GOST R 52599-2006
GOST R 52599−2006 Precious metals and their alloys. General requirements for methods of analysis
GOST R 52599−2006
Group B59
NATIONAL STANDARD OF THE RUSSIAN FEDERATION
PRECIOUS METALS AND THEIR ALLOYS
General requirements for methods of analysis
Precious metals and their alloys. General requirements for methods of analysis
OKS 77.120.99
AXTU 1709
Date of introduction 2008−01−01
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 «Irkutsk research Institute of noble and rare metals and diamonds» (JSC «Irgiredmet»)
2 SUBMITTED by the Technical Committee on standardization TC 304 «Noble metals, alloys, industrial and jewelry products made of them; secondary resources containing noble metals».
3 APPROVED AND put INTO EFFECT by the Federal Agency for technical regulation and Metrology dated November 29, 2006 N 286-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 establishes General requirements for methods of analysis of precious metals (gold, silver, platinum, palladium, rhodium, iridium, ruthenium and osmium), including refined, and alloys based on precious metals, as well as safety requirements.
The standard applies to newly developed and revised methods of quantitative chemical analysis (hereinafter — analysis techniques) used in the quality control of precious metals and their alloys.
2 Normative references
This standard uses the regulatory references to the following standards:
GOST R 8.563−96 State system for ensuring the uniformity of measurements. Methods of measurement
GOST R ISO 5725−1-2002 Accuracy (trueness and precision) of methods and measurement results. Part 1. General provisions and definitions
GOST R ISO 5725−2-2002 Accuracy (trueness and precision) of methods and measurement results. Part 2. The basic method for the determination of repeatability and reproducibility of a standard measurement method
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 5725−5-2002 Accuracy (trueness and precision) of methods and measurement results. Part 5. Alternative methods for determining the precision 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 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 12.0.004−90 System of standards of occupational safety. Organization of training safety. General provisions
GOST 12.1.004−91 System safety standards. Fire safety. General requirements
GOST 12.1.005−88 standards System of labor safety. General hygiene requirements for working zone air
GOST 12.1.019−79 System of standards of occupational safety. Electrical safety. General requirements and nomenclature of types of protection
GOST 12.4.011−89 System safety standards. Means of protection of workers. General requirements and classification
GOST 12.4.021−75 System safety standards. System ventilation. General requirements
GOST 12.4.068−79 System of standards of occupational safety. PPE dermatological. Classification and General requirements
GOST 1770−74 laboratory Glassware measuring glass. Cylinders, beakers, flasks, test tubes. General specifications
GOST 6709−72 distilled Water. Specifications
GOST 24104−2001 laboratory Scales. General technical requirements
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 29228−91 (ISO 835−2-81) oils. Pipettes are graduated. Part 2. Pipettes graduated without a set timeout
GOST 29229−91 (ISO 835−3-81) oils. Pipettes are graduated. Part 3. Pipettes are graduated with the waiting time
GOST 29251−91 (ISO 385−1-84) oils. Burette. Part 1. General requirements
ST SEV 543−77 Number. Record rules and rounding
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 document is replaced (modified), then the use of this standard should be guided by the replaced (modified) document. If the reference document is cancelled without replacement, then the situation in which the given link applies to the extent that does not affect this link.
3 General provisions
Techniques of quantitative chemical analysis (MCHE) used in the quality control of precious metals and alloys on their basis, must meet the requirements of GOST R 8.563, GOST R ISO 5725−1-GOST R ISO 5725−6 and of this standard.
4 Requirements to selection and preparation of samples
4.1 Selection of samples for analysis must be conducted in accordance with regulatory document (ND) for the production of precious metals and alloys in which this procedure is set out.
4.2 Samples (samples) can enter the analysis in the form of ingots, mill products (plate, strip), bars, wire, chips, granules, sponge and powder. In the method of analysis should be specified in which the samples are received for analysis, and should include the methods of preparing them for analysis.
4.3 Before performing the calibration and analysis of standard samples (SS) and laboratory samples (pure metals) are cleaned from surface contamination. The method for cleaning samples must be given in the method of analysis.
Allowed to clean not all the lab sample, and the sample taken from the laboratory sample. Samples of precious metals in powder and sponge materials chemical treatment not subjected to.
4.4 Upon dissolution of samples of refined silver and silver alloys in the used reagents, and the environment must be free of chlorine ions.
5 Requirements for accuracy of methods of analysis
5.1 the method of analysis should be presented to measure the accuracy of the methods and procedures to control the accuracy of analysis results when implementing the technique in the laboratory in accordance with GOST R 8.563 and GOST R ISO 5725−6.
