Kinetics of the C2H5O2 + NOx reactions: Temperature dependence of the overall rate constant and the C2H5ONO2 branching channel of C2H5O2 + NO

Title:
Kinetics of the C2H5O2 + NOx reactions: Temperature dependence of the overall rate constant and the C2H5ONO2 branching channel of C2H5O2 + NO
Authors:
Ranschaert, Dana L.; Schneider, Nicholas J.; Elrod, Matthew J.
Abstract:
The temperature dependence of the overall rate constant for the C2H5O2 + NO reaction and the rate constant for the minor branching channel resulting in the production of C2H5ONO2 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 C2H5O2 + NO reaction was investigated between 299 and 213 K at 100 Torr pressure, and the data was fit to the following Arrhenius expression (with 2 standard deviation error limits indicated):  × 10-12exp[(290 ± 110)/T] cm3 molecule-1 s-1. The temperature dependence of the overall rate constant agrees well with the current recommendation for atmospheric modeling. The minor reaction channel C2H5O2 + NO → C2H5ONO2 was directly observed for the first time, and the temperature dependence of the rate constant for this channel was investigated between 298 and 213 K at 100 Torr pressure. The following Arrhenius expression was determined for the minor channel:  × 10-15exp[(1160 ± 310)/T] cm3 molecule-1 s-1. The Arrhenius expressions for the overall rate and the C2H5ONO2 producing channel indicate a branching ratio of about 0.006 at 298 K and 0.02 at 213 K at 100 Torr pressure. The temperature dependence of the overall rate constant for the C2H5O2 + NO2 reaction was also investigated between 299 and 213 K at 100 Torr pressure, and the data was fit to the following Arrhenius expression:  × 10-13exp[(620 ± 89)/T] cm3 molecule-1 s-1.
Citation:
Ranschaert, D.L., N.J. Schneider, and M.J. Elrod. 2000. "Kinetics of the C2H5O2 + NOx Reactions: Temperature Dependence of the Overall Rate Constant and the C2H5ONO2 Branching Channel of C2H5O2 + NO." Journal of Physical Chemistry A 104(24): 5758-5765.
Publisher:
American Chemical Society
DATE ISSUED:
2000-06-22
Department:
Chemistry
Type:
article
PUBLISHED VERSION:
10.1021/jp000353k
PERMANENT LINK:
http://hdl.handle.net/11282/309793

Full metadata record

DC FieldValue Language
dc.contributor.authorRanschaert, Dana L.en_US
dc.contributor.authorSchneider, Nicholas J.en_US
dc.contributor.authorElrod, Matthew J.en_US
dc.date.accessioned2013-12-23T16:17:57Zen
dc.date.available2013-12-23T16:17:57Zen
dc.date.issued2000-06-22en
dc.identifier.citationRanschaert, D.L., N.J. Schneider, and M.J. Elrod. 2000. "Kinetics of the C2H5O2 + NOx Reactions: Temperature Dependence of the Overall Rate Constant and the C2H5ONO2 Branching Channel of C2H5O2 + NO." Journal of Physical Chemistry A 104(24): 5758-5765.en_US
dc.identifier.issn1089-5639en_US
dc.identifier.urihttp://hdl.handle.net/11282/309793en
dc.description.abstractThe temperature dependence of the overall rate constant for the C2H5O2 + NO reaction and the rate constant for the minor branching channel resulting in the production of C2H5ONO2 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 C2H5O2 + NO reaction was investigated between 299 and 213 K at 100 Torr pressure, and the data was fit to the following Arrhenius expression (with 2 standard deviation error limits indicated):  × 10-12exp[(290 ± 110)/T] cm3 molecule-1 s-1. The temperature dependence of the overall rate constant agrees well with the current recommendation for atmospheric modeling. The minor reaction channel C2H5O2 + NO → C2H5ONO2 was directly observed for the first time, and the temperature dependence of the rate constant for this channel was investigated between 298 and 213 K at 100 Torr pressure. The following Arrhenius expression was determined for the minor channel:  × 10-15exp[(1160 ± 310)/T] cm3 molecule-1 s-1. The Arrhenius expressions for the overall rate and the C2H5ONO2 producing channel indicate a branching ratio of about 0.006 at 298 K and 0.02 at 213 K at 100 Torr pressure. The temperature dependence of the overall rate constant for the C2H5O2 + NO2 reaction was also investigated between 299 and 213 K at 100 Torr pressure, and the data was fit to the following Arrhenius expression:  × 10-13exp[(620 ± 89)/T] cm3 molecule-1 s-1.en_US
dc.language.isoen_USen_US
dc.publisherAmerican Chemical Societyen_US
dc.identifier.doi10.1021/jp000353ken
dc.subject.departmentChemistryen_US
dc.titleKinetics of the C2H5O2 + NOx reactions: Temperature dependence of the overall rate constant and the C2H5ONO2 branching channel of C2H5O2 + NOen_US
dc.typearticleen_US
dc.identifier.journalJournal of Physical Chemistry Aen_US
dc.identifier.volume104en_US
dc.identifier.issue24en_US
dc.identifier.startpage5758en_US
All Items in The Five Colleges of Ohio Digital Repository are protected by copyright, with all rights reserved, unless otherwise indicated.