CHARGE-TRANSFER BETWEEN 2 IMMISCIBLE ELECTROLYTE-SOLUTIONS .2. INVESTIGATION OF CS+ ION TRANSFER ACROSS THE NITROBENZENE-WATER INTERFACE BY CYCLIC VOLTAMMETRY WITH IR DROP COMPENSATION

The transfer of Cs+ ion across the interface of two immiscible electrolyte solutions, 0.05 M LiCl in water and 0.05 M tetrabutylammonium tetraphenylborate in nitrobenzene, was investigated by cyclic voltammetry with four-electrode system. The positive feedback was used for the elimination of the ohmic potential drop between the tips of the Luggin capillaries. The standard potential differences for Cs+ and tetrabutylammonium cations and for tetraphenyl-borate anion, which were deduced from the present experimental results, are in very good agreement with those calculated from the extraction data. The value of the diffusion coefficient of Cs+ ion in water DCs+(w)=2.4×10-5 cm2 s-1 was estimated. The kinetics of Cs+ ion transfer across the nitrobenzene/water interface is characterized by the apparent rate constant kappø=5.5×10-2 cm s-1 and by the formal charge transfer coefficient α=0.46. © 1979 Elsevier Sequoia S.A.