(508d) Melting Points of Alkali Chlorides Evaluated for a Polarizable and Non-Polarizable Model
AIChE Annual Meeting
2020
2020 Virtual AIChE Annual Meeting
Engineering Sciences and Fundamentals
Thermophysical Properties and Phase Behavior III: Properties of Polar Compounds and Self-Assembly
Tuesday, November 17, 2020 - 8:45am to 9:00am
Here we report the performance of two models for predicting the melting points of the alkali chlorides. These include the non-polarizable rigid ion model (RIM) and the polarizable ion model (PIM). Though an important thermodynamic property in its own right, the accuracy of a modelâs melting point also represents a stringent test of model quality. The melting point arises from a delicate balance of the liquid and solid free energies, and errors of <1 kcal/mol in the solid-liquid free energy difference can result in errors >100 K in the melting point. The melting points for the RIM are calculated via two distinct methods: the pseudo-supercritical path method and the direct coexistence method. We then proceed to calculate the melting points of the PIM with the direct coexistence method alone.
The pseudo-supercritical path and direct coexistence methods show excellent agreement with each other; RIM melting points predicted with the two methods agree within 5 K for all four alkali chlorides. Nonetheless, when compared with experimental results, the RIM only predicts accurate (within 10 K) melting points for NaCl and KCl. The melting point of LiCl (RbCl) is under (over) predicted by ~100 K. The addition of polarizability in the PIM does not yield more accurate results; the predictions deviate from experiment by ~10 K - 140 K. To better understand the origins of the deviations from experiments, we report and discuss the effects of entropy and enthalpy of melting on the predicted melting points. We find that both models nearly always fail to accurately predict these properties. More often, the accuracy of model melting points are improved by a fortuitous cancellation of errors. We close by discussing how targeting an accurate enthalpy of melting during force field parameterization may offer one approach to improving molecular models of the alkali chlorides.