Determination of the rate of H + O2+M→HO2+M (M=N2, Ar, H2O)from ignition of syngas at practical conditions

摘要

In H2 and H2/CO oxidation, the H + O2 + Mtermination step is one of the most important reactions atelevated pressures. With the recent, increased interest in synthetic fuels, an accurate assessment of its ratecoefficient becomes increasingly important, especially for real fuel/air mixtures. Ignition delay times inshock-tube experiments at the conditions selected in this study are only sensitive to the rates of the titlereaction and the branching reaction H + O2 = OH + O, the rate of which is known to a high level of accuracy.The rate coefficient of the title reaction for M = N2, Ar, and H2O was determined by adjusting itsvalue in a detailed chemical kinetics model to match ignition delay times for H2/CO/O2/N2, H2/CO/O2/Ar, and H2/CO/O2/N2/H2O mixtures with fuel/air equivalence ratios of / = 0.5, 0.9, and 1.0. The rateof H + O2+N2=HO2+N2 was measured to be 2.7 (on0.7/+0.8) ×1015 cm6/mol2 s for T = 916–1265 K and P = 1–17 atm. The present determination agrees well with the recent study of Bates et al.[R.W. Bates, D.M. Golden, R.K. Hanson, C.T. Bowman, Phys. Chem. Chem. Phys. 3 (2001) 2337–2342], whose rate expressions are suggested herein for modeling the falloff regime. The rate ofH+O2+Ar =HO2 + Ar was measured to be 1.9 ×1015 cm6/mol2 s for T = 932–965 K andP = 1.4 atm. The rate of H + O2+H2O=HO2+H2O was measured to be 3.3×1016 cm6/mol2 s forT = 1071–1161 K and P = 1.3 atm. These are the first experimental measurements of the rates of the titlereactions in practical combustion fuel/air mixtures.