Kinetics and product of the gas-phase reaction of ClO with NO2
- 1 January 1986
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Journal of the Chemical Society, Faraday Transactions 2: Molecular and Chemical Physics
- Vol. 82 (3) , 275-289
- https://doi.org/10.1039/f29868200275
Abstract
The association reaction of ClO with NO2 has been studied by infrared absorption spectroscopy and molecular modulation spectroscopy. Photolysis of OClO–NO2–N2 mixtures produced ClO radicals over a wide range of reagent concentrations at 303 K, and total pressures of 10 and 25 Torr and 1 atm. The major product of the association reaction was chlorine nitrate, ClONO2, with no evidence for the formation of any other isomers. Observation of the kinetics of OClO removal, ClONO2 formation and the transient behaviour of ClO are consistent with the following reactions: ClO + NO2+ M → ClONO2+ M. (1), OClO +hν→ ClO + O (2), O + NO2→ NO + O2(3), OClO + NO → ClO + NO2. (4) The third-order rate coefficient, k1, measured from the photolysis of mixtures of [OClO] < 1014 molecule cm–3 was 1.40 ± 0.07 × 10–31 cm6 molecule–2 s–1, in good agreement with previous reports; however, k1 appeared to decline with increasing OClO concentration. This apparent decline is difficult to rationalize on the basis of existing knowledge.Keywords
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