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- W2001904000 abstract "Recent studies of the effect of high pressure upon the rates of redox, solvent exchange, nucleophilic substitution and hydrolysis reactions are reviewed. Quantitative predictions of volumes of activation for outer-sphere electron transfer processes are used to interpret redox reactions of uncertain mechanism. Both the volume of activation, and its pressure dependence, may be used to diagnose dissociative and associative substitution processes and also to ascertain the participation of solvent molecules in transition states. INTRODUCTION The effect of pressure upon the rate of a chemical reaction m 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 and these volumes may now be used routinely to interpret reaction mechanisms. 1' Address as from June 1973 Department of Inorganic Chemistry The University of Mel bourne, Parkville, Victoria 3052, Australia." @default.
- W2001904000 created "2016-06-24" @default.
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- W2001904000 date "1974-01-01" @default.
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- W2001904000 title "The elucidation of inorganic reaction mechanisms by high pressure studies" @default.
- W2001904000 doi "https://doi.org/10.1351/pac197438030303" @default.
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