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Kinetic and mechanistic study of the reaction of O( 1 D) with CF 2 HBr
Author(s) -
Strekowski R. S.,
Nicovich J. M.,
Wine P. H.
Publication year - 2001
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.1019
Subject(s) - chemistry , arrhenius equation , flash photolysis , branching fraction , branching (polymer chemistry) , excited state , kinetics , reaction rate constant , chemical kinetics , kinetic isotope effect , reactivity (psychology) , atmospheric temperature range , analytical chemistry (journal) , deuterium , activation energy , atomic physics , thermodynamics , organic chemistry , physics , quantum mechanics , medicine , alternative medicine , pathology
A laser flash photolysis–resonance fluorescence technique has been employed to investigate the kinetics and mechanism of the reaction of electronically excited oxygen atoms, O( 1 D), with CF 2 HBr. Absolute rate coefficients ( k 1 ) for the deactivation of O( 1 D) by CF 2 HBr have been measured as a function of temperature over the range 211–425 K. The results are well described by the Arrhenius expression k 1 (T) = 1.72 × 10 −10 exp(+72/T) cm 3 molecule −1 s −1 ; the accuracy of each reported rate coefficient is estimated to be ±15% (2σ). The branching ratio for nonreactive quenching of O( 1 D) to the ground state, O( 3 P), is found to be 0.39 ± 0.06 independent of temperature, while the branching ratio for production of hydrogen atoms at 298 K is found to be 0.02 −0.02 +0.01 . The above results are considered in conjunction with other published information to examine reactivity trends in O( 1 D) + CF 2 XY reactions (X,Y = H, F, Cl, Br). © 2001 John Wiley & Sons, Inc. Int J Chem Kinet 33: 262–270, 2001