After observing an irreversible step in the electrode process in all cases of coherent deposition of metals from molten fluorides, a chronopotentiometric study of the KCl ‐ LiCl ‐ K 3 MoCl 6 system which produces coherent molybdenum deposits was undertaken. It was found that in this case also, the electrode process was irreversible at 600 °C, a temperature at which coherent deposits are produced, and became more reversible as the temperature increased. The irreversible behavior of the electrode and the decrease of bath stability with decrease in concentration of molybdenum could be explained on the basis of the following mechanism (see PDF for fomula). The failure of the electrode to behave in a Nernstian manner at 600°C is ascribed to the slowness of the dissociation in step ( A ). Its more nearly Nernstian behavior at 700° and 800°C probably results from the increased rate of this dissociation and is associated with decreased coherency of deposits at these temperatures.
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Senderoff et al. (1967) studied this question.