Pressure dependence of butyl nitrate formation in the reaction of butylperoxy radicals with nitrogen oxide.
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.
†Institut de Combustion, Aérothermique, Réactivité et Environnement (ICARE), CNRS-INSIS, 1C Avenue de la Recherche Scientifique, 45071 Orléans cedex 2, France.
N I
NI
Butkovskaya
‡Laboratoire de Physique et Chimie de l'Environnement et de l'Espace (LPC2E), CNRS-INSU, 3A Avenue de la Recherche Scientifique, 45071 Orléans cedex 2, France.
A
A
Kukui
†Institut de Combustion, Aérothermique, Réactivité et Environnement (ICARE), CNRS-INSIS, 1C Avenue de la Recherche Scientifique, 45071 Orléans cedex 2, France.
G
G
Le Bras
§Institut des Sciences Moléculaires, CNRS/UMR5255, Université Bordeaux 1, 351 Cours de la Libération, 33405 Talence cedex, France.
M-T
MT
Rayez
§Institut des Sciences Moléculaires, CNRS/UMR5255, Université Bordeaux 1, 351 Cours de la Libération, 33405 Talence cedex, France.
J-C
JC
Rayez