This study deals with the fundamental aspects of the volatilisation of heavy metals (HM) during municipal solid waste (MSW) incineration. The thermal treatment of a model waste was theoretically and experimentally studied in a fluid-bed. A mathematical model was developed to predict the fate of metallic species according to the main phenomena controlling the process: heat and mass transfer (transport phenomena), chemical reactions involving HM, and mechanism of vapour metal species sorption inside the porous matrix. The model assumes local thermodynamic equilibrium between the vapour and the metal compound on the substrate in the pores of a particle. This approach permits to predict the extent of HM vaporisation from a mineral porous matrix when its physical properties are known. Experimental data concerning CdCl(2) release from an alumina matrix in a 850 degrees C fluidised bed are in good agreement with theoretical results.