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The gas phase reactions of hydroxyl radicals with a series of aliphatic ethers over the temperature range 240–440 K
Author(s) -
Wallington Timothy J.,
Liu Renzhang,
Dagaut Philippe,
Kurylo Michael J.
Publication year - 1988
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550200106
Subject(s) - chemistry , arrhenius equation , radical , reaction rate constant , tetrahydrofuran , atmospheric temperature range , diluent , flash photolysis , torr , gas phase , photodissociation , analytical chemistry (journal) , photochemistry , organic chemistry , kinetics , thermodynamics , activation energy , physics , quantum mechanics , solvent
Absolute rate constants were determined for the gas phase reactions of OH radicals with a series of linear aliphatic ethers using the flash photolysis resonance fluorescence technique. Experiments were performed over the temperature range 240–440 K at total pressures (using Ar diluent gas) between 25–50 Torr. The kinetic data for dimethylether ( k 1 ), diethylether ( k 2 ), and dipropylether ( k 3 ) were used to derive the Arrhenius expressions\documentclass{article}\pagestyle{empty}\begin{document}$$k_1 = (6.7 \pm 1.5) \times 10^{- 12} {\rm \,exp[- (300} \pm {\rm 70)/}T]{\rm \,cm}^{\rm 3}\, {\rm \,molecule}^{{\rm - 1}}\, {\rm s}^{{\rm - 1}}$$\end{document}\documentclass{article}\pagestyle{empty}\begin{document}$$k_2 = (5.6 \pm 1.7) \times 10^{- 12} {\rm \,exp[(270} \pm 10{\rm 0)/}T]{\rm \,cm}^{\rm 3}\, {\rm \,molecule}^{{\rm - 1}}\, {\rm s}^{{\rm - 1}}$$\end{document} and\documentclass{article}\pagestyle{empty}\begin{document}$$k_3 = (11 \pm 3) \times 10^{- 1 2} {\rm \,exp[(150} \pm 8{\rm 0)/}T]{\rm \,cm}^{\rm 3}\, {\rm \,molecule}^{{\rm - 1}}\, {\rm s}^{{\rm - 1}}$$\end{document} At 296 K, the measured rate constants (in units of 10 −13 cm 3 molecule −1 s −1 ) were: k 1 = (24.9 ± 2.2), k 2 = (136 ± 9), and k 3 = (180 ± 22). Room temperature rate constants for the OH reactions with several other aliphatic ethers were also measured. These were (in the above units): di‐ n ‐butylether, (278 ± 36); di‐ n ‐pentylether, (347 ± 20); ethyleneoxide, (0.95 ± 0.05); propyleneoxide, (4.95 ± 0.52); and tetrahydrofuran, (178 ± 16). The results are discussed in terms of the mechanisms for these reactions and are compared to previous literature data.