title: Theoretical study on the gas phase reaction of acrylonitrile with a hydroxyl radical.
abstract: The mechanism and kinetics of the reaction of acrylonitrile (CH(2)=CHCN) with hydroxyl (OH) has been investigated theoretically. This reaction is revealed to be one of the most significant loss processes of acrylonitrile. BHandHLYP and M05-2X methods are employed to obtain initial geometries. The reaction mechanism conforms that OH addition to C[double bond, length as m-dash]C double bond or C atom of -CN group to form the chemically activated adducts, 1-IM1(HOCH(2)=CHCN), 2-IM1(CH(2)=HOCHCN), and 3-IM1(CH(2)=CHCOHN) via low barriers, and direct hydrogen abstraction paths may also occur. Temperature- and pressure-dependent rate constants have been evaluated using the Rice-Ramsperger-Kassel-Marcus theory. The calculated rate constants are in good agreement with the experimental data. At atmospheric pressure with N(2) as bath gas, 1-IM1(OHCH(2)=CHCN) formed by collisional stabilization is the major product in the temperature range of 200-1200 K. The production of CH(2)CCN and CHCHCN via hydrogen abstractions becomes dominant at high temperatures (1200-3000 K).
authors.affiliation: Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun, Jilin, PR China.
authors.forename: Jingyu
authors.initials: J
authors.lastname: Sun
authors.forename: Rongshun
authors.initials: R
authors.lastname: Wang
authors.forename: Baoshan
authors.initials: B
authors.lastname: Wang
mesh_terms: D000181:Acrylonitrile / Q000737:chemistry*; D005740:Gases / Q000737:chemistry; D017665:Hydroxyl Radical / Q000737:chemistry*; D011789:Quantum Theory; D013696:Temperature
chemical_list: D005740:Gases; D017665:Hydroxyl Radical; D000181:Acrylonitrile