Abstract
CONCERN about the depletion of stratospheric ozone by nitrogen oxides released by high flying aircraft1 and by chlorine species from the decomposition of halocarbons2,3 has emphasised the need for laboratory data on the elementary reaction steps involved, particularly those which control the concentration of the hydroxyl radical (HO) in the stratosphere. HO has an important role in both ozone destruction mechanisms, since it combines with NO2 to form the relatively inert HNO3 molecule and converts the inactive HCl formed from Cl + CH4 back into active Cl atoms. In the stratosphere the ‘odd hydrogen’ species H, HO, and HO2 are formed by the reactions of O(1D) with H2O, H2 and CH4 and by the photolysis of H2O, processes which are comparatively well understood. The odd hydrogen species are interconverted largely by reactions such as HO + O3 → HO2 + O2 (1) O + HO → O2 + H (2) H + O2 + M → HO2 + M (3) O + HO2 → HO + O2 (4) and removed mainly by HO + HO2 → H2O + O2 (5) The rate coefficients for reactions (1) to (3) are relatively well established4–6 but there is no previous experimental determination of k4 and measurements of k5 (which have not been based on direct and unequivocal measurements of the concentration of HO2) have yielded values between 2 × 10−11 and 2 × 10−10 cm3 molecule−1 s−1 (refs 7–9). We report the first direct measurements of the rate coefficients k4 and k5 for which we have used the novel technique of laser magnetic resonance.
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BURROWS, J., HARRIS, G. & THRUSH, B. Rates of reaction of HO2 with HO and O studied by laser magnetic resonance. Nature 267, 233–234 (1977). https://doi.org/10.1038/267233a0
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DOI: https://doi.org/10.1038/267233a0
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