This work presents a study of the electrochemical properties of Th chloride ions dissolved in a molten LiCl-KCl eutectic, in a temperature range of 693-823 K. Transient electrochemical techniques such as cyclic voltammetry and chronopotentiommetry have been used in order to investigate the reduction mechanism on a tungsten electrode and the diffusion coefficient of dissolved Th ions. All techniques showed that only one valence state was stable in the melt.The reduction into Th metal was found to occur according to a one-step mechanism, through an irreversible reaction controlled by a nucleation process which requires an overpotential of several 100 mV. At 723 K, the diffusion coefficient is D Th(723K) = 3.7 ± 0.2·10 -5 cm 2 .s -1 . EMF measurements indicated that, at 723 K, the standard apparent potential is 0(723 K) = -2.582 V vs. Cl 2 /Cl -, and the activity coefficient γ ThCl4 (723 K) = 8·10 -3 on the mole fraction scale (based on a pure liquid reference state).

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a b s t r a c tThis article is focused on the electrochemical behaviour of U ions in molten LiF-CaF 2 (79-21 wt.%) eutectic. On a W electrode, U(III) is reduced in one step to U metal and U(III) can be also oxidised to U(IV). Both systems were studied by cyclic and square wave voltammetry. Reversibility of both systems for both techniques was verified and number of exchanged electrons was determined, as well as diffusion coefficients for U(III) and U(IV). The results are in a good agreement with previous studies. On a Ni electrode, the depolarisation effect due to intermetallic compounds formation was observed. Electrorefining of U metal in a melt containing U and Gd ions was carried out using a reactive Ni electrode with promising results.

U-Al alloy formation has been studied in the temperature range of 400 -550 °C by electrochemical techniques in the molten LiCl-KCl eutectic. Cyclic voltammetry showed that underpotential reduction of U(III) onto solid Al occurs at a potential about 0.35 V more anodic than pure U deposition. Open circuit potential measurements, recorded after small depositions of U metal onto the Al electrode, did not allow the distinction between potentials associated with UAl x alloys and the Al rest potential, as they were found to be practically identical. As a consequence, a spontaneous chemical reaction between dissolved UCl 3 and Al is thermodynamically possible and was experimentally observed.Galvanostatic electrolyses were carried out both on Al rods and Al plates. Stable and dense U-Al deposits were obtained with high faradic yields, and the possibility to load the whole bulk of a thin Al plate was demonstrated. The analyses (by SEM-EDX and XRD) of the deposits indicated the formation of different intermetallic phases (UAl 2 , UAl 3 and UAl 4 ) depending on the experimental conditions.

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