Collection of Czechoslovak Chemical Communications - digital archive 

Abstract

The kinetics and mechanism of the redox reactions of U³⁺ ions with mono- and dichloroacetic acids were studied. The influence of pH was observed mainly in the second case and led to the determination of the rate constants and activation parameters corresponding to two parallel steps, namely oxidation of U³⁺ with CHCl₂COO^- ions and oxidation of U³⁺ with CHCl₂.COOH molecules. The influence of binary mixtures of water with methanol, ethanol, isopropanol, or tert-butenol on the reaction rate was followed. Increasing alcohol concentration influences the rate constant not only through changing dielectric constant and solvation of the reactants but also through a change of the solvent structure which plays a role in reactions with an outer sphere mechanism of the electron transfer.