(209c) Extracting the RedOx Thermodynamics of Perovskites via Combined Experiment and Theory

The analysis and design of thermochemical looping systems for renewable fuel production and energy storage requires detailed knowledge of the partial molar enthalpies and entropies of reduction of the active metal oxides. Experimental data normally consists of measured non-stoichiometries at a series of temperatures and oxygen partial pressures. Thermodynamic properties are then extracted via the van’t Hoft or other analysis, such as the compound energy formula. These techniques often allow for trade off of enthalpy or entropy, providing non-unique solutions. In contrast computational methods such as density functional theory struggles to reproduce the complex temperature dependent behavior due to the large number of potential configurations. Here we present a new method for extracting thermodynamic properties which leverages a combination of DFT and experiment. This method removes the ambiguity between enthalpy and entropy, while providing temperature dependent behavior. The solution does not require pre-made assumptions.