MECHANISM OF THE TRANSFER OF ALKALI-EARTH-METAL AND ALKALINE-EARTH-METAL IONS ACROSS THE NITROBENZENE WATER INTERFACE FACILITATED BY HEXAETHYLENE AND OCTAETHYLENE GLYCOL DODECYL ETHERS

Transfer of Li+, Na+, K+, Rb+, Ca2+, Sr2+, and Ba2+ ions facilitated by hexa- and octaethylene glycol monododecyl ethers (C12E6 and C12E8) has been studied at the nitrobenzene (NB)-water (W) interface using cyclic voltammetry. When the concentration of C12En (n = 6 or 8) in NB is higher than 1 mM, cyclic voltammograms for all these ions show reversible transfer of ions facilitated by C12En. The current is mainly carried by 1:1 (metal:ligand) complex and is limited by the diffusion of C12En in N B. When the concentration of C12En in NB is lowered to the submillimolar range, the contribution of the adsorption of C12En to the current becomes significant. In the transfer of hydrophilic ions, e.g., Li+ and Ca2+, the contribution of the complex with 1:2 (metal:ligand) stoichiometry to the measured current becomes nonnegligible. This 1:2 complex formation becomes pronounced with increasing ligand concentration. © 1993 Academic Press, Inc.