Connect the Thermodynamics of Bulk and Confined Fluids: Confinement-Adsorption Scaling.

A fluid (a gas or a liquid) adsorbed in a porous material can behave very differently from its bulk counterpart. The advent of various synthesized materials with nanopores and their wide applications have provided strong impetus for studying fluids in confinement because our current understanding is still incomplete. From a large number of Monte Carlo simulations, we found a scaling relation that allows for connecting some thermodynamic properties (chemical potential, free energy per particle, and grand potential per particle) of a confined fluid to the bulk ones. Upon rescaling the adsorbed fluid density, the adsorption isotherms for many different confining environments collapse to the corresponding bulk curve. We also reveal the intimate connection of the reported scaling relation to Gibbs theory of inhomogeneous fluids and morphological thermodynamics. The advance in our understanding of confined fluids, gained from this study, also opens attractive perspectives for circumventing experimental difficulty for directly measuring some fluid thermodynamic properties in nanoporous materials.