Asymmetric criticality of the osmotic compressibility in binary mixtures

J Chem Phys. 2013 Jan 14;138(2):024504. doi: 10.1063/1.4770750.

Abstract

Heat capacities in the critical and the non-critical regions for {benzonitrile + tridecane} and {benzonitrile + pentadecane}, and light scattering for {benzonitrile + undecane}, {benzonitrile + dodecane}, {benzonitrile + tridecane}, {benzonitrile + tetradecane}, {benzonitrile + pentadecane}, and {benzonitrile + hexadecane} in the critical two-phase region were measured. Light scattering measurements confirmed the existence of the asymmetry for the osmotic compressibility while no such asymmetry was observed for the correlation length. An analysis of the osmotic compressibility asymmetry suggested the dominance of the singular term |ΔT[circumflex]|(β), which supports the complete scaling theory. The consistency of the complete scaling theory in descriptions of different asymmetry behaviors was also discussed. Moreover, it was found that the contribution of the heat capacity-related term is also important in describing the asymmetry of the osmotic compressibility as it was observed in studies of the diameters of the coexistence curves.