Cavity thermodynamics in the Gaussian model of particle density fluctuations

The thermodynamics of cavity creation emerging from the Gaussian model of particle density fluctuations are investigated. The analysis shows that the reversible work of cavity creation is dominated by entropy due to the exclusion of liquid particles from the cavity volume. The enthalpy change is due to a structural reorganization of liquid particles that is distinct from the excluded volume effect and proves to be entirely compensated for by a corresponding entropy term. These results are in line with a previous general analysis [B. Lee, J. Chem. Phys. 83 (1985) 2421].

Graphical abstractIt is analyzed the cavity thermodynamics emerging from the assumption that particle density fluctuations in liquids follow a Gaussian distribution.Download full-size image