GOST 15483.10-2004

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  ГОСТ 15483.10-2004

GOST 15483.10−2004 Tin. Methods of atomic-emission spectral analysis

GOST 15483.10−2004

Group B59

INTERSTATE STANDARD

TIN
Methods of atomic-emission spectral analysis

Tin. Methods of atomic-emission spectral analysis

ISS 77.120.60
AXTU 1709

Date of introduction 2005−07−01

Preface

1 DEVELOPED by the Russian Federation, the Interstate technical Committee for standardization MTK 500 «Tin"

2 INTRODUCED by Gosstandart of Russia

ADOPTED by the Interstate Council for standardization, Metrology and certification (Protocol No. 17 dated 1 April 2004, by correspondence)

The adoption voted:

3 by Order of the Federal Agency for technical regulation and Metrology dated October 25, 2004 N 40 St interstate standard GOST 15483.10−2004 introduced directly as a national standard of the Russian Federation from July 1, 2005

4 REPLACE GOST 15483.10−78

5. REPRINTING. October 2005


Revised (as of June 2008)

1 Scope

This standard specifies the methods of atomic-emission spectral analysis with the excitation spectrum of the spark discharge and inductively coupled plasma for the determination of the elements in the tin.

2 Normative references

The present standard features references to the following standards:

GOST 8.315−97 State system for ensuring the uniformity of measurements. Standard samples of composition and properties of substances and materials. The main provisions of the

GOST 61−75 acetic Acid. Specifications

GOST 83−79 Sodium carbonate. Specifications

GOST 195−77 Sodium sanitarily. Specifications

GOST 244−76 Sodium thiosulfate crystal. Specifications

GOST 849−97* Nickel primary. Specifications
________________
* On the territory of the Russian Federation the document is not valid. Standards 849−2008, here and hereafter. — Note the manufacturer’s database.

GOST 859−2001 Copper. Brand

GOST 860−75 Tin. Specifications

GOST 1089−82 Antimony. Specifications

GOST 1467−93 Cadmium. Specifications

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

GOST 3118−77 hydrochloric Acid. Specifications

GOST 3640−94 Zinc. Specifications

GOST 3778−98 Lead. Specifications

GOST 4160−74 Potassium bromide. Specifications

GOST 4461−77 nitric Acid. Specifications

GOST 6709−72 distilled Water. Specifications

GOST 9849−86 iron Powder. Specifications

GOST 10157−79 Argon gaseous and liquid. Specifications

GOST 10297−94 indium. Specifications

GOST 10928−90 Bismuth. Specifications

GOST 11069−2001 primary Aluminium. Brand

GOST 11125−84 nitric Acid of high purity. Specifications

GOST 14261−77 hydrochloric Acid of high purity. Specifications

GOST 15483.0−78 Tin. General requirements for methods of analysis

GOST 18300−87 ethyl rectified technical. Specifications

GOST 19627−74 Hydroquinone (paradoxians). Specifications

GOST 19671−91 tungsten Wire for light sources. Specifications

GOST 20298−74 ion-exchange Resins. Cation exchange resins. Specifications

GOST 22306−77 Metals of high and special purity. General requirements for methods of analysis

GOST 24104−2001* laboratory Scales. General technical requirements
________________
* On the territory of the Russian Federation the document is not valid. Valid GOST R 53228−2008, here and hereafter. — Note the manufacturer’s database.

GOST 25086−87* non-ferrous metals and their alloys. General requirements for methods of analysis
________________
* On the territory of the Russian Federation the document is not valid. Standards 25086−2011, here and hereafter. — Note the manufacturer’s database.

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

GOST 25664−83 Metol (4-methylaminophenol). Specifications

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

* Installations of buildings. Part 4. Requirements for security. Protection against electric shock
________________
* On the territory of the Russian Federation the document is not valid. Valid GOST R 50571.3−2009, here and hereafter. — Note the manufacturer’s database.

3 General requirements

3.1 General requirements for methods of analysis GOST 15483.0, 22306 GOST, GOST 25086.

3.2 Sampling and sample preparation of tin is carried out according to GOST 860.

3.3 To establish the calibration based on use of at least three standard samples or standard solutions with known concentrations of elements.

4 safety Requirements

4.1 When conducting tests, it is necessary to comply with the safety requirements according to GOST 15483.0.

4.1.1 in the use and operation of electrical appliances and electrical installations in the process of analysis should comply with the requirements of GOST 30331.3.

