C lassical thermodynamics presents broad relationships between macroscopic properties, but it is not concerned with quantitative prediction of these properties. Statistical thermodynamics, on the other hand, seeks to establish relationlships between macroscopic properties and intermolecular forces through partition functions; it is very much concerned with quantitative prediction of bulk properties. However, useful configurational partition functions have been constructed only for nearly ideal situations and, therefore, statistical thermodynamics is at present insufficient for many practical purposes.
Molecular thermodynamics seeks to overcome some of the limitations of both classical and statistical thermodynamics. Molecular phase-equilibrium thermodynamics is concerned with application of molecular physics and chemistry to the interpretation, correlation, and prediction of the thermodynamic properties used in phase-equilibrium calculations. It is an engineering science, based on classical thermodynamics but relying on molecular physics and statistical thermodynamics to supply insight into the behavior of matter. In application, therefore, molecule thermodynamics is rarely exact; it must necessarily have an empirical flavor.
In the present work I have given primary attention to gaseous and liquid mixtures. I have been concerned with the fundamental problem of how best to calculate fugacities of components in such mixtures; the analysis should therefore be useful to engineers engaged in design of equipment for separation operations. Chapters 1, 2, and 3 deal with basic thermodynamics and, to facilitate molecular interpretation of thermodynamic properties, Chapter 4 presents a brief discussion of intern~olecular forces. Chapter 5 is devoted to calculation of fugacities in gaseous mixtures and Chapter 6 is concerned with excess functions of liquid mixtures. Chapter 7 serves as an introduction to the theory of liquid solutions with attention to both "physical" and "chemical" theories. Fugacities of gases dissolved in liquids are discussed in Chapter 8 and those of solids dissolved in liquids in Chapter 9. Finally, Chapter 10 considers fluid-phase equilibria at high pressures.
While it is intended mainly for chemical engineers, others interested in fluidphase equilibria may also find the book useful. It should be of value to university seniors or first-year graduate students in chemistry or chemical engineering who have completed a standard one-year course in physical chemistry and who have had some previous experience with classical thermodynamics.
The subjects discussed follow quite naturally from my own professional activities. Phase-equilibrium thermodynamics is a vast subject, and no attempt has been made to be exhaustive. I have arbitrarily selected those topics with which I am familiar and have omitted others which I am not qualified to discuss; for example, I do not consider solutions of metals or electrolytes. In essence, I have written about those topics which interest me, which I have taught in the classroom, and which have comprised much of my research. As a result, emphasis is given to results from my own research publications, not because they are in any sense superior, but because they encompass material with which I am most closely acquainted.
Molecular Thermodynamics of Fluid-Phase Equilibria
Prausnitz, J. M. | Prentice Hall | ISBN 0-13-599564-7 | 1986 | PDF/RAR | 20,2 MB
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