Global phase behavior of supercritical water - environmentally significant organic chemicals mixtures.

Recent developments of the global phase equilibria studies of binary mixtures provide some basic ideas of how the required methods can be developed based on global phase diagrams for visualization of the phase behavior of mixtures. The mapping of the global equilibrium surface in the parameter space of the equation of state (EoS) model provides the most comprehensive system of criteria for predicting binary mixture phase behavior. The main types of phase behavior for environmentally significant organic chemicals in aqueous environments are considered using structure-property correlations for the critical parameters of substances. Analytic expressions for azeotropy prediction for cubic EoS are derived. A local mapping concept is introduced to describe thermodynamically consistently the saturation curve of water. The classes of environmentally significant chemicals (polycyclic aromatic hydrocarbons - PAH, polychlorinated biphenyls - PCB, polychlorinated dibenzo-p-dioxins and furans, and selected pesticides) are considered and main sources of the property data are examined. Vapor pressure, heat of vaporization, and critical parameter estimations for pure components were chosen for seeking a correlation between the octanol-water partition coefficients KOW and the EoS binary interaction parameters - k12. The assessment of thermodynamic and phase behavior of representatives for different pollutants is given. [ABSTRACT FROM AUTHOR]