The bioleaching of sulfide minerals involves electrochemical and chemical r
eactions of the mineral with the leach liquor and the extra-cellular polysa
ccharide layers on the microorganisms. The microorganisms derive energy by
oxidising the sulfur moiety and ferrous iron, which can be interpreted usin
g electrochemistry and chemiosmotic theory. Recently significant advances h
ave been made in understanding the mechanism by which the bioleaching of su
lfide minerals occurs. Kinetic models based on the proposed mechanism are b
eing used successfully to predict the performance of continuous bioleach re
actors. The measurement of oxygen and carbon dioxide consumption rates toge
ther with the measurement of redox potentials, has led to this further eluc
idation 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-processe
s, 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 th
e 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 ferr
ic form and maintain a high redox potential as well as oxidising the elemen
tal sulfur that is formed in some cases. The first two sub-processes of che
mical ferric reaction with the mineral and bacterial oxidation of the ferro
us iron are linked by the redox potential. The sub-processes are in equilib
rium when the rate of iron turnover between the mineral and the bacteria is
balanced. Rate equations based on redox potential or ferric/ferrous-iron r
atio have been used to describe the kinetics of these sub-processes. The ki
netics 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 py
rite 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. Th
e leach rate and steady state redox potential can be predicted from the bac
terial to mineral ratio. The implications of this model on bioleach reactor
design and operation are discussed. Research on the chemistry and electroc
hemistry of the ferric leaching of sulfide minerals and an electrochemical
mechanism for ferrous iron oxidation based on chemiosmotic theory will be p
resented and reviewed.