Infinite dilution fugacity coefficients and the general behavior of dilute binary systems

Abstract A universally valid formal expression for the composition dependence of solute and solvent fugacity coefficients in any dilute binary system far from criticality is derived in this paper. In the present context, dilution denotes the y1 → O limit, regardless of the mixture's molar density. The results are independent of the system under study and of the choice of equation of state. The solute fugacity coefficient is simply the product of a composition‐independent term (the infinite dilution fugacity coefficient) and an exponential decay composition correction. These two parameters have important thermodynamic implications: their temperature and pressure derivatives are related to the solute's partial molar enthalpy and volume, respectively. When applied to activity coefficients, the same theoretical analysis yields universal relationships for the composition dependence of activity coefficients which can be used as consistency checks for empirical correlations. The relationship between infinite dilution activity and fugacity coefficients can be used to estimate relative solubilities of a given solute in different solvents. Excellent agreement is found when the theoretical expressions are tested with three different binary systems involving a nonvolatile solid solute and a supercritical fluid.