Ab initio evaluation of primary cyclo-hexane oxidation reaction rates

Naphthenes are chemical species that are always present in liquid hydrocarbon fuels and their pyrolysis and oxidation can play an important role in real liquid fuel combustion. In spite of its practical relevance, the chemical kinetics of naphthene pyrolysis and oxidation is not yet thoroughly investigated and there is not a general agreement on the role and rate of several elementary reactions involved. In this paper, the kinetics of the pyrolysis and oxidation of a simple naphthene, namely cyclo-hexane, has been investigated through detailed kinetic modeling. Ab initio calculations were performed to estimate the kinetic parameters of some primary reactions following the oxygen attack to the cyclo-hexane radical. In fact, due to the complex behavior induced by the ring structure of cyclo-hexane, such data were difficult to determine through thermo-chemical methods. Density functional theory (B3LYP/6-31g(d, p)) was adopted to determine structure and vibrational frequencies of transition states and reaction intermediates, while energies were evaluated using the G2MP2 approach. The kinetic parameters of the investigated primary reactions were then introduced in a general detailed kinetic model consisting of elementary reactions whose kinetic constants were taken from the literature. The so obtained kinetic model was used to simulate ignition delay times and species concentrations measured in various experiments reported in the literature. The agreement between experimental data and theoretical predictions shows the validity of the chosen approach and supports the correctness of the proposed kinetic model.