1 Temperature Effects on Platinum Single-Crystal/Aqueous Solution Interphases. Combining Gibbs Thermodynamics with Laser-Pulsed Experiments

The rigorous analysis of the effect of temperature variations on interfacial properties is a key tool to provide new and valuable information on the structure and reactivity of the metal|solution interphase. The entropy of the components that form the interphase is a unique probe of their structural properties. Therefore, this experimental data is particularly useful for the validation of molecular models of electrified interphases. In addition, the use of fast temperature perturbations is especially suitable for the selective characterization of different interfacial components, based on their different response time towards the temperature change. In this way, the entropic properties of double-layer phenomena and charge-transfer adsorption processes can be evaluated separately. It will be shown in this chapter that the combination of Gibbs thermodynamics with results from laser-induced temperature jump experiments, allows the evaluation of key interfacial properties, such as the entropy of charge-transfer adsorbed species, the entropy of formation of the interfacial water network, and the potential of water reorientation.