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

Abstract

In H2 and H2/CO oxidation, the H+O2+M termination step is one of the most important reactions at elevated pressures. With the recent, increased interest in synthetic fuels, an accurate assessment of its rate coefficient becomes increasingly important, especially for real fuel/air mixtures. Ignition delay times in shock-tube experiments at the conditions selected in this study are only sensitive to the rates of the title reaction 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 its value 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 ϕ=0.5, 0.9, and 1.0. The rate of H+O2+N2=HO2+N2 was measured to be 2.7 (−0.7/+0.8)×1015cm6/mol2s for T=916–1265K and P=1–17atm. 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 of H+O2+Ar=HO2+Ar was measured to be 1.9×1015cm6/mol2s for T=932–965K and P=1.4atm. The rate of H+O2+H2O=HO2+H2O was measured to be 3.3×1016cm6/mol2s for T=1071–1161K and P=1.3atm. These are the first experimental measurements of the rates of the title reactions in practical combustion fuel/air mixtures.