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In the preface to his excellent textbook,
Thermodynamics: Principles and Applications (Wiley-Interscience,
1971), Frank C. Andrews remarks, "It is almost an act of
intellectual arrogance to write another thermodynamics text these
days, so many and varied are the texts already available." Since
I first read it, Andrews's comment has been my standard
for judging new thermodynamics textbooks: what does a
new book offer that is significantly different, and better, than
one of the many fine books already on my shelf?
Modern Thermodynamics by Dilip Kondepudi, Professor of Chemistry at
Wake Forest University, and 1977 Nobel Laureate Ilya Prigogine
does provide something quite different: a historically
conscious, integrated approach to both equilibrium and
nonequilibrium thermodynamics.
The essential role of fluctuations in determining
the properties of equilibrium and nonequilibrium systems
was first elucidated by Einstein at the turn of the century.
Subsequently, Lars Onsager used fluctuation theory to
demonstrate the famous reciprocal relations that provide the basis for
the theory of linear nonequilibrium thermodynamics.
Unfortunately, thermodynamics is often taught to chemists as if
it only applies to uniform equilibrium systems. Fluctuations
are rarely mentioned. One of the unusual features of this
book is that it begins by explicitly discussing both nonuniform
and nonequilibrium systems. While most of the traditional
topics of a course in chemical thermodynamics are included in
this book, these applications are treated in the context of a
more general formalism that can be used to discuss both linear
and nonlinear nonequilibrium systems.
Another interesting and important feature of this
book is the integration of historical material into the
presentation. While the presentation follows the usual
sequencepreliminary concepts, first law, second law, etc.the ideas are placed
in a historical context as they are developed. As expected,
there is considerable emphasis on the contributions of
Theophile De Donder, founder of the Brussels school of
thermodynamics. The text is generously illustrated with portraits of many of
the important figures in the development of
thermodynamics. The stories and pictures help to make the subject come alive.
The first 11 chapters of the book provide material for a
one-semester course in equilibrium thermodynamics.
The overall coverage in this section is fairly standard,
including real gases, solutions, electrochemical systems, and
phase transitions. As noted above, the important difference in
this presentation is that the traditional topics are presented in
terms of a general formalism that leads naturally to the
discussion of both nonuniform and nonequilibrium systems.
Chapters 12-19 explicitly consider fluctuations and stability
theory, linear nonequilibrium thermodynamics, and, finally,
nonlinear systems and dissipative structures. Each chapter is
followed by a number of problems and students are encouraged to
use Mathematica or Maple to do the more tedious
calculations. A brief appendix to Chapter 1 includes some
sample Mathematica codes. The book has relatively few
worked examples, however, so students who need to see a
lot of examples will have to look elsewhere. Unfortunately,
there are no worked examples in Chapters 12-19.
Since I first learned nonequilibrium
thermodynamics from Prigogine's earlier book, Introduction to the
Thermodynamics of Irreversible Processes (Interscience, 1961), I
found the treatment in the second part of the book to be clear
and logical. I think that most readers will agree. There is a
nice treatment of Gaussian fluctuation theory and a proof of
the Onsager reciprocal relations. Chapters 18 and 19 provide
an introduction to the most important ideas in
nonlinear nonequilibrium thermodynamics, including stability
analysis. The book concludes with a chapter on the frontiers
of research in thermodynamics.
As the title promises, this book is a modern treatment
of the full scope of thermodynamics emphasizing the
importance of fluctuations. I hope that the appearance of this
accessible treatment will stimulate faculty to rethink their teaching
of thermodynamics and present it as a general and powerful
way to understand both equilibrium and nonequilibrium systems.
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