This paper describes a mathematical model which calculates the time dependencies of the flow rate and composition of the vapour emerging from a pool. A large variety of accidental cases can be covered: continuous or instantaneous spills, on confined or unconfined ground, ideal or non-ideal liquid mixtures in boiling or evaporating conditions. The boiling, when present, is modelled through an equation system comprising the Rachford-Rice relation and the energy balance of the pool, which is assumed to be well-mixed. In the case of a volatile pool, interfacial mass rates are determined taking into account the Stefan flux, and the thermal resistance inside the liquid phase is also considered. In ail situations, the energy balance includes the contribution of ground, sun and air. Known experimental data have been used to validate the model.