GOST R 54313-2011

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  ГОСТ Р 54313-2011

GOST R 54313−2011 Palladium. Method of atomic-emission analysis with inductively coupled plasma

GOST R 54313−2011

Group B59

NATIONAL STANDARD OF THE RUSSIAN FEDERATION

PALLADIUM

Method of atomic-emission analysis with inductively coupled plasma

Palladium. Method of inductively coupled plasma atomic-emission analysis

OKS 77.120.99
AXTU 1709

Date of introduction 2012−01−01

Preface

The objectives and principles of standardization in the Russian Federation established by the Federal law of 27 December 2002 N 184-FZ «On technical regulation», and rules for the application of national standards of the Russian Federation — GOST R 1.0−2004 «Standardization in the Russian Federation. The main provisions"

Data on standard

1 DEVELOPED by the Open joint-stock company «Krasnoyarsk factory of nonferrous metals named after V. N. Gulidova» (OJSC Krastsvetmet)

2 SUBMITTED by the Technical Committee for standardization TC 102 «Platinum metals"

3 APPROVED AND put INTO EFFECT by the Federal Agency for technical regulation and Metrology dated 30 March 2011 N 39 St

4 INTRODUCED FOR THE FIRST TIME


Information about the changes to this standard is published in the annually issued reference index «National standards», and the text changes and amendments — in monthly indexes published information «National standards». In case of revision (replacement) or cancellation of this standard a notification will be published in a 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 covers refined palladium bullion and powder with a mass fraction of palladium is not less than 99.8%, designed for the production of alloys, semi-finished products, chemical compounds of palladium.

The standard establishes the method of atomic-emission analysis with inductively coupled plasma for determination of mass fraction of impurities, aluminum, barium, iron, gold, iridium, cadmium, calcium, cobalt, silicon, magnesium, manganese, copper, molybdenum, Nickel, tin, platinum, rhodium, ruthenium, lead, silver, antimony, titanium, chromium, zinc affilirovannomu palladium.

The analysis method is based on excitation of atoms of the sample in inductively coupled plasma and measuring the intensity of the analytical line of the designated chemical elements (hereafter element) in the spray solution of the sample into the plasma. The relationship of the intensity of lines with the concentration of the element in the solution set by using the calibration characteristics. To account for possible matrix effects, the determination is carried out using internal standard.

The method allows to determine the mass fraction of impurities in the ranges given in table 1.


Table 1 — Ranges of mass fraction of detectable elements

Percentage

Chemical composition of refined palladium bullion and powder meets the requirements of GOST 31291, GOST R 52244.

2 Normative references

This standard uses the regulatory references to the following standards:

GOST R 8.563−2009 State system for ensuring the uniformity of measurements. Techniques (methods) of measurements

GOST R ISO 5725−1-2002 Accuracy (trueness and precision) of methods and measurement results. Part 1. General provisions and definitions

GOST R ISO 5725−3-2002 Accuracy (trueness and precision) of methods and measurement results. Part 3. Intermediate indicators the precision of a standard measurement method

GOST R ISO 5725−4-2002 Accuracy (trueness and precision) of methods and measurement results. Part 4. The main methods of determining the correctness of a standard measurement method

GOST R ISO 5725−6-2002 Accuracy (correctness and precision) of methods and measurement results. Part 6. The use of precision values in practice

GOST R 52244−2004 Palladium refined. Specifications

GOST R 52245−2004 Platinum affilirovannaja. Specifications

GOST R 52361−2005 Control of the analytical object. Terms and definitions

GOST R 52599−2006 Precious metals and their alloys. General requirements for methods of analysis

GOST R 53228−2008 Scales non-automatic actions. Part 1. Metrological and technical requirements. Test

GOST 123−2008 Cobalt. Specifications

GOST 804−93 primary Magnesium ingots. Specifications

GOST 849−2008 Nickel primary. Specifications

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 3640−94 Zinc. Specifications

