Generalized solvent boundary potential approach

Half-Cells. The concept of a supported electrolyte has proven quite valuable in solution electrochemistry by allowing great theoretical simplification at (usually) only a small cost in accuracy. The several (often implicit) assumptions made in treating the electrolyte in a given cell as supported, however, deserve careful attention as they generally do not apply in the case of solid state electrochemical systems. It should also be noted that it is usually possible in solution electrochemistry to use a large, essentially kineticaUy reversible counterelectrode so that aU but a negligible fraction of the applied potential difference falls across the electrode-electrolyte interface of interest. In its simplest form, the supported approach assumes that all the potential difference in the system falls across the compact double layer—approximately one solvent molecule diameter in thickness— at this electrode, and the approach of the electroactive species to the boundary of the compact layer, the outer Helmholtz plane, occurs purely by diffusion. Corrections for the buildup of space... 

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