The direct anodic decomposition of copper-rich mattes using packed bed electrodes was investigated, because a practical solution to direct electrorefining of copper matte would lead to the potential elimination of copper converting and its associated sulphur dioxide emissions. Much greater copper extraction has been achieved experimentally at 50° C from a packed bed electrode consisting of 0.5-4mm diameter particles than from a massive or solid flat electrode composed of copper-rich matte, as found in earlier studies. This was shown to be attributable to natural convection mass transport processes within the inter-particle region that is not available in massive electrodes. However, while natural convection mass transfer is an important process in the packed bed electrodes, other factors were shown to be ultimately more important in terms of the maximum copper extraction which may be achieved prior to shut-down caused by total-bed polarization of these electrodes. Total-bed polarization of copper-rich mattes during direct anodic decomposition may be attributed to (a) deteriorating electrical contact (related to the formation of elemental sulphur and lead sulphate) between the current distributor and the adjacent particles, and in thick electrodes, between the particles across the anode, (b) relative nonreactivity of iron-containing phases and (c) physical association of these phases with the reactive phases, and under certain conditions (d) crystallization of copper sulphate within the inter-particle region, blocking ionic conduction paths. The maximum copper extraction from synthetic pure chalcocite, the predominant component of industrial copper-rich mattes, using the packed bed electrodes was found to be about 80%. The presence of 3-4wt% iron in the copper-rich mattes was shown to degrade the copper extraction considerably due to the presence of relatively nonreactive iron-rich phases which form as the matte is cooled from its liquid state. The presence of lead in copper matte was found to be a relatively unimportant impurity in terms of copper extraction, while oxygen was found to partially offset the negative effects of iron. A simple one-dimensional mathematical model was developed to estimate the variation of copper extraction across a 2cm-thick packed bed electrode. The copper extraction was found experimentally to vary by less than a factor of two across the anode. This was attributed to (a) the relatively high electrical conductivity of the electrolyte which minimizes reaction-process overpotential gradients across the anode, and (b) the increasing impedances of the decomposition processes in the most reacted particles. / Applied Science, Faculty of / Materials Engineering, Department of / Graduate