Voltammetric study on the oscillation of the potential difference at a liquid/liquid or liquid/membrane interface accompanied by ion transfer

The oscillations of potential difference at the interface between an aqueous solution (W) containing MgSO4 as a supporting electrolyte (SE) and an organic solution (Org) containing dilute ion i+ and j+•Y- as SE were investigated by forcing the transfer of i+ at the interface through an applied current. The Org employed were Cs+tetrapentylammonium tetraphenylborate (TpenA+•TPhB-) in nitrobenzene (NB), tetramethylammonium ion + TPenA+•TPhB- in NB, W++ tetraphenylarsonium dipicrylaminate (TPhAs+•DPA) in 1, 2-dichloroethane, etc. The necessary conditions for the oscillation were confirmed to be identical to those for the appearance of the maximum in the voltammogram for the transfer of i+ at the interface. By referring to the voltammogram and the electrocapillary curve at the interface and taking into account the ion pair (i+•Y-) formation equilibrium in Org, such characteristics of the oscillation as the amplitude, period, pulse width and range of the applied current available for the oscillation were elucidated, and a mechanism for the oscillation is proposed. The important roles of the adsorption -desorption of i+•Y- at the interface and the dissociation of the desorbed i+•Y- were emphasized.

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