Water vapor effect on the HNO3 yield in the HO2 + NO reaction: Experimental and theoretical evidence

Nadezhda Butkovskaya 1, 2 Marie-Thérèse Rayez 3 Jean-Claude Rayez 3 Alexandre Kukui 4 Georges Le Bras 2
1 Institute of Chemical Physics
2 ICARE - Institut de Combustion, Aérothermique, Réactivité et Environnement
3 ISM - Institut des Sciences Moléculaires
4 TROPO - LATMOS
LATMOS - Laboratoire Atmosphères, Milieux, Observations Spatiales
Abstract : The influence of water vapor on the production of nitric acid in the gas-phase HO2 + NO reaction was determined at 298 K and 200 Torr using a high-pressure turbulent flow reactor coupled with a chemical ionization mass spectrometer. The yield of HNO3 was found to increase linearly with the increase of water concentration reaching an enhancement factor of about 8 at [H2O] = 4 × 1017 molecules cm−3 (~50% relative humidity). A rate constant value k1bw = 6 × 10−13 cm3 molecule−1 s−1 was derived for the reaction involving the HO2*H2O complex: HO2*H2O + NO → HNO3 (1bw), assuming that the water enhancement is due to this reaction. k1bw is approximately 40 times higher than the rate constant of the reaction HO2 + NO → HNO3 (1b), at the same temperature and pressure. The experimental findings are corroborated by density functional theory (DFT) calculations performed on the H2O/HO2/NO system. The significance of this result for atmospheric chemistry and chemical amplifier instruments is briefly discussed. An appendix containing a detailed consideration of the possible contribution from the surface reactions in our previous studies of the title reaction and in the present one is included.
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https://hal.archives-ouvertes.fr/hal-00439172
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Submitted on : Sunday, December 6, 2009 - 4:03:19 PM
Last modification on : Friday, January 10, 2020 - 3:42:33 PM

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Nadezhda Butkovskaya, Marie-Thérèse Rayez, Jean-Claude Rayez, Alexandre Kukui, Georges Le Bras. Water vapor effect on the HNO3 yield in the HO2 + NO reaction: Experimental and theoretical evidence. Journal of Physical Chemistry A, American Chemical Society, 2009, 113 (42), pp.11327-11342. ⟨10.1021/jp811428p⟩. ⟨hal-00439172⟩

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