Publisher's Synopsis
The effect of pressure upon the rate of a chemical reaction in solution is attributed to a volume change which occurs in the activation step of that reaction. If the change in volume on activation is negative, then the reaction is accelerated by an increase of pressure; if the volume change is positive, then the reaction is retarded by an increase of pressure. This review aims to show how such volume changes can be interpreted to yield information on the detailed molecular rearrangements which make up the reaction mechanisms of inorganic complexes. Authoritative and comprehensive reviews of the application of these ideas to organic systems are available, but little is available for inorganic systems. A major reason for this is that only in the last four years has any body of systematic data begun to accumulate for inorganic reactions in solution. In principle, the interpretation of a volume change is based on inferred changes in nuclear positions. This involves a structural concept which should be intrinsically simpler to handle than the alternative concept of an entropy change which depends on inferred changes in both nuclear positions and energy. Traditionally, reaction mechanisms have been interpreted in terms of enthalpies and entropies of activation because the effect of temperature on reaction rates is readily investigated in the laboratory. However, simplifications in modem high pressure techniques and equipment now make volumes of activation readily accessible. This book may now be used routinely to interpret reaction mechanisms. It is intended that this book will be a valuable reference to the students and teachers of chemistry and biochemistry.. -
