Rate constants for the gas‐phase reactions of O₃with a series of cycloalkenes at 296 ± 2 K

Using a relative rate method, rate constants for the gas phase reactions of O₃with 1‐ and 3‐methylcyclopentene, 1‐, 3‐, and 4‐methylcyclohexene, 1‐methylcycloheptene,cis‐cyclooctene, 1‐ and 3‐methylcyclooctene, 1,3‐ and 1,5‐cyclooctadiene, and 1,3,5,7‐cyclooctatetraene have been measured at 296 ± 2 K and atmospheric pressure of air. The rate constants obtained (in units of 10⁻¹⁸cm³molecule⁻¹s⁻¹) are 1‐methylcyclopentene, 832 ± 24; 3‐methylcyclopentene, 334 ± 12; 1‐methylcyclohexene, 146 ± 10; 3‐methylcyclohexene, 55.3 ± 2.6; 4‐methylcyclohexene, 73.1 ± 3.6; 1‐methylcycloheptene, 930 ± 24;cis‐cyclooctene, 386 ± 23; 1‐methylcyclooctene, 1420 ± 100; 3‐methylcyclooctene, 139 ± 9;cis,cis‐1,3‐cyclooctadiene, 20.0 ± 1.4; 1,5‐cyclooctadiene, 152 ± 10; and 1,3,5,7‐cyclooctatetraene, 2.60 ± 0.19, where the indicated errors are two least‐squares standard deviations and do not include the uncertainties in the rate constants for the reference alkenes (propene, 1‐butene,cis‐2‐butene,trans‐2‐butene, 2‐methyl‐2‐butene, and terpinolene). These rate data are compared with the few available literature data, and the effects of methyl substitution discussed. © 2005 Wiley Periodicals, Inc. Int J Chem Kinet 37: 183–190, 2005