Kinetics and mechanism of the reaction of Ozone with Aliphatic alcohols

Kinetic parameters of the reaction of ozone with aliphatic alcohols of different structures are obtained. The ratio between the relative reactivities of the primary: secondary: tertiary alcohols was found to be 1:15:138. The bond energy changes in the same sense as the activation energy. The rate‐controlling step of ozone reaction with alcohols is the abstraction of a hydrogen atom being in α‐position with respect to the OH group. The pre‐exponential factors (A) are calculated by the collision and activated complex methods and compared with the experimentally obtained values. The results from the calculations represent convincing evidence that the mechanism of the rate‐controlling step of the reaction is associated with the formation of an activiated complex which has a linear shape ensuring free rotation of its fragments.