Collect. Czech. Chem. Commun. 1980, 45, 3266-3269

Distinguishing between outer-sphere and inner-sphere redox mechanism on the basis of the solvent effect

Ľudovít Treindl and Ľubica Adamčíková

Department of Physical Chemistry, Comenius University, 816 50 Bratislava


During kinetic studies of redox reactions of U3+ ions, we paid special attention to the influence of water-alcohol binary mixtures on the reaction rate. Kinetic data suggest that the water-tert-butanol system is of a high diagnostic value. The dependence of log kexp on the molar fraction of tert-butanol passes through a characteristic minimum in the case of an outer-sphere mechanism, whereas in the other case it decreases monotonously.