Bond cooperativity and ring formation in hydrogen fluoride thermodynamic properties: A two-density formalism framework

Abstract

In this work, we develop a thermodynamic perturbation theory using a two-density formalism framework to model the bond cooperativity effect for associating hard sphere and Lennard-Jones fluids. The theory predictions are compared with Monte Carlo simulation results and they are in excellent agreement. We incorporate bond angle dependent ring formation into the theory to calculate hydrogen fluoride thermodynamic properties. The liquid density and vapor pressure obtained by the theory are in good agreement with the experimental data. Comparing the thermo-physical properties of hydrogen fluoride calculated by this theory with previous studies reveals the importance of bond angle dependent ring formation and cooperative hydrogen bonding to capture its anomalous behavior especially in the vapor phase. The cooperativity ratio obtained in our model is close to the values reported by previous quantum studies.