5 the Method of atomic-emission spectral analysis with the excitation spectrum of the spark discharge

5.1 Method of analysis

The method is based on the excitation spectrum of spark discharge with subsequent registration of the radiation of spectral lines photographic, or photoelectric means. The analysis uses the dependence of the intensities of spectral lines of the elements to their content in the sample.

The method provides a quantitative determination of bismuth, iron, copper, lead, antimony, and arsenic in tin all brands except tin of high purity, when defined by the mass fraction of elements, %:

quantitative determination of aluminium, zinc and arsenic at a mass concentration less than 0.01%.

Permissible error of the results of the analysis are shown in table 1.


Table 1 — the error analysis results (at a confidence probability of 0.95)

Percentage

5.2 measurement Means, auxiliary devices, materials, reagents, solutions

The types of quartz spectrograph ISP-28, ES-30 or similar devices.

Spectrometer types of DFS-36 (40, 41, 51), MFS-4 (6, 8) or similar devices.

Generator spark types, IG-3, IVS-23, UGE-1 (4) or similar devices.

Microphotometer MF-2, MD-100 or other types.

Spectromancer PS-18, SP-2, DSP-2 or other types.

File or machine for sharpening electrodes.

Crucible muffle furnace or any type of thermostat.

A drying rack of any type for drying photographic plates.

Fotocity or other utensils for processing of photographic plates.

Tungsten GOST 19671.

Crucibles of graphite or gravitatie with lids.

Mold for casting electrodes of round crosssection with a diameter of 8 mm and a length of 70−80 mm or other shape depending on the type of the used device.

Coals spectral brands of high purity-7−3, C-2, C-3 in the form of bars with diameter 6 mm.

The technical rectified ethyl alcohol according to GOST 18300.

State standard samples of composition of tin, 669−75 GSO — GSO 672−75, standard samples of the enterprise (SOPS) developed according to GOST 8.315.

Photographic plates spectrographic types of PFS-01, the SFC-02 or another type, providing a normal density pucherani analytical, comparison and background [1].

Distilled water according to GOST 6709.

The developer consisting of two solutions:

Solution 1:

— metol (parameterindependent) according to GOST 25664 — 2.3 g;

sodium sanitarily crystal according to GOST 195 — 26 g;

— hydroquinone (paradoxians) according to GOST 19627 — 11.5 g;

— distilled water according to GOST 6709 — up to 1000 cm.

Solution 2:

the anhydrous sodium carbonate according to GOST 83 — 42 g;

— potassium bromide according to GOST 4160 — 7 g;

— distilled water according to GOST 6709 — up to 1000 cm.

Before the manifestation of the solutions 1 and 2 mixed in a volume ratio of 1:1.

Fixing solution:

— sodium thiosulfate crystal according to GOST 244 — 400 g;

sodium sanitarily according to GOST 195 — 25 g;

— acetic acid according to GOST 61 — 8 cm;

— distilled water according to GOST 6709 — up to 1000 cm.

Allowed the use of developer and fixer of other compositions which do not deteriorate the quality of the photographic registration of the spectrum.

5.3 Preparation for assay

5.3.1 Samples for analysis must be in the form of cast rods with a diameter of 8 mm, a length of 35−80 mm.

Allowed to change the shape of the sample of the samples depending on the type of an applied device.

5.3.2 Samples received for analysis in the form of chips, is melted in a preheated graphite crucible with a lid at a temperature of 240 °C — 250 °C under a layer of rosin and cast into a mold in the form of rods of the above dimensions.

5.3.3 as protivoelektrodom for standard samples (CO) use WITH corresponding, sample — electrode from a corresponding sample of tin. Allowed as protivoelektrodom use a carbon rod sharpened to a plane or a truncated cone with an area of 1−2 mm or an electrode made of tungsten GOST 19671.

5.3.4 Before shooting the ends of the rods to be analyzed and standard samples sharpen on a plane and some rubbing alcohol. On the treated surface of the analyzed samples and standard samples should be free of holes, cracks and other defects.

5.4 analysis

5.4.1 preparation of a spectrograph or spectrometer to conduct tests carried out in accordance with the instruction manual and device maintenance.

The source excitation spectrum is spark discharge between the terminals of analyzed samples and protivoelektrodom derived from the spark generator working in the regime of high-voltage sparks.

Modes of operation of the spark generator and the parameters of the spectrograph or spectrometer choose the optimum one depending on the type of device.