GOST 3765−78 Reagents. Ammonium molybdate. Specifications

GOST 3778−98 Lead. Specifications

GOST 4108−72 Reagents. Barium chloride 2-water. Specifications

GOST 4328−77 Reagents. Sodium hydroxide. Specifications

GOST 4530−76 Reagents. Calcium carbonate. Specifications

GOST 5905−2004 (ISO 10387:1994) metal Chrome. Technical requirements and delivery conditions

GOST 6008−90 metallic Manganese and nitrated manganese. Specifications

GOST 6709−72 distilled Water. Specifications

GOST 6835−2002 Gold and alloys on its basis. Brand

GOST 6836−2002 Silver and alloys on its basis. Brand

GOST 9428−73 Reagents. Silicon (IV) oxide. Specifications

GOST 10157−79 Argon gaseous and liquid. Specifications

GOST 11069−2001 primary Aluminium. Brand

GOST 11125−84 nitric Acid of high purity. Specifications

GOST 12338−81 Iridium powder. Specifications

GOST 12342−81 Rhodium powder. Specifications

GOST 12343−79 Ruthenium powder. Specifications

GOST 14261−77 hydrochloric Acid of high purity. Specifications

GOST 14262−78 sulphuric Acid of high purity. Specifications

GOST 19807−91 Titanium and titanium wrought alloys. Brand

GOST 22861−93 Lead of high purity. Specifications

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

GOST 28058−89 Gold bullion. Specifications

GOST 28595−90 Silver bullion. Specifications

GOST 29169−91 (ISO 648−77) oils. Pipette with one mark

GOST 31290−2005 Platinum affilirovannaja. Specifications

GOST 31291−2005 Palladium refined. Specifications

Note — When using this standard appropriate to test the effect of reference standards in the information system of General use — on the official website of the Federal Agency for technical regulation and Metrology on the Internet or published annually by the information sign «National standards» published as on January 1 of the current year and related information published monthly indexes 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 Terms and definitions

This standard applies the terminology according to GOST R 8.563, GOST R ISO 5725−1, GOST R 52361.

4 Accuracy (trueness and precision) of the method

4.1 indicators of the accuracy of the method

Indicators of accuracy of the method: limit of the interval in which with a probability of 0.95 is the absolute error of the results of the analysis (assigned error) , standard deviation of repeatability , standard deviation of intermediate precision , the values of the limit of repeatability , intermediate precision and reproducibility limit depending on the mass fraction of the element-impurities are shown in table 2.


Table 2 — indicators of the accuracy of the method (0,95)

Percentage

For intermediate values of the mass fraction of detectable elements the values of precision find using linear interpolation according to the formula

, (1)

where  — the value of the index of precision for test results , %;

,  — the value of the indicator of accuracy, corresponding to the lower and upper levels of the mass fraction of detectable elements, between which is the result of the analysis, %;

 — the result of the analysis, %;

, the lower and upper levels of a mass fraction of detectable elements, between which is the result of the analysis, %.

4.2 Correctness

To estimate the systematic error of the present method for determining all impurities in the palladium are used as reference values certified values of mass fractions of elements in the state standard samples of composition of GSO 7615−99 of palladium (set PD-36), GEO 7331−96 (set PD-28) or other GEO, the next set of detectable elements and metrological characteristics.

Systematic error of the method at a significance level of 5% according to GOST R ISO 5725−4на all defined levels of mass fractions of impurities in palladium insignificant.

4.3 Precision

Range of two results of determinations obtained for the same sample by one operator using the same equipment within the shortest possible time intervals that may exceed the specified in table 2 the limit of repeatability according to GOST R ISO 5725−6 on average not more than once in 20 cases with proper use of the method.

Within a single laboratory result analysis of the same sample obtained by different operators using the same equipment on different days, can vary with the excess specified in table 2 of the limit of intermediate precision according to GOST R ISO 5725−3 on average not more than once in 20 cases with proper use of the method.

The results of the analysis of the same samples, obtained in two laboratories (in accordance with sections 6−8 of this standard), can vary with the excess indicated in the table 2 reproducibility limit according to GOST R ISO 5725−1 on average not more than once in 20 cases with proper use of the method.

