Thermodynamic quantities and defect equilibrium in La 2−xSr xNiO 4+δ

Abstract

In order to elucidate the relation between thermodynamic quantities, the defect structure, and the defect equilibrium in La 2− x Sr x NiO 4+ δ , statistical thermodynamic calculation is carried out and calculated results are compared to those obtained from experimental data. Partial molar enthalpy of oxygen and partial molar entropy of oxygen are obtained from δ- P(O 2)– T relation by using Gibbs–Helmholtz equation. Statistical thermodynamic model is derived from defect equilibrium models proposed before by authors, localized electron model and delocalized electron model which could well explain the variation of oxygen content of La 2− x Sr x NiO 4+ δ . Although assumed defect species and their equilibrium are different, the results of thermodynamic calculation by localized electron model and delocalized electron model show minor difference. Calculated results by the both models agree with the thermodynamic quantities obtained from oxygen nonstoichiometry of La 2− x Sr x NiO 4+ δ .