Calorimetric Effects of Simple Ion Adsorption at the Metal Oxide/Electrolyte Interfaces: An Analysis Based on the Four Layer Complexation Model

A comparative theoretical study of the heat accompanying ion adsorption at the oxide/electrolyte interface, predicted by both the triple layer model (TLM) and the four layer model (FLM) of oxide/electrolyte interface, is presented. The four layer model predicts that even small differences reported between PZC and IEP may affect strongly by the heat effects below PZC. The developed expressions are successfully applied to describe quantitatively heat effects accompanying ion adsorption at the TiO 2 /NaCl solution interface. An assumption that the inner capacitances are temperature dependent is essential for that successful quantitative description.