Contribution of the radical-complex mechanism to the rate of the reaction CH(3) + O(2) (+ M) → CH(3)O(2) (+ M) at high pressures.
Earlier experimental studies of the falloff curves of the reaction CH(3) + O(2) (+ M) → CH(3)O(2) (+ M) in the bath gases M = Ar and N(2) (Fernandes et al., J. Phys. Chem. A 2006, 110, 4442), in addition to the usual behavior of the energy-transfer (ET) mechanism, showed first evidence for a participation of the radical-complex (RC) mechanism in the reaction at pressures above about 300 bar and at temperatures below 400 K. By extending these measurements to the bath gas M = CO(2), more pronounced deviations from the ET mechanism were now observed. This unambiguously confirms the presence of the RC mechanism at high pressures in a medium-sized molecular system, analogous to earlier observations for larger systems such as the dimerization of benzyl radicals (Luther et al., Phys. Chem. Chem. Phys. 2004, 6, 4133).
Fernandes
Ravi X
RX
Institut für Physikalische Chemie, Universität Göttingen, Germany.
Luther
Klaus
K
Troe
Jürgen
J
D000042:Absorption; D001128:Argon / Q000737:chemistry*; D004735:Energy Transfer; D005609:Free Radicals / Q000737:chemistry; D008697:Methane / Q000737:chemistry*; D008956:Models, Chemical; D009584:Nitrogen / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry*; D011312:Pressure
D005609:Free Radicals; D001128:Argon; D009584:Nitrogen; D008697:Methane; D010100:Oxygen