Extractive Metallurgy Division - Solutions of Metals in Fused Salts

IT has long been known that some metals are capable of being dispersed or dissolved in certain of their fused salts.' Davy' and Bunsen³ were among the first to observe that in some fused salt electrolyses, a highly colored, strongly reducing salt phase appeared in the neighborhood of the cathode. Later workers found that the current efficiency of the electrolysis was markedly reduced when such a phase appeared. It was also found that the strongly reducing salt could be made by melting the metal and normal salt together. Chemical analysis showed that in such salts the metal ion to anion ratio was always larger than in the normal salt. From such observations arose two different explanations of the nature of metal in salt solutions. When a solution of this type is quenched, it is possible to find small globules of metal in the salt. From this and other observations, Lorenz' and co-workers assumed the metal in salt solution to be a colloidal dispersion of metal in the fused salt and called it "metallnebel" or metal fog formation. They made a number of experiments to substantiate this point of view. Another school felt that when the metal dissolved it reduced the salt partially to a mixture or solution of normal salt and subsalt. Both of these ideas could explain the strong reducing character of the salt formed and the low current efficiency of the electrolysis. If either a metal colloid or a subsalt were formed at the cathode and diffused to the anode, it would be oxidized to the normal salt. Thus a cyclic process of oxidation and reduction could be set up conducting the current without giving rise to a net change in the system. These facts led the author to investigate some of the properties of metal in salt solutions with the hope of elucidating their nature further. Among the metal-salt systems that form metal in salt solutions most markedly are the alkaline earth metal-halide systems and cerium, bismuth, and cadmium halides. Other systems of halides, oxides and sulphides form such solutions to a lesser degree. The first work undertaken was a study of the temperature-composition diagrams of some of the systems." From such diagrams it would be possible to distinguish between a subhalide formation or a colloid. A subhalide should give rise to characteristic changes in the phase diagram, while a colloidal dispersion of metal in salt would not alter the freezing point of the salt. The results obtained on a number of alkaline earth metal-halide systems were all quite similar. Fig. 1 shows the barium-barium chloride system. The other