A range of materials are treated in zinc fuming processes to recover metal values and produce benign slag waste products. The selection of the optimum process conditions in these various technologies can be greatly assisted by the use of a chemical thermodynamic model of the system. In this paper the effects of slag chemistry on the liquidus temperatures, subliquidus phase equilibria and thermodynamic properties are described by a FACT model of the ZnO-PbO-FeO-Fe2O3-CaO-SiO2 system. In addition new experimental data on the effect of Al2O3 on the liquidus are presented. The implications of these findings for plant practice are discussed.