THERMOCHEMISTRY AND KINETICS OF C2H3+O2 REACTIONS

Kinetics and products are predicted for reactions of C2H3 + O2 by using a new Q-formalism of Bimolecular Quantum-RRK theory. Association forms a chemically activated adduct, (C2H3OO.), which may isomerize one or more times to other hot isomers before decomposing or being stabilized. At low temperatures and pressures, HCO + H2CO are predicted to be formed without thermal intermediates, as observed by Gutman and co-workers. At atmospheric pressure, however, collisional stabilization of C2H3OO and its subsequent thermal reactions can be important. Glyoxal + H and C2H2+ HO, are predicted to be the next most important products of C2H3 + O2 association. All of these rate constants decrease significantly at high temperatures where (C2H3OO.) reverts to reactants preferentially. Above 1500K, the dominant products could be C2H2 + HO2formed directly by pressure-dependent H-atom transfer. © 1992, Taylor & Francis Group, LLC. All rights reserved.