ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
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 (k1), diethylether (k2), and dipropylether (k3) 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 cm3 molecule-1 s-1) were: k1 = (24.9 ± 2.2), k2 = (136 ± 9), and k3 = (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.
Additional Material:
3 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550200106
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