Kinetics study of the OH + alkene --> H2O + alkenyl reaction class.
In this paper we report on the kinetics of hydrogen abstraction for the OH + alkene reaction class, using the reaction class transition state theory (RC-TST) combined with the linear energy relationship (LER) and the barrier height grouping (BHG) approaches. Parameters for the RC-TST were derived from theoretical calculations using a set of 15 reactions representing the hydrogen abstractions from the terminal and nonterminal carbon sites of the double bond of alkene compounds. Both the RC-TST/LER, where only reaction energy is needed at either density functional theory BH&HLYP or semiempirical AM1 levels, and RC-TST/BHG, where no additional information is required, are found to be promising methods for predicting rate constants for a large number of reactions in this reaction class. Detailed error analyses show that, when compared to explicit theoretical calculations, the averaged systematic errors in the calculated rate constants using both the RC-TST/LER and RC-TST/BHG methods are less than 25% in the temperature range 300-3000 K. The estimated rate constants using these approaches are in good agreement with available data in the literature.
Huynh
Lam K
LK
Departments of Mechanical Engineering and of Chemical Engineering, The University of Michigan, Ann Arbor, Michigan 48109-2125, USA.
Barriger
Kyle
K
Violi
Angela
A
D000475:Alkenes / Q000737:chemistry*; D003198:Computer Simulation; D005609:Free Radicals / Q000737:chemistry; D017665:Hydroxyl Radical / Q000737:chemistry*; D007700:Kinetics; D008956:Models, Chemical; D013696:Temperature; D014867:Water / Q000737:chemistry
D000475:Alkenes; D005609:Free Radicals; D014867:Water; D017665:Hydroxyl Radical