K. King, R. Gilbert
May 1, 1980
Citations
0
Influential Citations
6
Citations
Journal
International Journal of Chemical Kinetics
Abstract
The thermal unimolecular decomposition of bromocyclobutane has been investigated over the temperature range of 791–1224 K using the technique of very low-pressure pyrolysis (VLPP). HBr elimination is the sole mode of decomposition under the experimental conditions. No evidence could be found for the ring-cleavage pathway to ethylene and vinyl bromide. Assuming a four-center transition state and an Arrhenius A factor the same as that for HCl elimination from chlorocyclobutane, RRKM calculations show that the experimental unimolecular rate constants are consistent with the Arrhenius expression where θ = 2.303RT kcal/mol. The activation energy is higher than that for the open-chain analog, 2bromobutane. This finding is consistent with the results for the corresponding chloro and iodo compounds.