Studies of Electron-Transfer and Charge-Transfer Coupling Processes at a Liquid/Liquid Interface by Double-Barrel Micropipet Technique

Investigation of a heterogeneous electron-transfer (ET) reaction at the water/1,2-dichloroethane interface employing a double-barrel micropipet technique is reported. The chosen system was the reaction between Fe(CN) ₆^3- in the aqueous phase (W) and ferrocene in 1,2-dichloroethane (DCE). According to the generation and the collection currents as well as collection efficiency, the ET-ion-transfer (IT) coupling process at such an interface and competing reactions with the organic supporting electrolyte in the organic phase can be studied. In addition, this technique has been found to be an efficient method to distinguish and measure the charge-transfer coupling reaction between two ions (IT-IT) processes occurring simultaneously at a liquid/liquid interface. On this basis, the formal Gibbs energies of transfer of some ions across the W/DCE interface, such as NO₃^-, NO₂^-, Cl^-, COO^-, TBA⁺, TPAs⁺, Cs⁺, Rb ⁺, K⁺, Na⁺, and Li⁺, for which their direct transfers are usually difficult to obtain because of the IT-IT coupling processes, were quantitatively evaluated.