Rate Rules, Branching Ratios, and Pressure Dependence of the HO2 + Olefin Addition Channels

Abstract

In this work, we present high-pressure rate rules and branching ratios for the addition of HO2 to olefins through the concerted addition channel to form an alkyl peroxy radical (HO2 + olefin → RO2) and through the radical addition channel to form a β-hydroperoxy alkyl radical (HO2 + olefin → β-QOOH). These rate rules were developed by calculating rate constants for a series of addition reactions involving olefins with varying degrees of branching. The individual rate expressions were determined from electronic structure calculations performed at the CBS-QB3 level of theory combined with TST calculations. The calculated rate constants were found to be in good agreement with those reported in the literature. Next, we calculated apparent pressure- and temperature-dependent rate constants for HO2 addition to the terminal site of 1-butene using an energy-grained master equation (ME) approach and QRRK calculations with a modified strong collision (MSC) approximation. The two methods gave similar results for both reaction classes. We found that, for the radical addition reaction, the high-pressure limit for the stabilization channel is not reached until unusually high pressures (>1000 atm). Instead, this reaction leads to the direct formation of an oxirane + OH. In general, the results for the major channels are in reasonable agreement with prior theoretical and experimental data. Finally, to explicitly examine the effect of pressure, we compared concentration-time profiles for the reactions of HO2 plus butene in air that were obtained using both high-pressure and pressure-dependent mechanisms at 10 and 100 atm. These simulations showed that, contrary to general expectations, the manifestation of pressure falloff effects in kinetic modeling studies might be more prevalent at increasing pressures. This behavior is attributed to the reaction of β-QOOH with O2, the rate of which increases with increasing pressure of air. This bimolecular reaction competes with the unimolecular reactions of β-QOOH under conditions where falloff effects are important for that channel.