Kinetics of the C3H7O2 + NO reaction: Temperature dependence of the overall rate constant and the i-C3H7ONO2 branching channel

Title:
Kinetics of the C3H7O2 + NO reaction: Temperature dependence of the overall rate constant and the i-C3H7ONO2 branching channel
Authors:
Chow, Jessica M.; Miller, Angela M.; Elrod, Matthew J.
Abstract:
The temperature dependence of the overall rate constant for the C3H7O2 + NO reaction and the rate constant for the minor branching channel resulting in the production of i-C3H7ONO2 have been measured using the turbulent flow technique with high-pressure chemical ionization mass spectrometry for the detection of reactants and products. The temperature dependence of the overall rate constant for the C3H7O2 + NO reaction was investigated between 298 and 213 K at 100 Torr pressure, and the data were fit by the following Arrhenius expression (with 2 standard deviation error limits indicated):  × 10-12 exp[(268 ± 56)/T] cm3 molecule-1 s-1. This expression agrees well with previous isomer-specific measurements of the n-C3H7ONO2 and i-C3H7O2 + NO rate constants made at lower pressures. The temperature dependence of the rate constant for the minor reaction channel i-C3H7O2 + NO → i-C3H7ONO2 was investigated between 298 and 213 K at 100 Torr pressure. The following Arrhenius expression was determined for the minor channel:  × 10-16 exp[(1380 ± 230)/T] cm3 molecule-1 s-1. The Arrhenius expressions for the overall rate and the i-C3H7ONO2 producing channel indicate a branching ratio of about 0.006 at 298 K and 0.020 at 213 K at 100 Torr pressure, which is in good agreement with the predictions of a recently revised empirical model for alkyl nitrate branching ratios.
Citation:
Chow, J.M., A.M. Miller, and M.J. Elrod. 2003. "Kinetics of the C3H7O2 + NO Reaction: Temperature Dependence of the Overall Rate Constant and the i-C3H7ONO2 Branching Channel." Journal of Physical Chemistry A 107(17): 3040-3047.
Publisher:
American Chemical Society
DATE ISSUED:
2003-05
Department:
Chemistry
Type:
article
PUBLISHED VERSION:
10.1021/jp026134b
PERMANENT LINK:
http://hdl.handle.net/11282/309829

Full metadata record

DC FieldValue Language
dc.contributor.authorChow, Jessica M.en_US
dc.contributor.authorMiller, Angela M.en_US
dc.contributor.authorElrod, Matthew J.en_US
dc.date.accessioned2013-12-23T16:18:49Zen
dc.date.available2013-12-23T16:18:49Zen
dc.date.issued2003-05en
dc.identifier.citationChow, J.M., A.M. Miller, and M.J. Elrod. 2003. "Kinetics of the C3H7O2 + NO Reaction: Temperature Dependence of the Overall Rate Constant and the i-C3H7ONO2 Branching Channel." Journal of Physical Chemistry A 107(17): 3040-3047.en_US
dc.identifier.issn1089-5639en_US
dc.identifier.urihttp://hdl.handle.net/11282/309829en
dc.description.abstractThe temperature dependence of the overall rate constant for the C3H7O2 + NO reaction and the rate constant for the minor branching channel resulting in the production of i-C3H7ONO2 have been measured using the turbulent flow technique with high-pressure chemical ionization mass spectrometry for the detection of reactants and products. The temperature dependence of the overall rate constant for the C3H7O2 + NO reaction was investigated between 298 and 213 K at 100 Torr pressure, and the data were fit by the following Arrhenius expression (with 2 standard deviation error limits indicated):  × 10-12 exp[(268 ± 56)/T] cm3 molecule-1 s-1. This expression agrees well with previous isomer-specific measurements of the n-C3H7ONO2 and i-C3H7O2 + NO rate constants made at lower pressures. The temperature dependence of the rate constant for the minor reaction channel i-C3H7O2 + NO → i-C3H7ONO2 was investigated between 298 and 213 K at 100 Torr pressure. The following Arrhenius expression was determined for the minor channel:  × 10-16 exp[(1380 ± 230)/T] cm3 molecule-1 s-1. The Arrhenius expressions for the overall rate and the i-C3H7ONO2 producing channel indicate a branching ratio of about 0.006 at 298 K and 0.020 at 213 K at 100 Torr pressure, which is in good agreement with the predictions of a recently revised empirical model for alkyl nitrate branching ratios.en_US
dc.language.isoen_USen_US
dc.publisherAmerican Chemical Societyen_US
dc.identifier.doi10.1021/jp026134ben
dc.subject.departmentChemistryen_US
dc.titleKinetics of the C3H7O2 + NO reaction: Temperature dependence of the overall rate constant and the i-C3H7ONO2 branching channelen_US
dc.typearticleen_US
dc.identifier.journalJournal of Physical Chemistry Aen_US
dc.subject.keywordNox-air photooxidationsen_US
dc.subject.keywordAlkyl nitrate formationen_US
dc.subject.keywordPeroxy radicalsen_US
dc.subject.keywordN-alkanesen_US
dc.identifier.volume107en_US
dc.identifier.issue17en_US
dc.identifier.startpage3040en_US
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