Thermodynamic Study of Ce4+ /Ce3+ Redox Reaction in Aqueous Solutions at Elevated Temperatures: 1. Reduction Potential and Hydrolysis Equilibria of Ce4+ in HCIO4 Solutions

The redox potential (E) of the couple Ce4+/Ce3+ has been determined up to 368 K by means of cyclic voltammetric measurement in aqueous HClO4 solutions with cHClO4 decreasing from 7.45 to 0.023 mol kg-1 . A constant potential of (1.741 V)298 K, resp. (1.836 V)368K, indicating the existence of pure unhydrolysed Ce4+ was obtained at cHClO4 ≥ 6.05 m. At lower HClO4 concentration, the potential as a function of the HClO4 molality, as well as of the pH shows 4 further distinct steps. At 298 K, for instance, the potential became nearly constant at pH values of 0.103, 0.735,1.115, after which it drastically decreased, respectively at 1.679, just before the precipitation of Ce(OH)4 occurred. The curves indicate obviously the stepwise formation of the Ce(IV) mono-, di-, tri- and tetrahydroxo complexes. The slope of the curves E vs. pH increased gradually with increasing temperature. ΔS and ΔH of the redox reaction were determined as functions of T at the different HClO4 concentrations. ΔSis positive at cHClO4 > 1.85 m and turns to be negative at lower concentrations. ΔHis negative at all HClO4 concentrations studied. The cumulative formation constants ßi, of the Ce(IV) hydroxo complexes and the corresponding hydrolysis constants (Kh)i were calculated. An unusual decrease of ßi with increasing temperature has been discussed