5.2 ND to the method of analysis result values of the measure of the accuracy of the technique (assigned specifications of error) and indices of precision (repeatability, reproducibility and intermediate precision) in accordance with GOST R ISO 5725−1-GOST R ISO 5725−6 [1], [2].
The values assigned to the characteristics of error should not exceed the limits of error if these rules are specified in the normative documents for these products.
6 Requirements for measuring instruments, materials and reagents
6.1 the analysis used laboratory scales according to GOST 24104. In the method of analysis must indicate the class of accuracy of scales and the limit of permissible error of weighing.
6.2 analysis used reagents qualifications H. h, h. d. a. and OS.h.
For the preparation of solutions used distilled water according to GOST 6709, if the method of analysis does not provide otherwise.
6.3 the wording «diluted 1:1, 1:2», etc. the first digits indicate the volume of the reagent (acid, etc.), the second volume of the water.
6.4 the Term «hot» water (solution) means that the water (solution) has a temperature of above 70 °C.
6.5 Laboratory measuring utensils should not be below 2nd class of accuracy and meet the requirements of GOST 1770, GOST 25336, GOST 29227, 29228 GOST, GOST and GOST 29229 29251.
6.6 For the preparation of the basic solutions installed content of components (solutions for the calibration, certified mixtures, solutions of titrants, etc.) you must use the metals and compounds containing at least 99.9% of the basic substance, if the method of analysis does not provide otherwise.
6.7 the Main solutions of known concentration and the samples for calibration (certified mixtures) should be stored at room temperature in sealed plastic jars or flasks with labels, which must be specified: the name or designation certified value, the limit of the absolute error of its establishment, the date of preparation and expiration date.
The storage period for solutions must be specified in a particular method of analysis.
6.8 in the absence of the passport or specifications in the analyzed sample (metal or alloy) it is necessary to conduct preliminary qualitative analysis of samples to identify the main components.
7 Requirements analysis
7.1 the Calibration characteristics is obtained using standard samples of composition of the samples for calibration or certified mixtures prepared in accordance with [3]. In the method of analysis should be described the procedure for the preparation of certified mixtures (solutions).
7.2 Concurrently 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. The number of parallel definitions in a control experiment must be specified in the methodology analysis.
7.3 For the analysis used the means of measurement specified in specific MKHA. Measuring instruments must be calibrated or verified in the prescribed manner.
Allowed the use of other measurement means, auxiliary devices, materials and reagents, subject to obtaining the accuracy rate of a technique is not inferior to the specified in specific MKHA.
8 Requirements for the processing and presentation of analysis results
8.1 the Contents of impurity elements and the main component in metals and alloys, define at least two parallel definitions. The number of parallel definitions should be specified in the methodology analysis.
8.2 checking the admissibility of the results of parallel measurements obtained in conditions of repeatability, is carried out upon receipt of each result of the analysis of work samples. The procedure for checking the acceptability of the results is carried out in accordance with GOST R ISO 5725−2.
8.2.1 procedure for checking the acceptability of the results involves comparing the absolute differences between the highest 
the results of a single analysis
made in accordance with the method of analysis, with a limit of repeatability
.
If the condition
for the result of the analysis taking arithmetic mean value of results of a single analysis
(
1, …,
).
8.2.2 Limit of repeatability in the absence of its regulation in the method of analysis is calculated by the formula
where 
of individual analysis results, obtained in conditions of repeatability and confidence
. Coefficient values
for the acceptance probability of
0.95 is given in table 1;
— standard (RMS) deviation of repeatability corresponding to the average value of the results of a single analysis
(a measure of repeatability of methods of analysis), determined in accordance with the regulations on the method of analysis.
Table 1 — Values of coefficient 
of 0.95
|
2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
| 2,77 | 3,31 | 3,63 | 3,86 | Of 4.03 | 4,17 | 4,29 | 4,39 | 4,47 |
If condition (1) is not satisfied, carry out the procedure
8.2.3 Receive the parallel definitions,
1 if the analysis is expensive.
The result of the analysis taking arithmetic mean value of 
where 
The critical range 
where 
. Coefficient values
0.95 is given in table 1;
— standard deviation of repeatability corresponding to the average value of results of parallel measurements
.
8.3 If condition (3) is not fulfilled, you must find out the reasons of unsatisfactory results of analysis and take measures for their elimination or for the final result of the analysis can be accepted by the median 
8.4 in the event of necessity to obtain the final result of the analysis based on the two results obtained under intermediate precision procedure was to check the admissibility of the results of the analysis involving the comparison of the absolute differences between the two results of the analysis (and
representing the arithmetic mean value of
parallel measurements in accordance with the method of analysis) of the same samples obtained by the same method of analysis in one laboratory (at a variation of one or more factors: time, analyst, equipment, etc.) with a limit of intermediate precision
The results of the analysis and
is considered acceptable if the absolute difference between them does not exceed the limit of intermediate precision
For the final result of analysis take their overall average. If you exceed the limit intermediate precision find out the reasons of unsatisfactory results of the analysis, and eliminate them.
