GOST R 54335-2011

• gost-r-54335-2011.pdf (411.37 KiB)
  ГОСТ Р 54335-2011

GOST R 54335−2011 Palladium. Method of atomic-emission analysis with spark excitation spectrum

GOST R 54335−2011
Group B59

NATIONAL STANDARD OF THE RUSSIAN FEDERATION

PALLADIUM

Method of atomic-emission analysis with spark excitation spectrum

Palladium. Method of spark atomic-emission analysis

OKS 39.060*
_______________
* ICS 10−2011 GOST R 54335−2011 is with ACS 77.120.99. -
Note the manufacturer’s database.

Date of introduction 2011−11−01

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»), Open joint-stock company «Prioksky factory of nonferrous metals"

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 of June 24, 2011 N 145th 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 specifies atomic emission (spark excitation spectrum) method for determination of impurities, aluminum, barium, bismuth, tungsten, iron, gold, yttrium, iridium, cadmium, calcium, cobalt, silicon, magnesium, manganese, copper, molybdenum, arsenic, Nickel, tin, osmium, platinum, rhodium, ruthenium, lead, sulfur, silver, antimony, tellurium, titanium, phosphorus, chromium, zinc, zirconium affilirovannomu palladium. The requirements for the chemical composition of refined palladium bullion and powder established in GOST R and GOST 52244 31291.

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 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 6709−72 distilled Water. Specifications

GOST 10157−79 Argon gaseous and liquid. Specifications

GOST 14261−77 hydrochloric Acid of high purity. Specifications

GOST 18300−87 ethyl rectified technical. Specifications

GOST 24104−2001 laboratory Scales. General technical requirements*
_______________
* On the territory of the Russian Federation GOST R 53228−2008: from 01.01.2010 — in part newly developed and modernized scales; from 01.01.2013 — weights, designed to 01.01.2010.


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

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 ISO 5725−1, GOST R 8.563, GOST R 52361 and recommendations [1].

4 the essence of the method

The method of analysis is based on the evaporation and excitation of the atoms of the sample in the spark discharge, the photoelectric registration of spectrum, measuring the intensity of the analytical lines of the determined elements-impurities and the background, and the subsequent determination of content of impurities in the calibration characteristics. The method allows to determine the mass fraction of impurity elements in the ranges given in table 1 with measures of the accuracy of the method of analysis presented in table 2.


Table 1 — Ranges of definition of mass fraction of impurity elements

Percentage

5 Accuracy (trueness and precision) of the method

5.1 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 and intermediate precision , the values of the critical range , intermediate precision and reproducibility limit according to GOST R ISO 5725−3, depending on the mass fraction of the element-impurities are shown in table 2.

5.2 Correctness

To estimate the systematic error of the present method for the determination of impurity elements in palladium used as a reference certified value mass fraction of elements in the state standard samples of composition of GSO 7615−99 of palladium (set PD-36) or other GEO, whose set of designated elements-impurities 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 fraction of impurity elements in palladium insignificant.

5.3 Precision

5.3.1 Range () four 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 critical range for 4 on average not more than once in 20 cases.

5.3.2 within one laboratory two results of the analysis of the same sample obtained (in accordance with sections 7−10 of this standard) different operators using the same equipment on different days, can vary with the excess specified in table 2 of the limit of intermediate precision on the average not more than once in 20 cases.

5.3.3 Results of the analysis of the same samples, obtained in two laboratories (in accordance with sections 7−10 of this standard) may vary in excess of the limit of reproducibility indicated in table 2, on average not more than once in 20 cases.


Table 2 — Indicators of accuracy of the method when p = 0.95

Percentage

For intermediate values of the mass fraction values in terms of accuracy find using linear interpolation according to the following formula

, (1)

where  — the indicator of the accuracy of the analysis result ;

, the values of precision, corresponding to the lower and upper level mass fraction of detectable elements, between which is the result of the analysis;

,values of the lower and upper levels of the mass fraction of elements, between which there is the result;

 — the result of the analysis.

6 Requirements

6.1 General requirements and safety requirements

General requirements for method of analysis, the requirements for security of works and environmental safety — according to GOST R 52599.

6.2 qualifications of performers

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

7 measurement Means, auxiliary devices, materials and reagents

Optical emission spectrometer with spark excitation source spectrum and the working wavelength range 120−700 nm.

Laboratory scales according to GOST 24104 and scales according to GOST R 53228 with a limit of permissible absolute error of less than ±0.01 g.

Milling machine.

Press and mold with a diameter of 40 mm.

Argon gas according to GOST 10157.

Flap of tissue, the type of calico.

