oxide with a mass fraction of the basic substance of 99.9%;

— mercury oxide with a mass fraction of the basic substance of 99.9%;

lead oxide with a mass fraction of the basic substance of 99.9%;

the elementary selenium [2];

— tellurium metal, high purity [3].

Notes

1 allowed the use of other measuring instruments of the approved type, auxiliary devices and materials, technical and metrological characteristics are not inferior to mentioned above.

2 allowed the use of reagents produced by other normative documents, provided that their metrological characteristics of the measurement results given in the measurement technique.

3.4 Method of measurements

The method is based on measuring the intensity of spectral lines of the designated components during combustion of the sample from a crater of the carbon electrode.

3.5 preparing for the measurements

3.5.1 preparation of the device for measuring

The unit measurement is carried out in accordance with the requirements of the current operating instructions of the mass spectrometer. Set the operating parameters of the measurements in accordance with table 3.


Table 3 — Parameters measurements

Analytical lines of the designated components, free from spectral overlaps are shown in table 4.

3.5.2 calibration of the spectrometer

The spectrometer will graduate when you create a method by means of comparison of the composition of selenium with each series of samples and build the dependence of the intensity of the analytical line from the mass fraction for each component you define.

In future work adjust calibration parameters in accordance with the manual of the spectrometer.

3.5.3 Graphite electrodes.

Electrodes with a crater and «cone» machined on the grinding machine in accordance with the operating manual.


Table 4 — Analytical lines components

3.5.4 sample Preparation comparison. Samples for comparison are prepared in accordance with Annex A.

Value of mass fraction of aluminium, iron, copper, arsenic, mercury, lead and tellurium in samples of comparison composition of selenium SL-10SL-1, are presented in table 5.


Table 5 — Parameters of the samples of comparison

Percentage

3.6 performance measurement

3.6.1 General requirements for method of measurements in accordance with GOST 16273.0.

3.6.2 Mass fraction of impurities in the sample and the control sample to determine the parallel of the two batches, taking three individual measurements from each sample.

3.6.3 Sample is mixed with graphite in a ratio of 1:1, sodium chloride (10% of the total mass of the sample and graphite) to (0.3 g sample, 0.3 g graphite, and 0.6 g of sodium chloride) in a mortar made of organic glass.

Prepared samples and samples of comparison and into the craters of graphite electrodes by immersion.

Note — change of the mass of sample samples, graphite powder and sodium chloride, while maintaining the ratio of 1:1 samples and graphite and sodium chloride (10% of the total mass of the sample and graphite).

3.6.4 Simultaneously through all stages of sample preparation to the measurements carried out blank on the purity of reagents and materials.

Note — the Mass fraction of the designated component of experience the idle should not exceed the lower limit of the range of the designated contents.

3.7 processing of the results

3.7.1 Processing of results of measurements carried out using a software for a given program and present them in the form of a mass fraction of the designated component.

3.7.2 the measurement result taking the arithmetic mean of two parallel definitions, provided that the absolute difference between them in terms of repeatability does not exceed the value (at confidence probability P=0,95) repeatability limit rgiven in table 2.

If the discrepancy between the results of parallel measurements exceeds the limit value of the frequency of occurrence, perform the procedure described in GOST ISO 5725−6 (paragraph 5.2.2.1).

3.7.3 Differences between measurements obtained in two laboratories, should not exceed the values of the limit of reproducibility shown in table 2. In this case, the final result can be accepted their mean value. At default of this condition can be used the procedure set out in GOST ISO 5725−6.

4 Spectral emission method with inductively coupled plasma

4.1 Scope of applications

This section describes a spectral emission method with inductively coupled plasma measurements of the mass fraction of components in technical selenium in the ranges presented in table 1.

4.2 characteristics of the indicators of measurement accuracy

The accuracy of measuring the mass fraction of components in technical selenium corresponds to the characteristics given in table 6 (with R=0,95).

Limit values of repeatability and reproducibility of measurements for a confidence probability P=0.95 is given in table 6.


Table 6 — Values of the measure of the accuracy, limits of repeatability and reproducibility of measurements of mass fraction of components in technical Selene at confidence probability P=0,95

Percentage

4.3 measurement Means, auxiliary devices, materials, solutions

When performing measurements using the following measuring instruments and auxiliary devices:

— the atomic emission spectrometer with inductively coupled plasma as the excitation source with all accessories;

— the stove is electric with a closed heating element for temperature up to 400 °C;

— special laboratory scales of accuracy class according to GOST 24104, with a readability of 0.0001 g;

— volumetric flasks 2−50−2, 2−100−2, 2−200−2 according GOST 1770;

— flasks KN-2−250−13/23ТХС according to GOST 25336;

-glasses-1−150 TS, -1−250-TS, N-1−150 TCS, N-1−250 TCS according to GOST 25336;

pipettes 1−2-2−1, 1−2-2−2, 1−2-2−5, 1−2-2−10 according to GOST 29227;

— beakers 50 according to GOST 1770;

— hour glass.