8.5 Checking the acceptability of the results obtained in conditions of repeatability, involves comparing the absolute differences of the analysis results and
obtained in two laboratories according to the same method of analysis and representing the arithmetic mean value of
parallel measurements in accordance with MCHA, with a limit of repeatability —
— the standard deviation of reproducibility of the analysis, i.e. must satisfy the condition
If the absolute value of the difference between the results obtained in two laboratories will not exceed the limit of reproducibility , the results of the analysis are considered consistent and for the final result of analysis take their overall average.
8.6 In case of default of this condition in both laboratories conducted a re-analysis and compares the absolute difference of average results (first and recurrent) of each laboratory with a critical difference 
for the final result of the analysis taking arithmetic mean value of average results of each laboratory. Failure to comply with this condition find out the reasons of unsatisfactory results of analysis and take measures for their elimination.
8.7 in the analysis of refined metals the content of the main component determined by the difference between the 100% and the sum of mass fraction determined by impurities (in percent). The list of monitored elements-set impurities in ND for the products. When rounding the results of the analysis it is necessary to use ST SEV 543.
8.8 If the content of element impurities in the sample less than the bottom border of the element definition given in a particular MCHA, for the contents of this element are set to the lower limit of detection and use it when calculating the content of the main component in the finished products (refined metals).
8.9 the Calculation of the content of main component as the difference between 100% and sum of impurities is performed in the following sequence:
— calculate the sum of the mass fractions of the elements obtained by analysis on specific MCHA, with the precision noted in the methodology, namely, a numerical value analysis result (the mass fraction of the element) are rounded to the decimal point of the discharge, which ends the description of the error corresponding to the obtained value of the mass fraction of the element;
from 100% deduct the amount of impurities, the resulting value is rounded up to the decimal point, which is the normalized content of the main component in ND, by discarding the subsequent values:
| for example, 100%-0,016%=99,984%=99,98%, | |
| 100%-0,012%=99,988%=99,98%, | |
| 100%-0,003%=99,997%=99,99%. | |
The number of significant digits depends on the original requirements, set in normative document on a specific type of product.
8.10 the analysis of multicomponent alloys containing precious metals, allowed the contents of one of the main components calculated by the difference between the 100% and the sum of mass fraction of other components and impurities. The list of defined components and impurities and the requirements for accuracy of methods of analysis set in ND on production and methods of analysis. When rounding the results of the analysis it is necessary to use ST SEV 543.
9 Control of accuracy of analysis results
9.1 Requirements in terms of accuracy of analysis results
9.1.1 In the implementation of analysis techniques in a laboratory set index of precision (including repeatability, reproducibility and intermediate precision) and an indication of the correct assessment of the systematic errors of the laboratory.
Control of accuracy of analysis results is carried out in accordance with [2] and subject to GOST R ISO 5725−1-GOST R ISO 5725−6 .
9.2 Internal quality control the results of the analysis carried out for methods of analysis with the established indices of accuracy, are regulated by ND and approved for use in the prescribed manner.
9.3 At realization of methods in the laboratory provide operational control procedures for the analysis and control of stability analysis results.
Algorithm of operative control of the analysis procedures should be given in the document on the method of analysis.
Control procedures of stability analysis results reglamentary in the quality manual of the laboratory.
9.4 as a means of control can be used:
— samples for control (QA), standard samples (SS) according to GOST 8.315 or certified mixture (AC) [3];
— working samples with known additive detectable component;
— working samples of a stable composition;
— work samples are diluted in a certain ratio;
— other methods of analysis with the established indices of accuracy (control techniques).
9.5 Operational control the analyses carried out directly by the contractor to assess the accuracy of the results of the analysis of a series of samples obtained in conjunction with the results of control definitions.
9.6 the Control of reproduction upon receipt of results of control definitions is carried out in cases where the analysis method provides a parallel definition for the result of the analysis and implemented for each of the results of control definitions derived in accordance with the method of analysis and using the control procedures of [2].
9.7 Control procedures analysis of samples for control (QA) consists in the comparison result of the control determining the certified properties of the specimen to control with the certified value in [2]. At the same time OK must be adequate to the analyzed samples (possible differences in the compositions of the analyzed samples should not contribute to the results of the analysis of statistically significant error). The error of the certified value of CR should be not more than one-third of the accuracy specifications of the analysis.
