title: Kinetics of enol formation from reaction of OH with propene.
abstract: Kinetics of enol generation from propene has been predicted in an effort to understand the presence of enols in flames. A potential energy surface for reaction of OH with propene was computed by CCSD(T)/cc-pVDZ//B3LYP/cc-pVTZ calculations. Rate constants of different product channels and branching ratios were then calculated using the Master Equation formulation (J. Phys. Chem. A 2006, 110, 10528). Of the two enol products, ethenol is dominant over propenol, and its pathway is also the dominant pathway for the OH + propene addition reactions to form bimolecular products. In the temperature range considered, hydrogen abstraction dominated propene + OH consumption by a branching ratio of more than 90%. Calculated rate constants of enol formation were included in the Utah Surrogate Mechanism to model the enol profile in a cyclohexane premixed flame. The extended model shows consistency with experimental data and gives 5% contribution of ethenol formation from OH + propene reaction, the rest coming from ethene + OH.
authors.affiliation: Henry Eyring Center for Theoretical Chemistry, Department of Chemistry, University of Utah, Salt Lake City, Utah 84112, USA.
authors.forename: Lam K
authors.initials: LK
authors.lastname: Huynh
authors.forename: Hongzhi R
authors.initials: HR
authors.lastname: Zhang
authors.forename: Shaowen
authors.initials: S
authors.lastname: Zhang
authors.forename: Eric
authors.initials: E
authors.lastname: Eddings
authors.forename: Adel
authors.initials: A
authors.lastname: Sarofim
authors.forename: Matthew E
authors.initials: ME
authors.lastname: Law
authors.forename: Phillip R
authors.initials: PR
authors.lastname: Westmoreland
authors.forename: Thanh N
authors.initials: TN
authors.lastname: Truong
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D003198:Computer Simulation; D004583:Electrons; D000431:Ethanol / Q000031:analogs & derivatives* / Q000737:chemistry*; D017665:Hydroxyl Radical / Q000737:chemistry*; D007700:Kinetics; D008956:Models, Chemical; D008958:Models, Molecular; D008968:Molecular Conformation; D020005:Propanols / Q000737:chemistry*
chemical_list: D000475:Alkenes; D020005:Propanols; D017665:Hydroxyl Radical; D000431:Ethanol; C006463:allyl alcohol; C013658:propylene