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Temperature‐dependent kinetics study of the gas‐phase reactions of atomic chlorine with acetone, 2‐butanone, and 3‐pentanone
Author(s) -
Zhao Z.,
Huskey D. T.,
Nicovich J. M.,
Wine P. H.
Publication year - 2008
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.20321
Subject(s) - chemistry , arrhenius equation , chlorine atom , acetone , kinetics , flash photolysis , reaction rate constant , atmospheric temperature range , ketone , kinetic energy , resonance fluorescence , analytical chemistry (journal) , chlorine , thermodynamics , activation energy , medicinal chemistry , organic chemistry , fluorescence , physics , quantum mechanics
A laser flash photolysis–resonance fluorescence technique has been employed to study the kinetics of the reactions of atomic chlorine with acetone (CH 3 C(O)CH 3 ; k 1 ), 2‐butanone (C 2 H 5 C(O)CH 3 ; k 2 ), and 3‐pentanone (C 2 H 5 C(O)C 2 H 5 ; k 3 ) as a function of temperature (210–440 K) and pressure (30–300 Torr N 2 ). No significant pressure dependence is observed for any of the reactions studied. Arrhenius expressions (units are 10 −11 cm 3 molecule −1 s −1 ) obtained from the data are k 1 (T) = (1.53 ± 0.19) exp[(−594 ± 33)/T], k 2 (T) = (2.77 ± 0.33) exp[(+76 ± 33)/T], and k 3 (T) = (5.66 ± 0.41) exp[(+87 ± 22)/T], where uncertainties are 2σ and represent precision only. The accuracy of reported rate coefficients is estimated to be ±15% over the entire range of pressure and temperature investigated. The room temperature rate coefficients reported in this study are in good agreement with a majority of literature values. However, the activation energies reported in this study are in poor agreement with the literature values, particularly for 2‐butanone and 3‐pentanone. Possible explanations for discrepancies in published kinetic parameters are proposed, and the potential role of Cl + ketone reactions in atmospheric chemistry is discussed. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 40: 259–267, 2008