Thermodynamics of associating systems
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The Peng-Robinson equation of state (PR EOS) is incorporated with the infinite linear association model and the monomer-dimer association model as well as two different sets of mixing rules to result in four different forms of equations of state. The reformulated PR EOS have been used to represent the vapor pressures and liquid densities of pure associating compounds. The vapor pressure and liquid density values calculated by means of the reformulated PR EOS are in good agreement with the experimental data in the literature.The application of the reformulated PR EOS could be extended to represent the VLE behavior of associating systems. The capabilities of different association-incorporated EOS are compared with the Hong-Hu equation, the AMH equation and the Wilson equation, respectively. The results show that, in general, the reformulated PR EOS are superior to the Wilson equation for all tested systems with the exception of alkanol-hydrocarbon systems and at least as good as the Hong-Hu equation, the AMH equation, although the number of tested systems from Hong and Hu and Nan et al. are less than the one from the present work.The excess molar enthalpies of the ethanol-n-hexane and the ethanol-cyclohexane systems at 298.15 K were measured in an LKB 2107 microcalorimeter and compared with the experimental data in the literature. Additionally, new excess molar enthalpy data, measured at 298.15 K, have been reported for the ethanol-n-hexane-cyclohexane ternary system in the present work. Smooth representations of the results are described and used to construct contours of constant enthalpy on a Roozeboom diagram. The reasonable estimates of the excess enthalpies of the three constituent-binary mixtures can be obtained from both the Liebermann-Fried model and the Flory theory. Finally, an attempt has been made to represent, simultaneously, both VLE and excess enthalpy behavior of the ethanol-n-hexane and ethanol-cyclohexane systems by using the Wilson equation and one of the reformulated PR EOS. Both the reformulated PR EOS and the Wilson equation could be extended to predict the ethanol-n-hexane-cyclohexane ternary system at 298.15 K with the binary interaction parameters determined from the experimental VLE data of the three constituent-binary mixtures. The calculated results show that the reformulated PR EOS is better than or as good as the Wilson equation in predicting the excess enthalpies of selected binary and ternary systems involving one associating species. However, quantitative discrepancies with the experimental data are observed.
DegreeDoctor of Philosophy (Ph.D.)
CommitteeVerrall, Ronald E.; Phoenix, Aaron; Hill, Gordon A.; Ward, Dale E.
Copyright DateAugust 2006
Excess enthalpy behavior