5 Requirements

5.1 General requirements and safety requirements

General requirements for method of analysis, the requirements for security of works and ensuring environmental safety are carried out in accordance with GOST R 52599.

5.2 qualifications of performers

To perform analysis allowed persons over the age of 18, trained in the prescribed manner and allowed to work independently on used equipment.

6 measurement Means, auxiliary devices, materials and reagents

Aluminium metal according to GOST 11069.

Ammonium molybdate according to GOST 3765.

Argon gas or liquid of the highest grade according to GOST 10157.

Atomic emission spectrometer with inductively coupled plasma, with a working wavelength range from 170 to 500 nm, with the possibility of carrying out of procedure of correction of the background, with axial plasma review.

Barium chloride according to GOST 4108.

Barium peroxide (barium peroxide) purity [1].

Laboratory scales in accordance with GOST R 53228 with a limit of permissible absolute error of measurement no more than ±0,0003 g

Distilled water according to GOST 6709, further purified by distillation or by passing through ion exchange columns.

Funnel for laboratory, In-75−110 TC GOST 25336 or plastic.

Sealed containers of polyethylene, polypropylene or Teflon with a capacity of 50, 500 cm.

Iron restored [2].

Gold bullion according to GOST 6835 or GOST 28058 with a mass fraction of main substance not less than 99.99%.

Iridium powder according to GOST 12338 with a mass fraction of basic substance is no less than a 99.97%.

Cadmium GOST 1467.

Calcium carbonate according to GOST 4530.

Nitric acid of high purity according to GOST 11125, diluted 1:1.

Sulfuric acid of high purity according to GOST 14262, diluted 1:9.

Hydrochloric acid of high purity according to GOST 14261, diluted 1:1, 1:3, 1:5.

Cobalt GOST 123.

Volumetric flasks 1−50−2, 1−100−2, 1−500−2 according GOST 1770.

Silicon dioxide according to GOST 9428.

Magnesium GOST 804.

Manganese metal according to GOST 6008.

Copper according to the GOST 859.

Sodium hydroxide of high purity according to GOST 4328.

Nickel GOST 849.

Tin GOST 860.

Muffle furnace with temperature controller with heating temperature up to 1000 °C.

Pipette 2−2-1, 2−2-2, 2−2-5, 2−2-10, 2−2-20 according to GOST 29169.

Platinum affilirovannaja according to GOST R or GOST 52245 31290 with a mass fraction of the basic substance is not less than 99,98%.

Rhodium powder according to GOST 12342 with a mass fraction of basic substance is no less than a 99.97%.

Ruthenium powder according to GOST 12343 with a mass fraction of basic substance is no less than a 99.97%.

Lead of high purity according to GOST or GOST 22861 3778.

Silver bullion according to GOST 6836 or GOST 28595 mass fractions of the basic substance is not less than 99.99%.

Scandium technical [3].

Glasses In laboratory-1−600 TCS according to GOST 25336.

The Teflon beakers with lids capacity from 50 to 100 cm.

Standard samples of composition of GSO 7615−99 of palladium (set PD-36), GEO 7331−96 (set PD-28) or others, are not inferior to the composition of impurity elements and precision.

Watch-glasses with a diameter of 65 mm or plastic.

The agate mortar.

Antimony GOST 1089.

The corundum crucibles.

The glassy carbon crucibles with a capacity of 50 cm.

Titan according to GOST 19807.

The filter paper obestochennye «blue ribbon» at [4].

Chrome metal according to GOST 5905.

Zinc GOST 3640.

Watch for General use.

Drying oven with the temperature heating up to 150 °C.

An electric cooker with a sealed coil and adjustable heating temperature up to 300 °C.

Allowed the use of other measurement means, auxiliary devices, materials and reagents, subject to obtaining accuracy rate that rivals those in table 2.

7 Preparation for assay

7.1 Preparation of basic solutions

The following procedures for the preparation of standard solutions indicated the mass of batches of materials with a purity not lower of 99.96%. In the case of use of reagents lower qualifications introduce an amendment of the mass of sample in accordance with the content of the main component, specified in the passport. The prepared solutions were stored for not more than one year, except the silver solution according to 7.1.2, which has been stored not more than one month.

