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A temperature‐dependent kinetics study of the reaction of O( 3 P J ) with (CH 3 ) 2 SO

A temperature‐dependent kinetics study of the reaction of O( 3 P J ) with (CH 3 ) 2 SO A laser flash photolysis–resonance fluorescence technique has been employed to investigate the kinetics of the reaction of ground state oxygen atoms, O(3PJ), with (CH3)2SO (dimethylsulfoxide) as a function of temperature (266–383 K) and pressure (20–100 Torr N2). The rate coefficient (kR1) for the O(3PJ) + (CH3)2SO reaction is found to be independent of pressure and to increase with decreasing temperature. The following Arrhenius expression adequately describes the observed temperature dependence: kR1(T) = (1.68 ± 0.76) × 10−12 exp((445 ± 141)/T) cm3 molecule−1 s−1, where the uncertainties in Arrhenius parameters are 2σ and represent precision only. The absolute accuracy of each measured rate coefficient is estimated to be ±30%, and is limited predominantly by the uncertainties in measured (CH3)2SO concentrations. The observed temperature and pressure dependencies suggest that, as in the case of O(3PJ) reactions with CH3SH and (CH3)2S, reaction occurs by addition of O(3PJ) to the sulfur atom followed by rapid fragmentation of the energized adduct to products. The O(3PJ) + (CH3)2SO reaction is fast enough so that it could be a useful laboratory source of the CH3SO2 radical if this species is produced in significant yield. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 156–161, 2002; DOI 10.1002/kin.10040 http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png International Journal of Chemical Kinetics Wiley

A temperature‐dependent kinetics study of the reaction of O( 3 P J ) with (CH 3 ) 2 SO

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Publisher
Wiley
Copyright
Copyright © 2002 Wiley Periodicals, Inc.
ISSN
0538-8066
eISSN
1097-4601
DOI
10.1002/kin.10040
Publisher site
See Article on Publisher Site

Abstract

A laser flash photolysis–resonance fluorescence technique has been employed to investigate the kinetics of the reaction of ground state oxygen atoms, O(3PJ), with (CH3)2SO (dimethylsulfoxide) as a function of temperature (266–383 K) and pressure (20–100 Torr N2). The rate coefficient (kR1) for the O(3PJ) + (CH3)2SO reaction is found to be independent of pressure and to increase with decreasing temperature. The following Arrhenius expression adequately describes the observed temperature dependence: kR1(T) = (1.68 ± 0.76) × 10−12 exp((445 ± 141)/T) cm3 molecule−1 s−1, where the uncertainties in Arrhenius parameters are 2σ and represent precision only. The absolute accuracy of each measured rate coefficient is estimated to be ±30%, and is limited predominantly by the uncertainties in measured (CH3)2SO concentrations. The observed temperature and pressure dependencies suggest that, as in the case of O(3PJ) reactions with CH3SH and (CH3)2S, reaction occurs by addition of O(3PJ) to the sulfur atom followed by rapid fragmentation of the energized adduct to products. The O(3PJ) + (CH3)2SO reaction is fast enough so that it could be a useful laboratory source of the CH3SO2 radical if this species is produced in significant yield. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 156–161, 2002; DOI 10.1002/kin.10040

Journal

International Journal of Chemical KineticsWiley

Published: Mar 1, 2002

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