Predictions of the sulfur and carbon kinetic isotope effects in the OH + OCS reaction

Johan Albrecht Schmidt; Matthew Stanley Johnson; Y. Jung; S.O. Danielache; S. Hattori; N. Yoshida

doi:10.1016/j.cplett.2012.02.049

Predictions of the sulfur and carbon kinetic isotope effects in the OH + OCS reaction

Johan Albrecht Schmidt, Matthew Stanley Johnson, Y. Jung, S.O. Danielache, S. Hattori, N. Yoshida

Department of Chemistry

13 Citations (Scopus)

Abstract

The ³⁴S and ¹³C isotopic fractionations in the OCS + OH reaction are investigated using RRKM-theory. The reaction proceeds via different channels, at low pressures a channel leading to CO + SOH dominates. While with increasing pressure an adduct forming channel becomes competitive. The resulting overall rate constant is not strongly dependent on pressure and agrees well with experiments. The competition between channels makes the fractionation constants highly pressure dependent, however the sulfur-34 fractionation constant varies only from about -5‰ to 0‰ in the troposphere and lower stratosphere. The carbon-13 isotopic fractionation is stronger; between -40‰ and -70‰ in the troposphere and lower stratosphere.

Original language	English
Journal	Chemical Physics Letters
Volume	531
Pages (from-to)	64-69
Number of pages	6
ISSN	0009-2614
DOIs	https://doi.org/10.1016/j.cplett.2012.02.049
Publication status	Published - 2 Apr 2012

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10.1016/j.cplett.2012.02.049

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@article{f04389a791d44833a2c1e50b589743ba,

title = "Predictions of the sulfur and carbon kinetic isotope effects in the OH + OCS reaction",

abstract = "The 34S and 13C isotopic fractionations in the OCS + OH reaction are investigated using RRKM-theory. The reaction proceeds via different channels, at low pressures a channel leading to CO + SOH dominates. While with increasing pressure an adduct forming channel becomes competitive. The resulting overall rate constant is not strongly dependent on pressure and agrees well with experiments. The competition between channels makes the fractionation constants highly pressure dependent, however the sulfur-34 fractionation constant varies only from about -5‰ to 0‰ in the troposphere and lower stratosphere. The carbon-13 isotopic fractionation is stronger; between -40‰ and -70‰ in the troposphere and lower stratosphere.",

author = "Schmidt, {Johan Albrecht} and Johnson, {Matthew Stanley} and Y. Jung and S.O. Danielache and S. Hattori and N. Yoshida",

year = "2012",

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doi = "10.1016/j.cplett.2012.02.049",

language = "English",

volume = "531",

pages = "64--69",

journal = "Chemical Physics Letters",

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TY - JOUR

T1 - Predictions of the sulfur and carbon kinetic isotope effects in the OH + OCS reaction

AU - Schmidt, Johan Albrecht

AU - Johnson, Matthew Stanley

AU - Jung, Y.

AU - Danielache, S.O.

AU - Hattori, S.

AU - Yoshida, N.

PY - 2012/4/2

Y1 - 2012/4/2

N2 - The 34S and 13C isotopic fractionations in the OCS + OH reaction are investigated using RRKM-theory. The reaction proceeds via different channels, at low pressures a channel leading to CO + SOH dominates. While with increasing pressure an adduct forming channel becomes competitive. The resulting overall rate constant is not strongly dependent on pressure and agrees well with experiments. The competition between channels makes the fractionation constants highly pressure dependent, however the sulfur-34 fractionation constant varies only from about -5‰ to 0‰ in the troposphere and lower stratosphere. The carbon-13 isotopic fractionation is stronger; between -40‰ and -70‰ in the troposphere and lower stratosphere.

AB - The 34S and 13C isotopic fractionations in the OCS + OH reaction are investigated using RRKM-theory. The reaction proceeds via different channels, at low pressures a channel leading to CO + SOH dominates. While with increasing pressure an adduct forming channel becomes competitive. The resulting overall rate constant is not strongly dependent on pressure and agrees well with experiments. The competition between channels makes the fractionation constants highly pressure dependent, however the sulfur-34 fractionation constant varies only from about -5‰ to 0‰ in the troposphere and lower stratosphere. The carbon-13 isotopic fractionation is stronger; between -40‰ and -70‰ in the troposphere and lower stratosphere.

U2 - 10.1016/j.cplett.2012.02.049

DO - 10.1016/j.cplett.2012.02.049

M3 - Journal article

SN - 0009-2614

VL - 531

SP - 64

EP - 69

JO - Chemical Physics Letters

JF - Chemical Physics Letters

ER -

Predictions of the sulfur and carbon kinetic isotope effects in the OH + OCS reaction

Abstract

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