When performing measurements, use the following materials, solutions:

— distilled water according to GOST 6709;

— nitric acid of high purity according to GOST 11125;

acid salt of high purity according to GOST 14261 and diluted 1:5 and 1:19;

— argon gas according to GOST 10157;

— the state standard samples of composition of the solution ions: aluminum, iron, cadmium, potassium, calcium, magnesium, copper, arsenic, Nickel, lead, antimony, sodium, tellurium, sulfur, mercury, and the mass concentration of 1.0 mg/cm;

the elementary selenium [2].

Notes

1 allowed the use of other measuring instruments of the approved type, auxiliary devices and materials, technical and metrological characteristics are not inferior to mentioned above.

2 allowed the use of reagents produced by other normative documents, provided that their metrological characteristics of the measurement results given in the measurement technique.

4.4 Method of measurement

The method is based on measuring the intensity of spectral lines is determined by the components when excited atoms of the sample solution in inductively coupled plasma.

4.5 Preparation for measurement

4.5.1 preparation of the device for measurement

Preparing the spectrometer to the measurements carried out in accordance with the manual.

4.5.2 Preparation of solutions of known concentration

4.5.2.1 in preparing the solution of aluminum ions, iron, cadmium, calcium, magnesium with a mass concentration of 0.1 mg/cmin a volumetric flask with a capacity of 100 cmplaced at 10 cmof solutions of ions of aluminium, iron, cadmium, calcium, magnesium and the mass concentration of 1.0 mg/cm. Bring to mark with hydrochloric acid diluted 1:5 and stirred.

4.5.2.2 in preparing the solution of copper ions, arsenic, Nickel, lead, antimony with a mass concentration of 0.1 mg/cmin a volumetric flask with a capacity of 100 cmplaced at 10 cmof solutions of copper ions, arsenic, Nickel, lead, antimony with a mass concentration of 1.0 mg/cm. Bring to mark with hydrochloric acid diluted 1:5 and stirred.

4.5.2.3 in preparing the solution of aluminum ions, iron, cadmium, calcium, magnesium, copper, arsenic, Nickel, lead, antimony with a mass concentration of 0.01 mg/cmin a volumetric flask with a capacity of 100 cmplaced at 1.0 cmsolutions of aluminum ions, iron, cadmium, calcium, magnesium, copper, arsenic, Nickel, lead, antimony with a mass concentration of 1.0 mg/cm, made up to the mark with hydrochloric acid diluted 1:5 and stirred.

4.5.2.4 in the preparation of a solution of ions of tellurium, sodium and the mass concentration of 0.1 mg/cmin a volumetric flask with a capacity of 100 cmplaced at 10 cmof solutions of ions of tellurium, sodium and the mass concentration of 1.0 mg/cm, made up to the mark with hydrochloric acid diluted 1:5 and stirred.

4.5.2.5 in the preparation of a solution of ions of tellurium, sodium and the mass concentration of 0.01 mg/cmin a volumetric flask with a capacity of 100 cmis placed 10 cmof a solution containing 0.1 mg/cmions of tellurium, sodium, made up to the mark with hydrochloric acid diluted 1:5 and stirred.

4.5.2.6 in the preparation of a solution of sulfur ions with a mass concentration of 0.1 mg/cmin a volumetric flask with a capacity of 100 cmis placed 10 cmsolution of ions of sulfur mass concentration of 1.0 mg/cm, made up to the mark with hydrochloric acid diluted 1:5 and stirred.

4.5.2.7 in the preparation of a solution of sulfur ions with a mass concentration of 0.01 mg/cmin a volumetric flask with a capacity of 100 cmis placed 10 cmof a solution containing 0.1 mg/cmions of sulfur, made up to the mark with hydrochloric acid diluted 1:5 and stirred.

4.5.2.8 During the preparation of the solution of potassium ions with a mass concentration of 0.1 mg/cmin a volumetric flask with a capacity of 100 cmis placed 10 cmsolution of potassium ions containing 1.0 mg/cmpotassium ions, made up to the mark with hydrochloric acid diluted 1:5 and stirred.

4.5.2.9 in the preparation of a solution of potassium ions with a mass concentration of 0.01 mg/cmin a volumetric flask with a capacity of 100 cmis placed 1.0 cmof a solution containing 0.1 mg/cmpotassium ions, made up to the mark with hydrochloric acid diluted 1:5 and stirred.

