Isotope effect in the carbonyl sulfide reaction with O(3P)

Shohei Hattori; Johan Albrecht Schmidt; Denise W. Mahler; Sebastian O. Danielache; Matthew Stanley Johnson; Naohiro Yoshida

doi:10.1021/jp2120884

Isotope effect in the carbonyl sulfide reaction with O(³P)

Shohei Hattori, Johan Albrecht Schmidt, Denise W. Mahler, Sebastian O. Danielache, Matthew Stanley Johnson, Naohiro Yoshida

Department of Chemistry

13 Citations (Scopus)

Abstract

The sulfur kinetic isotope effect (KIE) in the reaction of carbonyl sulfide (OCS) with O(³P) was studied in relative rate experiments at 298 ± 2 K and 955 ± 10 mbar. The reaction was carried out in a photochemical reactor using long path FTIR detection, and data were analyzed using a nonlinear least-squares spectral fitting procedure with line parameters from the HITRAN database. The ratio of the rate of the reaction of OC ³⁴S relative to OC³²S was found to be 0.9783 ± 0.0062 (³⁴ε = (-21.7 ± 6.2)‰). The KIE was also calculated using quantum chemistry and classical transition state theory; at 300 K, the isotopic fractionation was found to be ³⁴Îμ = ε14.8‰. The OCS sink reaction with O(³P) cannot explain the large fractionation in ³⁴S, over +73‰, indicated by remote sensing data. In addition, ³⁴Îμ in OCS photolysis and OH oxidation are not larger than 10‰, indicating that, on the basis of isotopic analysis, OCS is an acceptable source of background stratospheric sulfate aerosol.

Original language	English
Journal	Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
Volume	116
Issue number	14
Pages (from-to)	3521-3526
Number of pages	6
ISSN	1089-5639
DOIs	https://doi.org/10.1021/jp2120884
Publication status	Published - 12 Apr 2012

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Isotope effect in the carbonyl sulfide reaction with O(³P). / Hattori, Shohei; Schmidt, Johan Albrecht; Mahler, Denise W. et al.
In: Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory, Vol. 116, No. 14, 12.04.2012, p. 3521-3526.

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title = "Isotope effect in the carbonyl sulfide reaction with O(3P)",

abstract = "The sulfur kinetic isotope effect (KIE) in the reaction of carbonyl sulfide (OCS) with O(3P) was studied in relative rate experiments at 298 ± 2 K and 955 ± 10 mbar. The reaction was carried out in a photochemical reactor using long path FTIR detection, and data were analyzed using a nonlinear least-squares spectral fitting procedure with line parameters from the HITRAN database. The ratio of the rate of the reaction of OC 34S relative to OC32S was found to be 0.9783 ± 0.0062 (34ε = (-21.7 ± 6.2)‰). The KIE was also calculated using quantum chemistry and classical transition state theory; at 300 K, the isotopic fractionation was found to be 34{\^I}μ = ε14.8‰. The OCS sink reaction with O(3P) cannot explain the large fractionation in 34S, over +73‰, indicated by remote sensing data. In addition, 34{\^I}μ in OCS photolysis and OH oxidation are not larger than 10‰, indicating that, on the basis of isotopic analysis, OCS is an acceptable source of background stratospheric sulfate aerosol.",

author = "Shohei Hattori and Schmidt, {Johan Albrecht} and Mahler, {Denise W.} and Danielache, {Sebastian O.} and Johnson, {Matthew Stanley} and Naohiro Yoshida",

year = "2012",

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doi = "10.1021/jp2120884",

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T1 - Isotope effect in the carbonyl sulfide reaction with O(3P)

AU - Hattori, Shohei

AU - Schmidt, Johan Albrecht

AU - Mahler, Denise W.

AU - Danielache, Sebastian O.

AU - Johnson, Matthew Stanley

AU - Yoshida, Naohiro

PY - 2012/4/12

Y1 - 2012/4/12

N2 - The sulfur kinetic isotope effect (KIE) in the reaction of carbonyl sulfide (OCS) with O(3P) was studied in relative rate experiments at 298 ± 2 K and 955 ± 10 mbar. The reaction was carried out in a photochemical reactor using long path FTIR detection, and data were analyzed using a nonlinear least-squares spectral fitting procedure with line parameters from the HITRAN database. The ratio of the rate of the reaction of OC 34S relative to OC32S was found to be 0.9783 ± 0.0062 (34ε = (-21.7 ± 6.2)‰). The KIE was also calculated using quantum chemistry and classical transition state theory; at 300 K, the isotopic fractionation was found to be 34Îμ = ε14.8‰. The OCS sink reaction with O(3P) cannot explain the large fractionation in 34S, over +73‰, indicated by remote sensing data. In addition, 34Îμ in OCS photolysis and OH oxidation are not larger than 10‰, indicating that, on the basis of isotopic analysis, OCS is an acceptable source of background stratospheric sulfate aerosol.

AB - The sulfur kinetic isotope effect (KIE) in the reaction of carbonyl sulfide (OCS) with O(3P) was studied in relative rate experiments at 298 ± 2 K and 955 ± 10 mbar. The reaction was carried out in a photochemical reactor using long path FTIR detection, and data were analyzed using a nonlinear least-squares spectral fitting procedure with line parameters from the HITRAN database. The ratio of the rate of the reaction of OC 34S relative to OC32S was found to be 0.9783 ± 0.0062 (34ε = (-21.7 ± 6.2)‰). The KIE was also calculated using quantum chemistry and classical transition state theory; at 300 K, the isotopic fractionation was found to be 34Îμ = ε14.8‰. The OCS sink reaction with O(3P) cannot explain the large fractionation in 34S, over +73‰, indicated by remote sensing data. In addition, 34Îμ in OCS photolysis and OH oxidation are not larger than 10‰, indicating that, on the basis of isotopic analysis, OCS is an acceptable source of background stratospheric sulfate aerosol.

U2 - 10.1021/jp2120884

DO - 10.1021/jp2120884

M3 - Journal article

C2 - 22424142

SN - 1089-5639

VL - 116

SP - 3521

EP - 3526

JO - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory

JF - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory

IS - 14

ER -

Isotope effect in the carbonyl sulfide reaction with O(3P)

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Isotope effect in the carbonyl sulfide reaction with O(³P)