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

Kemisk Institut

13 Citationer (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.

Originalsprog	Engelsk
Tidsskrift	Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
Vol/bind	116
Udgave nummer	14
Sider (fra-til)	3521-3526
Antal sider	6
ISSN	1089-5639
DOI	https://doi.org/10.1021/jp2120884
Status	Udgivet - 12 apr. 2012

Adgang til dokumentet

10.1021/jp2120884

Citationsformater

@article{bd699486ce1f4e58b102514f4266f044,

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",

month = apr,

day = "12",

doi = "10.1021/jp2120884",

language = "English",

volume = "116",

pages = "3521--3526",

journal = "Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory",

issn = "1089-5639",

publisher = "American Chemical Society",

number = "14",

}

TY - JOUR

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)

Abstract

Adgang til dokumentet

Fingeraftryk

Citationsformater

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