Gas Phase Kinetics and Equilibrium of Allyl Radical Reactions with NO and NO₂ Metadata
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- Main Title Gas Phase Kinetics and Equilibrium of Allyl Radical Reactions with NO and NO₂
Author: Rissanen, Matti P.Creator Type: PersonalCreator Info: University of Helsinki
Author: Amedro, DamienCreator Type: PersonalCreator Info: Université Lille
Author: Krasnoperov, Lev N.Creator Type: PersonalCreator Info: New Jersey Institute of Technology
Author: Marshall, PaulCreator Type: PersonalCreator Info: University of North Texas
Author: Timonen, Raimo S.Creator Type: PersonalCreator Info: University of Helsinki
Name: American Chemical SocietyPlace of Publication: [Washington, D.C.]
- Submission Date: 2012-08-30
- Acceptance Date: 2013-01-10
- Creation: 2013-01-11
- Content Description: Article on gas phase kinetics and equilibrium of allyl radical reactions with NO and NO₂.
- Physical Description: 13 p.
- Keyword: allyl radical reactions
- Keyword: bath gas density
- Keyword: nitrogen oxides
- Journal: Journal of Physical Chemistry A, 2013, Washington D.C.: American Chemical Society, pp. 793-805
- Publication Title: Journal of Physical Chemistry A
- Volume: 117
- Issue: 5
- Page Start: 793
- Page End: 805
- Pages: 13
- Peer Reviewed: True
Name: UNT Scholarly WorksCode: UNTSW
Name: UNT College of Arts and SciencesCode: UNTCAS
- Rights Access: public
- DOI: 10.1021/jp308621f
- Archival Resource Key: ark:/67531/metadc488138
- Academic Department: Chemistry
- Academic Department: Center for Advanced Scientific Computing and Modeling
- Display Note: Abstract: Allyl radical reactions with NO and NO2 were studied in direct, time-resolved experiments in a temperature controlled tubular flow reactor connected to a laser photolysis/photoionization mass spectrometer (LP-PIMS). In the C3H5 + NO reaction 1, a dependence on the bath gas density was observed in the determined rate coefficients and pressure falloff parametrizations were performed. The obtained rate coefficients vary between 0.30–14.2 × 10–12 cm3 s–1 (T = 188–363 K, p = 0.39–23.78 Torr He) and possess a negative temperature dependence. The rate coefficients of the C3H5 + NO2 reaction 2 did not show a dependence on the bath gas density in the range used (p = 0.47–3.38 Torr, T = 201–363 K), and they can be expressed as a function of temperature with k(C3H5 + NO2) = (3.97 ± 0.84) × 10–11 × (T/300 K) –1.55±0.05 cm3 s–1. In the C3H5 + NO reaction, above 410 K the observed C3H5 radical signal did not decay to the signal background, indicating equilibrium between C3H5 + NO and C3H5NO. This allowed the C3H5 + NO ⇄ C3H5NO equilibrium to be studied and the equilibrium constants of the reaction between 414 and 500 K to be determined. With the standard second- and third-law analysis, the enthalpy and entropy of the C3H5 + NO ⇄ C3H5NO reaction were obtained. Combined with the calculated standard entropy of reaction (ΔS°298 = 137.2 J mol–1K–1), the third-law analysis resulted in ΔH°298 = 102.4 ± 3.2 kJ mol–1 for the C3H5–NO bond dissociation enthalpy.
- Display Note: Reprinted with permission from the Journal of Physical Chemistry A. Copyright 2013 American Chemical Society.