Laser-induced fluorescence spectra of 4-methylcyclohexoxy radical and perdeuterated cyclohexoxy radical and direct kinetic studies of their reactions with O2.

Lei Zhang, Karen M Callahan, Dean Derbyshire, Theodore S Dibble

Index: J. Phys. Chem. A 109(41) , 9232-40, (2005)

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Abstract

The laser-induced fluorescence (LIF) excitation spectra of the 4-methylcyclohexoxy and d11-cyclohexoxy radicals have been measured for the first time. LIF intensity was used as a probe in direct kinetic studies of the reaction of O(2) with trans-4-methylcyclohexoxy and d11-cyclohexoxy radicals from 228 to 301 K. Measured rate constants near room temperature are uniformly higher than the Arrhenius fit to the lower-temperature data, which can be explained by the regeneration of cyclic alkoxy radicals from the product of their beta-scission and the effect of O(2) concentration on the extent of regeneration. The Arrhenius expressions obtained over more limited ranges were k(O2) = (1.4(+8)(-1)) x 10(-13) exp[(-810 +/- 400)/T] cm(3) molecule(-1) s(-1) for trans-4-methylcyclohexoxy (228-292 K) and k(O2) = (3.7(+4)(-1)) x 10(-14) exp )[(-760 +/- 400) /T] cm(3) molecule(-1) s(-1) for d11-cyclohexoxy (228-267 K) independent of pressure in the range 50-90 Torr. The room-temperature rate constant for the reaction of trans-4-methylcyclohexoxy radical with O2 (obtained from the Arrhenius fit) is consistent with the commonly recommended value, but the observed activation energy is approximately 3 times larger than the recommended value of 0.4 kcal/mol and half the value previously found for the reaction of normal cyclohexoxy radical with O2.