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The knowledge of thermodynamic properties and phase equilibria of pure and mixture fluids is crucial for the design, development and optimization of chemical, biochemical, and environmental engineering (Sandler, 2006). Conventional thermodynamic models, containing empirical or semi-empirical parameters, are very useful for the correlation of experimental data and have limited predictive capability for conditions beyond the experimental measurements. While a large amount of thermodynamic experiments have been conducted over the past decades, it has been estimated that about 2000 new chemicals are being synthesized everyday (Campbell, 2008). It would be a daunting and impractical task attempting to obtain the thermodynamic properties of these new chemicals and their mixtures with existing chemicals from experiment. Experimental determination of thermodynamic properties can also be quite challenging because of the toxic nature of some chemicals and the conditions of interest may reach the detection limit of modern apparatus (low vapor pressure, infinite dilution, etc.). It is therefore highly desirable to have a reliable means to estimate these important data prior to measurements, or even before the synthesis of the chemicals. In this chapter, we illustrate how the thermodynamic properties and phase behavior of fluids can be obtained from the combination of advances in computational chemistry and the theories of statistical and classical thermodynamics. Instead of regression to experimental data, the model parameters in an equation of state, such as the PengRobinson equation of state (Peng & Robinson, 1976), can be determined from the results of first principle solvation calculations. The consequence is a completely predictive approach for almost any thermodynamic properties of all types of fluids (pure and mixture) at all conditions (above and below the critical point) without the need of any experimental data. We show that this is a practical approach for the prediction of pure fluid properties (Hsieh & Lin, 2008) such as the vapor pressure, liquid density, the critical temperature and pressure, as well as the vapor-liquid (Hsieh & Lin, 2009b), liquid-liquid (Hsieh & Lin, 2010), and solid-liquid phase equilibria of mixture fluids. This method also allows for accurate predictions of the distribution of a trace amount of pollutant between two partially miscible liquids, such as the octanol-water partition coefficient (Hsieh & Lin, 2009a). Conventionally, models were developed for a certain specific property of interest.

Obtaining Thermodynamic Properties and Fluid Phase Equilibria without Experimental Measurements