Abstract

A fairly detailed knowledge of the chemistry and thermodynamics of molten salt breeder reactor fuels, typically LiF-BeF ₂ThF ₄-UF ₄ ( 72-16-12- < 1 mol % ), has been gained from measurements of heterogeneous equilibria involving various gases (e.g. HF, H ₂O) and solids (usually oxides). This information combined with the thermochemical data available for the pure compounds has given formation free energies for the fual components. Their entropies can be estimated from the known entropies of the corresponding solid oxides and the charge on the cation. Their activity coefficients depend primarily on the mol % of LiF in the salt mixture. The solubility of oxides generally decreases with the square of the cation charge divided by the radius. Thus the actinide dioxides and, especially, Pa ₂O ₂ (or an addition compound of it) are of low solubility. Pourbaix diagrams are presented which summarize the conditions of redox potential and oxide concentration wherein the fuel may be contained without significant corrosion or precipitation reactions, or conditions wherein selective oxide precipitation may be carried out for purposes of fuel reprocessing.