Curvature dependence of Henry's law constant and nonideality of gas equilibrium for curved vapor-liquid interfaces

Curved interfaces between coexisting vapor and liquid phases are ubiquitous in nature, and the question of whether the Henry's law is applicable for highly curved vapor/liquid interfaces remains unsolved. Using stable surface nanobubbles that have highly curved interfaces as examples, we investigate the viability of Henry's law with molecular simulations and thermodynamic analysis. We show that the prediction of Henry's law displays an increasingly deviation from the simulation results as nanobubble curvature increases. Such a curvature dependence of Henry's law constant is ascribed to the nonideality of gas in liquid phase because of the required gas supersaturation for stabilizing nanobubbles. Based on the effect, we develop a relationship for determining Henry's law constant from the level of gas supersaturation, as well as a robust relationship between gas supersaturation and nanobubble radius.