화학공학소재연구정보센터
Journal of Physical Chemistry B, Vol.103, No.24, 5106-5116, 1999
Configurational properties and corresponding states in simple fluids and water
Using accurate equations of state, contributions to the configurational entropy and energy of water are calculated and compared with six simple fluids and a model Lennard-Jones (LJ) fluid. The reorganizational entropy is calculated for the first time for water and other fluids. Comparisons are made at equal reduced densities from the triple point to the gas-liquid critical temperature. A corresponding states principle (CSP), suggested by the van der Waals model, is satisfied for certain configurational properties among the simple and LJ fluids. Saturated simple liquids in states of-equal free volume fractions have comparable configurational properties. Water deviates significantly from the CSP in some but not all cases, The normal boiling point of eight simple fluids is seen to be an isofree volume state that occurs at a reduced density (rho/rho(c)) of 2.63 +/- 0.02, or equivalently, an occupied volume fraction of 0.42. A nearly invariant entropy of vaporization at the normal boiling point among eight simple fluids ((9.1 +/- 0.3)k) is one manifestation of the CSP (Trouton's rule). The LJ model fluid accurately describes the configurational properties of argon and methane. This result lends credibility to the wide spread use of the LJ potential to describe atom-atom (or site-site) interactions in large and complex molecules.