Gibbs thermodynamics and surface properties at the nanoscale

Gibbs's classical thermodynamic framework approximates systems as infinitely large phases separated by infinitely thin surfaces. The range of validity of this classical framework naturally comes under scrutiny as we become interested in the properties of ever smaller systems. This Communication clarifies that while Gibbs's original framework of bulk phase thermodynamics did require modifications to describe the properties of very small (i.e., non-additive) phases, his classical framework remains fundamentally valid to describe the thermodynamic properties of surfaces. We explain why classical surface laws are applicable at the nanoscale, as suggested by simulations and confirmed by experiments. We also show that a generalized Gibbs-Tolman-Koenig-Buff equation and the resulting Tolman's law for surface tension are obtained from a classical thermodynamic analysis in the Tolman region, a region of interaction between the system and the environment.