Uranyl(VI) Nitrate Salts:  Modeling Thermodynamic Properties Using the Binding Mean Spherical Approximation Theory and Determination of “Fictive” Binary Data

This work is aimed at a description of the thermodynamic properties of highly concentrated aqueous solutions of uranyl nitrate at 25 °C. A new resolution of the binding mean spherical approximation (BIMSA) theory, taking into account 1−1 and also 1−2 complex formation, is developed and used to reproduce, from a simple procedure, experimental uranyl nitrate osmotic coefficient variation with concentration. For better consistency of the theory, binary uranyl perchlorate and chloride osmotic coefficients are also calculated. Comparison of calculated and experimental values is made. The possibility of regarding the ternary system UO₂(NO₃)₂/HNO₃/H₂O as a “simple” solution (in the sense of Zdanovskii, Stokes, and Robinson) is examined from water activity and density measurements. Also, an analysis of existing uranyl nitrate binary data is proposed and compared with our obtained data. On the basis of the concept of “simple” solution, values for density and water activity for the binary system UO₂(NO₃)₂/H₂O are proposed in a concentration range on which uranyl nitrate precipitates from measurements on concentrated solutions of the ternary system UO₂(NO₃)₂/HNO₃/H₂O. This new set of binary data is “fictive” in the sense that the real binary system is not stable chemically. Finally, a new, interesting predictive capability of the BIMSA theory is shown.