C. Cachet et R. Wiart, ZINC ELECTROWINNING IN ACIDIC SULFATE ELECTROLYTES - IMPEDANCE ANALYSIS AND MODELING OF THE INFLUENCE ON NICKEL IMPURITIES, Journal of the Electrochemical Society, 141(1), 1994, pp. 131-140
Using an electrolysis cell with separate compartments, the polarizatio
n and impedance of the zinc electrode have been investigated in highly
acidic sulfate electrolytes. It is shown that (i) zinc deposition imp
lies a multi-step mechanism and takes place when hydrogen evolution re
mains passivated on the deposit surface, and (ii) the presence of Ni2 ions and/or H2O2 molecules in the electrolyte depassivates the reacti
on of hydrogen evolution and enhances the rate of zinc corrosion. The
experimental results have been simulated on the basis of a reaction mo
del in which hydrogen evolution on the oxidized adsorbates (ZnO(ad) or
ZnOH(ad)) generated near the corrosion potential is clearly distinct
from hydrogen evolution on the metal surface involving ZnH(ad), which
inhibits zine deposition. Then the passivation of hydrogen evolution i
s associated with the reduction of oxidized adsorbates. The progressiv
e adsorption of Ni2+ ions competes with the formation of oxidized adso
rbates to slow down the passivation process, thus widening the potenti
al domain where hydrogen evolution predominates.