Oxygen nonstoichiometry (δ) of TiO2−δ-revisited

Oxygen nonstoichiometry (δ) of “undoped” polycrystalline TiO2−δ has been measured as a function of oxygen partial pressure in the widest ever examined range of 10-18⩽PO2/atm⩽10-1 at elevated temperatures (1073⩽T/K⩽1473) by thermogravimetry and coulometric titrometry combined and compared with all the reported values. Isothermal variation of nonstoichiometry against PO2 is explained with a defect model involving quadruply ionized titanium interstitials, electrons, holes, and unidentified acceptors which may be background impurity acceptors or cation vacancies. The equilibrium constants for intrinsic electronic excitation reaction and redox reaction are determined from the nonstoichiometry measured and compared exhaustively with all the reported values. The relative partial molar enthalpy and entropy of oxygen are evaluated as functions of nonstoichiometry and the inner workings of their variations discussed.