title: Hill's small systems nanothermodynamics: a simple macromolecular partition problem with a statistical perspective.
abstract: Using a simple example of biological macromolecules which are partitioned between bulk solution and membrane, we investigate T.L. Hill's phenomenological nanothermodynamics for small systems. By introducing a system size-dependent equilibrium constant for the bulk-membrane partition, we obtain Hill's results on differential and integral chemical potentials μ and [Formula: see text] from computations based on standard Gibbsian equilibrium statistical mechanics. It is shown that their difference can be understood from an equilibrium re-partitioning between bulk and membrane fractions upon a change in the system's size; it is closely related to the system's fluctuations and inhomogeneity. These results provide a better understanding of nanothermodynamics and clarify its logical relation with the theory of statistical mechanics.
authors: Department of Applied Mathematics, University of Washington, Seattle, WA 98195-2420 USA.
authors: Hong
authors: H
authors: Qian
keywords: Ensemble; Fluctuation; Nanothermodynamics; Small systems; Statistical mechanics