Scaled particle theory study of the length scale dependence of cavity thermodynamics in different liquids.

It has been noted that the work of cavity creation in water exhibits a crossover behavior, in that its cavity size dependence changes from volume dependence for small cavities to area dependence for larger cavities [Lum, K.; Chandler, D.; Weeks, J. D. J. Phys. Chem. B 1999, 103, 4570]. It is shown here that this behavior can be reproduced using the scaled particle theory in a straightforward manner for six different liquids (water, methanol, ethanol, benzene, cyclohexane, and carbon tetrachloride). It has also been suggested that the crossover is due to a change in the physical mechanism of the process, from one entropy-dominated to another enthalpy-dominated. However, the crossover behavior can be produced using the scaled particle theory without invoking any change in any physical mechanism. Also, the crossover occurs at a length scale of the size of the liquid molecules, as has been pointed out by others. This is the length regime where the work of cavity creation bears little relation to the bulk liquid surface tension. In addition, it is pointed out that cavity creation can always be considered as a purely entropy-driven process, which is usually accompanied by another process with compensating enthalpy and entropy changes.