Role of O₂ + QOOH in Low-Temperature Ignition of Propane. 1. Temperature and Pressure Dependent Rate Coefficients

Abstract

The kinetics of the reaction of molecular oxygen with hydroperoxyalkyl radicals have been studied theoretically. These reactions, often referred to as second O₂ addition, or O₂ + QOOH reactions, are believed to be responsible for low-temperature chain branching in hydrocarbon oxidation. The O₂ + propyl system was chosen as a model system. High-level ab initio calculations of the C₃H₇O₂ and C₃H₇O₄ potential energy surfaces are coupled with RRKM master equation methods to compute the temperature and pressure dependence of the rate coefficients. Variable reaction coordinate transition-state theory is used to characterize the barrierless transition states for the O₂ + QOOH addition reactions as well as subsequent C₃H₆O₃ dissociation reactions. A simple kinetic mechanism is developed to illustrate the conditions under which the second O₂ addition increases the number of radicals. The sequential reactions O₂ + QOOH → OOQOOH → OH + keto-hydroperoxide → OH + OH + oxy-radical and the corresponding formally direct (or well skipping) reaction O₂ + QOOH → OH + OH + oxy-radical increase the total number of radicals. Chain branching through this reaction is maximized in the temperature range 600–900 K for pressures between 0.1 and 10 atm. The results confirm that <i>n</i>-propyl is the smallest alkyl radical to exhibit the low-temperature combustion properties of larger alkyl radicals, but <i>n</i>-butyl is perhaps a truer combustion archetype