Pressure Dependence of Butyl Nitrate Formation in the Reaction of Butylperoxy Radicals with Nitrogen Oxide

Abstract : The yield of 1- and 2-butyl nitrates in the gas-phase reactions of NO with n-C4H9O2 and sec-C4H9O2, obtained from the reaction of F atoms with n-butane in the presence of O2, was determined over the pressure range of 100–600 Torr at 298 K using a high-pressure turbulent flow reactor coupled with a chemical ionization quadrupole mass spectrometer. The yield of butyl nitrates was found to increase linearly with pressure from about 3% at 100 Torr to about 8% at 600 Torr. The results obtained are compared with the available data concerning nitrate formation from NO reaction with other small alkylperoxy radicals. These results are also discussed through the topology of the lowest potential energy surface mainly obtained from DFT(B3LYP/aug-cc-pVDZ) calculations of the RO2 + NO reaction paths. The formation of alkyl nitrates, due essentially to collision processes, is analyzed through a model that points out the pertinent physical parameters of this system.
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Submitted on : Tuesday, April 14, 2015 - 2:34:00 PM
Last modification on : Thursday, July 25, 2019 - 4:16:02 PM

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N.I. Butkovskaya, Alexandre Kukui, G. Le Bras, Marie-Thérèse Rayez, Jean-Claude Rayez. Pressure Dependence of Butyl Nitrate Formation in the Reaction of Butylperoxy Radicals with Nitrogen Oxide. Journal of Physical Chemistry A, American Chemical Society, 2015, 119 (19), pp.4408-4417. ⟨10.1021/jp509427x⟩. ⟨insu-01142086⟩

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