Ion transfer reactions in media of low ionic strength

Facilitated ion transfer (FIT) and simple ion transfer (IT) reactions at the water|1,2-dichloroethane (W|DCE) interface with media of low ionic strength are investigated by employing micro- and nano-pipettes. The model systems chosen for the FIT and IT are K+ transfer facilitated by dibenzo-18-crown-6 (DB18C6) and tetramethylammonium (TMA+), respectively. For the FIT reaction at micro- and submicro-liquid|liquid interfaces, when the supporting electrolyte concentrations in the organic phase are at micromolar levels, its voltammetric waves are analyzed by the theory for one-electron oxidation of uncharged species in organic solution with little added supporting electrolyte on solid ultramicroelectrodes (UMEs) proposed by Oldham [K.B. Oldham, J. Electroanal. Chem. 250 (1988) 1]. Its chronoamperograms are strongly affected by the externally applied potentials, which is consistent with the theory proposed by Stojek and co-workers [A. Jaworski, M. Donten, Z. Stojek, Anal. Chim. Acta 305 (1995) 106, A. Jaworski, M. Donten, Z. Stojek, J. Electroanal. Chem. 407 (1996) 75, W. Hyk, M. Palys, Z. Stojek, J. Electroanal. Chem. 415 (1996) 13, W. Hyk, Z. Stojek, J. Electroanal. Chem. 422 (1997) 179] for reactions at solid UMEs with different concentrations of supporting electrolyte. In addition, the FIT reaction can exhibit well-defined steady-state waves at the nano-liquid|liquid interface when no supporting electrolyte is added to the organic phase. For the TMA+ transfer reaction from the aqueous phase to DCE (or from DCE to the aqueous phase), the magnitude of its steady-state limiting current depends on the concentration of supporting electrolyte in the same phase, and the shape and position of its transfer waves are influenced by the supporting electrolyte concentrations in the adjacent phase. We can observe clearly the migration effect on the transfer reaction of charged species.