The conditions of analysis and specifications of appliances given in Appendix A.

Recommended analytical lines and lines of comparison are shown in table 2.


Table 2 — Recommended analytical lines and lines comparison

In nanometers

The use of other analytical lines subject to receipt of the metrological characteristics meet the requirements of this standard.

5.4.2 analysis with photographic registration of spectrum

In the cassette of the spectrograph placed photographic plates of two types: long-wavelength part of the spectrum of type SFC-01, in the shortwave part of the spectrum — type PFS-02.

Spectrograms of the standard samples and the unknown samples are removed on the same photographic plate.

For each sample and the standard sample is removed, at least two spectrograms.

Exposed a photographic plate showing, fixed, washed and dried.

Photographic plates obtained with spectrograms mounted on microphotometer and measure the density of the blackening of analytical lines of the determined elements and lines of comparison. As a comparison, using a line of tin.

For semi-quantitative determination of aluminium, zinc and arsenic (in mass fraction less than 0.01%) visually compare the density of the blackening of analytical lines of aluminum, zinc, and arsenic in a standard sample of enterprises (SOP) and samples.

5.4.3 analysis with photoelectric registration of spectrum

Instrumental parameters of the spectrometer set within the range for maximum sensitivity to determine the mass fractions of elements.

For each sample and record at least two measurements.

For each of the designated impurities from the output of the measuring device of the spectrometer, take readings of the registered intensity values of radiations in the spectrum of the standard samples to construct calibration curve and samples for the assessment of the identified elements according to this schedule.

In the spectrometer control computer readings registered intensity values enter into long-term memory of the computer.

When semi-quantitative determination of aluminium, zinc or arsenic was compare the readings of the intensities of analytical lines of aluminum, zinc, and arsenic in a sample and a standard sample of enterprises (SOP) for the relevant impurity, making the semi-quantitative evaluation of the presence of these elements in the sample.

5.5 processing of the results

The mass fraction of elements in the analyzed samples is determined by the calibration graphs. To construct the calibration graphs used method of the three standards solid calibration curve, a test standard. In processing the results of the analysis on a computer calibration charts can be in the form of polynomial equations of different degrees.

The analysis of the photographic method of calibration curve constructed in the coordinates: , where  — average value of differences of the density of pochernenija analytical lines of the determined elements and the element comparison;  — the certified value of the mass fraction of the element.

By the photoelectric registration of spectrum of the calibration graphs constructed in the coordinates: where is the mean value of readings of the output measuring device for each standard sample is determined for each impurity;  — the certified value of the mass fraction of the element.

In the spectrometer control computer calibration of the spectrometer and receiving the results of the analysis carried out in accordance with the technical description attached to the spectrometer software. The results of parallel measurements and the arithmetic mean of the values read from the screen or printing device.

The result of the analysis taking the arithmetic mean of the two results of parallel measurements if the difference between them does not exceed the value of the standard operational control of convergence , are given in table 3.


Table 3 — Standards for operational quality control of analysis results (at a confidence probability of 0.95)

Percentage

When the divergence of the results of parallel measurements more than the permissible value of the samples is repeated.

With repeated exceeding of the standard operational control of convergence find out the reasons of unsatisfactory results of the analysis, and eliminate them.

5.6 quality Control of analysis results

Quality control of the results of the analysis carried out according to GOST 25086 and other regulatory documents.

Control of accuracy of analysis results is carried out at least once a month, and after prolonged breaks and other changes that affect the result of the analysis.

As standard for the control of accuracy of analysis results using values of the standard control error of the method of analysis given in table 3.

Standards of operational control of the convergence of the two results of parallel measurements and the reproducibility of the two analysis results are shown in table 3.

6 the Method of atomic-emission spectral analysis with the excitation spectrum of inductively coupled plasma

6.1 Method of analysis

The method is based on the excitation spectrum of inductively coupled plasma and subsequent radiation of spectral lines photoelectric method. The analysis uses the dependence of the intensities of spectral lines of the elements from their mass fraction in the sample. The sample is dissolved in a mixture of hydrochloric and nitric acids.

The method is intended for determining the mass fraction of lead, aluminum, bismuth, iron, indium, cadmium, copper, arsenic, Nickel, antimony and zinc in the tin.

The ranges of detectable concentrations of elements are given in table 4.


Table 4 — Ranges of detectable concentrations of the elements

Percentage

Permissible error of the results of the analysis are shown in table 5.


