Reaction kinetics of O(3P) with acrylonitrile and crotononitrile

The reaction of oxygen atoms O(3P) with unsaturated nitriles (RCN), viz. acrylonitrile (CH2=CHCN), and crotononitrile (CH3CH=CHCN), was studied in a flow discharge tube in the pressure range 1.2–1.7 Torr using the O(3P) chemiluminescence titration method. The rate constants for the reaction O(3P) + RCN → products was determined at room temperature to be (4.9 ± 1.0) × 10−13 and (5.4 ± 0.8) × 10−13 cm3 molecule−1 s−1 for acrylonitrile and crotononitrile respectively. The activation energies for the above reactions were estimated using the MNDO method. The formation of a biradical involving the addition of an oxygen atom to the double bond is proposed as the major channel for the reaction.