Charge transfer between two immiscible electrolyte solutions: Part x. Kinetics of tetraalkylammonium ion transfer across the water/nitrobenzene interface

Abstract

The kinetics of tetrabutylammonium, tetrapropylammonium and tetraethylammonium ion transfer across the water/nitrobenzene interface were investigated by using the galvanostatic pulse technique and convolution potential sweep voltammetry. The apparent ionic rate constants were corrected for the ion distribution in the electrical double layer and the corrected rate constants together with those reported in the literature for the transfer of tetramethylammonium, choline and acetylcholine ions, were correlated with the corrected Gibbs energy. The data for the tetraalkylammonium ions fall on a single line with a slope corresponding to the true charge transfer coefficient, α t ≈ 0.5 showing some tendency to drop from this line as the corrected Gibbs energy, Δ G rp, becomes large and negative. The conclusions was made that on crossing the interface the ion must overcome a symmetric potential energy barrier.