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Kinetics of the reactions of O( 3 P ) and Cl( 2 P ) with HBr and Br 2
Author(s) -
Nicovich J. M.,
Wine P. H.
Publication year - 1990
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.550220406
Subject(s) - chemistry , arrhenius equation , kinetics , flash photolysis , chemical kinetics , reagent , analytical chemistry (journal) , photodissociation , reaction rate constant , resonance fluorescence , fluorescence , activation energy , photochemistry , chromatography , physics , quantum mechanics
A laser flash photolysis‐resonance fluorescence technique has been employed to study the kinetics of reactions (1)–(4) as a function of temperature.In all cases, the concentration of the excess reagent, i.e., HBr or Br 2 , was measured in situ in the slow flow system by UV‐visible photometry. Heterogeneous dark reactions between X Br ( X = H or Br) and the photolytic precursors for Cl( 2 P ) and O( 3 P ) (Cl 2 and O 3 , respectively) were avoided by injecting minimal amounts of precursor into the reaction mixture immediately upstream from the reaction zone. The following Arrhenius expressions summarize our results (errors are 2σ and represent precision only, units are cm 3 molecule −1 s −1 ): 1 = (1.76 ± 0.80) × 10 −11 exp[(40 ± 100)/ T ]; 2 = (2.40 ± 1.25) × 10 −10 exp[−(144 ± 176)/ T ]; 3 = (5.11 ± 2.82) × 10 −12 exp[−(1450 ± 160)/ T ]; 4 = (2.25 ± 0.56) × 10 −11 exp[−(400 ± 80)/ T ]. The consistency (or lack thereof) of our results with those reported in previous kinetics and dynamics studies of reactions (1)–(4) is discussed.