Buoyancy Effect of Ionic Vacancy on the Change of the Partial Molar Volume in Ferricyanide-Ferrocyanide Redox Reaction under a Vertical Gravity Field

With a gravity electrode (GE) in a vertical gravity field, the buoyancy effect of ionic vacancy on the change of the partial molar volume in the redox reaction between ferricyanide (FERRI) and ferrocyanide (FERRO) ions was examined. The buoyancy force of ionic vacancy takes a positive or negative value, depending on whether the rate-determining step is the production or extinction of the vacancy. Though the upward convection over an upward electrode in the FERRO ion oxidation suggests the contribution of the positive buoyancy force arising from the vacancy production, the partial molar volume of the vacancy was not measured. On the other hand, for the downward convection under a downward electrode in the FERRI ion reduction, it was not completely but partly measured by the contribution of the negative buoyancy force from the vacancy extinction. Since the lifetime of the vacancy is decreased by the collision between ionic vacancies during the convection, the former result was ascribed to the shortened lifetime due to the increasing collision efficiency in the enhanced upward convection over an upward electrode, whereas the latter was thought to arise from the elongated lifetime due to the decreasing collision efficiency by the stagnation under the downward electrode.