The kinetics study of the S + S2 → S3 reaction by the chaperone mechanism

Shiyu Du, Timothy C. Germann, Joseph S. Francisco, Kirk A. Peterson, Hua Gen Yu, James Lyons

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

The recombination of S atoms has been found to be stepwise from the smallest unit, the elemental S atom, to the most abundant molecule S 8. The reaction between S S2 → S3 has not been reported either experimentally or by theory, but may be a key intermediate step in the formation of sulfur aerosols in low-O2 atmospheres. In this work, the kinetics of this reaction is reported with Ar gas used as the chaperone molecule in the production of S3 via two complex intermediates: SAr + S2 and S2Ar + S. Quasi-classical and classical trajectory methods are used. The rate constant of the S + S 2 + Ar → S3 + Ar reaction is determined to be 2.66 × 10-33 cm6 mol-1 s-1 at 298.15 K. The temperature dependence of the reaction is found to be 2.67 × 10-33 exp[143.56(1/T-1298.15)]. The second-order rate constant of S + S2 → S3 is 6.47 × 10-14 cm 3 molecule-1 s-1 at 298.15 K and the Arrhenius-type rate constant is calculated to be 6.25 × 10-14 exp[450.15(1/T-1298.15)] cm3 molecule-1 s-1. This work provides a rate coefficient for a key intermediate species in studies of sulfur formation in the modern Venus atmosphere and the primitive Earth atmosphere, for which assumed model rate coefficients have spanned nearly 4 orders of magnitude. Although a symmetry-induced mass-independent isotope effect is not expected for a chaperone mechanism, the present work is an important step toward evaluating whether mass-independence is expected for thiozone formation as is observed for ozone formation.

Original languageEnglish (US)
Article number154508
JournalJournal of Chemical Physics
Volume134
Issue number15
DOIs
StatePublished - Apr 21 2011
Externally publishedYes

Fingerprint

Rate constants
Molecules
Kinetics
kinetics
Sulfur
primitive Earth atmosphere
molecules
sulfur
Atoms
Earth atmosphere
Venus atmosphere
Ozone
Aerosols
lower atmosphere
Isotopes
coefficients
Gases
isotope effect
Trajectories
ozone

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Du, S., Germann, T. C., Francisco, J. S., Peterson, K. A., Yu, H. G., & Lyons, J. (2011). The kinetics study of the S + S2 → S3 reaction by the chaperone mechanism. Journal of Chemical Physics, 134(15), [154508]. https://doi.org/10.1063/1.3572226

The kinetics study of the S + S2 → S3 reaction by the chaperone mechanism. / Du, Shiyu; Germann, Timothy C.; Francisco, Joseph S.; Peterson, Kirk A.; Yu, Hua Gen; Lyons, James.

In: Journal of Chemical Physics, Vol. 134, No. 15, 154508, 21.04.2011.

Research output: Contribution to journalArticle

Du, Shiyu ; Germann, Timothy C. ; Francisco, Joseph S. ; Peterson, Kirk A. ; Yu, Hua Gen ; Lyons, James. / The kinetics study of the S + S2 → S3 reaction by the chaperone mechanism. In: Journal of Chemical Physics. 2011 ; Vol. 134, No. 15.
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