Abstract
Abstract. The radical terminating, termolecular reaction between OH and NO2
exerts great influence on the NOy∕NOx ratio and O3 formation in the atmosphere. Evaluation panels (IUPAC and NASA) recommend rate coefficients for this reaction that disagree by as much as a factor of 1.6 at low temperature and pressure. In this work, the title reaction was studied by pulsed laser photolysis and laser-induced fluorescence over the pressure range 16–1200 mbar and temperature range 217–333 K in N2 bath gas, with experiments at 295 K (67–333 mbar) for O2. In situ measurement of NO2 using two optical absorption set-ups enabled generation of highly precise,
accurate rate coefficients in the fall-off pressure range, appropriate for
atmospheric conditions. We found, in agreement with previous work, that O2 bath gas has a lower collision efficiency than N2 with a relative collision efficiency to N2 of 0.74. Using the Troe-type formulation for termolecular reactions we present a new set of parameters with k0(N2) = 2.6×10-30 cm6 molecule−2 s−1, k0(O2) = 2.0×10-30 cm6 molecule−2 s−1, m=3.6, k∞=6.3×10-11 cm3 molecule−1 s−1, and Fc=0.39 and compare our results to previous studies in
N2 and O2 bath gases.
Reference41 articles.
1. Anastasi, C. and Smith, I. W. M.: Rate measurements of reactions of OH by
resonance absorption. Part 5. – Rate constants for OH + NO2 (+ M) → HNO3 (+ M) over a wide range of temperature and pressure, J. Chem. Soc., Faraday T. 2, 72, 1459–1468, 1976.
2. Anderson, J. G. and Kaufman, F.: Kinetics of reaction OH + NO2 + M → HNO3 + M, Chem. Phys. Lett., 16, 375–379, 1972.
3. Anderson, J. G., Margitan, J. J., and Kaufman, F.: Gas-phase recombination of OH with NO and NO2, J. Chem. Phys., 60, 3310–3317, 1974.
4. Anderson, L. G.: Absolute rate constants for the reaction of OH with
NO2 in N2 and He from 225 to 389 K, J. Phys. Chem., 84, 2152–2155, 1980.
5. Atkinson, R., Baulch, D. L., Cox, R. A., Crowley, J. N., Hampson, R. F., Hynes, R. G., Jenkin, M. E., Rossi, M. J., and Troe, J.: Evaluated kinetic and photochemical data for atmospheric chemistry: Volume I – gas phase reactions of Ox, HOx, NOx and SOx species, Atmos. Chem. Phys., 4, 1461–1738, https://doi.org/10.5194/acp-4-1461-2004, 2004.
Cited by
8 articles.
订阅此论文施引文献
订阅此论文施引文献,注册后可以免费订阅5篇论文的施引文献,订阅后可以查看论文全部施引文献