Molecular Thermodynamics of Fluid-Phase Equilibrium (3rd Edition)

Author: John M. Prausnitz [USA]
Publisher:
Publish Date: 2006-08-31
Features: The purpose of molecular thermodynamics is to provide quantitative estimates of the equilibrium properties of mixtures required for chemical process design. In this sense, molecular thermodynamics can be considered an engineering science. To provide such estimates, molecular thermodynamics not only employs classical thermodynamics but also utilizes concepts from statistical thermodynamics and physical chemistry. The steps involved in its work can be summarized as follows: ① Use statistical thermodynamics wherever possible, at the very least, start with it; ② Apply appropriate concepts from molecular science; ③ Construct models with a solid physical foundation to express abstract thermodynamic functions in terms of measurable properties; ④ Obtain model parameters from a small amount of representative experimental data; ⑤ Implement the model through computational programs that meet the needs of engineering design. Like the previous edition, the second edition aims to provide guidance in developing molecular thermodynamics methods. The primary audience for this book is upper-level undergraduate or first-year graduate students in chemical engineering, but it will also be beneficial to engineers in the industry. When writing the second edition, I adopted a compromise approach in two aspects: on one hand, as a "scientific" book, it should emphasize molecular theory; on the other hand, as an "engineering" book, it should provide practical advice on specific design methods. Like the previous edition, this book focuses on introducing fundamental concepts and exploring how to apply them to obtain useful results. Like the previous edition, the second edition consists of 10 chapters and several appendices. Most chapters have been partially revised and updated: the main changes are in Chapters 4, 6, 7, and 8, and much of Chapter 10 is entirely new; Appendix II provides a brief introduction to statistical mechanics as a supplement to Chapter 7; Appendices VIII and IX offer an overview of specialized topics in solution theory. Additionally, many new problems have been added, which are an indispensable training for serious students. In the final appendix, numerical solutions to many of the problems are provided. Since the completion of the previous edition in 1968, remarkable progress has been made in many areas of molecular thermodynamics. Therefore, it is impossible to correctly evaluate all, even the major, advancements within the appropriate space. To avoid making the book overly lengthy, I had to omit some content that should have been included. To save space, if the contributions of some of my colleagues are not mentioned in the book, I can only ask for their understanding. Over the past 15 years, the progress in statistical thermodynamics of fluids and fluid mixtures, particularly through perturbation theory and computer simulations, has been perhaps the most promising. These advancements will undoubtedly continue and eventually find application in engineering design. However, such applications are unlikely to be realized in the near future. Therefore, for a considerable time, the semi-empirical methods discussed in this book will still be applicable. Nevertheless, students of chemical engineering must at least acquire some basic knowledge of fluid statistical thermodynamics, not only for future needs but also because modern theoretical results in statistical thermodynamics have provided many guidelines for developing semi-empirical thermodynamic property correlations. Therefore, Chapters 4, 7, and 10 also include discussions on the application of statistical thermodynamics. I am deeply grateful to many colleagues who have helped me understand molecular thermodynamics and its applications, thereby contributing to this book, among whom B. J. Alder benefited me the most. In addition to the acknowledgments mentioned in the previous edition's preface, I would like to express my gratitude to R. A. Heidemann, E. U. Franck, K. E. Gubbins, R. C. Reid, T. K. Sherwood, H. Knapp, F. Kohler, C. Tsonopoulos, L. C. Claitor, H. C. van Ness, F. Selleck, and C. J. King. I also thank my many collaborators (graduate students and visiting scholars) for bringing new insights, thought-provoking questions, and friendship. I would like to express my special thanks to the two co-authors, R. N. Lichtenthaler and E. G. Azevedo, who excellently assisted me in revising and supplementing the manuscript, making significant contributions to the publication of this book. They deserve all the credit for any achievements this book may achieve. All three authors are particularly grateful to P. Rasmussen for his rigorous review, S. F. Barreiros for compiling the index, and R. Spontak for proofreading. Most of the new and revised chapters in the second edition were written between 1978 and 1980. Unfortunately, due to various reasons, the publication was delayed, and the final manuscript was submitted to the publisher in February 1983. The second edition retains the practical engineering science features of the previous edition: while it is effective and economical to use appropriate theoretical concepts, it is also important to always keep the ultimate application goal in mind. To achieve this goal, theory alone is insufficient; in any case, some experimental data are essential. We must always maintain a proper balance between theory and practice to avoid bias. Many years ago, the pioneer of applied science, Sir Francis Bacon, recognized the necessity of maintaining this balance. He drew an analogy between scientific endeavors and the insect world. In Novum Organum (1620), Bacon wrote about ants, spiders, and bees: Those who master science are either practitioners or theorists. Practitioners are like ants, collecting and using only; theorists are like spiders, weaving webs with their own substance. But bees combine the strengths of both: they collect raw materials from gardens and fields and transform and absorb them with their own efforts. Therefore, through a closer and more perfect combination of experimental and theoretical capabilities, people can expect greater rewards. Finally, as mentioned in the preface of the previous edition, I would like to reemphasize: Research, application, and development of molecular thermodynamics are not only beneficial but also can bring joy and satisfaction. If readers are inspired and can derive as much benefit from molecular thermodynamics as I have, I will be delighted.