On the relationship between volume fluctuations in liquids and the Gibbs free energy of cavity formation
Résumé
Microscopic volume fluctuations in liquids are a reflection of their structure and intermolecular energy. Microscopic volume fluctuations in liquids are associated with cavity formation. The latter is considered of fundamental importance for the solvation process. The relationship between volume fluctuations and cavity formation is investigated in the present study. Scaled particle theory calculations provide a relationship between the Gibbs free energy of cavity formation and the average density fluctuations in volume at 298 K. The already foreseen correlation between the Gibbs free energy of cavity formation and the isothermal compressibility is confirmed and adjusted using no less than 200 liquids, covering a large category of organic compounds, plus water.