Abstract
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 K OW and the EoS binary interaction parameters – k 12. The assessment of thermodynamic and phase behavior of representatives for different pollutants is given.
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References
van Konynenburg, P. H. and Scott, R. L. (1980) Critical lines and phase equilibria in binary van der Waals mixtures, Phil. Trans. Roy. Soc. London 298, 495-540.
Furman, D. and Griffiths, R. B. (1978) Global phase diagram for a van der Waals model of a binary mixture, Phys. Rev A 17, 1139-1149.
Boshkov, L. Z. (1992) The phase tree of binary fluids: principle, development and thermodynamics, Proc. Int. Symp. On Solubility Phenomena, pp.12-13.
Mazur, V. A., Boshkov, L. Z., and Murakhovsky, V. G. (1984).Global phase behavior in binary Lennard-Jones mixtures, Phys. Lett. A 104, 415-418.
Deiters, U. K. and Pegg, J. L. (1989) Systematic investigation of the phase behavior of binary fluid mixtures. I. Calculations based on the Redlich-Kwong equation of state, J. Chem. Phys. 90, 6632-6641.
Soave, G. (1972) Equilibrium constants from a modified Redlich-Kwong equation of state, Chem. Eng. Sci. 27, 1197-1203.
Nebelenchuk, V. and Mazur, V. (1991) Transport properties of dense fluids via spherical models of the interaction potential, Physica A 178, 123-148.
Mollerup, J. (1998) Unification of the two-parameter equation of state and the principle of corresponding states, Fluid Phase Equilibria 148, 1-19.
Wagner, W. and Pruß, A. (2002) The IAPWS formulation 1995 for the thermodynamic properties of ordinary water substance for general and scientific use, J. Phys. Chem. Ref. Data 31, 387-535.
Boshkov, L. Z. and Mazur, V. A. (1985) Phase behaviour of the two-component Lennard-Jones fluid, Dep. at the VINITI, No. 6844-B85.
Sadus, R. and Wang, Ji. (2003) Phase behaviour of binary mixtures: a global phase diagram solely in terms of pure component properties, Fluid Phase Equil. 214, 67-78.
Wakeham, W., Cholakov, G., and Roumiana, S. (2002) Liquid density and critical properties of hydrocarbons estimated from molecular structure, J. Chem. Eng. Data 47, 559-570.
Tsonopoulos, C. and Wilson, G. M. (1983) High-temperature mutual solubilities of hydrocarbons and water, AIChE J. 29(6), 990-993.
Tsonopulos, C. (1999) Thermodynamic analysis of the mutual solubilities of normal alkanes and water, Fluid Phase Equil. 156, 21-33.
Polischuk, I., Wisniak, J., and Segura, H. (2003) Simultaneous prediction of the critical and subcritical phase behaviour in mixtures using equations of state. II Carbon dioxide - heavy n-alkanes, Chem. Eng. Sci. 58, 2529-2550.
Delle Site, A. (1996) Vapor pressure of environmentally significant organic chemicals: A review of methods and data at ambient temperature, J. Phys. Ref. Data 26, 157-193.
Verhaar, H., Ramos, E., and Hermens, J. (1996) Classifying environmental pollutants. 2.: Separation of class 1 (baseline toxity) and class 2 (polar narcosis) type compounds based on chemical descriptors, Journal of Chemometrics 10, 149-162.
Hehre, W., Burke, L., and Shusterman, A.(1993) SPARTAN User’s Guide (Wavefuncion. Inc., Irvine, CA).
Alwani, Z. and Schneider, G., (1967) Phase equilibria and critical phenomena in the system benzene - H2O between 250 and 368 °C up to 3700 bar, Ber. Bunsenges. Phys. Chem. 71, p.633.
Connolly, J. (1966) Solubility of hydrocarbons in water near the critical solution temperature, J. Chem. Eng. Data 11, 13.
Sangster, J. (1997) Octanol-Water Partition Coefficients: Fundamentals and Physical Chemistry (John Willey & Sons Inc., NY).
Mazur, V., Boshkov, L., and Artemenko, S. (1998) Global phase behaviour of natural refrigerant mixtures, Proc. IIR-Gustav Lorentzen Conference: Natural Working Fluids, 495-504.
Kolafa, J. (1999) Azeotropic phenomena in the global phase diagram of the Redlich- Kwong equation of state, Phys. Chem. Chem. Phys. 1, 5665-5670.
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Artemenko, S.V., Mazur, V.A. (2007). Global phase behavior of supercritical water – environmentally significant organic chemicals mixtures. In: Rzoska, S.J., Mazur, V.A. (eds) Soft Matter under Exogenic Impacts. NATO Science Series II: Mathematics, Physics and Chemistry, vol 242. Springer, Dordrecht. https://doi.org/10.1007/978-1-4020-5872-1_18
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DOI: https://doi.org/10.1007/978-1-4020-5872-1_18
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