Gp. Smith et al., RELATIONSHIP BETWEEN BOND-DISSOCIATION ENERGIES AND ACTIVATION-ENERGIES FOR BOND SCISSION REACTIONS, International journal of chemical kinetics, 26(1), 1994, pp. 211-217
Bond dissociation energies are frequently derived from values of the h
igh pressure activation energy for bond scission reactions. The value
derived depends on the transition state structure chosen for the react
ion. We consider several models of the transition state and show that
the variation in derived BDE values can be quite substantial, 3 to 6 k
cal/mol at the high temperatures of pyrolysis kinetics. Application of
the restricted Gorin model of the transition state results in BDE val
ues in good agreement with current thermochemistry, while the other mo
dels tested result in lower to much lower values. (C) 1994 John Wiley
and Sons, Inc.