Direct Measurement of the OH + HO2 Cross Reaction Using Infrared Kinetic Spectroscopy

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Abstract
The cross reaction between the free radicals OH and HO2 plays a critical role in a wide range of environments, including combustion and the atmospheres of Earth and Mars. In the middle atmosphere on Earth, it is the ultimate terminating step of odd-hydrogen chemistry, which has significant implications for the abundance of ozone. Recent laboratory measurements have brought established rate coefficients into question, introducing additional uncertainties into chemical models of the upper stratosphere and mesosphere. In this work, we present measurements of the rate coefficient from 265-350 K using high-resolution infrared and ultraviolet kinetic spectroscopy. A scheme was developed which almost entirely avoids interfering reactions, providing a direct measurement of the decay of OH due to HO2 and reduces uncertainties associated with absolute calibration of OH and HO2 concentrations. We find a room temperature rate coefficient of k(295) = (9.0 ± 1.9) × 10-11 cm3 molecule-1 s-1 (1σ error) and a slight temperature dependence over 265-330 K with an E/R of -155 ± 50 K.
Funding Information
  • NASA Headquarters
  • Earth Sciences Division
  • Jet Propulsion Laboratory (80NM0018D0004)
  • Arnold and Mabel Beckman Foundation

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