Correlational Approach to Predict the Enthalpy of Mixing for Chloride Melt Systems.

A methodology to estimate the heat of mixing (Δ mix H ) for salt liquids in unexplored AkCl-AnCl x /LnCl x (Ak = alkali, An = actinide, Ln = lanthanide) systems is developed. It improves upon previous empirical approaches by eliminating the need for arbitrarily choosing the required composition at maximum short-range ordering, the minimum Δ mix H prior to performing the estimation, which avoids the intrinsic ambiguity of that approach. This semiempirical method has computationally reproduced the behavior of NaCl-UCl 3 and KCl-UCl 3 systems, providing Δ mix H values that agree well with the reported measurements within a propagated two standard deviations (2σ). The capability of the approach is demonstrated in its application to the entirety of the AkCl-UCl 3 and AkCl-PuCl 3 systems, the results from which have facilitated the accurate thermodynamic modeling of these and other AkCl-AnCl 3 /LnCl 3 systems. The resultant assessed Gibbs energy functions and models have been incorporated in the Molten Salt Thermal Properties Database-Thermochemical (MSTDB-TC).