KINETICS OF PB AND PB-AG ANODES FOR ZINC ELECTROWINNING .1. FORMATION OF PBSO4 LAYERS AT LOW POLARIZATION

被引:23
作者
REROLLE, C
WIART, R
机构
[1] UPR15 du CNRS, Physique des Liquides et Electrochimie, Université Pierre et Marie Curie, 75252 Paris Cedex 05, Tour 22
关键词
PB AND PB-AG ANODES; IMPEDANCE; CORROSION; MODEL FOR SULFATE GROWTH;
D O I
10.1016/0013-4686(95)00026-B
中图分类号
O646 [电化学、电解、磁化学];
学科分类号
081704 ;
摘要
Electrochemical impedance spectroscopy and scanning electron microscopy have been utilized to investigate the mechanism of reactions taking place on Pb and Pb-Ag alloy anodes in acidic zinc sulphate electrolytes, during the formation of PbSO4 layers in the potential domain (0.9 to 1.1 V/SSE). Independent of the Ag content, the anode behaviour is essentially determined by the electrolysis time. From a comparison of experimental data to a kinetic model for the Pb/PbOn/PbSO4 electrode, it is shown that the layer growth is first controlled by the solid state diffusion of SO42- ions, and then by a chemical step associated with a change in charge carriers, from O-upsilon(2+) vacancies in the PbOn sublayer into Pb2+ ions in the PbSO4 layer. In Mn2+-containing electrolytes the additional formation of MnO2 occurs under diffusion control of the Mn2+ oxidation, and it modifies both the layer properties and the kinetics of reactions.
引用
收藏
页码:939 / 948
页数:10
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