Asymmetric criticality in weakly compressible liquid mixtures.

The thermodynamics of asymmetric liquid-liquid criticality is updated by incorporating pressure effects into the complete-scaling formulation earlier developed for incompressible liquid mixtures [C. A. Cerdeirina et al., Chem. Phys. Lett. 424, 414 (2006); J. T. Wang et al., Phys. Rev. E 77, 031127 (2008)]. Specifically, we show that pressure mixing enters into weakly compressible liquid mixtures as a consequence of the pressure dependence of the critical parameters. The theory is used to analyze experimental coexistence-curve data in the mole fraction-temperature, density-temperature, and partial density-temperature planes for a large number of binary liquid mixtures. It is shown how the asymmetry coefficients in the scaling fields are related to the difference in molecular volumes of the two liquid components. The work resolves the question of the so-called "best order parameter" discussed in the literature during the past decades.

Heat capacity and thermal expansion anomalies in the nitromethane-1-butanol mixture near its upper critical point.

The heat capacity per unit volume C(p) and density rho of the nitromethane-1-butanol critical mixture near its upper consolute point are determined in this work. C(p) data are obtained at atmospheric pressure as a function of temperature in the one-phase and two-phase regions, using a differential scanning calorimeter. The suitability of DSC for recording C(p) as a function of T in the critical region is confirmed by measurements of the nitromethane-cyclohexane mixture, the results being quite consistent with reported data. By fitting the C(p) data in the one-phase region, the critical exponent alpha is found to be 0.110+/-0.014-and hence consistent with the universal accepted value-and the critical amplitude A(+)=0.0606+/-0.0006 J K(-1) cm(-3). Rho data were only obtained in the one-phase region, using a vibrating tube densimeter. The amplitude of the density anomaly was found to be C(+)(1)=-0.017+/-0.003 g cm(-3), which is moderately low in spite of the large difference between the densities of the pure liquids. The thermodynamic consistency of the A+ and C+1 values was examined in relation to the previously reported value for the slope of the critical line dT(c)/dp. The results of this analysis were consistent with previous work on this matter.