FT-IR kinetic and product study of the Br-radical initiated oxidation of α, β-unsaturated organic carbonyl compounds

Using the relative kinetic technique the kinetics of the gas-phase reactions of Br radicals with acrolein, methacrolein and methylvinyl ketone have been investigated at (301±3) K in 1013 mbar of (N2+O2) bath gas at varying proportions. In 1013 mbar of synthetic air the following rate coefficients have been obtained (in units of cm3 molecule−1 s−1): acrolein (3.21±0.11)×10−12; methacrolein (2.33±0.08)×10−11; methyl vinyl ketone (1.87±0.06)×10−11. This study represents the first determination of the rate coefficients for these compounds. As for other unsaturated hydrocarbons the rate coefficient with Br was found to increase with increasing partial pressure of O2. From the product studies of the reactions it has been established that addition of Br radicals to the terminal C-atom is the major pathway in all three cases. However, for acrolein H atom abstraction from the -CO–H group is also significant. Mechanisms are proposed to explain the observed products, mainly β-brominated carbonyl compounds.