Effect of temperature and illumination on pyrite oxidation between pH 2 and 6

The effect of heat and illumination with visible light on the oxidation of pyrite with dissolved molecular oxygen in solutions between pH 2 and 6 has been investigated using a combination of surface science experiments and batch oxidation experiments. The rate of the oxidation of pyrite is strongly dependent on temperature. It is, however, not possible to cast the temperature dependence in a simple Arrhenius equation because the magnitude of the activation energy depends on the progress variable chosen. Activation energies based on proton release rate, sulfate release rate, and total iron release rate vary by as much as 40 kJ mol^-1, suggesting that the oxidation mechanism of the sulfur and iron component of pyrite are largely independent of each other. This difference in mechanism can also explain why the reaction rates on the basis of these three different progress variables do not show the same pH dependence. Exposed to visible light, the rate of pyrite oxidation is under most conditions accelerated by less than a factor of two. Some of this acceleration may be accounted for by a light-induced heating of the pyrite surface. Surface science experiments employing photoelectron spectroscopy show no evidence for significant changes in the chemical composition of the surface as a function of exposure to visible light. The batch sorption experiments show, however, that the reaction stoichiometry changes somewhat, which indicates that there might be a change in reaction mechanism as a result of exposure to visible light.