Experimental study of ignition kinetics in H2−O2−CO−Ar mixtures by time-resolved photoelectric measurement of the growth of spatially integrated CO−O recombination radiation in reflected shock waves has been extended to cover the ranges 0.1≤H2:O2≤10.0, 1000°≤T≤2500°K, by confining the reactive gas to the downstream end of the shock tube and increasing sensitivity through a large solid angle optical view. The induction period regime of exponential growth of emission intensity, I(t)≈I0*exp(α*t), yields precise values of α* whose dependence upon [H2], [O2], and T determines, for the reactions H + O 2 → k 1 O H + O O + H 2 → k 2 O H + H O H + H 2 → k 3 H 2 O + H the functions: k1=8.6×108 exp {−(12.3±1) kcal/mole (1/T−1/1600)/R} liter/mole/sec and k2k3=1.5×1019 exp {−(20±4) kcal/mole (1/T−1/1600)/R} liter2/mole2/sec2, and indicates that k2 and k3 are, at most, about a factor of 3 from each other, in the present temperature range. The early growth of I(t) prior to the exponential regime, now observed directly, and the parameter I0*, now fairly precisely measured, bear upon the kinetics of chain initiation but require further investigation.
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