Condensed-phase solvolysis

This analysis of temperature effects and kinetics in chemical ionization must be considered as tentative and in need of further verification. However, if it is correct, or substantially correct, the activation energies for comparable reactions provide measures of the relative energies of product ions produced by the thermal decompositions, and the frequency factors provide information about entropies of activation. It is clear that reactions such as those producing benzyl ion, (28) and (29), are analogous to A lI acid-catalyzed solvolysis reactions in solution, and we suggest that the significance of the kinetic quantities in the gas-phase chemical ionization process is analogous with that in condensed-phase solvolysis. In the gas phase, solvent interactions are absent, and the prospect is that much new and valuable information will be obtained from this technique. 

This volume seeks in a small way to bridge the wide gap between organic chemistry in the gas and condensed phases. The same types of chiral ion-dipole complexes that form as intermediates of solvolysis may be generated in the gas phase by allowing neutral molecules to cluster with chiral cations. The reactions of these chiral clusters have been characterized in exquisite detail by mass spectrometry. The results of this work are summarized by Maurizio Speranza in a chapter that is notable for its breadth and thoroughness of coverage. This presentation leaves the distinct impression that further breakthroughs on the problems discussed await us in the near future. 

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