Infrared chemiluminescence studies of chlorine substitution reactions with brominated unsaturated hydrocarbons

Abstract
The arrested relaxation infrared chemiluminescence technique has been used to investigate the chlorine atom substitution reactions of various olefinic compounds and bromobenzene. Analysis of the infrared emission spectra of the reaction products allows the determination of the product vibrational energy distribution. The observed vibrational energy distributions are compared to those which would be obtained if the products exhibited a statistical vibrational energy distribution. It was found that for the aromatic substrate the product vibrational energy distribution was statistical, while nonstatistical distributions were obtained for olefinic substrates in which Cl was substituted for Br. The implications of the results are discussed in the framework of the current theory of intramolecular energy transfer.