Hydrogen Bonding and Vaporization Thermodynamics in Hexafluoroisopropanol-Acetone and -Methanol Mixtures. A Joined Cluster Analysis and Molecular Dynamic Study

G Marchelli and J Ingenmey and O Holloczki and A Chaumont and B Kirchner, CHEMPHYSCHEM (2021).

DOI: 10.1002/cphc.202100620

Binary mixtures of hexafluoroisopropanol with either methanol or acetone are analyzed via classical molecular dynamics simulations and quantum cluster equilibrium calculations. In particular, their populations and thermodynamic properties are investigated with the binary quantum cluster equilibrium method, using our in-house code Peacemaker 2.8, upgraded with temperature-dependent parameters. A novel approach, where the final density from classical molecular dynamics, has been used to generate the necessary reference isobars. The hydrogen bond network in both type of mixtures at molar fraction of hexafluoroisopropanol of 0.2, 0.5, and 0.8 respectively is investigated via the molecular dynamics trajectories and the cluster results. In particular, the populations show that mixed clusters are preferred in both systems even at 0.2 molar fractions of hexafluoroisopropanol. Enthalpies and entropies of vaporization are calculated for the neat and mixed systems and found to be in good agreement with experimental values.

Return to Publications page