Dynamics of reactions of O(3P) atoms with CS, CS2 and OCS

D. S.Y. Hsu; W. M. Shaub; T. L. Burks; Ming-Chang Lin

doi:10.1016/0301-0104(79)80114-7

Dynamics of reactions of O(³P) atoms with CS, CS₂ and OCS

D. S.Y. Hsu^*, W. M. Shaub, T. L. Burks, Ming-Chang Lin

^*Corresponding author for this work

Department of Applied Chemistry

Research output: Contribution to journal › Article › peer-review

35 Scopus citations

Abstract

The reactions of CS(X ¹Σ⁺), CS₂(X ¹Σ⁺ _g) and OCS(X ¹Σ⁺) with O(³P) were studied at 298 K by means of a CO laser resonance absorption technique. The CO(ν) population distribution produced from the reaction O(³P) + CS(X ¹Σ⁺) studied in a quartz flash photolysis tube (λ >/ 200 nm) is similar to distributions observed previously for ν > 7. For ν < 7 an energetically colder vibrational population was observed which is attributed to the reaction of O(³P) atoms with undissociated CS₂(X ¹Σ⁺ _g). Subsequent experiments carried out in a Pyrex flash photolysis tube (λ >/ 300 nm) in which the O(³P) + CS₂(X ¹Σ⁺ _g) reaction is the only one which can occur confirmed that the colder population observed is attributable to this process. The branching ratio for the reaction channel O(³P) + CS₂(X ¹Σ⁺ _g) → CO(X ¹Σ⁺) + S₂(³Σ^- _g) has been measured. We find that 1.4 ± 0.2% of the O + CS₂ reaction proceeds through this channel, and that the rate constant for this reaction channel is, k = 3.5 (±0.5) × 10¹⁰ cm³/mole s. Isotope labeled experiments using ¹⁸O atoms show that the O(³P) + OCS(X ¹Σ⁺) reaction takes place by a direct stripping mechanism, wherein CO(ν) is produced exclusively from the parent OCS molecule. The CO(ν) formed in this reaction carries about 9% of the total available energy.

Original language	English
Pages (from-to)	143-150
Number of pages	8
Journal	Chemical Physics
Volume	44
Issue number	2
DOIs	https://doi.org/10.1016/0301-0104(79)80114-7
State	Published - 1 Dec 1979

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@article{d5b2e574007649d78ec1ed932df28428,

title = "Dynamics of reactions of O(3P) atoms with CS, CS2 and OCS",

abstract = "The reactions of CS(X 1Σ+), CS2(X 1Σ+ g) and OCS(X 1Σ+) with O(3P) were studied at 298 K by means of a CO laser resonance absorption technique. The CO(ν) population distribution produced from the reaction O(3P) + CS(X 1Σ+) studied in a quartz flash photolysis tube (λ >/ 200 nm) is similar to distributions observed previously for ν > 7. For ν < 7 an energetically colder vibrational population was observed which is attributed to the reaction of O(3P) atoms with undissociated CS2(X 1Σ+ g). Subsequent experiments carried out in a Pyrex flash photolysis tube (λ >/ 300 nm) in which the O(3P) + CS2(X 1Σ+ g) reaction is the only one which can occur confirmed that the colder population observed is attributable to this process. The branching ratio for the reaction channel O(3P) + CS2(X 1Σ+ g) → CO(X 1Σ+) + S2(3Σ- g) has been measured. We find that 1.4 ± 0.2% of the O + CS2 reaction proceeds through this channel, and that the rate constant for this reaction channel is, k = 3.5 (±0.5) × 1010 cm3/mole s. Isotope labeled experiments using 18O atoms show that the O(3P) + OCS(X 1Σ+) reaction takes place by a direct stripping mechanism, wherein CO(ν) is produced exclusively from the parent OCS molecule. The CO(ν) formed in this reaction carries about 9% of the total available energy.",

author = "Hsu, {D. S.Y.} and Shaub, {W. M.} and Burks, {T. L.} and Ming-Chang Lin",

year = "1979",

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T1 - Dynamics of reactions of O(3P) atoms with CS, CS2 and OCS

AU - Hsu, D. S.Y.

AU - Shaub, W. M.

AU - Burks, T. L.

AU - Lin, Ming-Chang

PY - 1979/12/1

Y1 - 1979/12/1

N2 - The reactions of CS(X 1Σ+), CS2(X 1Σ+ g) and OCS(X 1Σ+) with O(3P) were studied at 298 K by means of a CO laser resonance absorption technique. The CO(ν) population distribution produced from the reaction O(3P) + CS(X 1Σ+) studied in a quartz flash photolysis tube (λ >/ 200 nm) is similar to distributions observed previously for ν > 7. For ν < 7 an energetically colder vibrational population was observed which is attributed to the reaction of O(3P) atoms with undissociated CS2(X 1Σ+ g). Subsequent experiments carried out in a Pyrex flash photolysis tube (λ >/ 300 nm) in which the O(3P) + CS2(X 1Σ+ g) reaction is the only one which can occur confirmed that the colder population observed is attributable to this process. The branching ratio for the reaction channel O(3P) + CS2(X 1Σ+ g) → CO(X 1Σ+) + S2(3Σ- g) has been measured. We find that 1.4 ± 0.2% of the O + CS2 reaction proceeds through this channel, and that the rate constant for this reaction channel is, k = 3.5 (±0.5) × 1010 cm3/mole s. Isotope labeled experiments using 18O atoms show that the O(3P) + OCS(X 1Σ+) reaction takes place by a direct stripping mechanism, wherein CO(ν) is produced exclusively from the parent OCS molecule. The CO(ν) formed in this reaction carries about 9% of the total available energy.

AB - The reactions of CS(X 1Σ+), CS2(X 1Σ+ g) and OCS(X 1Σ+) with O(3P) were studied at 298 K by means of a CO laser resonance absorption technique. The CO(ν) population distribution produced from the reaction O(3P) + CS(X 1Σ+) studied in a quartz flash photolysis tube (λ >/ 200 nm) is similar to distributions observed previously for ν > 7. For ν < 7 an energetically colder vibrational population was observed which is attributed to the reaction of O(3P) atoms with undissociated CS2(X 1Σ+ g). Subsequent experiments carried out in a Pyrex flash photolysis tube (λ >/ 300 nm) in which the O(3P) + CS2(X 1Σ+ g) reaction is the only one which can occur confirmed that the colder population observed is attributable to this process. The branching ratio for the reaction channel O(3P) + CS2(X 1Σ+ g) → CO(X 1Σ+) + S2(3Σ- g) has been measured. We find that 1.4 ± 0.2% of the O + CS2 reaction proceeds through this channel, and that the rate constant for this reaction channel is, k = 3.5 (±0.5) × 1010 cm3/mole s. Isotope labeled experiments using 18O atoms show that the O(3P) + OCS(X 1Σ+) reaction takes place by a direct stripping mechanism, wherein CO(ν) is produced exclusively from the parent OCS molecule. The CO(ν) formed in this reaction carries about 9% of the total available energy.

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U2 - 10.1016/0301-0104(79)80114-7

DO - 10.1016/0301-0104(79)80114-7

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AN - SCOPUS:0040866094

SN - 0301-0104

VL - 44

SP - 143

EP - 150

JO - Chemical Physics

JF - Chemical Physics

IS - 2

ER -

Dynamics of reactions of O(³P) atoms with CS, CS₂ and OCS

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