7.1.1 Solutions with mass concentrations of rhodium, iridium, ruthenium of 1 mg/cm

A portion of each metal by weight of 0.5 g is weighed with an accuracy of ±0.0003 g, ground in an agate mortar with a 5-fold quantity of peroxide of barium to obtain a homogeneous mass. The resulting mixture is transferred to a corundum crucible, put in a cold muffle furnace and sintered at temperatures (950±50) °C for 2−3 h.

Crucible sintering was cooled to room temperature, transferred to a beaker with a capacity of 600 cm, sintered is moistened with water and treated with a solution of hydrochloric acid 1:1. The beaker was heated until complete dissolution of the cake, not bringing the solution to boiling. Cooled to room temperature, the solution was filtered through filter «blue ribbon». The filter 5−6 times washed with hot hydrochloric acid 1:5.

If the dark sediment filter it is transferred to a corundum crucible with the filter, dried in air, placed in the cold crucible muffle furnace, include heating and calcined at a temperature of (750±50) °C for 30−40 min. the Cooled residue was triturated with 1.0 g of peroxide of barium, is sintered, dissolved, filtered as described above.

The filtrates are United, evaporated to a volume of 20−30 cm, is diluted with water to a volume of 250−300 cm, heated to boiling and precipitated barium sulfate in hot sulfuric acid 1:9. After 2−3 hours check the completeness of the precipitation of barium sulfate, adding a few drops of sulfuric acid 1:9. The solution was filtered through filter «blue ribbon» in a volumetric flask with a capacity of 500 cm, for washing the precipitate on the filter with hot hydrochloric acid 1:5, then 5−6 times with hot water. The volume of the solution was adjusted to the mark with hydrochloric acid 1:1 and stirred.

7.1.2 Solution the mass concentration of silver is 1 mg/cm

A portion of the silver weight of 0.2 g is weighed with an accuracy of ±0.0003 g, dissolved in 20 cmof nitric acid solution 1:1 under heating. To the solution was added to 100 cmof hydrochloric acid, heated to dissolve the precipitate of silver chloride. The cooled solution is transferred to a volumetric flask with a capacity of 200 cm, the volume was adjusted to the mark with hydrochloric acid 1:1 and stirred.

7.1.3 Solutions of the mass concentrations of platinum, gold, aluminum, cobalt, tin, antimony, cadmium 1 mg/cm

A portion of each metal by weight of 0.5 g is weighed with an accuracy of ±0.0003 g, was dissolved with heating in a mixture of hydrochloric and nitric acids 3:1. After the dissolution of the hitch and stop the allocation of brown fumes of nitrogen oxides the solutions were evaporated to a volume of 3−5 cm, add 50 cmof a hydrochloric acid solution of 1:5. The solutions were cooled and transferred to volumetric flasks with a capacity of 500 cmeach, the volume was adjusted to the mark with hydrochloric acid 1:5, mix.

7.1.4 Solutions with mass concentrations of lead, iron, copper, Nickel 1 mg/cm

A portion of each metal by weight of 0.5 g is weighed with an accuracy of ±0.0003 g when heated was dissolved in 50 cmof nitric acid solution 1:1. The solutions were heated to remove oxides of nitrogen (stop the release of brown fumes), not boiling, cooled, transferred to volumetric flasks with a capacity of 500 cmeach, the volume was adjusted to the mark with water, mix.

7.1.5 Solutions with mass concentrations of zinc, chromium, manganese, magnesium, titanium 1 mg/cm

A portion of each metal by weight of 0.5 g is weighed with an accuracy of ±0.0003 g, is dissolved in 50 cmof a hydrochloric acid solution 1:1 when heated, not boiling. The solutions were cooled, transferred to volumetric flasks with a capacity of 500 cmeach, the volume was adjusted to the mark with water and mix.

