Theoretical investigation on the reaction kinetics of NO2 with cyclopentane, cyclopentene and cyclohexane

Exhaust Gas Recirculation (EGR) provides opportunities for chemical reactions between hydrocarbon fuels and NOx, and cyclic hydrocarbons are an important component of transport fuels. In this work, the reaction kinetics of cyclopentane (cyc-C5H10), cyclopentene (cyc-C5H8) and cyclohexane (cyc-C6H12) with nitrogen dioxide (NO2) were studied theoretically. The rate constants over a broad temperature range of 298 K-2400 K were calculated by using multistructural canonical variational transition state theory (MS-VTST) with multidimensional tunneling method. We found that the tunneling effect is particularly pronounced below 350 K for three reaction systems. Due to the difference between the five- and six-membered rings, there exists a large difference between cyc-C5H10 + NO2 and cyc-C6H12 + NO2. The addition path for cyc-C5H8 + NO2 plays a dominant role in the low temperature region (≤1200 K), and the hydrogen abstraction path gradually becomes the dominant path with the increase of temperature. It provides useful data for exploring the reaction of hydrocarbon fuel and nitrogen dioxide, and can be used as a starting point for high-precision numerical calculation of large cyclic hydrocarbons. © 2024 Elsevier Ltd