New insight into dissociation of molecular oxygen at temperatures below 5000 K

The data available in the literature on measurements of the rate coefficient of molecular oxygen dissociation were considered and structured. Modern models of hydrocarbons combustion were analyzed considering values of the O2 dissociation rate constant. Precision measurements of the rate of O2 dissociation behind shock waves at temperatures of 2500–5000 ± 50 K and pressures of 1.2–2.5 bar were carried out using atomic resonance absorption spectrometry on O atom (O-ARAS). The ARAS measurements of the absolute concentration of oxygen atoms were calibrated in the conditions of complete dissociation of N2O and O2, considering the temperature splitting of the calibration curves. Using kinetic modeling, a detailed analysis of experimental uncertainties was carried out with an assessment of the influence of impurities of various origin at the dissociation of O2. An updated expression for the rate constant of the reaction O2 + Ar = 2O + Ar was obtained in the form kdiss(±15%)=1.30·1014·exp(−108.95[kcalmol]/RT) cm3 mol−1 s−1. A significant influence of the O2 dissociation rate constant on the predictive ability of modern models of hydrocarbons (on the example of biofuels) combustion at high temperatures was shown. Recommendations were formulated on the use of the corresponding oxygen dissociation rate constant in the development and/or refinement of combustion kinetic models.