Rate coefficients for the reaction of OH radicals with cis-3-hexene: an experimental and theoretical study

THAÍS DA SILVA BARBOSA; SILVINA A. PEIRONE; JAVIER A. BARRERA; JUAN P. A. ABRATE; SILVIA I. LANE; GRACIELA ARBILLA; GLAUCO FAVILLA BAUERFELDT

PHYSICAL CHEMISTRY CHEMICAL PHYSICS

ROYAL SOC CHEMISTRY

Lugar: CAMBRIDGE; Año: 2015 vol. 17 p. 8714 - 8714

1463-9076

he kinetics of the cis-3-hexene + OH reaction were investigated by an experimental relative rate method and at the density functional theory level. The experimental set-up consisted of a 200 L Teflon bag, operated at atmospheric pressure and 298 K. OH radicals were produced by the photolysis of H2O2 at 254 nm. Relative rate coefficients were determined by comparing the decays of the cis-3-hexene and reference compounds (cyclohexene, 2-buten-1-ol and allyl ether). The mean second-order rate coefficient value found was (6.27 0.66) 1011 cm3 molecule1 s1, the uncertainty being estimated by propagation of errors. Theoretical calculations for the addition reaction of OH to cis-3-hexene have also been performed, at the BHandHLYP/aug-cc-pVDZ level, in order to investigate the reaction mechanism, to clarify the experimental observations and to model the reaction kinetics. Different conformations of the reactants, pre-barrier complexes and saddle points were considered in our calculations. Th