TABLE OF CONTENTS The term physical organic chemistry is commonly attributed to Louis Hammett, who used it in the title of a book in 1940. 1 Previously, in the 1930s books dealing with essentially the same area of chemistry had referred to physical aspects of organic chemistry [2] and modern theories of organic chemistry. [3] According to Hammett, the term implied the investigation of the phenomena of organic chemistry by quantitative and mathematical methods. He noted that one of the chief directions that the development of the subject had taken had been the study by quantitative methods of the mechanism of reactions and of the related problem of the effect of structure and environment on reactivity.
Hammett's view of the scope of the subject is summarized in the rarely mentioned sub-title of his book: Reaction Rates, Equilibria, and Mechanisms . His conception of the subject still defines its core, but requires amplifying; certain other topics are now usually deemed part of physical organic chemistry. Thus the rationalization of the experimental results of studies of reaction rates, equilibria, and mechanisms involves the application of the electronic theory of the structures and reactions of organic molecules, either in its early forms as developed by Robinson, Ingold, and others on the basis of the electron-pair covalent bond, or in its later forms involving quantum mechanical treatments.
The application of physical techniques to the study of the...
