Journal of Physical Chemistry A, Vol.102, No.1, 168-172, 1998
Kinetics of the reactions of N(S-4) atoms with O-2 and CO2 over wide temperatures ranges
Rate coefficients for the depletion of ground-state nitrogen atoms by O-2 have been measured using a high-temperature photochemistry reactor. The N atoms were generated by VUV flash photolysis of N2O, and the relative concentrations were monitored by resonance fluorescence. The data are best fitted by the expression k(400-1220 K) = 2.0 x 10(-18)(T/K)(2.15) exp(-2557 WT) cm(3) molecule(-1) s(-1) with 2 sigma precision limits varying from +/-7% to +/-20% depending upon temperature, and corresponding 2 sigma accuracy limits of +/-23% to +/-30%. Good agreement is found with earlier, electrical discharge initiated, rate coefficient measurements for the 280-910 K domain. Semiempirical theory-based calculations are presented that lead to a plot nearly indistinguishable from those of the present results and the Baulch et al. recommendation for the 300-5000 K temperature range. These yield a classical barrier E-0(double dagger) of 27.4 kJ mol(-1). No reaction with CO2 could be observed; upper Limit rate coefficients were obtained from 285 to 1140 K. These upper limits indicate that the reverse reaction is insignificant for models of nitrate ester and nitramine propellant dark zones.