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Refining Electrolysis of the Secondary Silver Alloys

Refining Electrolysis of the Secondary Silver Alloys

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11/12/2012

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REFINING ELECTROLYSIS OF THE SECONDARY SILVER ALLOYS
 
 Rabatin
 Ľ 
., Vadász P., Tomášek K.
 
Technical University of Kosice, Faculty of Metallurgy, Department of Ceramics, Slovakia
Abstract
Experimental results of the electrolytic refining of silver aimed to study of the influence of metallic impurities on thecathode metal purity from secondary resources are presented in this paper. Horizontal Thumb electrolyser was usedfor these experiments. Influence of the concentration of the metallic impurities in the electrolyte on the purity of cathode silver was studied after redistribution of the impurities between electrolyte, anode slime and cathode metal.The influence of silver concentration in electrolyte on the cathode silver was studied in the first set of experiments.Decreasing of silver content in the nitrate electrolyte under 55 g.dm
-3
caused decreasing of the cathode silver purity.The influence of the Cu, Zn, Pd, Ni, Au, Pt, Sn, Pb, Fe, Bi and Sb content in the anodes and in the electrolyte on theresulting purity of cathode silver was studied in the second set of experiments. The results obtained are presented inthe figures and tables in this paper.
It is possible to divide the metallic impurities into three groups. Copper and palladium is the in the first groupand their concentration in the cathode silver were more than 10
-1
wt.%. Palladium is dissolved in the electrolyteand due to higher electrochemical potential than that silver has, is precipitated in the cathode preferably. Copperhas much higher concentration in the electrolyte as silver and at lower potential is mechanically precipitatedtogether with silver as a copper “cathode sponge”.Zinc is in the second group only. Zn content was 10
-2
wt.% in the cathode at 20 g.dm
-3
of Zn concentration in theelectrolyte. Mechanism of Zn precipitation in the cathode metal was very similar as at copper. Zinc at lawelectrochemical potential is precipitated in the cathode mechanically at its high concentration in the electrolyte.The third group is created by other metallic impurities and their content were under 10
-2
wt.% in the cathodesilver. Gold and platinum is not dissolved in the electrolyte and so its influence is negligible and these metalsare concentrated in the anode slime. Ni, Fe, Sn, Pb, Sb and Bi have similar dissolving and precipitatingmechanism as Cu and Zn but their content in the anode were very low.
Key words:
silver, electrolysis, silver refining
1. Introduction
The aim of this work was to study the behaviour of metallic impurities in the process of electrolyticrefining of silver and measure the impact of concentrations of metals in the supporting electrolyteon the cathode silver purity. Secondary raw materials were formed by silver metal electrical waste,dental metals, jewellery and scrap processed in the electrolytic refining of nitrate electrolyte onsterling silver. Diversity processed metallised silver waste was also reflected in the quality andquantity of accompanying metals. Among the impurities in refining silver, except for base metalsinclude platinum and gold and silver metals in dental waste and jewellery. Silver cathode must meetthe requirements of STN 42 38 30 [1], ie must have a purity of at least 99.9 wt.% Ag.2. Experimental sectionIn the experimental section describing the work of laboratory equipment, experimentalmethodology and methods of chemical analysis of metals in the studied products, electrolyticrefining of silver.2.1 Experimental device
 
Experiments were performed in laboratory electrolysis Thumovom [2], polypropylene, with ahorizontal arrangement of electrodes. Anode compartment was separated by a diaphragm and thecathode was stainless steel. Technical parameters of the experimental facility were as follows:
 
Surface anode / cathode: 0.0225 m2 / 0.0225 m2
 
Electrode distance: 50 mm
 
Electrolyte volume: about 3 dm3
 
Current density: 400 A. m
Fig.1 Thumb silver refining laboratory electrolyser (1 and 2 – electric stream line, 3 - PP vessel with perforated bottom,
4 - Ag anodes, 5 - diaphragm limen, 6 - PP vessel of electrolyser, 7 - stainless steel cathode, 8-PP holders).
 
2.2 Methodology of experiments
Silver metal scrap is melted and cast into anodes, which valcovali to ensure a constant anode area.Anode thickness was 2-3 mm and weighed 900 to 1300 g. Overall, during the experiment redraft 6012 g of metal. Table 1 shows the composition interval the silver anodes for electrolytic refining.Vyvalcované anodes were placed in the anode compartment of the diaphragm. Electrolyte was anaqueous solution of silver nitrate on initial concentration of 15 to 200 g.dm-3 Ag and1% HNO3 free, electrolyte temperature was 25 to 30 ° C, a source of direct current was controllablerectifier [3]. After connecting the gold contacts to the electrodes led DC and began the electrolyticrefining of silver. Voltage between the electrodes were in the range 2 to 2.5 V and depended on thechange in transition resistance of contacts, changing the distance between the electrodes,diaphragms permeability, etc. Electrolytic refining products were silver cathode, anode andelectrolyte slurry. During the experiments the samples were taken electrolyte and cathode silver forchemical analysis. Given the main objective of the experiment, the composition of the anode sludgeat this stage studied.
Table 1 Composition interval of silver anodes used for electrolytic refining
 
Table 1Compositioninterval of silver anodesused forelectrolyticrefiningMetalAg Au Cu Zn Pd NiContents [hm.% ]60 70 22 30 7 - 10 1,0 1,3 0,2 0,3 0,15 0,2Metal Sn Pb Pt Fe Bi SbContents [hm.% ]0,01 0,03 0,1 0,12 < 0,004 0,01 0,015 < 0,003 < 0,00022
The aim was to ascertain the impact of metallic impurities on the quality of the cathode silverand try to determine the concentration limits of observed impurities in the electrolyte tocathode silver suit STN 42 38 30th This standard specifies the minimum content of silver,99.9 wt.% and maximum content of accompanying elements (Table 2).
Table 2 Maximum contents of accompanying elements in silver according to STN 42 38 30Element Bi Cu Fe Pb Sb OtherMax.Contents [hm%]0,02 0,015 0,035 0,003 0,002 0,043
During the electrolytic refining were studied composition cathodic silver depending on thecomposition of the electrolyte. The results obtained were processed into graphs and tables.2.3 Analytical methodsSubjected to chemical analysis products from electrolytic refining and silver cathode and electrolyte.

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