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The title of this volume edited by Z. B. Alfassi, General Aspects of Free Radical Chemistry, implies that the book is written to provide the reader with a broad overview of introductory material about radical chemistry. The topics covered in its fifteen chapters are very heavily weighted toward theoretical and physical aspects of radical chemistry, with only one short section dealing with synthetic applications, one chapter on polymers, and none dealing with biological aspects of radicals. This is reasonable, in light of the adequate coverage of these topics in several reasonably current and available books. In fact, one of the strengths of this book is that Alfassi manages to avoid the pitfalls common to edited volumes by usually maintaining the focus of the articles within the apparent theme while still providing enough breadth to warrant the use of the term "general" in the title. The primary goal of this book is to provide a broad survey of important information relevant to the theoretical and physical aspects of radical chemistry. Particular attention is paid throughout the book to the experiments and theoretical models available to obtain this data.
Four chapters on the measurement of rate constants for radical reactions in the gas and liquid phases and on the redox potentials of organic and inorganic molecules survey and compare physical methods for obtaining this data, as well as important experimental variables to be considered. The redox chapters and a chapter on the thermochemistry of free radicals include valuable tabulation of experimental and theoretical results, which should prove of value to practicing radical scientists, and provide references to the primary literature for all data. There is very little in the way of actual rate constant data in the chapters focused on kinetics.
The more theoretically oriented chapters cover topics including abstraction and addition reactions and numerical simulations of free-radical dynamics. These chapters compare the outcomes of the various models with each other and with known experimental data when possible. An entire chapter is devoted to ESR spectroscopy and focuses on experimental aspects and interpretation of spectra, rather than theoretical aspects of the technique. A similar chapter on CIDNP would have been a nice addition, but the technique only receives scant coverage within the context of several articles.
Other chapters in this volume are on combination and disproportionation reactions, radical ions, reactions in supercritical fluids, correlations between rate parameters and molecular properties, and the empirical correlation of solvent effects in free-radical chemistry. The final chapter, dealing with organic syntheses using radical reactions, seems rather out of place in this book heavily weighted toward physical methodology. Nonetheless, it is very well presented, and manages to cover the most important radical reactions relevant to synthetic organic chemists, with particular stress given to issues related to control of stereochemistry. It would provide a superb introduction to radicals in synthesis for a second- or third-year graduate student in synthetic organic chemistry who was preparing for cumulative exams or starting a project along these lines.
Some sections, most notably the short chapters on ESR and the thermochemistry of free radicals, are written at a level appropriate for graduate students early in their studies, or even particularly advanced undergraduates. However, most of the articles, after a short introduction, plunge into material more suitable for scholars at a more advanced level. While the price ($295.00) is a bit steep for the private collections of most individuals, it would make a valuable and unique addition to the libraries of institutions where one or more research groups are actively engaged in studies involving radicals. It would be particularly valuable for researchers already expert in some aspects of radical chemistry who wish to become familiar with other applications. For these researchers, this book will provide an efficient means of establishing familiarity with basic concepts and will provide for a focused entry into the primary literature on the topics of interest.
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