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Effects of ring strain on gas‐phase rate constants. 2. OH radical reactions with cycloalkenes
Author(s) -
Atkinson Roger,
Aschmann Sara M.,
Carter William P. L.
Publication year - 1983
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.550151105
Subject(s) - chemistry , cyclopentene , cyclohexene , radical , cycloheptene , reaction rate constant , cycloalkene , bicyclic molecule , double bond , medicinal chemistry , photochemistry , isoprene , hydrocarbon , organic chemistry , kinetics , catalysis , physics , polymer , quantum mechanics , copolymer
Relative rate constants for the gas‐phase reactions of OH radicals with a series of cycloalkenes have been determined at 298 ± 2 K using methyl nitrite photolysis in air as a source of OH radicals. Using a rate constant for the reaction of OH radicals with isoprene of 9.60 × 10 −11 cm 3 molecule −1 s −1 , the rate constants obtained were (X 10 11 cm 3 molecule −1 s −1 ): cyclopentene 6.39 ± 0.23, cyclohexene 6.43 ± 0.17, cycloheptene 7.08 ± 0.22, 1,3‐cyclohexadiene 15.6 ± 0.5, 1,4 cyclohexadiene 9.48 ± 0.39, bicyclo[2.2.1]‐2‐heptene 4.68 ± 0.39, bicyclo[2.2.1] 2,5 heptadiene 11.4 ± 1.0, and bicyclo[2.2.2] 2 octene 3.88 ± 0.19. These data show that the rate constants for the nonconjugated cycloalkenes studied depend on the number of double bonds and the degree of substitution per double bond, and indicate that there are no obvious effects of ring strain energy on these OH radical addition rate constants. A predictive technique for the estimation of OH radical rate constants for alkenes and cycloalkenes is presented and discussed.