Kinetics of the Methyl-Vinyl Radical + O Reactions Associated with Propene Oxidation.

The bimolecular rate coefficients of reactions CHCCH + O (1) and cis/ trans-CHCHCH + O (2a/3a) have been measured using a tubular laminar flow reactor coupled with a photoionization mass spectrometer (PIMS). These reactions are relevant in the combustion of propene. Pulsed excimer laser photolysis of a ketone or a bromide precursor molecule at 193 or 248 nm wavelength was used to produce radicals of interest homogeneously along the reactor. Time-resolved experiments were performed under pseudo-first-order conditions at low pressure (0.3-1.5 Torr) over the temperature range 220-660 K. The measured bimolecular rate coefficients were found to be independent of bath gas concentration. The bimolecular rate coefficients possess negative temperature dependence at low temperatures ( T < 420 K) and appear to be independent of temperature at high temperatures ( T > 420 K). Observed products of the reaction CHCCH + O were CH and HCO, while for the reaction cis/trans-CHCHCH + O, observed products were CHCHO and HCO. Current results indicate that the reaction mechanism of both reactions is analogous to that of CH + O. Methyl substitution of the vinyl radical changes its reactivity toward O upward by ca. 50% if it involves the α-position and downward by ca. 30% if the methyl group takes either of the β-positions, respectively.