Table 5 — the error analysis results (at a confidence probability of 0.95)

Percentage

6.2 measurement Means, auxiliary devices, materials, reagents, solutions

Automated atomic emission spectrometer with inductively coupled plasma as the excitation source spectrum with all accessories.

Argon according to GOST 10157.

Laboratory scales of high accuracy class according to GOST 24104.

Volumetric flasks with a capacity of 100, 200 and 1000 cmaccording to GOST 1770.

Pipette graduated capacity 1, 2, 5 and 10 cmaccording to GOST 29227.

Glasses with a capacity of 250 cmaccording to GOST 25336.

Beakers with a capacity of 25 and 50 cmaccording to GOST 1770.

Column to obtain deionized water with a cation exchange resin KU-2−8 according to GOST 20298.

Nitric acid according to GOST 11125, OS h, or according to GOST 4461, x h, purified by distillation.

Hydrochloric acid according to GOST 14261, OS.CH., or GOST 3118, H. h, purified by distillation.

The mixture of acids (hydrochloric and nitric) in the ratio of 5:1.

Tin with a purity not less than 99.9999% [2].

Aluminum brand A995 according to GOST 11069, or grade A5 at [3].

The brand Vi00 bismuth GOST 10928.

Iron powder brand MLB-1 according to GOST 9849 or iron restored.

Indium metal according to GOST 10297.

Cadmium grade not lower Кд0 according to GOST 1467.

Copper brand M0k according to the GOST 859.

Arsenic metal [4].

Nickel GOST 849 not below grade H1.

Tin GOST 860 below grade O1.

Lead of C1 grade according to GOST 3778.

Antimony GOST 1089 not below grade SU000.

Zinc GOST 3640 not below grade C0.

Standard samples of composition of tin GSO 669, 672 notes, standard samples of the enterprise (SOPS) developed according to GOST 8.315.

India standard solution mass concentration of 1 mg/cm: linkage India mass 0,1000 g dissolved in 10 cmof hydrochloric acid.

The solution was transferred to volumetric flask with a capacity of 100 cmand then filled to the mark with water.

Standard solution of arsenic mass concentration of 1 mg/cm: a portion of the arsenic mass 0,1000 dissolved in 10 cmof the mixture of acids when heated. The solution was transferred to volumetric flask with a capacity of 100 cmand then filled to the mark with water.

Standard solution of lead mass concentration of 1 mg/cm: linkage of lead weight 0,100 g dissolved under moderate heating in 5 cmof nitric acid, diluted 1:5. The solution was transferred to volumetric flask with a capacity of 100 cmand then filled to the mark with water.

Standard solution of antimony mass concentration of 1 mg/cm: a portion of the antimony by weight 0,100 g dissolved with moderate heating in a 10 cmmixture of acids. The solution was transferred to a volumetric flask with a capacity of 100 cmand then filled to the mark with hydrochloric acid diluted 1:2.

Multi-element standard solution (MES-1) of aluminium, bismuth, cadmium, copper, iron, Nickel, and zinc mass concentrations of 50 µg/cm: sample of aluminum, bismuth, cadmium, copper, iron, Nickel, and zinc mass 0,1000 g placed in a beaker with a capacity of 250 cmand dissolved under moderate heating in 25 cmof a mixture of acids. The resulting solution was transferred to volumetric flask with a capacity of 2000 cm, add 50 cmof hydrochloric acid and topped up to the mark with water.

Multi-element standard solution (MES-2) arsenic, indium, antimony, and lead mass concentrations of 50 µg/cm: in a volumetric flask with a capacity of 200 cmis injected at the 10 cmstandard solutions of arsenic, indium, antimony, and lead, added 40 cmof hydrochloric acid and topped up to the mark with water.

For the preparation of solutions with known concentrations of elements allowed to use the state standard samples of solutions of metals.

6.3 Preparation for analysis

6.3.1 Preparation of solutions of comparison for the analysis of batches of tin with a mass of 5 g

Reference solution (RS-0) of the mass concentration of tin is 50 mg/cm: linkage of tin weighing 5 g is dissolved with moderate heating in 25 cmof a mixture of acids. The resulting solution was transferred to a volumetric flask with a capacity of 100 cmand then filled to the mark with water. A solution of RS-0 is used as the background solution.

