Temperature metal—solution interphase

The rigoroiis 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 stmctural 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 inter-facial components, based on their different response time towards the temperature change. In this way, the entropic properties of doublelayer phenomena and charge-transfer adsorption processes can be evaluated separately. It will be shown in this chapter that the combina-... 

If one is challenged with the study of the effect of the temperature on a metal solution interphase, the first approach that will probably come to mind is the use of a thermostatized bath or a jacketed cell... 

The Chapter by N. Garcia, V. Climent and J. Feliu provides a lucid and authoritative overview of the use of laser-pulsed induced temperature variations at the platinum single-ciystal/aqueous solution interphases and of the rigorous analysis of these experiments via Gibbs thermodynamics to extract new and very valuable information on the stracture and reactivity of the metal/solution interphase. The authors show how some key interfacial properties can be evaluated directly via this elegant analysis, such as the entropy of charge-transfer adsoibed species, the entropy of formation of the interfacial water network and the potential of water reorientation. 

We have seen that the electrochemical variables, C and T are all related to the surface tension of the electrode. Measurements of surface tension as a function of electrode potential and solution concentration, thus play a very important part in the study of the double layer. It is obviously quite simple to measure surface tension of a liquid electrode and very difficult to do the same with solid ones. Mercury once more has a decisive advantage over all other metals for the study of the interphase at around room temperature. 

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