Relationship between interfacial transfer and adsorption-desorption of surface-active bis-ammonium ions at a liquid/liquid interface

Cyclic voltammograms and interfacial tension-applied potential curves were recorded at the interface between water containing surface-active bis-quaternary ammonium ions, bis-A(2+), and an organic solvent such as 1,2-dichloroethane or nitrobenzene. An ordinary diffusion-controlled voltammetric wave for the transfer of bis-A(2+) from aqueous phase to organic phase, the first wave, was followed by a typical adsorption-related wave, the second wave. It was found from the potential dependence of the interfacial tension of bis-A(2+) that the second wave was due to the desorption of bis-A(2+) toward the organic phase. The influence of the structure of bis-A(2+) on voltammograms was investigated, and the potential for the first wave was found to depend on both the length of the side chain and that of the spacer chain, whereas the potential for the second wave depended on the latter only. The thermodynamic relations among three processes of the ion transfer, adsorption, and desorption were discussed based on the experimental results.