Shock tube kinetic study of the CH sub 3 + H sub 2 r equilibrium H + CH sub 4 reaction and the methane dissociation reaction

In this kinetic study of (1) the reaction of CH{sub 3} radicals with H{sub 2} and (2) the thermal dissociation of methane, primary product H atoms were monitored directly using the sensitive atomic resonance absorption detection technique. The detection limit for the (H) was about 3{times}10{sup 10} atoms cm{sup {minus}3}. Rate constants for both reactions were obtained under pseudo-first-order conditions. In addition, computer simulations verified that kinetic complications were avoided. For the reaction of CH{sub 3}+H{sub 2}, experiments were performed using either acetone or ethane to generate CH{sub 3} radicals rapidly by thermal dissociation in argon. Twenty-four experiments were performed over the temperature range 1346K to 1793K and a rate constant expression derived using linear least-squares analysis: k{sub {minus}2}(T) = (6.0{plus minus}0.7){times}10{sup {minus}12} exp ({minus}5920{plus minus}190K/T) cm{sup 3} molecule{sup {minus}1} s{sup {minus}1}. 46 refs., 5 figs., 5 tabs.