Electrochemical Kinetics of Ferric/Ferrous Reduction-Oxidation on Sphalerite

"In this work, the kinetics of ferric-ferrous redox reaction on a passivated sphalerite electrode is studied by the application of chronoamperometry method in 0.5 mol L-1 H2SO4 solution. The electrochemical behaviour of ferric and ferrous couple was investigated on two sphalerite minerals acquired from two different geological regions (Iran and Canada). The carbon paste electrode (CPE) of sphalerite was initially prepared and passivated in 0.5 mol L-1 H2SO4 solution and after reaching the steady-state condition, ferric and ferrous sulfate solution was added. The registered current density differences between the current density of the passivated electrode and that of the electrode in the iron salts added solution were interpreted for kinetics of ferric-ferrous reduction-oxidation reaction. The equilibrium potential for ferric-ferrous couple on sphalerites surface was about 500 mV vs. Ag/AgCl. The exchange current density (i0) for ferric-ferrous redox reactions on the sphalerite samples had the same magnitude of 10–6 A cm–2. The electrochemical impedance spectroscopy (EIS) measurements at 550 mV vs. Ag/AgCl illustrated that sphalerite oxidation was controlled by two charge transfer process in both of Fe-free and Fe-containing solutions. The charge transfer resistance remarkably decreased when Fe salts added to the 0.5 mol L-1 H2SO4 solution, owing to the ferric-ferrous redox reactions being the predominant reactions on sphalerite surface.INTRODUCTION Direct atmospheric leaching processes for sphalerite concentrates are performed by reduction of an oxidant (e.g. ferric ion and oxygen) and oxidation of sphalerite to zinc ions. Oxygen could be an oxidizing agent as well, but the concentration of oxygen is very low in the solution. The role of ferric ions is predominate in this oxidation (Babu, Sahu, & Pandey, 2002). The oxidation reaction for sphalerite in the presence of ferric in can be presented as follows (Lampinen, Laari, & Turunen, 2015):"