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 the
cathode metal purity from secondary resources are presented in this paper. Horizontal Thumb electrolyser was used
for 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.
-3
Decreasing of silver content in the nitrate electrolyte under 55 g.dm 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 the
resulting purity of cathode silver was studied in the second set of experiments. The results obtained are presented in
the 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 group
-1
and their concentration in the cathode silver were more than 10 wt.%. Palladium is dissolved in the electrolyte
and due to higher electrochemical potential than that silver has, is precipitated in the cathode preferably. Copper
has much higher concentration in the electrolyte as silver and at lower potential is mechanically precipitated
together with silver as a copper “cathode sponge”.
-2 -3
Zinc is in the second group only. Zn content was 10 wt.% in the cathode at 20 g.dm of Zn concentration in the
electrolyte. Mechanism of Zn precipitation in the cathode metal was very similar as at copper. Zinc at law
electrochemical potential is precipitated in the cathode mechanically at its high concentration in the electrolyte.
-2
The third group is created by other metallic impurities and their content were under 10 wt.% in the cathode
silver. Gold and platinum is not dissolved in the electrolyte and so its influence is negligible and these metals
are concentrated in the anode slime. Ni, Fe, Sn, Pb, Sb and Bi have similar dissolving and precipitating
mechanism 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 electrolytic
refining of silver and measure the impact of concentrations of metals in the supporting electrolyte
on 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 on
sterling silver. Diversity processed metallised silver waste was also reflected in the quality and
quantity of accompanying metals. Among the impurities in refining silver, except for base metals
include platinum and gold and silver metals in dental waste and jewellery. Silver cathode must meet
the requirements of STN 42 38 30 [1], ie must have a purity of at least 99.9 wt.% Ag.

2. Experimental section

In the experimental section describing the work of laboratory equipment, experimental

methodology and methods of chemical analysis of metals in the studied products, electrolytic
refining of silver.

2.1 Experimental device

Experiments were performed in laboratory electrolysis Thumovom [2], polypropylene, with a
horizontal arrangement of electrodes. Anode compartment was separated by a diaphragm and the
cathode 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 6
012 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 an
aqueous solution of silver nitrate on initial concentration of 15 to 200 g.dm-3 Ag and

1% HNO3 free, electrolyte temperature was 25 to 30 ° C, a source of direct current was controllable
rectifier [3]. After connecting the gold contacts to the electrodes led DC and began the electrolytic
refining of silver. Voltage between the electrodes were in the range 2 to 2.5 V and depended on the
change in transition resistance of contacts, changing the distance between the electrodes,
diaphragms permeability, etc. Electrolytic refining products were silver cathode, anode and
electrolyte slurry. During the experiments the samples were taken electrolyte and cathode silver for
chemical analysis. Given the main objective of the experiment, the composition of the anode sludge
at this stage studied.

Table 1 Composition interval of silver anodes used for electrolytic refining

Table 1
Composition
interval of
silver anodes
Ag Au Cu Zn Pd Ni
used for
electrolytic
refining
Metal
Contents [
60 – 70 22 – 30 7 - 10 1,0 – 1,3 0,2 – 0,3 0,15 – 0,2
hm.% ]
Metal Sn Pb Pt Fe Bi Sb
Contents [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 silver
and try to determine the concentration limits of observed impurities in the electrolyte to
cathode 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 30

Element Bi Cu Fe Pb Sb Other
Max.
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 the
composition of the electrolyte. The results obtained were processed into graphs and tables.

2.3 Analytical methods

Subjected to chemical analysis products from electrolytic refining and silver cathode and electrolyte.
Chemical analysis of silver nitrate electrolyte was performed by potentiometric titration with
volumetric NaCl solution, copper was determined by iodometric titration method, palladium were
determined by atomic emission spectroscopy and other monitored elements (Ni, Sn, Zn, Pb, Pt, Fe,
Bi and Sb) are determined the atomic absorption spectroscopy.

Silver cathode was transferred to a solution and laid down by potentiometric titration with a
volumetric solution of NaCl, palladium atomic emission spectroscopy and other metals were
analysed by AAS.

3. Experimental results

It is known that in the electrolytic refining of metals exceeding the limit concentrations of the
ingredients in the electrolyte resulting adverse effects on the quality of refined metal. In the case of
electrolytic refining of silver is also critical minimum concentration of silver in the electrolyte as well
as the maximum concentration of impurities in the electrolyte.

In the first series of experiments on laboratory equipment, we investigated the effect of silver
concentration in the electrolyte to the metal purity excluded. The anode was made up of binary

Acta Metallurgica Slovaca, 11, 2005, 1 (78-87) 82

Alloy containing 99.5 wt.% Ag and 0.5 wt.% Cu, which was located on the diaphragm. Nitrate
electrolyte containing 90 to 100 g.dm-3 Cu, 1% HNO3 and the concentration of free silver is varied in
the range 15 to 200 g.dm-3 Ag. In Figure 2 shows the effect of silver concentration in the electrolyte
to a final purity of the cathode metal.

