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Absolute determinations of the addition rate constants for the reactions of O( 3 P) atoms with halogenated propenes and butenes. A structure–activity relationship for the estimation of rate constants
Author(s) -
Cometto Pablo M.,
Teruel Mariano A.,
Taccone Raúl A.,
Lane Silvia I.
Publication year - 2005
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.873
Subject(s) - chemistry , reaction rate constant , alkene , reactivity (psychology) , substituent , kinetics , kinetic energy , medicinal chemistry , molecule , computational chemistry , organic chemistry , catalysis , medicine , physics , alternative medicine , pathology , quantum mechanics
The kinetics of the reactions of O( 3 P) atoms with CF 3 CHCH 2 , CF 3 CClCCl 2 , CF 3 CFCClCF 3 and CF 3 CClCClCF 3 were studied at 298 K using a discharge flow tube system. This is the first absolute kinetic study of these reactions. The overall rate constants based on the measured afterglow reactions were (3.4±0.4) × 10 −14 , (3.3±0.6) × 10 −14 , (1.3±0.3) × 10 −14 and (1.9±0.4) × 10 −14 cm 3 molecule −1 s −1 , respectively. The experiments were carried out under pseudo‐first‐order conditions with [O( 3 P)] 0 ≪ [alkene] 0 . The effect of substituent atoms or groups on the reactivity was analyzed. A simple method, using a structure–activity relationship based on the structure of the alkene, was applied for the first time to the reactions of O( 3 P) with haloalkenes. It is shown that this approach is useful in obtaining an initial estimate of unknown rate constants for reactions of O( 3 P) with alkenes. Copyright © 2004 John Wiley & Sons, Ltd.