The following review was written by Marc-Olivier Coppens and published in Angewandte Chemie, International Edition, volume 45(08), pp. 1183-84, 2006.

Thermodynamics: Fundamentals for Applications

John P. O'Connell and J.M. Haile
Cambridge University Press, New York and London, 2005.

Albert Einstein was deeply impressed by classical thermodynamics, it being the

"only physical theory of universal content, which [he was] convinced, that within the framework of applicability of its basic concepts will never be overthrown."

The Laws of Thermodynamics are indeed so fundamental that all chemical processes either rely on them or need to account for them as a boundary condition. Therefore, thermodynamics is one of the most important subjects for chemical engineering students. However, the practical engineering relevance stands in stark contrast to the rather abstract scientific formalisms, making thermodynamics also one of the most challenging subjects to teach, to learn, or to write a textbook on.

Well aware of these challenges, O'Connell and Haile are weathered experts in the field, and in teaching thermodynamics. This clearly shows in their new textbook, which is primarily intended for beginning graduate students in chemical engineering. Their experience is visible through the special care they take to gradually build up the subject with the utmost attention to details, from a qualitative discussion on the "Primitives," via the development of the Fundamentals (Part 1), to the scientific derivations for single-phase systems (Part 2), non-reacting and reacting multi-phase systems (Part 3), and finally to a number of engineering applications (Part 4).

This structured, systematic approach void of vague terminology is very suitable for graduate students. Each of the four Parts of the book starts with a diagram that shows how the three chapters within a Part are related to each other and which key information they introduce. The book reads like a beautiful story, written in the language of calculus, which is also the classical language of thermodynamics. The mathematically inclined reader will immediately appreciate this clear, formal approach. But also engineers and chemists with little prior exposure to thermodynamics should find this book useful as a reference text, because the authors managed not to obscure the text by unnecessarily difficult symbols and formulas: The Appendix provides all the necessary mathematical background, the derivations are easy to follow, some sections can be skipped without losing the thread, and the handy list of notations includes the location where a symbol is used for the first time.

Another strong point of the book is that it always attempts to justify why a new term is introduced, not just formally, but also in the human language appealing to engineers wishing to apply these concepts. More precisely, a clear distinction is made between abstract "conceptuals" like entropy or internal energy and practical "measurables" like pressure and temperature. While the conceptuals are the necessary ingredients to build the thermodynamic fundamentals, linking them to measurables is essential for engineering applications. The authors do a superb job in establishing these links in a natural, didactic way.

There are many creative exercises, and a number of worked out examples. Less applications are discussed than some engineers may wish—however, this is a defendable choice, because, as the authors state it: "Truly fundamental concepts are permanent and universal, it is only the applications that go in and out of style." (p.8; p. 588). Researchers may nevertheless wish to complement this book with a text focussing on particular applications (refrigeration and power cycles, fuel cells, supercritical fluids, hydrates, polymers and other complex fluids, etc.) as well as with "The Properties of Gases and Liquids," the 5th edition of which happens to be co-authored by the first author (B.E. Poling, J.M. Prausnitz, and J.P. O'Connell, McGraw-Hill, New York, 2001).

Every author needs to make the hard choice of which interesting material to nevertheless skip, especially when it comes to such a field as broad as thermodynamics. The authors explicitly took a classical approach, i.e., with minimum reference to statistical mechanics and the molecular basis of thermodynamics. This is one aspect that I somewhat regret. Richard Feynman wrote his Lecture Notes in Physics based on the philosophy that the newest scientific breakthroughs and modern concepts should be included even in a first-year undergraduate (freshman) course: Why only discuss Newton and wait with quantum physics and the theory of relativity until later years? Even if graduate students might have a separate course on statistical mechanics, I have to agree with Feynman, and would have liked to see more excursions to density functional theory, kinetic theory and the molecular basis that is essential for many of the applications today's graduate students encounter when dealing with confined environments, supramolecular chemistry, and various applications in nanotechnology. Chapter 8, on "Criteria for Observability," discusses metastability in a brilliant, yet classical way; why not make students at least aware of the existence of Onsager's powerful formalism of non-equilibrium thermodynamics?

This point aside, and given the chosen context of classical thermodynamics, the book excells. Feynman was also convinced that we have not really understood a subject unless we can explain it at the freshman level. This book may have been written with first-year graduate students in mind, but an undergraduate with the right mathematical background should also be able to read it, to the credit of O'Connell and Haile, who certainly "understand" their subject at a very deep level. Excellent writers, they are able to convey their deep understanding to us, and their book should make many students enthusiastic about thermodynamics.

To bring classical thermodynamics to life in such an appealingly vivid yet also mathematically rigorous way is an accomplishment that makes this book highly recommendable.


Marc-Olivier Coppens is in the Department of Physical Chemistry and Molecular Thermodynamics at Delft University of Technology, The Netherlands.