Rate constants of the reactions of OH radicals with cyclopropane and cyclobutane

The kinetics of the reactions of hydroxy radicals with cyclopropane and cyclobutane has been investigated in the temperature range of 298–492 K with laser flash photolysis/resonance fluorescence technique. The temperature dependence of the rate constants is given by k 1 = (1.17 ± 0.15) × 10 −16 T 3/2 exp[−(1037 ± 87) kcal mol −1 / RT ] cm 3 molecule −1 s 1 and k 2 = (5.06 ± 0.57) × 10 −16 T 3/2 exp[−(228 ± 78) kcal mol −1 / RT ] cm 3 molecule −1 s −1 for the reactions OH + cyclopropane → products (1) and OH + cyclobutane → products (2), respectively. Kinetic data available for OH + cycloalkane reactions were analyzed in terms of structure‐reactivity correlations involving kinetic and energetic parameters.