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 -