Photooxidation of 1,3‐butadiene containing systems: Rate constant determination for the reaction of acrolein with ⋅OH radicals

The photooxidation of the 1,3‐butadiene–NO–air system at 298 ± 2 K was investigated in an environmental chamber under simulated atmospheric conditions. The irradiation gave rise to the formation of acrolein in a 55% yield, based on 1,3‐butadiene initial concentration for all the experimental runs. The rate of formation of acrolein was the same as that of 1,3‐butadiene consumption, indicating that acrolein is the major product of the 1,3‐butadiene oxidation in air. The dependence of acrolein concentration on irradiation time showed thata secondary process, identified as an oxidation of acrolein by ⋅OH radicals, was occurring during the photochemical runs. The rate constant of this secondary process was determined by measuring the relative rates of disappearance of acrolein and n‐butane during the irradiation of acrolein‐n‐butane‐NO‐air mixtures. The so obtained relative rate constant value was placed on an absolute basis using a reported rate constant for the n‐butane + ⋅OH reaction; a ...