Thermogravimetric studies of non-stoichiometric cerium oxides under isothermal and quasi-isothermal conditions

Abstract

Quasi-isothermal thermogravimetry is a new technique in which the programmed heating of a furnace automatically ceases when the rate of a reaction taking place in a sample, which is indicated by the DTG-signal, exceeds a preset limit. In this way reactions can be studied under nearly isothermal conditions. In this paper the data obtained using this method during oxidation and reduction experiments on nonstoichiometric cerium oxides are compared with the data obtained by conventional isothermal thermogravimetry. The kinetics of the composition changes during isothermal reduction and oxidation of CeO2−x are also analyzed. It appears that, with some reservations, the experimental data are best described by the rate equation for a diffusion-controlled reaction. Finally, both the isothermal and the quasi-isothermal data suggest that the CeO2−x phase region in the phase diagram consists of several subphases, each with a characteristic activation energy for the diffusion-controlled reactions.