High Resolution Variable Pressure NMR for Chemical Kinetics

  • André E. Merbach
  • J. W. Akitt
Part of the NMR Basic Principles and Progress book series (NMR, volume 24)

Abstract

In order to study chemical kinetics with any precision it is necessary to have good resolution similar to that accepted for normal analytical studies, and excellent control of temperature. We show how it has been possible to satisfy these two requirements with a high pressure probe constructed for use at the highest magnetic fields. The use of high pressure NMR is then illustrated by a series of specific examples which involve widely differing exchange rates and which embrace a range of rate constants varying over 18 orders of magnitude. The majority of the systems discussed are of solvent exchange on solvated cations, but an example of electron exchange and one of fluxional processes within a protein are also included. The examples illustrate well the unique understanding that knowledge of activation volumes gives to mechanistic processes and the inherent superiority of volume determinations over entropy determinations alone. The specific examples are followed by a more concise overall review of work in the field dealing with solvation complexes of a variety of geometries and with rate processes at pressure in the areas of bioinorganic, organometallic and organic chemistry.

Keywords

Benzene Acetonitrile MeOH Allyl Rhodium 

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Copyright information

© Springer-Verlag, Berlin Heidelberg 1990

Authors and Affiliations

  • André E. Merbach
    • 1
  • J. W. Akitt
    • 1
  1. 1.Institut de chimie minérale et analytiqueUniversité de LausanneLausanneSwitzerland

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