7.1.6 Solution of the mass concentration of molybdenum 1 mg/cm

The weight of ammonium molybdate [(NH)MoO·4HO] weight 0,920 g dissolved in 50 cmof hot water, cooled, transferred to a volumetric flask with a capacity of 500 cm, the volume was adjusted to the mark with water, mix.

7.1.7 Solution mass concentration of barium 1 mg/cm

A sample of barium chloride (BaCI·2HO) ground 0,889 g dissolved in 50 cmof water, transferred to a volumetric flask with a capacity of 500 cm, the volume was adjusted to the mark with hydrochloric acid 1:5, stirred and poured into a re-sealable polyethylene, polypropylene or Teflon container.

7.1.8 the Solution of the mass concentration of calcium 1 mg/cm

Calcium carbonate (CACO) was dried to constant weight at a temperature of (100±5) °C, selected weighed mass 1,249 g, is dissolved in 50 cmof a hydrochloric acid solution of 1:5. The solution was transferred to a volumetric flask with a capacity of 500 cm, the volume was adjusted to the mark with hydrochloric acid 1:5, stirred and poured into a re-sealable polyethylene, polypropylene or Teflon container.

7.1.9 Solution mass concentration of silicon of 1 mg/cm

In a glassy carbon crucible with a capacity of 50 cmis placed 3.0 g of sodium hydroxide and a portion of the silicon dioxide (SiO) weighing 1,070 g. the Crucible is placed in an oven at a temperature of (450±50) °C and fused for 20 min. the Crucible is removed from the muffle furnace and cooled to room temperature. In the crucible, add 20 cmof water, heated to dissolve the salts, then cooled, the contents of the crucible transferred to a volumetric flask with a capacity of 500 cm, the volume was adjusted to the mark with water, mixed and immediately transferred to a re-sealable polyethylene, polypropylene or Teflon container.

7.1.10 Solution mass concentration of scandium 1 mg/cm

A portion of the scandium with a mass of 0.5 g is weighed with an accuracy of ±0.0003 g, dissolved in 100 cmof hydrochloric acid, transferred to a volumetric flask with a capacity of 500 cm, the volume was adjusted to the mark with water, mixed and poured into a re-sealable polyethylene, polypropylene or Teflon container.

The use of other methods of preparation of key solutions and ready-to-use solutions of standard samples and certified mixtures, subject to receipt of the accuracy rate that rivals those in table 2.

7.2 Preparation of multi-element intermediate solutions

7.2.1 Solution A: In a volumetric flask with a capacity of 100 cmplaced at 10 cmsingleton basic solutions containing 1 mg/cmof platinum, rhodium, iridium, ruthenium, gold, silver. The volume of the solution was adjusted to the mark with hydrochloric acid 1:3, mix.

The mass concentration of each of the elements in the solution is of 100.0 µg/cm.

The limit of the absolute error values of the mass concentration of each element in the solution is ±0.5 µg/cm.

7.2.2 Solution: In a volumetric flask with a capacity of 100 cmplaced at 10 cmsingleton basic solutions containing 1 mg/cmcopper, iron, Nickel, cobalt, zinc, chromium, manganese, lead. The volume of the solution was adjusted to the mark with hydrochloric acid 1:5, mix.

The mass concentration of each of the elements in the solution is of 100.0 µg/cm.

The limit of the absolute error values of the mass concentration of each element in the solution is ±0.5 µg/cm.

7.2.3 Solution: In a volumetric flask with a capacity of 100 cmplaced at 10 cmsingleton basic solutions containing 1 mg/cmtin, antimony, aluminum, magnesium, barium, cadmium, molybdenum, titanium. The volume of the solution was adjusted to the mark with hydrochloric acid 1:5, mix.

The mass concentration of each of the elements in the solution is of 100.0 µg/cm.

The limit of the absolute error values of the mass concentration of each element in the solution is ±0.5 µg/cm.

7.2.4 K Solution: In a volumetric flask with a capacity of 100 cmplaced at 10 cmbasic solutions containing 1 mg/cmof silicon, calcium. The volume of the solution was adjusted to the mark with hydrochloric acid 1:5, stirred, poured storage in resealable polyethylene, polypropylene or Teflon container.

