Abstract
The reduction of to in molten salt at 716°C has been shown by chronopotentiometry to be diffusion controlled at a platinum electrode. Furthermore, the potential‐time curves indicated that the reaction occurred in two steps at nearly the same potential. This observation was verified by measuring the pseudo capacity of the polarized cathode as a function of its potential for which a plot of the data shows two peaks in capacity. The first was found to be symmetric with a concentration‐independent potential, which is indicative of an electrode reaction producing a soluble product. The second peak was asymmetric with a concentration‐dependent potential, which is indicative of an electrode reaction producing an insoluble product. These observations suggested that the electrode reaction proceeds by a reduction of to followed by the reduction of the to Additional verification of this mechanism was provided by the reduction of by to yield a stable solution of . The heterogeneous rate constant for the reduction of to was estimated to be 2 cm sec−1, but a value for the reduction of could not be determined because of the solid deposit. The diffusion coefficient was estimated from the chronopotentiometric data to be .
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