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Rate coefficients for the reaction of OH with Cl 2 , Br 2 , and I 2 from 235 to 354 K
Author(s) -
Gilles M. K.,
Burkholder J. B.,
Ravishankara A. R.
Publication year - 1999
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/(sici)1097-4601(1999)31:6<417::aid-kin3>3.0.co;2-a
Subject(s) - chemistry , analytical chemistry (journal) , molecule , photodissociation , laser , systematic error , statistics , organic chemistry , optics , physics , mathematics
Rate coefficients for the reaction of OH with Cl 2 , ( k 1 ), Br 2 , ( k 2 ) and I 2 , ( k 3 ), were measured under pseudo‐first‐order conditions in OH. OH was produced by pulsed laser photolysis of H 2 O 2 (or HNO 3 ) and its temporal profile was monitored by laser‐induced fluorescence. The measured rate coefficients for k 1 (231–354 K) and k 2 (235–357 K) are: k 1 ( T ) = (3.77 ± 1.02) × 10 −12 exp[−(1228 ± 140)/ T ] cm 3 molecule −1 s −1k 2 ( T ) = (1.98 ± 0.51) × 10 −11 exp[(238 ± 70)/ T ] cm 3 molecule −1 s −1k 3 was independent of temperature between 240 and 348 K with an average value of (2.10 ± 0.60) × 10 −10 cm 3 molecule −1 s −1 . The quoted uncertainties are 2σ (95% confidence limits, 1σ A = Aσ lnA ) and include estimated systematic errors. Our measurements significantly im‐prove the accuracy of k 1 . This is the first report of a slight negative temperature dependence for k 2 and of the temperature independence of k 3 . © 1999 John Wiley & Sons, Inc.* Int J Chem Kinet 31: 417–424, 1999