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Global phase diagrams (GPD) of binary mixtures in phase equilibria modeling are analyzed. 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. One may obtain the relationships for azeotropic boundaries from the global phase diagram [A (azeotrope) and H (hetero-azeotrope)] regions. Analytical expressions to predict azeotrope and double azeotrope phenomena in terms of critical parameters of pure components were derived using global phase diagram. The problem estimations of phase behavior modeling under the uncertainty are formulated applying the Pareto-optimum parameter and different (crisp and fuzzy) convolution schemes. The Pareto-optimum parameters in the Redlich-Kwong equation of state used different conflicting data sets (simultaneous description of the phase equilibria and critical line data in binary mixtures, thermodynamically consistent description of the inhomogeneous data). Ionic liquids (ILs) are one of prospective new working media for different environmentally friendly technologies. Practically undetectable vapor pressure is considered the ILs as ideal solvents replacing conventional solvents in the frame of a ,Äúgreen chemistry.,Äù Combination of ionic liquids with conventional natural and synthetic refrigerants promotes the increasing efficiency of absorption processes due to nonvolatile ionic liquids (absorbents).
The high pressure phase behaviour of binary fluid mixtures has been extensively studied during the last three decades. There is ample experimental data for a wide variety of binary mixtures and extensive methods for prediction have been developed. In contrast, the investigation of ternary and other multicomponent fluids is in its infancy. Experimental ternary mixture critical data are very rare and theoretical studies have been limited to data correlation rather than genuine prediction. The phase behaviour of ternary and other multicomponent fluid mixtures has many novel aspects which are not manifested in binary mixtures. The properties of ternary mixtures are also likely to be more difficult to characterize experimentally. It is in this context that calculated phase diagrams have an important role in leading the discovery of new phenomena and guiding experimental work. The criteria for phase equilibria of multicomponent fluids with particular emphasis on the critical state are examined in this book, and models for predicting fluid equilibria (e.g., different equations of state) are compared. Particular attention is paid to the critical state of ternary mixtures which has hitherto been largely neglected. The problems associated with predicting ternary equilibria are discussed, and some novel aspects of ternary critical phenomena are illustrated. The books also describes a novel type of critical transition which appears to be a common feature of the equilibria of ternary mixtures. Extensive phase diagrams of a wide range of ternary mixtures including systems containing carbon dioxide, water, nitrogen and tetrafluoromethane as one or more component are presented. The theoretical treatment is detailed in the appendix and a computation of known experimental critical points is also included.
Phase Equilibrium in Mixtures deals with phase equilibrium and the methods of correlating, checking, and predicting phase data. Topics covered range from latent heat and vapor pressure to dilute solutions, ideal and near-ideal solutions, and consistency tests. Molecular considerations and their use for the prediction and correlation of data are also discussed. Comprised of nine chapters, this volume begins with an introduction to the role of thermodynamics and the criteria for equilibrium between phases, along with fugacity and the thermodynamic functions of mixing. The discussion then turns to some of the phase phenomena which may be encountered in chemical engineering practice; methods of correlating and extending vapor pressure data and practical techniques for calculating latent heats from these data; the behavior of dilute solutions both at low and high pressures for reacting and non-reacting systems; and the behavior of ideal and near-ideal solutions. The remaining chapters explore non-ideal solutions at normal pressures; practical methods for testing the thermodynamic consistency of phase data; and the extent to which the broad aspects of phase behavior may be interpreted in the light of simple molecular considerations. This book is intended primarily for graduate chemical engineers but should also be of interest to those graduates in physics or chemistry who need to use phase equilibrium data.
Phase equilibrium knowledge is required for the design of all sorts of chemical processes that may involve separations, reactions, fluids flow, particle micronization, etc. Indeed, different phase behavior scenarios are required for a rational conceptual process design. The aim of this chapter is to present the possible fluid mixture phase behavior that can be found in binary, ternary, and multicomponent systems. Moreover, representation of phase behavior in terms of phase diagrams is discussed. Dealing with phase diagrams of complex mixtures is not an easy task for beginners; however, very simple concepts are behind the rules for their construction. Phase diagrams are essential tools for phase equilibrium engineering as they provide valuable hints to understand the process and to assess the feasible and optimum operating regions. In this chapter, the “phenomenological” meaning of each phase behavior and its relation with molecular properties is discussed. A special attention is given to binary system phase behavior. Even though, in practice we rarely found such simple mixtures, they furnish a great deal of information for the understanding of multicomponent systems.
This chapter starts with the analysis of the distillation path of binary mixtures on the general phase behavior P–T diagram of binary mixtures. The univariant lines of these diagrams limit the region of vapor–liquid equilibria where binary distillation can be applied. On this basis, the conditions under which distillation is possible for types I, II, IV, and V of binary mixtures are discussed. Furthermore, in this chapter, the principles of fractional distillation, as well as the computational procedures, are discussed. The thermodynamic modeling of a train of distillation columns to separate the components of an ethane-cracked gas mixture is used to develop a strategy for an equation of state parameter tuning. This strategy is based on the analysis of the distillation column phase equilibrium sensitivity and leads to an unique matrix of equation of state dominant binary parameters for the whole fractionation train. The chapter ends with a list of phase equilibrium engineering guidelines to make a realistic design/simulation of distillation columns.