Chemical Potential Analysis as an Alternative to the van't Hoff Method: Hypothetical Limits of Solar Thermochemical...

The van't Hoff method is a standard approach for determining reaction enthalpies and entropies, e.g., in the thermochemical reduction of oxides, which is an important process for solar thermochemical fuels and numerous other applications. However, by analyzing the oxygen partial pressure pO₂, e.g., as measured by thermogravimetric analysis (TGA), this method convolutes the properties of the probe gas with the solid-state properties of the examined oxides, which define their suitability for specific applications. The "chemical potential method" is here proposed as an alternative. Using the oxygen chemical potential Δμ_O instead of pO₂ for the analysis, this method does not only decouple gas-phase and solid-state contributions but also affords a simple and transparent approach to extracting the temperature dependence of the reduction enthalpy and entropy, which carries important information about the defect mechanism. For demonstration of the approach, this work considers three model systems; (1) a generic oxide with noninteracting, charge-neutral oxygen vacancy defects, (2) Sr_0.86Ce_0.14MnO_3(1-δ) alloys with interacting vacancies, and (3) a model for charged vacancy formation in CeO₂, which reproduces the extensive experimental TGA data available in the literature. The reduction behavior of these model systems obtained from the chemical potential method is correlated with simulated results for the thermochemical water splitting cycle, highlighting the exceptional behavior of CeO₂, which originates from defect ionization. The theoretical performance limits for solar thermochemical hydrogen within the charged defect mechanism are assessed by considering hypothetical materials described by a variation of the CeO₂ model parameters within a plausible range.