Nature of vapor-liquid asymmetry in fluid criticality.
We have investigated the nature and experimental consequences of vapor-liquid asymmetry in near-critical fluids within the framework of "complete scaling" [M. E. Fisher and G. Orkoulas, Phys. Rev. Lett. 85, 696 (2000); Y. C. Kim, Phys. Rev. E 67, 061506 (2003)]. We used the thermodynamic freedom for a choice of the critical-entropy value to simplify "complete scaling" to a form with only two independent parameters, responsible for two different sources of the asymmetry. We then developed a procedure to obtain these two parameters from mean-field equations of state. By combining accurate liquid-vapor coexistence and heat-capacity data, we have unambiguously separated two nonanalytic contributions from the two sources of vapor-liquid asymmetry and proved the validity of "complete scaling." Since the nonanalytic asymmetry effects in the critical region are fully determined by the Ising critical exponents for the symmetric lattice-gas model, there is no need for a special renormalization-group theoretical treatment of "non-Ising" asymmetry in fluid criticality.
Department of Chemical and Biomolecular Engineering and Institute for Physical Science and Technology, University of Maryland, College Park, MD 20742, USA.
Jingtao
J
Wang
Mikhail A
MA
Anisimov