(455g) Scaled-Particle Theory and the Thermodynamics of Solvation Over a Range of States

The hydrophobic effect plays a predominant thermodynamic impetus for self-assembly. Theories of the hydrophobic driving force typically parse solvation into the introduction of a hard  excluded volume solute into solution followed by the addition of realistic attractive van der Waals interactions. Scaled particle theory describes the process of introducing hard excluded volume cavities into solution over a range of sizes, from the molecular scale to macroscopic scale solutes, relevant to self-assembly processes. In this presentation, we describe ongoing work in our group in applying scaled particle theory to dissolution in aqueous, organic, Lennard-Jones, and Hard Sphere solvents. We also consider dissolution in the Lennard-Jones solvent from state points along the saturation curve well into the compressed liquid, as well as the extension of scaled particle theory to cylindrical solutes. Results from simulations of model solvents are applied to water as a solvent as well in an effort to interpret hydrophobic contributions to solvation over a range of conditions.