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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.
* Guidelines are provided on the reliability of various methods, as well as information for selecting the appropriate technique. * Unique coverage of the whole range of solubility measurements. * Very useful for investigators interested in embarking upon solubility measurements.
This chapter illustrates the wide variety of binary fluid phase equilibrium diagrams that can be obtained using models based on equations of state (EOS). It also highlights the need for paying attention to the predicted binary key lines, such as the critical and the liquid–liquid–vapor equilibrium lines, when fitting binary interaction parameters of an EOS model. In addition, efficient algorithms for the EOS-based automated computation of complete Univariant Lines Phase Equilibrium Diagrams and of complete restricted binary phase equilibrium diagrams, such as isoplethic, isothermal, or isobaric diagrams, are described.
Supercritical fluids are neither gas nor liquid, but can be compressed gradually from low to high density and they are therefore interesting and important as tunable solvents and reaction media in the chemical process industry. By adjusting the density the properties of these fluids can be customised and manipulated for a given process - physical or chemical transformation. Separation and processing using supercritical solvents such as CO2 are currently on-line commercially in the food, essential oils and polymer industries. Many agencies and industries are considering the use of supercritical water for waste remediation. Supercritical fluid chromatography represents another, major analytical application. Significant advances have recently been made in materials processing, ranging from particle formation to the creation of porous materials. The chapters in this book provide tutorial accounts of topical areas centred around: (1) phase equilibria, thermodynamics and equations of state; (2) critical behaviour, crossover effects; (3) transport and interfacial properties; (4) molecular modelling, computer simulation; (5) reactions, spectroscopy; (6) phase separation kinetics; (7) extractions; (8) applications to polymers, pharmaceuticals, natural materials and chromatography; (9) process scale-up.
Traditionally, the teaching of phase equilibria emphasizes the relationships between the thermodynamic variables of each phase in equilibrium rather than its engineering applications. This book changes the focus from the use of thermodynamics relationships to compute phase equilibria to the design and control of the phase conditions that a process needs. Phase Equilibrium Engineering presents a systematic study and application of phase equilibrium tools to the development of chemical processes. The thermodynamic modeling of mixtures for process development, synthesis, simulation, design and optimization is analyzed. The relation between the mixture molecular properties, the selection of the thermodynamic model and the process technology that could be applied are discussed. A classification of mixtures, separation process, thermodynamic models and technologies is presented to guide the engineer in the world of separation processes. The phase condition required for a given reacting system is studied at subcritical and supercritical conditions. The four cardinal points of phase equilibrium engineering are: the chemical plant or process, the laboratory, the modeling of phase equilibria and the simulator. The harmonization of all these components to obtain a better design or operation is the ultimate goal of phase equilibrium engineering. Methodologies are discussed using relevant industrial examples The molecular nature and composition of the process mixture is given a key role in process decisions Phase equilibrium diagrams are used as a drawing board for process implementation
The book begins with an overview of the phase diagrams of fluid mixtures (fluid = liquid, gas, or supercritical state), which can show an astonishing variety when elevated pressures are taken into account; phenomena like retrograde condensation (single and double) and azeotropy (normal and double) are discussed. It then gives an introduction into the relevant thermodynamic equations for fluid mixtures, including some that are rarely found in modern textbooks, and shows how they can they be used to compute phase diagrams and related properties. This chapter gives a consistent and axiomatic approach to fluid thermodynamics; it avoids using activity coefficients. Further chapters are dedicated to solid-fluid phase equilibria and global phase diagrams (systematic search for phase diagram classes). The appendix contains numerical algorithms needed for the computations. The book thus enables the reader to create or improve computer programs for the calculation of fluid phase diagrams. introduces phase diagram classes, how to recognize them and identify their characteristic features presents rational nomenclature of binary fluid phase diagrams includes problems and solutions for self-testing, exercises or seminars
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.