Chemistry of the cyclopentoxy and cyclohexoxy radicals at subambient temperatures

The Cl-atom initiated oxidation mechanisms of both cyclopentane and cyclohexane have been studied as a function of temperature using an environmental chamber/FTIR technique. The oxidation of cyclohexane leads to the formation of the cyclohexoxy radical, the chemistry of which is characterized by a competition between ring-opening (R5) and reaction with O-2 (R6) to form cyclohexanone. The yield of cyclohexanone is shown to increase with decreasing temperature, and a rate coefficient ratio k(6)/k(5) = (1.3 +/- 0.3) x 10(-27) exp(5550 +/- 1100/T) cm(3) molecule(-1) is obtained. The energy barrier to ring-opening is estimated to be 11.5 +/- 2.2 kcal/mol. The dominant fate of the cyclopentoxy radical, formed in the Cl-atom initiated oxidation of cyclopentane, is ring-opening under all conditions studied here (230 - 300 K 50-500 Torr O-2) with only a minor contribution from the O-2 reaction at the lowest temperatures studied. The barrier to ring-opening for the cyclopentoxy radical is probably less than 10 kcal/mol.