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Abstract:
Liquid|liquid interfaces (LLIs) between redox-type electrolytes are investigated with a 2-electrode technique by subtraction of the volume effects of the adjacent bulk phases and a correction of equipment errors. In this system, the electron transfer through the LLI turns out to be over-dominating the ion transfer. Surprisingly, not any indication for a barrier in the charge transfer was found. The measured resistances assignable to the LLI are extremely low. The efficient charge transfer through the LLI is ascribed to an ionic adsorption layer acting as a buffer for the electrons and opening a new channel for the charge transport. The impedance spectra show a specific peculiarity, a “capacitance lag” at high frequencies. This lag is interpreted by a new model of delayed transport. Microscopically, such kind of transport is explained by an adsorbed ion layer with variable charge. It acts as a buffer and causes a time delay in the charge transfer.
