Mechanistic studies of the OH-initiated oxidation of CS2 in the presence of O2

R. E. Stickel, M. Chin, E. P. Daykin, Anthony J Hynes, P. H. Wine, T. J. Wallington

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Abstract

We have investigated production of carbon- and sulfur-containing end products of the OH-initiated oxidation of CS2 in the presence of O2, an important atmospheric chemical reaction which is known to proceed via the following three elementary steps: OH + CS2 + M ↔ CS2OH + M; CS2OH + O2 → products. Two different experimental approaches were employed. In one set of experiments (CP-FTIR studies) continuous photolysis of CH3ONO/NO/CS2/Air mixtures at 298 K and 700-Torr total pressure was combined with product detection by Fourier transform infrared spectroscopy; these studies measured moles of products formed per mole of CS2 consumed. In a second set of experiments (LFP-TDLAS studies) 248-nm laser flash photolysis of H2O2/ CS2/N2O/He/O2 mixtures at 298 K and 25-100-Torr total pressure was combined with product detection by time-resolved tunable diode laser absorption spectroscopy; in this case, the quantity measured was moles of product formed per mole of OH consumed. In both studies OCS and CO are observed as carbon-containing products with yields of 0.83 ± 0.08 and 0.16 ± 0.03, respectively; uncertainties represent estimates of absolute accuracy at the 95% confidence level. The LFP-TDLAS experiments demonstrate that the above yields represent "prompt" product formation; i.e., OCS and CO are formed either as primary products of the CS2OH + O2 reaction or as products of a fast (k > 10-15 cm3 molecule-1 s-1) secondary reaction of a primary product with O2. The CP-FTIR experiments show that, under atmospheric conditions, SO2 is produced with a yield of 1.15 ± 0.10; in this case, the LFP-TDLAS results strongly suggest that only about three-fourths of the SO2 is formed as a prompt product, with the remainder generated via slow reaction of SO (generated as a prompt product of the CS2OH + O2 reaction) with O2. The implications of our results for understanding the detailed mechanism of the very complex CS2OH + O2 reaction are discussed, as are their implications for understanding the atmospheric cycles of CS2 and OCS.

Original languageEnglish (US)
Pages (from-to)13653-13661
Number of pages9
JournalJournal of Physical Chemistry
Volume97
Issue number51
StatePublished - 1993

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Oxidation
oxidation
Photolysis
Carbon Monoxide
products
Carbon
Experiments
Laser spectroscopy
Absorption spectroscopy
Sulfur
Fourier transform infrared spectroscopy
Semiconductor lasers
Chemical reactions
Molecules
hydroxide ion
Lasers
photolysis
Air
carbon
meteorology

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Stickel, R. E., Chin, M., Daykin, E. P., Hynes, A. J., Wine, P. H., & Wallington, T. J. (1993). Mechanistic studies of the OH-initiated oxidation of CS2 in the presence of O2 . Journal of Physical Chemistry, 97(51), 13653-13661.

Mechanistic studies of the OH-initiated oxidation of CS2 in the presence of O2 . / Stickel, R. E.; Chin, M.; Daykin, E. P.; Hynes, Anthony J; Wine, P. H.; Wallington, T. J.

In: Journal of Physical Chemistry, Vol. 97, No. 51, 1993, p. 13653-13661.

Research output: Contribution to journalArticle

Stickel, RE, Chin, M, Daykin, EP, Hynes, AJ, Wine, PH & Wallington, TJ 1993, 'Mechanistic studies of the OH-initiated oxidation of CS2 in the presence of O2 ', Journal of Physical Chemistry, vol. 97, no. 51, pp. 13653-13661.
Stickel RE, Chin M, Daykin EP, Hynes AJ, Wine PH, Wallington TJ. Mechanistic studies of the OH-initiated oxidation of CS2 in the presence of O2 . Journal of Physical Chemistry. 1993;97(51):13653-13661.
Stickel, R. E. ; Chin, M. ; Daykin, E. P. ; Hynes, Anthony J ; Wine, P. H. ; Wallington, T. J. / Mechanistic studies of the OH-initiated oxidation of CS2 in the presence of O2 . In: Journal of Physical Chemistry. 1993 ; Vol. 97, No. 51. pp. 13653-13661.
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AU - Chin, M.

