A flash photolysis resonance fluorescence investigation of the reactions of Oxygen O(3P) atoms with aliphatic ethers and diethers in the gas phase

Rate constants for the gas phase reactions of O( 3 P) atoms with a series of symmetric aliphatic ethers have been determined using the flash photolysis resonance fluorescence technique over the temperature range 240-400 K. The Arrhenius parameters derived from these data are (in units of cm 3 molecule −1 s −1 ): dimethyl ether, k=(5.39±1.94)×10 −12 exp([(−1320±120)/T]; diethyl ether, k=(1.42±0.18)×10 −11 exp([(−1070±40)/T]; di-n-propyl ether, k=(1.41±0.21)×10 −11 exp([(−960±50)/T]; di-n-butyl ether, k=(1.37±0.29)×10 −11 exp([(−880±70)/T]; di-n-pentyl ether, k=(1.26±0.84)×10 −11 exp([(−780±20/T]. The error limits are two standard deviations derived from the least-square fit. Rate constants for several other ethers were determined only at 298 K. The values obtained were (in units of 10 −14 cm 3 molecule −1 s −1 ): tetrahydrofuran (37.5±1.1); 1,4-dioxane (6.81±0.46); diethoxymethane (40.4±1.8); ethyl-t-butylether (37.0±1.3); and methyl-t-amylether (57.3±2.3)