Overall rate constant measurements of the reaction of hydroxy- and chloroalkylperoxy radicals derived from methacrolein and methyl vinyl ketone with nitric oxide

Title:
Overall rate constant measurements of the reaction of hydroxy- and chloroalkylperoxy radicals derived from methacrolein and methyl vinyl ketone with nitric oxide
Authors:
Hsin, Hong Yuan; Elrod, Matthew J.
Abstract:
The overall rate constants of the reactions of NO with hydroxy- and chloroalkylperoxy radicals, derived from the OH- and Cl-initiated oxidation of methacrolein and methyl vinyl ketone, respectively, were directly determined for the first time using the turbulent-flow technique and pseudo-first-order kinetics conditions with high-pressure chemical ionization mass spectrometry for the direct detection of peroxy radical reactants. The individual 100 Torr, 298 K hydroxyalkylperoxy + NO rate constants for the methacrolein [(0.93 ± 0.12) (2σ) × 10-11 cm3 molecule-1 s-1] and methyl vinyl ketone [(0.84 ± 0.10) × 10-11 cm3 molecule-1 s-1] systems were found to be identical within the 95% confidence interval associated with each separate measurement, as were the chloroalkylperoxy + NO rate constants for both methacrolein [(1.17 ± 0.11) × 10-11 cm3 molecule-1 s-1] and methyl vinyl ketone [(1.14 ± 0.14) × 10-11 cm3 molecule-1 s-1]. However, the difference in the rate constants between the hydroxyperoxy + NO and chloroalkylperoxy + NO systems was found to be statistically significant, with the chloroalkylperoxy + NO rate constants about 30% higher than the corresponding hydroxyalkylperoxy + NO rate constants. This substitutent effect was rationalized via a frontier molecular orbital model approach.
Citation:
Hsin, Hong Yuan, and Matthew J. Elrod. 2007. "Overall Rate Constant Measurements of the Reaction of Hydroxy- and Chloroalkylperoxy Radicals Derived from Methacrolein and Methyl Vinyl Ketone with Nitric Oxide." Journal of Physical Chemistry A 111(4): 613-619.
Publisher:
American Chemical Society
DATE ISSUED:
2007-02
Department:
Chemistry
Type:
article
PUBLISHED VERSION:
10.1021/jp0665574
PERMANENT LINK:
http://hdl.handle.net/11282/309740

Full metadata record

DC FieldValue Language
dc.contributor.authorHsin, Hong Yuanen_US
dc.contributor.authorElrod, Matthew J.en_US
dc.date.accessioned2013-12-23T16:16:49Zen
dc.date.available2013-12-23T16:16:49Zen
dc.date.issued2007-02en
dc.identifier.citationHsin, Hong Yuan, and Matthew J. Elrod. 2007. "Overall Rate Constant Measurements of the Reaction of Hydroxy- and Chloroalkylperoxy Radicals Derived from Methacrolein and Methyl Vinyl Ketone with Nitric Oxide." Journal of Physical Chemistry A 111(4): 613-619.en_US
dc.identifier.issn1089-5639en_US
dc.identifier.urihttp://hdl.handle.net/11282/309740en
dc.description.abstractThe overall rate constants of the reactions of NO with hydroxy- and chloroalkylperoxy radicals, derived from the OH- and Cl-initiated oxidation of methacrolein and methyl vinyl ketone, respectively, were directly determined for the first time using the turbulent-flow technique and pseudo-first-order kinetics conditions with high-pressure chemical ionization mass spectrometry for the direct detection of peroxy radical reactants. The individual 100 Torr, 298 K hydroxyalkylperoxy + NO rate constants for the methacrolein [(0.93 ± 0.12) (2σ) × 10-11 cm3 molecule-1 s-1] and methyl vinyl ketone [(0.84 ± 0.10) × 10-11 cm3 molecule-1 s-1] systems were found to be identical within the 95% confidence interval associated with each separate measurement, as were the chloroalkylperoxy + NO rate constants for both methacrolein [(1.17 ± 0.11) × 10-11 cm3 molecule-1 s-1] and methyl vinyl ketone [(1.14 ± 0.14) × 10-11 cm3 molecule-1 s-1]. However, the difference in the rate constants between the hydroxyperoxy + NO and chloroalkylperoxy + NO systems was found to be statistically significant, with the chloroalkylperoxy + NO rate constants about 30% higher than the corresponding hydroxyalkylperoxy + NO rate constants. This substitutent effect was rationalized via a frontier molecular orbital model approach.en_US
dc.language.isoen_USen_US
dc.publisherAmerican Chemical Societyen_US
dc.identifier.doi10.1021/jp0665574en
dc.subject.departmentChemistryen_US
dc.titleOverall rate constant measurements of the reaction of hydroxy- and chloroalkylperoxy radicals derived from methacrolein and methyl vinyl ketone with nitric oxideen_US
dc.typearticleen_US
dc.identifier.journalJournal of Physical Chemistry Aen_US
dc.identifier.volume111en_US
dc.identifier.issue4en_US
dc.identifier.startpage613en_US
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