화학공학소재연구정보센터
Chemical Physics Letters, Vol.658, 37-42, 2016
Ideality contours and thermodynamic regularities in supercritical molecular fluids
Using Expanded Wang-Landau simulations, we calculate the ideality contours for 3 molecular fluids (SF6, CO2 and H2O). We analyze how the increase in polarity, and thus, in the strength of the intermolecular interactions, impacts the contours and thermodynamic regularities. This effect results in the increase in the Boyle and H parameters, that underlie the Zeno line and the curve of ideal enthalpy. Furthermore, a detailed analysis reveals that dipole-dipole interactions lead to much larger enthalpic contributions to the Gibbs free energy. This accounts for the much higher temperatures and pressures that are necessary for supercritical H2O to achieve ideal-like thermodynamic properties. (C) 2016 Elsevier B.V. All rights reserved.