4.5.2.10 in the preparation of a solution of mercury ions with a mass concentration of 0.1 mg/cmin a volumetric flask with a capacity of 100 cmis placed 10 cmsolution of mercury ions with a mass concentration of 1.0 mg/cm, made up to the mark with nitric acid, diluted 1:5 and stirred.

4.5.2.11 For preparation of a solution of selenium ions with the mass concentration of 100.0 mg/cmin a flask with a capacity of 250 cmis placed a portion of elemental selenium by weight of 20.00 g pour 50 cmof nitric acid, cover with watch glass and heated until complete decomposition of sample. Watch glass and walls of the flask is washed with water. The solution was cooled, transferred to a volumetric flask with a capacity of 200 cm, made up to the mark with water and mix.

4.5.3 Preparation of the calibration solutions

To prepare the calibration solutions in a volumetric flask with a capacity of 100 cmconsistently placed aliquots of solutions of known concentration according to the table 7 (for the determination of aluminium, iron, cadmium, calcium, magnesium, copper, arsenic, Nickel, lead, antimony, sodium, tellurium) and table 8 (for determining sulfur and potassium), made up to the mark with hydrochloric acid diluted 1:5, according to table 9 solutions for mercury determination top up to the mark with nitric acid, diluted 1:5 volumetric flasks with a capacity of 200 cmand mixed. Solutions are stable for 5 days.


Table 7

Table 8

Table 9

4.5.4 the Relationship of radiation intensity and the mass concentration of component in solution set two ways:

— with the help of calibration curve (method 1);

— using the addition method (method 2).

To measure mass proportions of the components according to the method 2 use solutions prepared according to 4.5.2.1−4.5.2.8.

4.5.5 In accordance with the manual of the spectrometer, launch a work program and perform at least two measurements of the analytical signal of the zero solution, then the corresponding calibration solution.

Expect calibration characteristics.

Note — the determination of the calibration parameters, processing and storage of the results of the calibration performed using standard software supplied with the spectrometer.


Stability control calibration parameters is carried out using a solution of N 2 comparisons. Calibration characteristics recognize stable if the deviation of the result from the set of content component in the solution of the comparison does not exceed 10% (Rel.)

The settings of the measurements are shown in table 10.


Table 10 — Parameters of measurement mode

4.5.6 Measuring the intensity of analytical spectral lines of defined components is carried out at wavelengths specified in table 11, to achieve the optimal values for sensitivity and precision components.


Table 11 — wavelengths

4.6 performance measurement

4.6.1 Simultaneously through all stages of sample preparation to the measurement carried out control and experience on the purity of the reagents.

4.6.2 Measurement of mass fractions of impurities in calibration schedule (method 1).

4.6.2.1 Mass fraction of impurities is determined in parallel in two batches.

4.6.2.2 Preparation of samples and measurement of the mass fraction of mercury is carried out apart from determining other components.

4.6.2.3 Sample sample weight from 1,9990 to 2,0010 g is placed in a conical flask with a capacity of 100 cm, flow 15 to 20 cmof a mixture of hydrochloric and nitric acids (3:1), covered with a lid and dissolve by heating for 20 min. Then cover and wall of the flask is washed with hydrochloric acid, diluted 1:19. The solution was cooled, transferred to a volumetric flask with a capacity of 50 cm, made up to the mark with water and mix.

4.6.2.4 For measuring the mass fraction of mercury in two samples sample weight (6,0000±0,0010) g are placed in two glasses with a capacity from 150 to 250 cm, moistened with water and poured 20 cmof nitric acid, cover with watch glass and heated until complete dissolution, add 5 cmof hydrochloric acid, then evaporated the beaker contents from 5 to 10 cm. After cooling, the solutions were transferred to volumetric flasks with a capacity of 100 cm, made up to the mark with nitric acid, diluted 1:5 and stirred.

4.6.2.5 the measurements are carried out in accordance with the manual of the spectrometer.

If the concentration of the component in the sample solution exceeds the concentration in the calibration solutions (the amount of signal above the last point of curve) carried out the dilution of the analyzed solution.

4.6.3 Measurement of the mass fraction of impurities using the addition method (method 2)

4.6.3.1 Mass fraction of the impurities measured in parallel in two batches.

4.6.3.2 the Mass fraction of potassium and sulfur are measured separately from the definition of other components.

4.6.3.3 Sample sample weight from 1,9990 to 2,0010 grams are placed in eight volumetric flasks with a capacity of 50 cmeach and dissolved in accordance with 4.6.2.2.

In six of the eight volumetric flasks with solutions samples introduced additives according to table 12. The solutions in all flasks is poured to the mark with water and mix.


Table 12

Percentage

4.6.3.4 performance measurement is carried out in accordance with the manual of the spectrometer sequentially performs measurement of samples, the sample with addition of 1, samples with the addition of 2, samples with the addition of 3 (in ascending order of magnitude of supplements).