Fig.2 The effect of silver concentration in the electrolyte on the quality of cathode silver

The above dependence shows that the decrease of silver concentration in the electrolyte below 50
g.dm-3 causes a significant reduction in quality (purity) cathode silver excluded.
In the next series of experiments, we investigated the effect of impurities present in the electrolyte
to the cathode purity silver. Choice of metal pollutants has been made on the basis of the elements
listed in the STN 42 38 30 and that of silver metal waste. During the electrolytic refining of silver
anode there were the partitioning of metals present in the following products:

• Silver cathode,

• Anode sludge;

• Electrolyte.

Silver cathode must STN 42 38 30 have purity min. 99.9 wt.% Ag and max. 0.1 wt.% Impurities, which
consists mainly of Cu and Pd, to a lesser extent Zn, Sb, Bi, Sn, Pb, Fe, Ni, or Au and Pt [1]. The anode
sludge remained metals that are insoluble or nitrate environment. very slightly soluble (mainly Au, Pt
and Sn) and the residual concentration of Ag and Cu. Soluble metals are concentrated in the
electrolyte, while in terms of their concentration is these impurities can be divided into three basic
groups:

1. Group (concentration above 10 g.dm-3): Cu and Zn

2. Group (concentration to 10 to 10 g.dm-3): Ni, Pb and Pd

3. Group (concentration below 1 g.dm-3): Au, Pt, Fe, Sn, Bi and Sb

The methodology of experiments show that in the course of those experiments, analyzed the
composition of nitrate electrolyte composition and cathode metal. Composition of the anode sludge
in these experiments was not pursued. In experiments, the concentration of silver in the electrolyte
fluctuated from 103 to 90 g.dm-third Fig. 3-7 are graphically depicted the effects of concentration of
metallic impurities (Cu, Zn, Ni, Pd and Fe) in the electrolyte to a final purity silver cathode.
Fig.5 The effect of nickel concentration in the electrolyte on the concentration of nickel in cathode
silver
Table 3 shows the concentrations of metals in the electrolyte content in the cathode metal was
below the proof of the analytical methods (AAS). Reported levels of gold, platinum, tin, lead,
bismuth and antimony are threshold of proof for the metal in terms of the chemical analysis.

Table 3 Concentrations of observed metals in electrolyte and the corresponding limits of detection
of the given metal in cathode silver

Concentration
Metal -3
Electrolyte [ g . dm ] Silver cathode [ hm. % ]
Au 0 – 0,0028 < 0,0036
Pt < 0,008 < 0,004
Sn 0 - 0,24 < 0,002
Pb 0 – 2,0 < 0,0033
Bi < 0,00044 < 0,003
Sb < 0,0005 < 0,00022

4. Debate

Crucial metallic impurities in the electrolytic refining of silver from secondary sources, gold and
copper (Table 1). Despite the high content of gold in the transition
electrolyte and then in the cathode silver minimum. Gold is concentrated solely in the anode sludge
and the quality of the silver cathode is reflected. This is due to insolubility of gold in ammoniacal
electrolyte in these conditions. The second major impurity is copper, which is located in the anode
metal in concentrations of 5 to 10 wt.%. During the electrolytic refining of silver nitrate in the
environment of the copper is dissolved in a concentrated electrolyte. When increasing
concentrations of copper in the electrolyte above 120 g.dm-3, the intensive copper begins to secrete
the cathode. After crossing the concentrations above 170 g.dm Cu-3 in the electrolyte, the cathode
silver content exceeded 0.1 wt.% Cu. In tab. 4 shows some of the standard potentials of metals at 25
° C [4].
o
Table 4 Standard potentials of some metals at 25 C [4 a 5 ]

o
Electrode E [V]
3+
Au / Au + 1,68 [5], + 1,5
2+
Pt / Pt + 1,2
2+
Pd / Pd + 0,987
+
Ag / Ag + 0,799
2+
Cu / Cu + 0,337
+
H /H 0
2+
Pb / Pb - 0,126
2+
Sn / Sn - 0,136
2+
Ni / Ni - 0,25
2+
Fe / Fe - 0,44
2+
Zn / Zn - 0,763

Effect of zinc on the course of electrolytic refining of silver is shown in Fig. 4. The concentration of
zinc in the electrolyte ranged from 0 to 19 g.dm-third Increasing the zinc content in the electrolyte to
5 g.dm-3 on the purity of the cathodic silver uninterested. After exceeding this value, the Zn content
in the cathodic silver strongly increases. The maximum concentration during the experiment reached
up to 18.83 g.dm-3 Zn and Zn content in the cathodic silver amounted to 0.01 wt. % Zn.

Another reference was nickel metal (Fig. 5), its concentration in the electrolyte range was 0 to 3.7
g.dm-3 Ni, in concentrations of 0.5 g.dm-3 to its silver content in cathodic moved below the proof .
The maximum content of nickel in the cathodic silver, ie 0.0023 wt. % Was achieved at a
concentration of 3.7 g.dm-3 Ni in the electrolyte.

