The bioleaching of sulfide minerals involves electrochemical and chemical reactions of the mineral with the leach liquor and the extra-cellular polysaccharide layers on the microorganisms. The microorganisms derive energy by oxidising the sulfur moiety and ferrous iron, which can be interpreted using electrochemistry and chemiosmotic theory. Recently significant advances have been made in understanding the mechanism by which the bioleaching of sulfide minerals occurs. Kinetic models based on the proposed mechanism are being used successfully to predict the performance of continuous bioleach reactors. The measurement of oxygen and carbon dioxide consumption rates together with the measurement of redox potentials, has led to this further elucidation of the mechanism of bioleaching of sulfide minerals and enabled the kinetics of the sub-processes involved to be determined separately. It has been shown that bioleaching involves at least three important sub-processes, viz., attack of the sulfide mineral, microbial oxidation of ferrous iron and some sulfur moiety. The overall process occurs via one of two pathways depending on the nature of the sulfide mineral, a pathway via thiosulfate resulting in sulfate being formed or a polythionate pathway resulting in the formation of elemental sulfur. For the case of pyrite, the primary attack of the sulfide mineral is a chemical ferric leach producing ferrous iron. The role of the bacteria is to re-oxidise the ferrous iron back to the ferric form and maintain a high redox potential as well as oxidising the elemental sulfur that is formed in some cases. The first two sub-processes of chemical ferric reaction with the mineral and bacterial oxidation of the ferrous iron are linked by the redox potential. The sub-processes are in equilibrium when the rate of iron turnover between the mineral and the bacteria is balanced. Rate equations based on redox potential or ferric/ferrous-iron ratio have been used to describe the kinetics of these sub-processes. The kinetics have been described as functions of the ferric/ferrous-iron ratio or redox potential which enables the interactions of the two sub-processes to be linked at a particular redox potential through the rate of ferrous iron turn-over. The use of these models in predicting bioleach behaviour for pyrite presented and discussed. The model is able to predict which bacterial species will predominate at a particular redox potential in the presence of a particular mineral, and which mineral will be preferentially leached. The leach rate and steady state redox potential can be predicted from the bacterial to mineral ratio. The implications of this model on bioleach reactor design and operation are discussed. Research on the chemistry and electrochemistry of the ferric leaching of sulfide minerals and an electrochemical mechanism for ferrous iron oxidation based on chemiosmotic theory will be presented and reviewed.
