Kinetics of HO2 + HO2 -> H2O2 + O2: Implications for Stratospheric H2O2

Details Kinetics of HO2 + HO2 -> H2O2 + O2: Implications for Stratospheric H2O2 Kinetics of HO2 + HO2 -> H2O2 + O2: Implications for Stratospheric H2O2

May 2002

adsabs.harvard.edu/cgi-bin/nph-data_query?bibcode=2002georl..29i..13c&link_type=abstract

Geophysical Research Letters, Volume 29, Issue 9, pp. 13-1, CiteID 1299, DOI 10.1029/2001GL014525

Physics

9

Atmospheric Composition And Structure: Chemical Kinetic And Photochemical Properties, Atmospheric Composition And Structure: Constituent Sources And Sinks, Atmospheric Composition And Structure: Middle Atmosphere-Composition And Chemistry

Scientific paper

The reaction HO2 + HO2 -> H2O2 + O2(1) has been studied at 100 Torr and 222 K to 295 K. Experiments employing photolysis of Cl2/CH3OH/O2/N2 and F2/H2/O2/N2 gas mixtures to produce HO2 confirmed that methanol enhanced the observed reaction rate. At 100 Torr, zero methanol, k1 = (8.8 +/- 0.9) 10-13 × exp[(210 +/- 26)/T] cm3 molecule-1 s-1 (2σ uncertainties), which agrees with current recommendations at 295 K but is nearly 2 times slower at 231 K. The general expression for k1, which includes the dependence on bath gas density, is k1 = (1.5 +/- 0.2) × 10-12 × exp[(19 +/- 31)/T] + 1.7 × 10-33 × [M] × exp[1000/T], where the second term is taken from the JPL00-3 recommendation. The revised rate largely accounts for a discrepancy between modeled and measured [H2O2] in the lower to middle stratosphere.

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