Is presented in Figure 6 Effect of the concentration of palladium in the electrolyte content in the
cathodic metal. Relatively low concentrations of palladium in electrolyte levels correspond to high
cathodic palladium in silver. The maximum concentration of Pd in the electrolyte during the
experiments was 2.73 g.dm-3, what said content 0.19 wt.% Pd in silver. This intensive deposition of
palladium on the cathode is due to the higher elektropozitivitou palladium to silver (Table 4).

Opposite effect can be characterized by iron, whose concentration in the electrolyte was low (0 to
0.24 g.dm-3) and its content in the cathodic metal does not exceed 0.0014 wt. % Fe.

Based on the results we observed metallic impurities were divided into three groups according to
their content in the cathodic silver.
The first group includes metals, whose content was above 10-1 wt. %. This can include copper and
palladium. From the results shown in Fig. 4 shows that the increase in copper content in the cathodic
silver is crucially due to its high concentration in the electrolyte. Copper during the electrolytic
refining of silver dissolves in concentrated nitrate electrolyte. At high concentration of copper in the
electrolyte (over 120 g.dm-3) are

Acta Metallurgica Slovaca, 11, 2005, 1 (78-87) 86

cations copper mechanically captured on the surface of silver excluded. In spite of lower standard
potential such as the silver occurs to the exclusion of copper cathode, especially in reducing the
concentration of silver in the electrolyte below 50 g.dm-3 and increased copper concentrations
above 100 to 120 g.dm-3 Cu. The opposite mechanism assumed in the excretion of palladium on the
cathode. Palladium is also soluble in nitrate electrolyte but due to the higher value of standard
potential, as the silver (Figure 4) is predominantly excreted in the cathode. This assumption is
confirmed by the results presented in Figure 6.

The second group can include zinc, the silver content in cathodic reached 10-2 wt.%. The
concentration of zinc in the electrolyte reached 19 g.dm-3, what answered concentration 0.01 wt.%
Zn in the cathodic silver. Zinc nitrate in the environment behaves like copper, has the lowest
standard potential value (- 0.763 V) of the examined metal and still ranked in the second group of
metal pollutants. Probably the zinc showed a similar mechanism, ie mechanical cathodic metal
pollution due to high concentration of zinc in the electrolyte.

The third group can include metals, whose content in the cathodic silver was below 10-2 wt.%, This
includes metals: Ni, Fe, Au, Pt, Sn, Sb, Pb and Bi. Mentioned group of metals can then be divided into
metals in nitrate electrolyte insoluble (Au, Pt and partly Sn) and soluble metals but whose content in
an anode metal was very small (Table 1). For the vast majority of these metals content in the
cathodic silver was fixed, as boundary evidence of these metals in the environment and the
analytical method (AAS) was higher than their content. Of this group, leaving only the nickel and
iron, which affect the purity of the cathodic metal is shown in Figure 5 and 7 Nickel and iron in
nitrate-soluble but elektropozitivita is compared with the low silver (Table 4) and their concentration
in the electrolyte is on order, respectively. two orders lower than for zinc.

5. Conclusion

Based on the results obtained can be said that the observed metallic impurities have worst effect on
the purity of silver palladium cathodic. Since nitrate is soluble in the electrolyte, passes into the
electrolyte and consequently the influence of higher value than the standard potential of silver is
predominantly excreted in the cathode. Even at concentrations above 2 g.dm Pd-3 in the electrolyte,
increasing the silver content in cathodic than 0.1 wt.% Pd. Effect of gold and platinum, i.e. metals
with a higher potential than the standard silver and palladium, was inhibited by their insolubility in
nitrate electrolyte. On the other hand, the metal impurities soluble in nitrate electrolyte, but
elektropozitivita which is lower than that of silver. For these metals, i.e. especially in the case of
copper and zinc had an impact of their high concentration in the electrolyte. Assuming that were
mechanically trapped at the surface cathodic silver. In the case of nickel, iron, partly of tin, lead,
antimony and bismuth is a mechanism similar to that of copper and zinc, but shown their low
content in the anode, and consequently in the electrolyte. The results obtained can be considered
the initial findings of electrolytic silver refining of secondary metals, which need to be more detailed
study of the mechanism of elimination of metallic phases on the cathode using other identification
methods (eg optical microscopy and electron microscopy with local microanalysis).

Literature

[1] STN 42 38 30

[2] Maslenickij IN, Čugajev LV, Borba BF, MV Nikitin, Střížkov LS: Metallurgija blagorodnych metallov.
2. edition, ed. - Metallurgija, Moscow, 1987

Acta Metallurgica Slovaca, 11, 2005, 1 (78-87) 87

[3] L. Rabatin., Vadász P. and Tomasek, K.: electrolytic refining of silver and gold. Mineralia Slovaca,
31 (1999) 3-4, p. 381

[4] J. Gažo et al.: General inorganic chemistry. 3. edition, ALFA - Bratislava, 1981

[5] Rimmer BF: Gold Refining of Precious Metal from concentrates by Liquid-Liquid Extraction.
Chemistry and Industry. January 19, 1974