Chemical Engineering Science, Vol.63, No.6, 1490-1496, 2008
A new generalized corresponding-states equation of state for the extension of the Lee-Kesler equation to fluids consisting of polar and larger nonpolar molecules
The Lee-Kesler equation of state for the thermodynamic properties of small nonpolar fluids is extended to all fluids consisting of polar and larger nonpolar molecules, based on the general corresponding-states theory for highly nonspherical fluids. The thermodynamic functions are represented by an analytical equation of state. The results for polar fluids are substantially better than those obtainable from other currently available methods, while the results for nonpolar fluids are equivalent to and mostly better than those obtained by the Lee-Kesler method. The input data required are the critical temperature, the critical volume, the acentric factor and the aspherical factor, which is related to the critical compression factor; the critical volume is therefore required in the present method. The method developed in this work shows good accuracy for 15 representative nonpolar, polar, hydrogen bonding and associating fluids and provides a simple method for industrial applications. Average deviations for the compressibility factor, the heat capacity and the speed of sound for six nonpolar and nine polar fluids from the new equation of state are 0.74%, 2.1% and 2.3%, which are about 8 times smaller than those obtained from the Lee-Kesler equation (about 5.6%, 17% and 29%, respectively). (C) 2007 Elsevier Ltd. All rights reserved.
Keywords:corresponding states;equation of state;fundamental equation;Helmholtz energy;Lee-Kesler equation;nonpolar;nonspherical;phase equilibria;polar;supercritical fluid;theory of liquids;thermodynamic properties