Asymmetric criticality in weakly compressible liquid mixtures.

J Chem Phys

Departamento de Física Aplicada, Universidad de Vigo, As Lagoas s/n, Ourense 32004, Spain.

Published: April 2010

AI Article Synopsis

  • The paper updates the thermodynamics of asymmetric liquid-liquid criticality by including pressure effects in the scaling framework for liquid mixtures.
  • It demonstrates that pressure mixing influences weakly compressible liquid mixtures due to the pressure-dependent nature of critical parameters.
  • The research analyzes coexistence-curve data across various binary liquid mixtures and clarifies how asymmetry coefficients relate to the molecular volumes of the components, addressing a longstanding question about the "best order parameter."

Article Abstract

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.

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http://dx.doi.org/10.1063/1.3378626DOI Listing

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