Abstract
Abstract The catalytic action of ferric ions in the U(IV)–U(VI) electron exchange reaction has been studied in the presence of a high concentration of hydrochloric acid. The exchange rate is found to be accelerated by the addition of ferric ions; the observed rate law is given by: R=k_0[U(IV)][U(VI)]+k_c[Fe(III)]_0\sqrt[U(IV)][U(VI)] An activation energy of 19.7 kcal/mol was calculated for the iron-catalyzed reaction in the U(IV)–U(VI) electron exchange reaction. This value is much smaller than that of 32.2 kcal/mol, which was found in the non-catalytic reaction. The kinetics and equilibrium of the reaction between Fe(III) and U(IV) have also been studied in order to investigate in detail the mechanism of the catalytic reaction. A one-electron-transfer mechanism producing U(V) as an intermediate is estimated from the rate law and supported by the kinetics and equilibrium studies of the Fe(III)–U(IV) reaction.
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