Original scientific paper

The Upper Limit on Rates of Proton Transfer

A. I. Hassid ; Chemical Dynamics Laboratory, University of Minnesota, Minneapolis, Minnesota 55455, U.S.A.
T.-M. Liang ; Chemical Dynamics Laboratory, University of Minnesota, Minneapolis, Minnesota 55455, U.S.A.
R. Eliason ; Chemical Dynamics Laboratory, University of Minnesota, Minneapolis, Minnesota 55455, U.S.A.
M. M. Kreevoy ; Chemical Dynamics Laboratory, University of Minnesota, Minneapolis, Minnesota 55455, U.S.A.

Abstract

The Bronsted plot for hydrolysis of diphenyldiazomethane by
carboxylic acids is smooth but curved, approaching an asymptotic
limit below 10 mo1-1 dm3 s-1• Regardless of the details of the theory
used, such a limit requires that the transition state is approached
via a state (or virtual state) substantially (- 70 kJ mol-1) above the
starting state in free energy, but still having an intact bond from
H+ to its original conjugate base. Such a state has been called a
reaction complex,6 and is thought to be analogous to the intimate
ion pair of solvolysis reactions.

Keywords

Hrčak ID:

196149

URI

https://hrcak.srce.hr/196149

Publication date:

26.4.1978.

Visits: 640 *