Articles | Volume 14, issue 1
Atmos. Chem. Phys., 14, 255–266, 2014
Atmos. Chem. Phys., 14, 255–266, 2014

Research article 09 Jan 2014

Research article | 09 Jan 2014

Direct estimation of the rate constant of the reaction ClO + HO2 → HOCl + O2 from SMILES atmospheric observations

K. Kuribayashi1,2, H. Sagawa2, R. Lehmann3, T. O. Sato1,2, and Y. Kasai1,2 K. Kuribayashi et al.
  • 1Tokyo Institute of Technology, 4259 Nagatsuta-cho, Midori-ku, Yokohama, Kanagawa 226-8503, Japan
  • 2National Institute of Information and Communications Technology (NICT), Nukui-kita, Koganei, Tokyo, 184-8795, Japan
  • 3Alfred Wegener Institute for Polar and Marine Research, Potsdam, Germany

Abstract. Diurnal variations of ClO, HO2, and HOCl were simultaneously observed by the Superconducting Submillimeter-Wave Limb-Emission Sounder (SMILES) between 12 October 2009 and 21 April 2010. These were the first global observations of the diurnal variation of HOCl in the upper atmosphere. A major reaction for the production of HOCl is ClO + HO2 → HOCl + O2 (Reaction (R1)) in extra-polar regions. A model study suggested that in the mesosphere, this is the only reaction influencing the amount of HOCl during the night. The evaluation of the pure reaction period, when only Reaction (R1) occurred in the Cly chemical system, was performed by checking the consistency of the HOCl production rate with the ClO loss rate from SMILES observation data. It turned out that the SMILES data at the pressure level of 0.28 hPa (about 58 km) in the autumn mid-latitude region (20–40°, February–April 2010) during night (between modified local time 18:30 and 04:00) were suitable for the estimation of the rate constant, k1. The rate constant obtained from SMILES observations was k1(245 K) = (7.75 ± 0.25) × 10−12 cm3 molecule−1 s−1. This result is consistent with results from a laboratory experiment and ab initio calculations for similar low-pressure conditions.

Final-revised paper