Rectified ethyl alcohol according to GOST 18300.

Distilled water according to GOST 6709.

Hydrochloric acid OS. h according to GOST 14261, diluted 1:1.

Glasses glass with a capacity of 100 cmaccording to GOST 25336.

Standard samples of composition of palladium GSO 7615−99 or the other, not inferior to the composition of impurity elements and precision.

Samples for control.

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

8 Selection and preparation of samples

The selection of laboratory samples for analysis from the ingots or powder of refined palladium is carried out in accordance with GOST R 52244. Requirements for the size and mass of the samples are determined depending on the used spectrometer. Samples received for analysis in the form of ingots, rods, plates, strips, shavings and powder. The surface of the rods and plates should be flat, and processed by cutting or grinding, the tape surface should be smooth and without delamination. Samples in the form of ingots, rods, plates, wipe with a cloth moistened with rubbing alcohol. Samples in the form of ribbons, shavings boiled in a solution of hydrochloric acid diluted 1:1 for 3−5 min to remove surface contamination. The resulting solution was decanted, the sample was washed 6−7 times with distilled water by decantation and dried in air. From the sample in the form of chips or powder taken weighed 20−30 g and pressed with a force equal to 500 kN per tablet.

9 Preparation of equipment for measurement

Spectrometer ready to work according to the instruction manual of the device.

The recommended mode of operation of the spectrometer:

discharge frequency of 300 Hz;

capacity — 2−5 UF;

inductance — µh 130;

purging with argon — 3.

The wavelengths of the analytical lines, background, and line of internal standard is recommended to perform the analysis shown in table 3.


Table 3 — wavelengths of the analytical lines

In nanometers

10 measurements

To obtain the calibration dependencies consistently reinforce the cell spark discharge standard samples of composition of palladium and is incorporated in the spectrometer of the program conducted by the measuring the intensity of the analytical lines of the determined elements, background, and lines the internal standard. For graduation choose three or more standard samples of composition of palladium so that the value of the content of each analyzed element-impurities in the sample was within the range between the highest and lowest values of the mass fraction of this element in the standard samples. For each standard sample perform measurement in four different points of the surface.

The calibration relationships are obtained in the coordinates: the average value of the intensity of the analytical lines of the determined elements of the four points of the sample surface — the mass fraction of the element in the standard sample.

Measured intensity of analytical lines of the determined elements, background, and lines the internal standard in four points on the surface of the sample and sample control (OK). Embedded in the spectrometer program using a calibration dependencies get four results of parallel measurements in the sample.

11 Evaluation of the acceptability of the results of parallel measurements and obtaining the final result of the analysis

The acceptability of the results of parallel measurements was evaluated in accordance with GOST R ISO 5725−6 by matching range, results () with the critical range , the values of which are given in table 2 or calculated by the formula (1).

If the range of the four results of the parallel definition (a) does not exceed the critical range , all the results and recognise acceptable for the final result of the analysis taking the arithmetic mean of the four results of parallel measurements.

If the range of the four results of parallel measurements exceeds , spend four parallel determinations.

The critical range is calculated by the following formula

, (2)

where is the number of parallel definitions;

 — coefficient depending on the number of individual analysis results, obtained in conditions of repeatability and confidence probability of 0.95. For eight parallel measurements of 4.29;

 — standard deviation of repeatability are given in table 2.

If the received eight results of parallel measurements, the value () does not exceed the critical range , as a final result of the analysis taking the arithmetic mean value of the eight results of parallel measurements. Otherwise, as a final result of the analysis taking the median of the eight results of parallel measurements. The lower bits of the numerical result and the numeric values of the accuracy metrics should be the same.

12 Control of accuracy of analysis results

12.1 Control of intermediate precision and reproducibility

When monitoring intermediate precision (taking into account the influencing factors of time, operator) 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 or calculated by the formula (1).

Under the control of the reproducibility of the absolute disparity of the two results of the analysis of the same samples, obtained in two laboratories, in accordance with the requirements of this standard must not exceed the limit of reproducibility shown in table 2 or calculated by the formula (1).

12.2 verification of correct

The checking is carried out by analysis of standard samples (co), and samples for control (s) composition of the palladium. The samples used for control of correctness should not be used to obtain the calibration dependencies.

When checking the difference between the analysis result and the accepted reference (certified) value of the content of element impurities in the co should not exceed a critical value .

Critical value calculated by the following formula

, (3)

where  — the error of setting the reference (certified) value of mass fraction of element-impurities in co or OK.

 — the indicator of the accuracy of the analysis result, the corresponding certified value, WITH or OK.

Bibliography