Mass concentration of silicon and calcium in solution is of 100.0 µg/cm.

The limit of the absolute error values of mass concentration of elements in solution is ±0.5 µg/cm.

7.2.5 Solution Sc: In a volumetric flask with a capacity of 100 cmis placed 10 cmbasic solution containing 1 mg/cmscandium. The volume of the solution was adjusted to the mark with hydrochloric acid 1:5, stirred, poured storage in resealable polyethylene, polypropylene or Teflon container. Mass concentration of scandium in the solution is of 100.0 µg/cm.

The limit of the absolute error values of the mass concentration of scandium in solution is ±0.5 µg/cm.

The solution is used as the internal standard.

7.2.6 solution prepared in 7.2, to keep no more than one month.

7.3 Preparation of calibration samples

7.3.1 For determination of impurities in palladium using the calibration samples: the solutions with mass concentration of determined elements up to 20 µg/cmwith the addition of the element internal standard of scandium, prepared according to 7.3.2, or solutions of standard samples of composition of palladium prepared according to 7.3.3.

7.3.2 In a volumetric flask with a capacity of 100 cmpipettes taken aliquote part of the interim solutions according to table 3, adds 2 cmof the solution Sc, adjusted to the mark with hydrochloric acid 1:5, stirred and immediately poured into a re-sealable polyethylene, polypropylene or Teflon containers. In the zero solution immediately add 2cmof a solution of Sc, the volume adjusted to the mark with hydrochloric acid 1:5, stirred and poured into polyethylene, polypropylene or Teflon container.


Table 3 — Calibration samples

7.3.3 For calibration by standard samples of composition of palladium choose two or more of the sample so that the values of the mass fraction of each of the element in the analyzed sample were in the range between the smallest and largest values of the mass fraction of this element in the standard samples.

From each standard sample weighed 1.0 g weighed with an accuracy of ±0.0003 grams and translate it into a solution for 8.1.2−8.1.4.

The solutions prepared according to 7.3, store no more than 5 days at room temperature.

8 analysis

8.1 Selection and preparation of samples

8.1.1 the Selection of laboratory samples for analysis from the ingot or powder of refined palladium is carried out in accordance with the procedure according to GOST R 52244. Laboratory a sample of palladium powder was dried in a drying Cabinet at a temperature of from 95 °C to 105 °C to constant weight.

8.1.2 laboratory From samples of palladium selected two sample mass of 1.0 g each, weighed with an accuracy of ±0.0003 g, placed in Teflon beakers with a capacity of 100 cmeach. In the analysis of palladium in powder form are transferred to 8.1.3. In the analysis of palladium in the form of chips weighed pre-cleaned from surface contamination. To do this in a glass add 20 cmof a hydrochloric acid solution of 1:1 and boiled for 5 min. the Solution is decanted and washed weighed 6−7 times with water by the method of decantation.

8.1.3 In the beaker was added 20 cm ofa freshly prepared mixture of hydrochloric and nitric acids 3:1, close the cap and dissolve palladium when heated, not allowing to boil. After complete dissolution of the sample solution was cooled and quantitatively transferred to a volumetric flask with a capacity of 50 cm, add 1 cmof the Sc solution, the solution volume adjusted to the mark with water, mixed and poured into a re-sealable polyethylene, polypropylene or Teflon container.

8.1.4 along with the analysis of samples under the same conditions is carried out the control («blank») experience for the amendment of the results of the analysis on the purity of the reagents.

If the calibration samples are prepared from standard samples of composition of palladium, the control experience of the purity of reagents is not carried out, provided for the dissolution of batches of standard samples and analyzed samples using the same acid solutions.

8.2 measurements

8.2.1 preparing the spectrometer to work and work on the device carried out according to the instruction manual of the spectrometer. The measurement programme is introduced in the table the concentrations of the calibration solutions, the wavelengths of the analytical lines, the point of correction of the background plasma parameters.

Recommended wavelengths of the analytical lines given in table 4.


