Physical Chemistry. By Peter Atkins

Physical Chemistry. By Peter Atkins, Oxford University Press: Oxford, U.K. xvi + 997 pp. £28.99. Includes CD. ISBN 0-19-850101-3. Student’s Solutions Manual and Instructor’s Solutions Manual are also available.

Hugh Cartwright, Physical and Theoretical Chemistry Laboratory, Oxford University, Hugh.Cartwright@chem.ox.ac.uk

It is perhaps appropriate that this, the one hundredth media review in The Chemical Educator, should have as its subject one of the modern classics in chemistry textbooks: Physical Chemistry, by Peter Atkins.

In contrast with the Arts, in science one gets used to the regular appearance of new editions of established, successful textbooks. Many of us, when undergraduates, will have been encouraged to buy a new edition of a textbook when it appeared, rather than choosing the cheaper option of buying an older edition at a knock-down price from a colleague. We might at the time have wondered if the primary motivation of publishers who introduce new editions of established textbooks is to make money. The topics covered in most general undergraduate textbooks do not change much from year to year, so why should new editions be required, if it is not that publishers (and their authors) would like the extra money? If not to make money, could the need for a new edition perhaps be that earlier editions were so full of errors that a new edition must be printed to correct them?

Once one gets beyond being a poor (and skeptical) undergraduate, most scientists become less jaundiced about the appearance of new editions. Peter Atkins’ textbook has now reached its sixth edition—a rare, but certainly not unheard-of degree of maturity in chemistry publishing—so there has been plenty of opportunity to weed out errors since the book first made an appearance in 1978. There are substantial changes in this edition, and these maintain its steady evolution over a period of more than two decades. Few errors must remain; I have come across none so far. There have been changes to the contents of chapters, to the very large number of figures, to the problems and to the Further Reading sections. These changes are not mere tinkering with the text, but introduce significant improvements.

As in previous editions, this text covers physical chemistry in considerable depth (there are almost one thousand pages in this edition) and with rigor. The book is divided into three broad sections, covering “Equilibrium,” “Structure,” and “Change”. A glance at the chapter titles provides an indication of the coverage. The section on “Equilibrium” includes chapters entitled: The properties of gases, The First Law: the concepts, The First Law: the machinery, The Second Law: the concepts, The Second Law: the machinery, Physical transformations of pure substances, Simple mixtures, Phase diagrams, Chemical equilibrium, and Equilibrium electrochemistry.

“Structure” opens with chapters titled Quantum theory: introduction and principles, and Quantum theory: techniques and applications. These are followed by Atomic structure and atomic spectra, Molecular structure, Molecular symmetry, Spectroscopy 1: rotational and vibrational spectra, Spectroscopy 2: electronic transitions, Spectroscopy 3: magnetic resonance, Statistical thermodynamics: the concepts, Statistical thermodynamics: the machinery, Diffraction techniques, The electric and magnetic properties of molecules, and Macromolecules and colloids.

The final section of the book, “Change,” includes the chapters: Molecules in motion, The rates of chemical reactions, The kinetics of complex reactions, Molecular reaction dynamics, Processes at solid surfaces, and Dynamic electrochemistry.

The author has managed to retain the flexibility characteristic of earlier editions, which allows lecturers in different institutions, who may teach chemistry in an order quite different to that adopted in the book, to still use this as their primary text. This is no mean feat, bearing in mind the way in which the different parts of the subject are interconnected.

To a degree, the style reflects the approach to physical chemistry in the undergraduate program at Oxford University, where Atkins has taught for many years, with the emphasis which that course has on fundamental principles. More applied areas, such as colloids and fuel cells make an appearance, but one senses that these form a kind of side show, brought in primarily to illustrate the principles of the subject; throughout, the emphasis is on the core material of physical chemistry.

