Cation distributions and thermodynamic properties of binary spinel solid solutions.

Abstract

A general model is presented to enable the calculation of the cation distribution and thermodynamic properties of any binary solid solution between oxide spinels containing 2+,3+ and 4+ cations. The model includes the effect of disordering enthalpy which depends linearly on the degree of disorder. In addition there are important contributions to the thermodynamic properties from the size mismatch of the substituting cations, which may be accounted for adequately using the simplest possible approach, that of a strictly regular solution. The regular solution parameter, W, depends on the difference in volume of the substituting cations. The model has been tested against the extensive literature data on spinel solutions; in the great majority of cases agreement with experimental observation is good. The model may be used to explain a diverse array of phenomena associated with the cation distribution in spinel solutions, to discriminate among conflicting experimental data, to extrapolate experimental data to other temperatures and pressures, and to predict the properties of unstudied systems.