Solvation thermodynamics of gas solubility at sub- and near-critical conditions

The recently developed formalism for describing the solute‐induced effect in dilute near‐critical mixtures is extended to fluids composed of anisotropic molecules through the statistical mechanical interpretation of the derivative (∂P/∂x2) T,p∞ whose critical value is the Krichevskii parameter. Rigorous expressions for Henry's constant and the solute distribution factor along the orthobaric curve are derived in terms of the volumetric and entropic solute‐induced local effects, and the quasi‐linear behavior of their orthobaric density dependence away from the solvent's critical point is rationalized. The formalism is illustrated with integral equation calculations of the orthobaric density dependence of several solvation thermodynamic quantities for an infinitely dilute volatile solute in near‐critical solutions of hard‐sphere Yukawa fluids.