309f The Nature of Asymmetry in Fluid Criticality

Mikhail A. Anisimov and Jingtao Wang. University of Maryland, Department of Chemical and Biomolecular Engineering, University of Maryland, College Park, MD 20742

We address a controversial issue of liquid-gas asymmetry in fluids that has been a subject of prolonged discussions for more than a century since Cailletet and Mathias' discovery of the empirical "law' of rectilinear diameter. By combining accurate liquid-vapor coexistence and heat-capacity data, we have unambiguously separated two non-analytical contributions of liquid-gas asymmetry in fluid criticality and proved the validity of "complete scaling" [Fisher et al., Phys. Rev. Lett. 85, 696 (2000)]. We have also developed a method to obtain two scaling-field coefficients, responsible for the two sources of the asymmetry, from mean-field equations of state. Since the asymmetry effects are completely determined by Ising critical exponents, there is no need for a special renormalization-group theoretical treatment of asymmetric fluid criticality.