Prediction and Estimation of Thermodynamic Quantities in Rare Earth Chloride Hydrates (RClx*NH2O)

"The prevalent metal extraction processes for most reactive metals are fused salt electrolysis and metallothermic reduction. The feed material for both of these processes is the anhydrous chloride of the metal under consideration. Dehydration of the feed material is then a critical step in the production of most reactive metals and requires rigorous thermodynamic analysis. Thermodynamic data for most of the reactive metal chloride hydrates have not been measured. Improper dehydration of the metal chloride may lead to a prohibitive amount of hydroxychloride, oxychloride, and oxide. To prevent hydrolysis a certain pressure of hydrogen chloride is required. An estimation and prediction model is presented for the vapour pressures of reactive metal chloride hydrates in an attempt to deduce the conditions necessary for dehydration to proceed without hydrolysis. Thermodynamic data including heat capacities, standard entropies, and standard enthalpies are estimated/predicted for all conceivable intermediate hydrate compounds. Estimations are based on published data as well as trends proven in similar systems. The thermodynamic estimations and predictions are presented for the magnesium, neodymium, praseodymium, and dysprosium chloride hydrates. INTRODUCTIONThe high reactivity of metals such as the alkalis, alkaline earths, and lanthanides prevents their reduction by traditional pyro- or hydrometallurgy. In their elemental form, these metals are raw materials in the manufacture of intermediate products such as alloys and electronic components. Currently the only two viable metal production methods are fused salt electrolysis and metallothermic reduction. Various feed materials have been proposed for these processes. Using the chloride of the metal as a feed material offers advantages in separation and purity of the final product, as well as lower energy input. Chlorides, however, are hygroscopic and must be dehydrated before use. Improper dehydration will lead to a prohibitive amount of oxychloride which will lower efficiencies and contaminate the final product.Optimum conditions for proper dehydration of MgCl2•6H2O to produce pure MgCl2 without hydrolysis have been calculated from existent thermodynamic data and have been reported previously (Kipouros, 1987; 2001). Calculations were also performed for the case of production of pure anhydrous NdCl3 from NdCl3•6H2O (Roy, 1997)] and the mechanism of dehydration was elucidated. Some thermodynamic studies on the dehydration of chlorides of the rare earths have also been conducted (Sundstrom, 1997; Hong, 1997; Aschcroft, 1968; Haeseler, 1965; Ukraintseya, 1989)."