Electrode Potential - Origin and Interpretation

Origin and Interpretation

Electrode potential appears at the interface between an electrode and electrolyte due to the transfer of charged species across the interface, specific adsorption of ions at the interface, and specific adsorption/orientation of polar molecules, including those of the solvent.

The measured electrode potential may be either that at equilibrium on the working electrode ("reversible potential"), or a potential with a non-zero net reaction on the working electrode but zero net current ("corrosion potential", "mixed potential"), or a potential with a non-zero net current on the working electrode (like in galvanic corrosion or voltammetry). Reversible potentials can be sometimes converted to the standard electrode potential for a given electroactive species by extrapolation of the measured values to the standard state.

The value of the electrode potential under non-equilibrium depends on the nature and composition of the contacting phases, and on the kinetics of electrode reactions at the interface (see Butler-Volmer equation).

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