Thermal ignition of acetonitrile. Experimental results and kinetic modeling

Ignition delay times of acetonitrile (CH₃CN) in mixtures containing acetonitrile and oxygen diluted in argon were studied behind reflected shock waves. The temperature range covered was 1420–1750 K at overall concentrations behind the reflected shock wave ranging from 2 to 4×10^?5 mol/cm³. Over this temperature and concentration range the ignition delay times varied by approximately one order of magnitude, ranging from ca. 100 μs to slightly above 1 ms. From a total of some 70 tests the following correlation for the ignition delay times was derived: t_ign=9.77×10^?12 exp(41.7×10³/RT)×{CH₃CN]^0.12O₂]^?0.76Ar]^0.34} s, where concentrations are expressed in units of mol/cm³ and R is expressed in units of cal/(K mol). The ignition delay times were modeled by a reaction scheme containing 36 species and 111 elementary reactions. Good agreement between measured and calculated ignition delay times was obtained. A least-squares analysis of 60 computed ignition delay times from six different groups of initial conditions gave the following temperature and concentration dependence: E=46.2×10³ cal/mol, β=0.43, β=?1.18, and β_Ar=0.18. The ignition process is initiated by H-atom ejection from acetonitrile. The addition of oxygen atoms to the system from the dissociation of molecular oxygen and from the reaction CH₃CN+O₂ → HO₂·+CH₂CN·is negligible. In view of the relatively high concentration of methyl radicals obtained in the reaction CH₃CN+H → CH₃+HCN, the branching step CH₃+O₂ → CH₃O+O plays a more important role than the parallel step H+O₂→ OH+O. A discussion of the mechanism in view of the sensitivity analysis is presented. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 839–849, 1997