Kinetics of the recombination reaction SH + O₂ + Ar: Implications for the formation and loss of HSOO and SOO in the atmosphere

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Article on kinetics of the recombination reaction SH + O₂ + Ar and implications for the formation and loss of HSOO and SOO in the atmosphere.

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3 p.

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Goumri, Abdellatif; Rocha, John-David Ray & Marshall, Paul July 1995.

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Article on kinetics of the recombination reaction SH + O₂ + Ar and implications for the formation and loss of HSOO and SOO in the atmosphere.

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3 p.

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Abstract: Unimolecular pathways for the dissociation of thiylperoxyl have been investigated computationally. Gaussian-2 (G2) theory was employed to calculate the thermochemistry, and the kinetics of SH + O₂ → HSOO are analyzed by RRKM theory. Under atmospheric conditions the rate constant is close to the low-pressure limit of k₀ ≈ 9.2 x 10⁻³⁴ (T/298 K)(-1.69) molecule⁻² cm⁶ s⁻¹ for T = 200-400 K. By comparison to other tropospheric oxidation reactions of thiyl radicals, addition to oxygen yields the shortest lifetime, although the low G2 S-O bond dissociation enthalpy implies a small equilibrium constant and means that HSOO formation is likely to be important only below 298 K. Singlet and triplet SOO have been characterized, and ∆H(f.298) (¹SOO) is predicted to be 185.5 kJ mol⁻¹. The results are discussed in the context of atmospheric chemistry.

Reprinted with permission from the Journal of Physical Chemistry. Copyright 1995 American Chemical Society.

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  • Journal of Physical Chemistry, 1995, Washington D.C.: American Chemical Society, pp. 10834-10836

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  • Publication Title: Journal of Physical Chemistry
  • Volume: 99
  • Issue: 27
  • Page Start: 10834
  • Page End: 10836
  • Pages: 3
  • Peer Reviewed: Yes

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  • July 1995

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  • April 25, 2015, 8:59 p.m.

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Goumri, Abdellatif; Rocha, John-David Ray & Marshall, Paul. Kinetics of the recombination reaction SH + O₂ + Ar: Implications for the formation and loss of HSOO and SOO in the atmosphere, article, July 1995; [Washington, D.C.]. (digital.library.unt.edu/ark:/67531/metadc503260/: accessed November 21, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT College of Arts and Sciences.