Reference solution (RS-1) with the mass concentration of tin is 50 mg/cm1 mg/cmof aluminium, bismuth, cadmium, copper, arsenic, iron, indium, Nickel, antimony and zinc: the weight of tin weighing 5 g is dissolved with moderate heating in 25 cmof a mixture of acids. The resulting solution was transferred to a volumetric flask with a capacity of 100 cm, is administered at 2 cmthe solutions of the MES-1 and MES-2 and topped to the mark with water.

Reference solution (RS-2) with the mass concentration of tin is 50 mg/cmand 2.5 µg/cmof aluminum, bismuth, cadmium, copper, arsenic, iron, indium, Nickel, antimony and zinc: the weight of tin weighing 5 g is dissolved with moderate heating in 25 cmof a mixture of acids. The resulting solution was transferred to a volumetric flask with a capacity of 100 cm, injected at 5 cmof solutions of the MES-1 and MES-2 and topped to the mark with water.

Reference solution (MS-3) mass concentration of tin is 50 mg/cmand 10 ug/cmlead: the portion tin weighing 5 g is dissolved with moderate heating in 25 cmof a mixture of acids. The resulting solution was transferred to a volumetric flask with a capacity of 100 cm, is introduced 1 cmof a standard solution of lead and bring to mark with water.

6.3.2 Preparation of solutions of comparison for the analysis of batches of tin with a mass of 1 g

Solutions comparison for the analysis of batches of tin with a mass of 1 g is prepared analogously to 6.3.1 on solutions, dissolving a portion of tin with a mass of 1 g.

6.3.3 Preparation of solutions samples

A portion of the sample tin weight of 5,000 g (or 1000 g depending on the mass fraction of impurities) in the form of chips are dissolved with moderate heating in 25 cmof a mixture of acids. The solution was transferred to a volumetric flask with a capacity of 100 cmand then filled to the mark with water.

6.4 analysis

Preparing the spectrometer to the measurements carried out in accordance with the instruction manual and device maintenance.

Instrumental parameters of the spectrometer set within the range for maximum sensitivity to determine the mass fractions of elements.

Recommended analytical lines are given in table 6.


Table 6 — Recommended analytical lines

The use of other analytical lines subject to receipt of the metrological characteristics meet the requirements of this standard.

Successively introduced into the plasma solutions and comparison with the help of a special program least-squares build calibration graphs, which are administered in long-term memory of the computer in the form of addiction.

The mass concentration of the elements , µ g/cm, determined by the formula

, (1)

where , the regression coefficients for -th item, determined by the method of least squares;

 — the intensity of spectral lines -th element;

 — the intensity of the line comparison.

Solutions of samples analysed successively introduced into the plasma and measure the intensity of the analytical lines of the determined elements. In accordance with the program for each solution perform at least two measurements of the intensity and calculate the average value, which using the calibration characteristics find the mass concentration of element (µg/cm) in the sample solution.

6.5 processing of the results

Mass fraction of the element in the sample in % is calculated by the formula

, (2)

where is the mass concentration of element in sample solution, µg/cm;

 — the volume of the sample solution, cm;

 — the weight of the portion of the sample,

The mass fraction of detectable elements in the sample and their arithmetic mean values read from the screen or the tape printing device.

Records of the mass of sample, sample dilution and other variables is carried out automatically at the stage of introduction of analytical program in the computer.

The result of the analysis taking the arithmetic mean of the two results of parallel measurements if the difference between them does not exceed the value of the standard operational control of convergence , are given in table 7.


Table 7 — Standards for operational quality control of analysis results (at a confidence probability of 0.95)

Percentage

When the divergence of the results of parallel measurements permitted the analysis of more samples is repeated.

With repeated exceeding of the standard operational control of convergence find out the reasons of unsatisfactory results of the analysis, and eliminate them.

6.6 quality Control of analysis results

Quality control of the results of the analysis carried out according to GOST 25086 and other regulatory documents.

Control of accuracy of analysis results is carried out at least once a month, and after prolonged breaks and other changes that affect the result of the analysis.

As standard for the control of accuracy using the values of the norm of the control error , given in table 7.

Standards of operational control for the convergence of the results of two parallel measurements and the reproducibility of the results of the analysis are shown in table 7.

Annex a (recommended). The conditions of analysis and specifications of the devices

APPENDIX A
(recommended)

Table A. 1

ANNEX B (reference). Bibliography

APPENDIX B
(reference)

ANNEX b (informative). Regulations applicable on the territory of the Russian Federation

THE APP
(reference)

MI 2335−2003 State system for ensuring the uniformity of measurements. Internal quality control of results of quantitative chemical analysis