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Rate constants for the gas‐phase reactions of O 3 with a series of cycloalkenes and α,β‐unsaturated ketones at 296 ± 2 K
Author(s) -
Greene Chipper R.,
Atkinson Roger
Publication year - 1994
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.550260106
Subject(s) - chemistry , cycloheptene , propene , reaction rate constant , cyclohexane , heptene , bicyclic molecule , cyclopentane , cyclohexene , gas phase , kinetics , medicinal chemistry , thermodynamics , organic chemistry , catalysis , physics , quantum mechanics
The kinetics of the gas‐phase reactions of O 3 with a series of alkenes and two α,β‐unsaturated ketones have been investigated at atmospheric pressure (ca. 740 torr) of air and 296 ± 2 K, using a relative rate method in the presence of sufficient cyclohexane to scavenge OH radicals generated in these reactions. Combined with our previous relative rate measurements (Int. J. Chem. Kinet., 24, 803 (1992)), the rate constants obtained relative to k (O 3 + propene) = 1.00 were: 3‐penten‐2‐one, 3.62 ± 0.16; 2‐cyclohexen‐1‐one, <0.19; bicyclo[2.2.2]‐2‐octene, 7.44 ± 0.48; 1,3‐cycloheptadiene, 16.1 ± 1.1; cycloheptene, 23.7 ± 1.6; 1,3‐cyclohexadiene, 134 ± 13; bicyclo[2.2.1]‐2‐heptene, 170 ± 16; and bicyclo[2.2.1]‐2,5‐heptadiene, 390 ± 36. The resulting rate constants then lead to a self‐consistent set of room temperature data for the reactions of O 3 with these alkenes and α,β‐unsaturated ketones. These rate constants are compared with the literature data, and the effects of ring size discussed. © 1994 John Wiley & Sons, Inc.