Electrochemical behaviour of zinc in alkaline solutions

Abstract

The cathodic and anodic polarization of zinc in different concentrations of alkaline solutions has been studied under constant-current conditions. The changes of zinc electrode-potential with reference to a Hg/HgO/KOH system have been measured both in KOH and zincate solutions using a “Luggin” capillary and a specially designed cell, current being drawn from an electronic current stabilizer. Time-potential curves have been plotted and it is found that the anodic zinc passivates at a certain stage showing a sudden rise in potential by as much as 3–4 volts. Before the passivation, the main electrode reaction is the formation of Zn++, while after the passivation it changes to gas evolution. No definite relationship as previously suggested by Muller, between the current density and the passivation time was found, perhaps due to migration and non-linear diffusion effects and other reasons discussed in the paper. It has been found that the behaviour of zinc differs in concentrated alkaline solutions (i.e., 0·5 N to 5 N) from that in dilute solutions (0·2 N to 0·01 N), in which case the open circuit rest-potential of zinc is indefinite and may vary by as much as 500–600 mV., while the maximum passivation jump in potential is about 2 volts only. Also the passivation and the decay of current on breaking the circuit are found to be slower than in the case of concentrated solutions. Colour changes of the zinc electrode, during the polarization, are also briefly described and discussed.