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Kinetics and mechanism of the C 2 H 5 O 2 + NO reaction: A temperature and pressure dependence study using chemical ionization mass spectrometry
Author(s) -
Bardwell Max W.,
Bacak Asan,
Raventós M. Teresa,
Percival Carl J.,
SanchezReyna Gabriela,
Shallcross Dudley E.
Publication year - 2005
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.20078
Subject(s) - chemistry , arrhenius equation , analytical chemistry (journal) , atmospheric temperature range , torr , branching (polymer chemistry) , chemical kinetics , branching fraction , mass spectrometry , ionization , thermodynamics , kinetics , activation energy , atomic physics , ion , organic chemistry , chromatography , quantum mechanics , physics
Abstract The overall rate coefficient ( k 1 ) for the reaction of C 2 H 5 O 2 + NO has been measured using the turbulent flow CIMS technique. The temperature dependence of the rate coefficient was investigated between 203 and 298 K. Across the temperature range, the experimentally determined rate coefficients showed good agreement with previous studies and were fitted using an Arrhenius type analysis to yield the expression k 1 = (1.75 +0.14 −0.13 ) × 10 −12 exp[(462 ± 19)/ T ] cm 3 molecule −1 s −1 . Experiments were carried out in the pressure range of 100–200 Torr within the stated temperature range, where the rate coefficients were shown to be invariant with pressure. The branching ratio of the reaction was also assessed as a function of temperature and was found to proceed 100 ± 5% via the C 2 H 5 O + NO 2 reactive channel. This work represents the first temperature and pressure study over which the branching ratio has been studied. © 2005 Wiley Periodicals, Inc. Int J Chem Kinet 37: 253–260, 2005