ANODE POLARIZATION OF Pb-Bi ALLOYS IN THE KCl-PBCl2

MELT
Yu. Khalimullina1, P. Arkhipov1, Yu. Zaikov1, V. Ashikhin2, G. Skopov2
1
The Institute of High Temperature Electrochemistry, Ural Branch of Russian
Academy of Sciences, S. Kovalevskaya/Academicheskaya St, 22/20, 620990
Yekaterinburg, e-mail:dir@ihte.uran.ru
2
Open Joint-Stock Company ELECTROMED, Scientific Research Centre,
Lenin St, 1, 624091, Verkhnyaya Pyshma

Abstract

Temperature and current density influence on anodic polarization of the Pb-Bi

alloy electrode in the KCl-PbCl2 equimolar melt was studied. Anodic current
efficiency at temperature 772 K depending on Bi content in the alloy was determined.

Introduction

Nowadays scientific researches aimed development of ecologically safe and

relatively low-cost and low-waste technologies of secondary lead containing materials
recycling are of great importance. Development of new technology needs the study of
electrode processes, taking place on liquid metal electrodes. Knowledge of the
regularities allows finding the solution of both scientific and technological problems,
determination of electrolysis technological parameters. Electrode processes at Pb-Bi
alloys dissolution were studied in order to understand these phenomena.
Pb-Bi alloys equilibrium potentials [1] containing from 1.5 to 95.0 mol % of
Pb at temperature 723-873 K in melted potassium and lead chlorides mixture were
previously measured. On the basis of the direct experimental data lead activities and
lead activity coefficients in the Pb-Bi system were found. Pb partial thermodynamic
functions were calculated. The negative insignificant deviations from Raoults Law
were found in the system. Physical and chemical properties of KCl-PbCl2 mixture [2]
were determined; Pb-Sb alloys [3] anodic processes were under study.
Pb-Bi alloys anodic behavior was studied in works [4-6]. Authors [4]
measured lead anode polarization in the equimolar mixture KCl NaCl, eutectic melt
KCl LiCl as well as with addition 1 and 10 mol % of PbCl2 to KCl LiCl mixture.
It is established that the polarization curve shifts to the positive side due to lead ions
addition.
Delimarskii with co-authors studied lead and bismuth alloys separation [5].
They confirmed the results previously obtained by Alabyshev A.F. and Guelman E.
M. [6] and proved that anodic polarization in 90 minutes after electrolysis at
i=0.2 /2 reached constant value of 45-50 mV by passing electric current through
the cell. Authors suggested that anodic polarization source is concentration changes,
appearing in the electrolysis process on the border of salt and metal phases.
No data about electrode anode polarization from Pb-Bi alloy in lead and
potassium chlorides equimolar mixture were found in literature.

Experimental technique

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 The experiments were carried out in the three electrode cell. Pb-Bi alloys
anodic solution was studied by the method of switching off the current from steady
state in galvanostatic regime using galvanostat-potentiostat IPC-Pro. Polarization was
measured in the moment of current switching off; constant current impulses amplitude
was varying from 0.001 1 A, polarization time 7-8 seconds.
Anodic polarization experiments were carried out in quartz glass cell (fig. 1)
hermetically closed with fluoroplastic cover (2) with openings for electrodes and
thermocouple.

1
Ar
2 A
Vacuum
r

3 8

5
9
10
6
11
7

Fig.1 Electrochemical cell scheme

1 rubber plugs; 2 - fluoroplastic cover; 3 thermocouple; 4 alundum crucible;
5 quartz tube; 6 working electrode; 7- fire brick support;
8 lead current contact; 9 electrolyte; 10 reference electrode;
11 counter electrode.

Alundum crucible (4) was placed on the special fire brick support (7) on the
cell bottom. Previously prepared alloy (11), electrolyte (9), reference electrode (10),
working electrode (6) and thermocouple (3) were loaded into the crucible. The cell
was sealed, put under vacuum and then filled with purified argon. Then it was placed
into the resistance furnace and heated till the given temperature under abundant argon
pressure.
Pb-Bi alloys containing 18, 40, 67, 83 and 97 mol % of Bi were used as
working electrode (anode). The alloy of the same composition as the working
electrode placed on the crucible bottom was used as auxiliary electrode. Metallic lead

