Principle of isomorphism and complete scaling for binary-fluid criticality.

The extension of the principle of critical-point universality to binary fluid mixtures, known as isomorphism of critical phenomena, has been reformulated in terms of complete scaling, a concept that properly matches asymmetric fluid-phase behavior with the symmetric Ising model. The controversial issue of the proper definition of the order parameter in binary fluid mixtures is clarified. We show that asymmetry of liquid-liquid coexistence in terms of mole fractions originates from two different sources: one is associated with a correlation between concentration and entropy fluctuations, whereas the other source is the correlation between concentration and density fluctuations. By analyzing the coexistence curves of liquid solutions of nitrobenzene in a series of hydrocarbons (from n -pentane to n -hexadecane), we have separated these two sources of asymmetry and found that the leading nonanalytical contribution to the asymmetry correlates linearly with the solute-solvent molecular-volume ratio. Other thermodynamic consequences of complete scaling for binary mixtures, such as an analog of the Yang-Yang anomaly in the behavior of the heat capacity and a curvature correction to the interfacial tension, are also discussed.