High-Pressure-Limit and Pressure-Dependent Rate Rules for Unimolecular Reactions Related to Hydroperoxy Alkyl Radicals in Normal-Alkyl Cyclohexane Combustion. 2. Cyclization Reaction Class.

Abstract

The hydroperoxy alkyl radicals are important intermediates in the low-temperature combustion for normal-alkyl cycloalkanes, and the cyclization reactions of hydroperoxy alkyl radicals to form cyclic ethers are responsible for a major fraction of the OH formation, which has the potential to promote ignition. In most of the previous modeling studies for normal-alkyl cycloalkane combustion, the kinetic data of the cyclization reactions in the detailed combustion mechanism were mainly taken from the analogous reactions in cyclohexane, methyl cyclohexane, and alkanes in published literature studies. In this work, the kinetics of the cyclization reaction class of hydroperoxy alkyl radicals in normal-alkyl cycloalkanes is studied, where the reaction class is divided into subclasses depending upon the ring size of the transition states, the types of the carbons on which the -OOH site is located and the types of the carbons on which the radical site is located, and the positions of the cyclization (on the alkyl side chain, on the cycle, or between the alkyl side chain and the cycle). Energy barriers and high-pressure-limit site rate constants and pressure-dependent rates for reactions in all subclasses are calculated, and rate rules for all subclasses are developed. The high-pressure-limit rate constants are determined from CBS-QB3 electronic structure calculations combined with canonical transition-state theory calculations, and pressure-dependent rate constants are calculated by using the Rice-Ramsberger-Kassel-Marcus/Master Equation theory at pressures varying from 0.01 to 100 atm. Comparisons of the rate constants for cyclization reactions of hydroperoxy alkyl cyclohexylperoxy radicals calculated in this work with the values of the corresponding reactions in some of the popular combustion mechanisms show that it is unreasonable to use the kinetic data of analogous reactions in alkanes, cyclohexanes, or smaller normal-alkyl cyclohexanes. Therefore, the accurate kinetic calculations and the construction of rate rules for normal-alkyl cycloalkanes are necessary and significant for the reliable modeling of the low-temperature combustion of normal-alkyl cyclohexanes.