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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.
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
This book provides you with a sound foundation for understanding abstract concepts (eg physical properties such as fugacity, etc or chemical processes, ie distillation, etc) of phase and reaction equilibria and shows you how to apply these concepts to solve practical problems using numerous and clear examples.
Phase Equilibria in Chemical Engineering is devoted to the thermodynamic basis and practical aspects of the calculation of equilibrium conditions of multiple phases that are pertinent to chemical engineering processes. Efforts have been made throughout the book to provide guidance to adequate theory and practice. The book begins with a long chapter on equations of state, since it is intimately bound up with the development of thermodynamics. Following material on basic thermodynamics and nonidealities in terms of fugacities and activities, individual chapters are devoted to equilibria primarily between pairs of phases. A few topics that do not fit into these categories and for which the state of the art is not yet developed quantitatively have been relegated to a separate chapter. The chapter on chemical equilibria is pertinent since many processes involve simultaneous chemical and phase equilibria. Also included are chapters on the evaluation of enthalpy and entropy changes of nonideal substances and mixtures, and on experimental methods. This book is intended as a reference and self-study as well as a textbook either for full courses in phase equilibria or as a supplement to related courses in the chemical engineering curriculum. Practicing engineers concerned with separation technology and process design also may find the book useful.
This textbook takes an interdisciplinary approach to the subject of thermodynamics and is therefore suitable for undergraduates in chemistry, physics and engineering courses. The book is an introduction to phenomenological thermodynamics and its applications to phase transitions and chemical reactions, with some references to statistical mechanics. It strikes the balance between the rigorousness of the Callen text and phenomenological approach of the Atkins text. The book is divided in three parts. The first introduces the postulates and laws of thermodynamics and complements these initial explanations with practical examples. The second part is devoted to applications of thermodynamics to phase transitions in pure substances and mixtures. The third part covers thermodynamic systems in which chemical reactions take place. There are some sections on more advanced topics such as thermodynamic potentials, natural variables, non-ideal mixtures and electrochemical reactions, which make this book of suitable also to post-graduate students.
Computational tools allow material scientists to model and analyze increasingly complicated systems to appreciate material behavior. Accurate use and interpretation however, requires a strong understanding of the thermodynamic principles that underpin phase equilibrium, transformation and state. This fully revised and updated edition covers the fundamentals of thermodynamics, with a view to modern computer applications. The theoretical basis of chemical equilibria and chemical changes is covered with an emphasis on the properties of phase diagrams. Starting with the basic principles, discussion moves to systems involving multiple phases. New chapters cover irreversible thermodynamics, extremum principles, and the thermodynamics of surfaces and interfaces. Theoretical descriptions of equilibrium conditions, the state of systems at equilibrium and the changes as equilibrium is reached, are all demonstrated graphically. With illustrative examples - many computer calculated - and worked examples, this textbook is an valuable resource for advanced undergraduates and graduate students in materials science and engineering.
The classic guide to mixtures, completely updated with new models, theories, examples, and data. Efficient separation operations and many other chemical processes depend upon a thorough understanding of the properties of gaseous and liquid mixtures. Molecular Thermodynamics of Fluid-Phase Equilibria, Third Edition is a systematic, practical guide to interpreting, correlating, and predicting thermodynamic properties used in mixture-related phase-equilibrium calculations. Completely updated, this edition reflects the growing maturity of techniques grounded in applied statistical thermodynamics and molecular simulation, while relying on classical thermodynamics, molecular physics, and physical chemistry wherever these fields offer superior solutions. Detailed new coverage includes: Techniques for improving separation processes and making them more environmentally friendly. Theoretical concepts enabling the description and interpretation of solution properties. New models, notably the lattice-fluid and statistical associated-fluid theories. Polymer solutions, including gas-polymer equilibria, polymer blends, membranes, and gels. Electrolyte solutions, including semi-empirical models for solutions containing salts or volatile electrolytes. Coverage also includes: fundamentals of classical thermodynamics of phase equilibria; thermodynamic properties from volumetric data; intermolecular forces; fugacities in gas and liquid mixtures; solubilities of gases and solids in liquids; high-pressure phase equilibria; virial coefficients for quantum gases; and much more. Throughout, Molecular Thermodynamics of Fluid-Phase Equilibria strikes a perfect balance between empirical techniques and theory, and is replete with useful examples and experimental data. More than ever, it is the essential resource for engineers, chemists, and other professionals working with mixtures and related processes.
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
In this chapter, the basic methodologies of phase equilibrium engineering are introduced through the systematic analysis of several case studies. Some of the thermodynamic tools that have been presented in the previous chapters are applied to illustrate how the phase and conceptual process design of complex engineering problems can be tackled from a phase equilibrium engineering approach. In all the case studies, the first step is to consider in great detail the properties of the process feed, the components, their physical properties, concentrations, and molecular interactions. This information is then used for the selection of thermodynamic models, a suitable technology, pressure, temperature, and compositional operating boundaries. It is shown how the mixture composition and the process goals and specifications determine the process scheme and the unit thermodynamic sensitivity. In addition, the importance of the mixture composition is highlighted in combination with the energy and material balance in the case study for the selection of the desirable natural gas cryogenic technologies. The use of a pressure versus temperature drawing board is used to plot the process trajectory and the mixture phase envelopes from the initial conditions to the key phase engineering design problem. Moreover, the phase design provides also a sound basis for the process initial specification and computer simulation. As another example of phase equilibrium engineering, the heat integration in a complex process is solved by the application of the Gibbs phase rule to the LLV equilibria of a ternary mixture.
This is an on-line textbook for an Introductory General Chemistry course. Each module develops a central concept in Chemistry from experimental observations and inductive reasoning. This approach complements an interactive or active learning teaching approach. Additional multimedia resources can be found at: http: //cnx.org/content/col10264/1.5