Structure of the metal/electrolyte solution interface: new data for theory

Existing experimental data have been reconsidered in the light of new conceptual approaches, and new data have been scrutinized with the purpose of offering new suggestions and new fundamental arguments for the theoretical modelling of the electrical double layer. The points touched on in this paper include: (1) the conceptual and quantitative relationship between electrode potential and work function measurements impacting on the experimental determination of the so-called “absolute” electrode potential; (2) the interfacial behaviour of Ag, Au and Cu compared with the group of sp-metals; (3) the temperature coefficient of Eσ = 0 for single crystal faces; (4) the inconsistency of the experimental and interpretative picture issuing from different laboratories in the case of single crystal faces of Ag. The general significance of the “interfacial parameter” ΔX as derived from Eσ = 0 vs Φ plots is discussed in particular. Such a parameter includes electronic and solvent effects and measures the degree of coupling between the metal surface and the solvent. It is shown that ΔX can arrange the various metals and the different crystal faces into a common picture.