Foundations of Chemical Kinetics

Chemical kinetics, the study of the rates of chemical reactions, can be studied at a number of levels and from different perspectives. In a student's initial exposure, the emphasis is typically on the development of rate laws, the relationships between concentrations and rates, and on the Arrhenius dependence of the rate constants on temperature. This leads to a discussion of reaction mechanisms and of their relationship to reaction rates. These basic ideas allow students to engage in practical experimental studies of kinetics in every area of chemistry and biochemistry. Eventually though, students will start to ask deeper questions. Why do apparently similar reactions sometimes have very different rates? Is the Arrhenius relationship universal? Can we predict rate constants, or only measure them? This book focuses on the foundational theories of chemical kinetics, the key ideas that provide a basis for thinking about the factors that determine, at the level of individual reactive events, the rates of chemical reactions. In favorable cases, these theories even allow us to calculate rate constants using computational tools that are, by now, widely available to students.

The first part of the book covers gas-phase kinetics, while the second focuses on reactions in solution. Whenever possible, we turn from theoretical discussions to step-by-step descriptions of calculation procedures, enabling students to directly apply the theories described. Additional chapters and appendices provide background material necessary to apply these theories.

This book is intended for undergraduate students and new graduate students who have had the typical introduction to chemical kinetics and now want to go deeper. While the basic theory has perhaps not changed all that much in the last few decades, the availability of powerful desktop computers has revolutionized how this subject can be taught. Now, well-selected examples can be carried out on standard laptop computers. Students can therefore go beyond learning the theory to applying it. The aim is that students will leave with an appreciation of the theory of chemical kinetics and the calculation of rate constants even in more complex cases. Accompanied by detailed examples using Gaussian (with GaussView) and Matlab , this practical hands-on book provides a first step towards doing more sophisticated calculations as part of a research project.