Absolute and relative rate constants for the reactions of hydroxyl radicals and chlorine atoms with a series of aliphatic alcohols and ethers at 298 K

Abstract

Abstract Rate constants for the gas‐phase reactions of hydroxyl radicals and chlorine atoms with aliphatic alcohols and ethers have been determined at 298 ± 2 K and at a total pressure of 1 atmosphere. The OH radical rate data were obtained using both the absolute technique of pulse radiolysis combined with kinetic UV spectroscopy and a conventional photolytic relative rate method. The Cl atom rate constants were measured using only the relative rate method. Values of the rate constants in units of 10 −12 cm 3 molecule −1 s −1 are: equation image The above relative rate constants are based on the values of 𝓀(OH + c ‐C 6 H 12 ) = 7.49 × 10 −12 cm 3 molecule −1 s −1 and 𝓀(Cl + c ‐C 6 H 12 ) = 311 × 10 −12 cm 3 molecule −1 s −1 . Attempts to corre late the trends in the rate constant data in terms of the bond dissociation energies and inductive effects are discussed.