Gas Phase Kinetics and Equilibrium of Allyl Radical Reactions with NO and NO₂ Metadata

Metadata describes a digital item, providing (if known) such information as creator, publisher, contents, size, relationship to other resources, and more. Metadata may also contain "preservation" components that help us to maintain the integrity of digital files over time.

Title

  • Main Title Gas Phase Kinetics and Equilibrium of Allyl Radical Reactions with NO and NO₂

Creator

  • Author: Rissanen, Matti P.
    Creator Type: Personal
    Creator Info: University of Helsinki
  • Author: Amedro, Damien
    Creator Type: Personal
    Creator Info: Université Lille
  • Author: Krasnoperov, Lev N.
    Creator Type: Personal
    Creator Info: New Jersey Institute of Technology
  • Author: Marshall, Paul
    Creator Type: Personal
    Creator Info: University of North Texas
  • Author: Timonen, Raimo S.
    Creator Type: Personal
    Creator Info: University of Helsinki

Publisher

  • Name: American Chemical Society
    Place of Publication: [Washington, D.C.]

Date

  • Submission Date: 2012-08-30
  • Acceptance Date: 2013-01-10
  • Creation: 2013-01-11

Language

  • English

Description

  • Content Description: Article on gas phase kinetics and equilibrium of allyl radical reactions with NO and NO₂.
  • Physical Description: 13 p.

Subject

  • Keyword: allyl radical reactions
  • Keyword: bath gas density
  • Keyword: nitrogen oxides

Source

  • Journal: Journal of Physical Chemistry A, 2013, Washington D.C.: American Chemical Society, pp. 793-805

Citation

  • Publication Title: Journal of Physical Chemistry A
  • Volume: 117
  • Issue: 5
  • Page Start: 793
  • Page End: 805
  • Pages: 13
  • Peer Reviewed: True

Collection

  • Name: UNT Scholarly Works
    Code: UNTSW

Institution

  • Name: UNT College of Arts and Sciences
    Code: UNTCAS

Rights

  • Rights Access: public

Resource Type

  • Article

Format

  • Text

Identifier

  • DOI: 10.1021/jp308621f
  • Archival Resource Key: ark:/67531/metadc488138

Degree

  • Academic Department: Chemistry
  • Academic Department: Center for Advanced Scientific Computing and Modeling

Note

  • 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.