The reaction of nitric oxide with vibrationally excited ozone. II

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Abstract
The reaction of nitric oxide and vibrationally excited ozone was studied using a CO2 TEA laser to excite O3(001) and a photomultiplier tube to measure the decay of the NO2* chemiluminescence. In experiments with 3, a single, rapid rise rate was observed, suggesting that for ozone lean mixtures the laser‐induced signal is caused primarily by the two stretching modes of ozone, with comparatively little V–V transfer to the bending mode. The linear dependence of the NO2* peak height on the laser intensity and background reaction indicates that second order effects do not contribute appreciably. Using a simple model which includes only contributions from the stretching modes and the ground state, the rate constants k3a(308 °K) =4.3±0.7×109 and k3b(308 °K) =5.4±0.7×1010 cm3 mole−1⋅sec−1 were obtained for the laser‐enhanced luminescent and nonluminescent reactions, respectively. In addition the rate constants for V–T relaxation of O3(001) by nine buffer gases were measured. It was found that the laser enhancement of the luminescent reaction is less than the thermal enhancement that would be obtained if one quantum of energy (3.0 kcal/mole) were distributed statistically among all reagent degrees of freedom, while for the nonluminescent reaction the laser and thermal enhancements are about equal.