Effect of isosymmetric phase transition in MIEC perovskite on the kinetic parameters of its interaction with oxygen

Oxygen partial pressure relaxation technique was used to study transient kinetics of reequilibration in the reaction of nonstoichiometric oxide Ba0.5Sr0.5Co0.75Fe0.2Mo0.05O3-delta with oxygen within a region of 3-delta stoichiometry close to the nominal oxidation state 3+ for cobalt where an isosymmetric phase transition cubic perovskite P1 - cubic perovskite P2 is observed. The relaxation data were analyzed using a macrokinetic model that explicitly takes into account the power-law dependence of the surface reaction rate on the oxygen partial pressure. A twofold decrease in the power-law exponent (n = 0.7 to n = 0.3) was found at the point of the P1-P2 phase transition, which indicates a change in the mechanism of the rate-determining step of the reaction caused by the transition. At the same time, the functional dependence of the diffusion mobility of oxygen vacancies on the equilibrium oxygen pressure does not change at the transition point, which means that the transition does not affect the mechanism of bulk vacancy mobility.

Automated summary

The transient kinetics of reequilibration in the reaction of nonstoichiometric oxide Ba0.5Sr0.5Co0.75Fe0.2Mo0.05O3-delta with oxygen was studied using the oxygen partial pressure relaxation technique. The study revealed a change in the mechanism of the rate-determining step of the reaction at the phase transition point.