Numerical calculations of the evaporation kinetics of bulk volatile liquids and of water from smectite clay granules are compared with experimental results. The weight loss of the volatiles is analyzed by thermogravimetry and differential calorimetry. Under the thermodynamic conditions of the experiments, finite element calculations are in good agreement with the experimental data, and an approximate semi-analytical model is developed in order to explain the dependence of the rate of evaporation on the temperature, the chemical species and the carrier gas flow rate. The initial rate of evaporation of water from the clay granule is close to that for bulk water. Its decrease with time is determined mainly by changes in the gas/condensed phase partition given by the equilibrium desorption isotherm, with little limitations due to internal diffusion effects for the present experimental conditions. Its temperature dependence could also be approximately described by an Arrhenius-type equation derived from the semi-analytical model. Further analysis of the experimental measurements reveals steps in the heat of vaporization of water as a function of water concentration, that could be related to the equilibrium desorption isotherm. (C) 2011 Published by Elsevier Ltd.