Kinetic Mechanism Study on Low Temperature for Decalin Combustion

The kinetic mechanism of low-temperature decalin combustion was studied, including reaction types such as dehydrogenation reaction, radical oxygenation reaction and 1, 5 H-shift reaction. The thermodynamic parameters of species were obtained at CBS-QB3 level. The high pressure limit rate constants for reactions with transition state were obtained by transition state theory calculations, while the rate constants for barrierless reactions were obtained by variational transition state theory. Based on this mechanism, the kinetic and thermodynamic behavior of decalin oxidation reactions at low temperature were analyzed. Compared with the corresponding results from linear alkanes and monocycloalkane, the rate constants of O-2-addition to decalin radical change more fast with temperature and the energy barriers of 1 ,5 H-shift reactions are higher, which reveal the influence of reactant structure on kinetics. The analysis result of thermodynamic equilibrium constants showed that the O-2-addition reaction to decalin radical plays a leading role at low temperature. The rate constants of Arrhenius form for all reactions were fitted and these parameters can be used in the construction and optimization of low temperature combustion mechanism of bicycloalkane.