A new model is presented for the metal-electrolyte interface which takes explicit account of the mobility of electrons at a metallic interface. The model can be described as a simple modification of the classical Stern-Gouy-Chapman double layer theory, but it contains an essential new feature of fundamentally quantum mechanical origin. A basic prediction of the theory is that at high enough temperatures the inverse 1/C//c of the compact part of the differential capacitance C//c is linear in the charge sigma //m per unit area for small sigma //m if adsorption does not occur. The authors confirm this for Hg, In, Ag, Cd and (Pb) with NaF (KF) electrolyte. The slope of the 1/C//c vs. sigma //m line is predicted in a simple model to be proportional to the inverse 1/ rho //m of the metallic charge density rho //m and predict the coefficient on the basis of two detailed models. The results are compared with experiment on a variety of metal electrolyte interfaces. The limitations of the theory are discussed.
|Original language||English (US)|
|Number of pages||7|
|Journal||Journal of electroanalytical chemistry and interfacial electrochemistry|
|Issue number||1 - 2|
|State||Published - Jan 1 1982|
|Event||Electron and Mol Struct of Electrode-Electrolyte Interfaces, Proc of the Int Conf - Logan, UT, USA|
Duration: Jul 25 1982 → Jul 30 1982