Atomistic simulation framework for molten salt vapor–liquid equilibrium prediction and its application to NaCl

Abstract

Knowledge of the vapor-liquid equilibrium (VLE) properties of molten salts is important in the design of thermal energy storage systems for solar power and nuclear energy production applications. The high temperatures involved make their experimental determination problematic, and the development of both macroscopic thermodynamic correlations and predictive molecular-based methodologies are complicated by the requirement to appropriately incorporate the chemically reacting vapor-phase species. We derive a general thermodynamic-based atomistic simulation framework for molten salt VLE prediction and show its application to NaCl. Its input quantities are temperature-dependent ideal-gas free energy data for the vapor phase reactions, and density and residual chemical potential data for the liquid. If these are not available experimentally, the former may be predicted using standard electronic structure software, and the latter by means of classical atomistic simulation methodology. The framework predicts the temperature dependence of vapor pressure, coexisting phase densities, vapor phase composition, and vaporization enthalpy. It also predicts the concentrations of vapor phase species present in minor amounts (such as the free ions), quantities that are extremely difficult to measure experimentally. We furthermore use the results to obtain an approximation to the complete VLE binodal dome and the critical properties. We verify the framework for molten NaCl, for which experimentally based density and chemical potential data are available in the literature. We then apply it to the analysis of NaCl simulation data for two commonly used atomistic force fields. The framework can be readily extended to molten salt mixtures and to ionic liquids.

Use of molecular simulation for evaluating adsorption equilibrium of inhalation anaesthetic agents on metal–organic frameworks

“…The cut-off beyond 12.0 Å are shifted to zero without tail-correction. To account for the Coulombic interactions, partial atomic charges are calculated using the charge equilibration method [26] in electrostatic interactions with a relative precision of 10 À5 . All MOF frameworks were assumed to be rigid, but the flexibility of the adsorbate molecules was considered using available FFs in RASPA.…”

“…Table 2 summarizes critical properties of sevoflurane and desflurane based on the forcefield (FF) by Arcario et al [24] as recommended by Skvara and Smith. [26] Finally, the simulation results were validated by comparison with data from volumetric-adsorption experiments using our BELSORP-max (Bell, Japan) and are summarized independently in Supplementary Information Section I and included in combination with the graphs in the Results and Discussion Section (Section 3).…”