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AU - Wine, P. H.

AU - Wallington, T. J.

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N2 - We have investigated production of carbon- and sulfur-containing end products of the OH-initiated oxidation of CS2 in the presence of O2, an important atmospheric chemical reaction which is known to proceed via the following three elementary steps: OH + CS2 + M ↔ CS2OH + M; CS2OH + O2 → products. Two different experimental approaches were employed. In one set of experiments (CP-FTIR studies) continuous photolysis of CH3ONO/NO/CS2/Air mixtures at 298 K and 700-Torr total pressure was combined with product detection by Fourier transform infrared spectroscopy; these studies measured moles of products formed per mole of CS2 consumed. In a second set of experiments (LFP-TDLAS studies) 248-nm laser flash photolysis of H2O2/ CS2/N2O/He/O2 mixtures at 298 K and 25-100-Torr total pressure was combined with product detection by time-resolved tunable diode laser absorption spectroscopy; in this case, the quantity measured was moles of product formed per mole of OH consumed. In both studies OCS and CO are observed as carbon-containing products with yields of 0.83 ± 0.08 and 0.16 ± 0.03, respectively; uncertainties represent estimates of absolute accuracy at the 95% confidence level. The LFP-TDLAS experiments demonstrate that the above yields represent "prompt" product formation; i.e., OCS and CO are formed either as primary products of the CS2OH + O2 reaction or as products of a fast (k > 10-15 cm3 molecule-1 s-1) secondary reaction of a primary product with O2. The CP-FTIR experiments show that, under atmospheric conditions, SO2 is produced with a yield of 1.15 ± 0.10; in this case, the LFP-TDLAS results strongly suggest that only about three-fourths of the SO2 is formed as a prompt product, with the remainder generated via slow reaction of SO (generated as a prompt product of the CS2OH + O2 reaction) with O2. The implications of our results for understanding the detailed mechanism of the very complex CS2OH + O2 reaction are discussed, as are their implications for understanding the atmospheric cycles of CS2 and OCS.

AB - We have investigated production of carbon- and sulfur-containing end products of the OH-initiated oxidation of CS2 in the presence of O2, an important atmospheric chemical reaction which is known to proceed via the following three elementary steps: OH + CS2 + M ↔ CS2OH + M; CS2OH + O2 → products. Two different experimental approaches were employed. In one set of experiments (CP-FTIR studies) continuous photolysis of CH3ONO/NO/CS2/Air mixtures at 298 K and 700-Torr total pressure was combined with product detection by Fourier transform infrared spectroscopy; these studies measured moles of products formed per mole of CS2 consumed. In a second set of experiments (LFP-TDLAS studies) 248-nm laser flash photolysis of H2O2/ CS2/N2O/He/O2 mixtures at 298 K and 25-100-Torr total pressure was combined with product detection by time-resolved tunable diode laser absorption spectroscopy; in this case, the quantity measured was moles of product formed per mole of OH consumed. In both studies OCS and CO are observed as carbon-containing products with yields of 0.83 ± 0.08 and 0.16 ± 0.03, respectively; uncertainties represent estimates of absolute accuracy at the 95% confidence level. The LFP-TDLAS experiments demonstrate that the above yields represent "prompt" product formation; i.e., OCS and CO are formed either as primary products of the CS2OH + O2 reaction or as products of a fast (k > 10-15 cm3 molecule-1 s-1) secondary reaction of a primary product with O2. The CP-FTIR experiments show that, under atmospheric conditions, SO2 is produced with a yield of 1.15 ± 0.10; in this case, the LFP-TDLAS results strongly suggest that only about three-fourths of the SO2 is formed as a prompt product, with the remainder generated via slow reaction of SO (generated as a prompt product of the CS2OH + O2 reaction) with O2. The implications of our results for understanding the detailed mechanism of the very complex CS2OH + O2 reaction are discussed, as are their implications for understanding the atmospheric cycles of CS2 and OCS.

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