A Temperature-Dependent Kinetics Study of the Important Stratospheric Reaction...

Estupiñan, E. G., J. M. Nicovich, and P. Wine (2001), A Temperature-Dependent Kinetics Study of the Important Stratospheric Reaction O(3P) + NO2 --> O2 + NO, J. Phys. Chem. A, 105, 9697-9703, doi:10.1021/jp011940o.

A laser flash photolysis-resonance fluorescence technique has been employed to investigate the kinetics of the important stratospheric reaction O(3P) + NO2 f O2 + NO (k1) as a function of temperature (221-425 K) with particular attention paid to obtaining the most accurate values possible for k1(T). The following Arrhenius expression adequately describes the observed temperature dependence: k1(T) ) (4.21 ( 0.25) × 10-12 exp{(273 ( 18)/T} cm3 molecule-1 s-1, where the uncertainties represent precision at the 2σ level. The accuracy of the reported values for k1(T) is estimated to be (6% over the entire temperature range investigated. At room temperature the rate coefficient measured in this study is in excellent agreement with that reported in a recent paper by Gierczak et al. [J. Phys. Chem. A 1999, 103, 877] while the activation energy of the rate coefficient is somewhat more negative than that reported by Gierczak et al. Incorporation of the results of the present study into models of stratospheric chemistry would lead to somewhat lower mid-stratospheric ozone levels than would be obtained using results of previous studies.

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Upper Atmosphere Research Program (UARP)