Chemical properties of some elements in a molten lithium chloride, potassium chloride eutectic (1962)

The increasing use of molten media especially in chemical preparations and for certain technological applications, has made it more necessary to have a knowledge of the chemical properties of elements in these solvents. Structural studies on molten solutions show the existence of certain species such as ions and complexes known to exist in aqueous solutions. This fact, together with certain experiments on chemical reactions in molten media has led us to establish a comparison between these media and aqueous solutions. We wish to show that the same fundamental phenomena occur in these media as are found in the chemistry of aqueous solutions and that this makes it possible to predict certain reactions. We have taken as examples the chemical properties of vanadium, uranium and sulphur in a LiCl-KCl eutectic melted at 480 deg. C. The first problem is to identify the various degrees of oxidation of these elements existing in the solvent chosen. We have tried to resolve it by comparing the absorption spectra obtained in aqueous solution and in the molten eutectic. We consider the possibilities of this method in a chapter on absorption spectrophotometry in the LiCl-KCl eutectic. During the study of the chemical properties we stress the various methods of displacing the equilibria: complex formation, variation of the oxidation-reduction properties with complex formation. The complexes of the O2- ion are considered in particular. The study of the exchange of this particle is facilitated by the use of a classification of some of its complexes which we call the pO2- scale by analogy with the pH scale; the value pO2- is defined by the relationship: pO2- = log O2- Similarly, the use of apparent potential diagrams pO2- makes it possible to predict and to interpret reactions involving the simultaneous exchange of electrons and O2- ions between the various degrees of oxidation of the same element. It is possible, by studying some reactions of this type between two elements. We give the diagrams of uranium and sulphur as examples. The chemical properties of sulphur show that the dismutation phenomenon operates also in molten media reactions, thus emphasising the resemblance with aqueous solutions. Finally, we show briefly how it is possible to predict qualitatively the chemical properties of a given element in a molten solvent other than the LiCl-KCl eutectic. (author)