In accordance with the software of the spectrometer to build a chart — value of analytical signals of analysed sample solution and sample solution with the additive is applied to the y-axis, and the abscissa shows the delay values of the concentrations of the additives. Thus obtained direct extrapolat on the x-axis. The point of intersection on the x-axis indicates the mass concentration of the component in the analyzed sample solution.

4.6.4 Measurement should start after 20−30 minutes after ignition of the plasma to stabilize the measurement conditions.

4.7 processing of the results of measurements

4.7.1 measurement results of the mass concentration of a specific component in the sample is automatically displayed on the monitor screen.

4.7.2 Mass fraction of the designated component, X, %, is calculated by the formula

, (1)

where And — mass concentration of the component in the sample obtained on the schedule or by way of supplements, µg/cm;

V — solution volume, cm;

m — weight of sample, g.

4.7.3 For the measurement result taking the arithmetic mean of two parallel definitions, provided that the absolute difference between them in terms of repeatability does not exceed the value (at confidence probability P=0,95) repeatability limit r given in table 6.

If the discrepancy between the results of parallel measurements exceeds the limit value of the frequency of occurrence, perform the procedure described in GOST ISO 5725−6 (paragraph 5.2.2.1).

4.7.4 Differences between measurements obtained in two laboratories, should not exceed the limit values for the reproducibility given in table 6. In this case, the final result can be accepted their mean value. At default of this condition can be used the procedure set out in GOST ISO 5725−6.

Annex a (recommended). Sample preparation comparison of the composition of Selena

Appendix A
(recommended)

A. 1 For preparation of the main solution And the composition of aluminum with a mass concentration of 10 mg/cmthe weight of aluminium metal weight of 0,500 g was placed in a conical flask with a capacity of 100 cm, poured when heated 30 cmof hydrochloric acid, then hydrochloric acid is added by portions until complete dissolution, the solution was cooled, transferred to a volumetric flask with a capacity of 50 cm, made up to the mark with water and mix.

A. 2 For the preparation of the basic solution B of the composition of iron with a mass concentration of 10 mg/cma sample of iron metal with a mass of 0.5 g was placed in a conical flask with a capacity of 100 cm, poured when heated 15 cmof nitric acid, diluted 1:1, can withstand up to complete dissolution. The solution is evaporated to wet salts, add 10 cmof hydrochloric acid and heated until complete dissolution, cooled, transferred to a volumetric flask with a capacity of 50 cm, made up to the mark with water and mix.

A. 3 For the preparation of the basic mixture composition of graphite powder G-1 And with a mass fraction of aluminum, iron, copper, arsenic, mercury, lead and tellurium of 1% in a mortar put the hitch components and aliquote parts of solutions «A» and «B» according to table A. 1. The sample is stirred with the use of ethyl alcohol at the rate of 1.0 to 1.5 cmper 1 g of the mixture before drying and kept in a desiccator for 1 h at a temperature of from 100 °C to 105 °C.

A. 4 a Series of mixtures of the composition of graphite Gr-10Gr-1 is prepared by the method of successive dilution of the primary mixture of Gr-1 graphite powder. Sample of the mixture is adopted for the main and graphite powder, according to table A. 2, placed in a mortar and stirred with the use of ethyl alcohol at the rate of 1 to 1.5 cmper 1 g of the mixture before drying and kept in a desiccator for 1 h at a temperature of from 100 °C to 105 °C. the Values of mass fraction of aluminium, iron, copper, arsenic, mercury, lead and tellurium in certified mixtures of the composition of graphite powder is presented in table A. 1.

A. 5 a Series of mixtures of selenium composition SL-10SL-1 is prepared by mixing each mixture composition of graphite Gr-10Gr-1 with selenium in a 1:1 ratio with addition of 10% sodium chloride in a mortar with the use of ethyl alcohol at the rate of 1 to 1.5 cmper 1 g of the mixture before drying and kept in a desiccator for 1 h at a temperature of from 100 °C to 105 °C. the composition of Mixtures of selenium assigns values of mass fractions of impurities of the corresponding mixtures of graphite composition, each of the compounds was made. The mixture composition of selenium are used as comparison samples in constructing the calibration graph. Value of mass fraction of aluminium, iron, copper, arsenic, mercury, lead and tellurium in samples of comparison composition of selenium SL-1SL-10, is presented in table A. 3.


Table A. 1

Table A. 2

Table A. 3

Shelf life of samples comparison of the composition of selenium in one year.

Bibliography

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669.776 UDC:543.42:006.354 ISS 77.120.99

Key words: selenium technical, the spectral emission method of measurement with photoelectric registration of spectrum, spectral emission method with inductively coupled plasma, measurements, indicators of accuracy of measurements, means of measurement, processing of measurement results