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of C1 grade being in contact with the alloy of the same composition was used as the
reference electrode. Electrolytes of working electrode and reference electrode were
divided by the diagram made of Gooch asbestos. The current-conducting wire to
liquid-metal electrodes was performed with the help of molybdenum rods (8),
protected from contact with chloride melt byh alundum tubes. Free end of alundum
tubes was covered with rubber plugs (1) to keep the cell sealed.
Reagents of AR grade additionally purified from oxygen admixtures by
electrolysis with insoluble carbon anode were used to prepare the electrolyte. The
alloys were made from lead of C1 grade and bismuth of Bi-0 grade. Composition of
the alloys under investigation and components content in electrolyte were analyzed
before and after the experiment by atomic-absorption analysis. Alloy composition
changes during experiment were not found within the analysis accuracy. The set up
was equipped with the system of atomized temperature stabilization. Temperature
fluctuations were 2 .

Measurements results and their discussion

Fig. 2 presents measurement results of electrode anodic polarization from Pb-

Bi alloy containing from 18 to 97 mol % of Bi at temperature 795 K. Anode
equilibrium potential shifts to the area of more positive values with increasing of
bismuth content in the alloy and reaches 0.16 V at 97 mol % of Bi. Insignificant
electrode potential deviation from equilibrium value to the positive side is seen on
polarization curves 1-4 on the whole interval of current density from 0.001 to
1 A/cm2. Two characteristic sections are seen on the curve 5: with i increasing from
0.001 to 0.01 A/cm2 alloy dissolution takes place with small polarization changes.
Current density increasing from 0.01 to 1 A/cm2 leads to anode potential shift to the
positive side up to the potential of bismuth deposition.
Electrode anodic polarization temperature dependence is given on the fig. 3.
Electrode is made from Pb-Bi alloys containing 40 mol % of Bi. Metallic lead
dissolution at potentials close to equilibrium is seen on polarization curves at the
temperature 746, 795, and 851 K in 0.001 0.1 A/cm2 current density interval. Such
lead electrode behavior in eutectic melt KCl LiCl was observed by the authors of the
work [4].
Electrode potential shift to the positive side up to 0.022, 0.024 and 0.026 V
values for 1-3 curves takes place with i increasing correspondingly. We can make a
suggestion about anodic process diffusion character on Pb-Bi alloys in the KCl-PbCl2
(50-50 mol %) in the 746 - 851 interval according to the form of concentration and
temperature dependencies of polarization curves.

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 Fig. 2. Polarization curves of the Pb-Bi anode at temperature 795 K; mol % of Bi:
1 18, 2 40, 3 67, 4 83 and 5 97.

Fig. 3. Polarization curves of anode from Pb-Bi (40 mole % Bi) at temperatures 851
(1), 795 (2) and 746 (3)

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 Dissolution mechanism could be as follows. Metallic lead solution was
obtained according to the following reaction at small deviations from equilibrium
values
Pb(Pb-Bi) Pb2+ + 2e. (1)
Anodic polarization increase was caused by lead deficit in near-electrode layer
due to insufficient supply of electronegative component. Bi content increases on the
boundary: metallic alloy salt alloy. Anodic potential shifts to the positive side. It
leads to bismuth solution according to the reaction
Bi(Pb-Bi) Bi3+ + 3e. (2)

Conclusions

1. Pb-Bi alloys anodic dissolution in KCl PbCl2 melt at the temperature 746 -
851 in the current density interval from 0.001 to 1 A/cm2 with 18; 40; 67; 83 and 97
mol % of bismuth in the alloy were studied.
2. It was found that Pb-Bi alloys solubility has diffusion regime conditions
according to the polarization curves analysis and anodic current efficiency values.
Limiting stage is electronegative component supplying from the liquid alloy volume
to the electrode surface.

References

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Thermodynamic properties of Pb-Bi alloys.- Proceedings of the 8th Israel-Russian Bi-
national, 2009. June 28 July 03, p. 24-30.
2. Yefremov A.N., Apisarov A.P., Arkhipov P.A., Zaikov Yu. P. Electro
conductivity and temperature of liquidus alloy system PbCl2 KCl PbO. Alloys,
2010, 1, p. 29-34.
3. Zaikov Yu., Arkhipov P., Ashikhin V., Khalimullina Yu. et al. Pb-Sb alloys
anodic solution in potassium and lead chloride mixtures. Izvestiya Vuzov, Non-
ferrous metallurgy, 2008, 4, p. 11-17.
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arsenium and stannic double alloys electrochemical separation in melted electrolyte.
Ucranian Chemical Journal, 1955, 21, p. 687-693
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in melted electrolyte. - Ferrous metals, 1946, 2, p. 37-43.

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