The fine-tuning which one would expect to result from the production of six editions over twenty years is apparent in various ways. The writing, as in all of Atkins’ books, is a model of clarity. No attempt is made to avoid mathematics—indeed the mathematical soundness of Physical Chemistry has always been one of its strengths—but it is introduced and used without overwhelming the qualitative treatment of topics. Figures are simple, clear, and relevant; very many of them have been redrawn or redesigned for this edition. Tables of data in the textbook are generally brief—often consisting of four or five lines—and provide just the right amount of information to illustrate the arguments in the body of the text.

Helpfully, numerous tables are then expanded in the Appendices, which provide fuller numerical data on such diverse topics as diffusion coefficients, screening constants, isothermal compressibilities, third-law entropies, Henry’s law constants, electronic affinities, and numerous other parameters. End-of-chapter problems have been revised and expanded (there are around one thousand in all) and microprojects, which bring together topics from several chapters within a section to form more challenging tasks, have been added.

Broad-based and thorough the book certainly is, but no instructor would ever admit to liking every morsel in a textbook (unless he or she is the author). I was occasionally disappointed to find that a “mechanical” or mathematical explanation of a physical phenomenon was chosen over a descriptive one, when a combination of the two might have been more effective.

For example, Atkins takes the conventional approach to explain why a change in pressure may affect the position of equilibrium in a gas phase reaction, using Le Chatelier’s principle. The explanation, in terms of an equilibrium constant, is one with which many students will be familiar—the position of equilibrium moves so as to try to nullify the change imposed upon the system—but why do chemical systems behave in this way? This approach, in which Le Chatelier’s principle is given as a simple statement of fact, mirrors that which is adopted in most textbooks, but it does not address the question of how the position of equilibrium responds through changes at the molecular level to alterations in the values of parameters such as the pressure. How do individual molecules know that they must obey Le Chatelier? Le Chatelier’s principle is often taught to students in this fashion, and when asked for an explanation in physical terms they not surprisingly fail to come up with anything meaningful, even though explanations in terms of what the molecules themselves are doing are straightforward.

In a discussion of spectroscopy, Atkins points out that infrared transitions between molecular vibrational levels for which |D v| > 1 are weak, and therefore difficult to observe. This is followed almost immediately by a discussion of Birge–Sponer extrapolation, which, for its success, requires knowledge of the position of many vibrational levels. Some readers may be left wondering how, if few transitions to vibrational energy levels can be observed, it is possible to determine the position of a sufficiently large number to carry out the extrapolation. The explanation is simple, but appears in a quite different portion of the text.

The CD that accompanies Physical Chemistry was something of a disappointment. Repeated revision of the text has refined it into an impressive and satisfying work, but the CD by comparison seems rather unimaginative. Instead of detailed and flexible simulations that might enhance the text, most of the animations fail to illustrate chemistry in a particularly dynamic or interesting way; in truth, they are rather dull. Much of the CD is taken up with textual or mathematical material that mirrors what is presented in the text, and while the CD may offer a marginally faster way of finding information on some topics, I suspect that most lecturers (and students) may find it of limited value. It is unfortunate that the quality of the CDs which accompany textbooks these days seems all too often to fall below the quality of the texts themselves; I have yet to find one that I would regularly use with my students.

These are minor criticisms, though. Overall, Physical Chemistry continues to be the book by which other texts are judged. There is considerable competition in this area—several impressive textbooks are available—but it is hard to match the authority and readability of this book. It is one of perhaps a dozen textbooks in chemistry that instructors all over the world would recognize. Indeed the name of the author occupies an area on the cover of the book three times as great as the title—a telling indication of the respect that the name Peter Atkins commands in scientific publishing.

Not every lecturer will find the level of the textbook appropriate for their course; those working in liberal arts colleges, for example, may find the depth and rigor are greater than they require. However, Atkins’ writing remains as clear and persuasive as ever. This book provides solid value, whether one is building a library in chemistry from scratch, or simply ensuring one’s understanding is up-to-date. It should be an essential item on the shelf of every practicing chemist; indeed, if there is room on the shelf for only one physical chemistry textbook, this should be it.