KrF laser induced telomerization of bromides with olefins. Part 1. Self-inhibition and kinetic analysis

Article abstract of DOI:10.1002/bbpc.19900940810

The chain reaction of several organic bromides with olefins was induced by a KrF laser. In all cases we found a self-inhibition, leading to a termination of first order in the radical concentration. There is indirect evidence that it is due to molecular bromine, accumulated during the reaction in spite of the presence of olefins. It has not been noticed previously. We show that kinetic analysis is easy also for pulsed excitation, and the example CF₃Br + C₂H₄ is studied in detail. We found rate constants for CF₃ + C₂H₄ → CF₃C₂H₄ (7.2·10⁹ cm³ mol^-1 s^-1; this is in between two previous values) and for CF₃C₂H₄ + CF₃Br → CF₃C₂H₄Br + CF₃(1.2·10⁹ cm³ mol^-1 s^-1) as well as preliminary values for some other reactions.