Electrochemical behaviour of zinc in alkaline solutions

Abstract

As the whole passivation phenomenon in the case of zinc is very quick and sudden and as it cannot be fully studied and followed by galvanostatic techniques alone, the constant over-potential technique has, for the first time, been applied to zinc and results reported. A special apparatus consisting of suitable oscillator, modulator, demodulator and a stable D.C. amplifier with a gain of 100,000 was used for the purposes and is described. Potential curves for equilibrium current rates, achieved on 0·1 V. and 25 mV. steps after 1 minute each, have been obtained in 6N, N, 0·1 N KOH and zincate solutions for the complete range of −1·3 to about −2·0 volts with reference to Hg/HgO/KOH reference electrode. It has been found that in the first truly active region, the main electrode reaction is the formation of zinc ions while after the passivation it changes to gas evolution. Potentiostatic techniques reveal intermediary stages, undisclosed by constant current methods, of pseudo-passivation and current-plateau regions in which the anodic layer thickens, controlled by the high field cation transport. These observations and explanations are further supported by plotting rate-time transients obtained by suddenly dropping the potentials from higher to lower values, when the rates were found to cut off. Some anomalies and sudden reversal of currents with increasing over-voltages, have also been fully discussed. The influence of other factors,e.g., concentration, stirring, sudden changes in over-voltages, presence of zincate, sulphate, etc., has also been considered. Studies such as these are found to throw considerable light on the electrochemical behaviour of zinc.