A computer model is used to simulate the volatility of some radioelements cesium (Cs-137), cobalt (Co-60), and ruthenium (Ru-106) during the radioactive wastes vitrification by thermal plasma. This model is based on the calculation of system composition using the free enthalpy minimization method, coupled with the equation of mass transfer at the reactional interface. The model enables the determination of the effects of various parameters (e.g., temperature, plasma current, and matrix composition) on the radioelement volatility. The obtained results indicate that any increase in molten bath temperature causes an increase in the cobalt volatility; while ruthenium has a less obvious behavior. It is also found that the oxygen flux in the carrier gas supports the radioelement incorporations in the containment matrix, except in the case of the ruthenium which is more volatile under an oxidizing atmosphere. For electrolyses effects, an increase in the plasma current considerably increases both the vaporization speed and the vaporized quantities of Cs-137 and Co-60. The increase of silicon percentage in the containment matrix supports the incorporation of Co-60 and Cs-137 in the matrix. The simulation results are compared favorably to the experimental measurements obtained by emission spectroscopy. (C) 2008 Elsevier B.V. All rights reserved.