Table 4 — wavelengths of the analytical lines

The use of other analytical lines, as well as other elements of comparison, subject to receipt of the accuracy rate that rivals those in table 2.

8.2.2 In the plasma are administered sequentially to the calibration samples and the measured intensity of the analytical lines of the determined elements and the internal standard minus the background (the intensity measured near the analytical line of the element and internal standard). For each solution perform the three measurements, calculate the average value of intensity.

Calibration samples, prepared according to 7.3.2, is used to plot in coordinates: where a is the mass concentration of the determined element in the solution for calibration, mg/cm;  — the intensity of the line of this element minus the background;  — the intensity of the line scandium (internal standard) minus background.

Calibration samples, prepared according to 7.3.3, is used to plot in coordinates: where a is the mass fraction of the element in a standard sample of composition of palladium, %;  — the intensity of the line of this element minus the background.

8.2.3 When performing measurements sequentially injected into the plasma solutions control experiments and analyze samples. For each solution perform three measurements of the intensity of analytical lines (minus background) of the designated elements, the internal standard; calculating the average values of the intensities or relations of the intensities. Using the calibration characteristics are the value of the mass concentration of the element in solutions of the sample and the reference experiment (if you used the calibration samples 7.3.2) or from the value of the mass fraction of the element in the sample (if you used the calibration samples 7.3.3).

9 evaluating the acceptability of the results of parallel measurements and obtaining the final result of the analysis

9.1 Mass fraction of the element in % calculated in the following way.

9.1.1 If the calibration samples were prepared from standard samples of composition of palladium in 7.3.3, the value of the mass fraction of the element is obtained directly from the calibration characteristics.

9.1.2 If the calibration samples were prepared from intermediate solutions according to 7.3.2, the value of the mass fraction of the element in % is calculated by the formula

, (2)

where and  — mass concentration of the element in the analyzed solution and the solution in the reference experiment, respectively, µ g/cm;

 — the volume of the analyzed solution, cm;

 — the weight of the portion of the sample,

9.1.3 Mass concentration of the element in solution in the reference experiment is calculated as the arithmetic mean value of two results of parallel measurements of the item in the solution control experience in 8.1.4.

9.2 the acceptability of the results of parallel measurements was evaluated in accordance with GOST R ISO 5725−6 by comparing the absolute discrepancy of the two results of parallel measurements with a limit of repeatability in table 2.

If not exceed , two parallel definitions recognize acceptable and for the final result of the analysis is to take their arithmetic mean value.

If exceeds , hold two parallel definitions. If the range of the four results of parallel measurements does not exceed the critical range for the 4, , the final result of the analysis taking the arithmetic mean of the four results of parallel measurements.

The critical range is calculated by the formula

, (3)

where the 3.6 — the ratio of the critical range for four parallel measurements;

 — standard deviation of repeatability, the values of which are given in table 2.

If the range of the four results of parallel measurements exceeds , the final result of the analysis taking the median of four results of parallel measurements. The lower bits of the numerical result and the numeric values of the accuracy metrics should be the same.

10 Control of accuracy of analysis results

10.1 Control of intermediate precision and reproducibility

When monitoring intermediate precision (variable factors of the operator and time) is the absolute difference of the two results of the analysis of the same sample obtained by different operators using the same equipment on different days, should not exceed the limit of intermediate precision specified in table 2.

Under the control of the reproducibility of the absolute disparity of the two results of the analysis of the same samples obtained by two laboratories in accordance with the requirements of this standard must not exceed the limit of reproducibility shown in table 2.

10.2 verification of correct

The checking is carried out by analyzing standard samples of composition of palladium.

When checking the absolute value of the difference between the analysis result and the accepted reference (certified) value of the mass fraction of element-impurities in the standard sample should not exceed the critical value .

The critical value is calculated by the formula

, (4)

where  — the error of setting the reference (certified) value of mass fraction of element-impurities in the standard sample, %;

 — the boundaries of the interval of the absolute error corresponding certified value mass share of element-impurities in the standard sample, %. The values given in table 2.

Bibliography