If during the inspection, samples are used to control that have not been used in establishing the measure of the accuracy of the analysis results, the standard control is allowed to count according to the formula
where — error certified value is OK;
— the indicator of the accuracy of analysis results corresponding to the certified value approx.
9.8 Operational control procedures of the analysis using the addition method, the reference methods of analysis or method of a sample dilution implemented in accordance with the algorithms given in [2].
Allowed to use other methods of operational control, analysis.
9.9 If you need to compare the analysis results obtained in two laboratories by different techniques, the control procedure consists in the comparison of the absolute differences of the analysis results , and
representing the arithmetic mean value of
parallel measurements in accordance with the methodology, with a critical difference
where 
9.10 the Choice of method of control depends on the objects analysed and indicators methods of analysis, cost and duration analysis, etc.
10 security Requirements
10.1 In the laboratories is permitted to store chemicals in a Cabinet, equipped with a ventilation system with corrosion-resistant coating, in accordance with the requirements of GOST
10.2 When carrying bottles with acids, alkalis and ammonia must be provided reliable protection of the container against damage (crates, baskets with shavings).
10.3 If the initial materials with hazardous properties should comply with the safety requirements regulated by normative documents to the appropriate reagents.
10.4 Laboratory space, in which analyses are performed, shall be equipped with a system of supply and exhaust ventilation in accordance with GOST
10.5 Jobs must have lighting in accordance with sanitary norms and applicable rules [5].
10.6 Electrical appliances must comply with the rules of electrical devices, their operation must be conducted in accordance with the rules of technical operation of electrical installations and safety rules at operation of electrical installations, approved Glavgosenergonadzora, and relevant GOST
10.7 devices for carrying out spectral analysis shall be equipped with locks in the generator, local exhaust ventilation from a source of excitation spectrum, the glass screen on a tripod generator for protection from ultraviolet radiation, a protective earthing connection on the alternator and the tripod.
10.8 Spectrometer for atomic emission analysis with inductively coupled plasma needs to be grounded. Do not remove the caps from the appliance to avoid electric shock of high voltage.
10.9 When performing x-ray analysis it is necessary to observe the rules of radiation safety in accordance with the sanitary-epidemiological rules and norms of radiation safety [6].
10.10 When conducting atomic absorption analysis using flame (fuel gas) all work shall be conducted in accordance with the rules of safety in the gas sector, approved by Gosgortekhnadzor, and in accordance with fire safety according to GOST
10.11 the Maximum permissible concentration of harmful substances in the air of working zone and hazard class of these substances — according to GOST
10.12 Waste acid and alkali should be collected separately in special containers; after neutralizing, drain into the sewer or in accordance with local conditions in the designated place.
10.13 To work in analytical laboratories is open to persons under 18 years of age, pass a preliminary medical examination and be approved for health reasons to work with hazardous substances.
10.14 Each worker must undergo a preliminary training on labor protection with the exams and subsequent periodic certification. All employees are required to undergo training, instruction, inspection, knowledge, norms and instructions on labor protection in accordance with GOST
10.15 Working in the chemical and spectral laboratories should be provided with PPE according to current standards of issue of clothing, footwear and protective equipment according to GOST
10.16 the analysis needs to be taken that prevent the release of acids and alkalis on the skin and to apply individual means of protection according to GOST 12.4.011, to observe measures of personal hygiene, use protective dermatological products according to GOST
10.17 Laboratory spaces must be equipped with primary fire extinguishing means. Fire safety laboratory facilities shall be provided in accordance with [7] and requirements of GOST
Bibliography
| [1] MI 2335−2002* | State system for ensuring the uniformity of measurements. Internal quality control of results of quantitative chemical analysis | |
| ________________ * Probably, the error of the original. Should read: MI 2335−2003. — Note the manufacturer’s database. | ||
| [2] RMG 61−2003 | State system for ensuring the uniformity of measurements. Indicators of accuracy, trueness, precision methods of quantitative chemical analysis. Methods of evaluation | |
| [3] RMG 60−2003 | State system for ensuring the uniformity of measurements. Mix certified. General requirements for the development | |
| [4] Recommendations standardization R 50.2.003−2000 |
State system for ensuring the uniformity of measurements. The internal quality control. Software package. Q-Control | |
| [5] SNiP 23−05−95 | Sanitary rules and regulations. Natural and artificial lighting | |
| [6] SP 2.6.1.758−99 NRB-99 |
Ionizing radiation, radiation safety. Radiation safety standards | |
| [7] PPB-01−2003 | The rules of fire safety in the Russian Federation | |
| UDC 669.21/23:543.06:006.354 |
OKS 77.120.99 |
B59 | AXTU 1709 |
| Key words: precious metals, alloys, methods of quantitative chemical analysis, General requirements for methods of analysis | |||
