Defect equilibrium in PrBaCo2O5+δ at elevated temperatures

Abstract

A defect equilibrium model for PrBaCo2O5+δ is suggested based on oxygen non-stoichiometry data. The model includes reactions of oxygen exchange and charge disproportionation of Co3+ cations. The respective equilibrium constants, enthalpies and entropies for the reactions entering the model are obtained from the fitting of the experimental data for oxygen non-stoichiometry. The enthalpies of oxidation Co2+→ Co3+ and Co3+→Co4+ are found to be equal to 115±9 kJ mol-1 and 45±4 kJ mol-1, respectively. The obtained equilibrium constants were used in order to calculate variations in concentration of cobalt species with non-stoichiometry, temperature and oxygen pressure. © 2013 Elsevier Inc.