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The gas phase reactions of hydroxyl radicals with a series of aliphatic ethers over the temperature range 240–440 K

✍ Scribed by Timothy J. Wallington; Renzhang Liu; Philippe Dagaut; Michael J. Kurylo

Publisher
John Wiley and Sons
Year
1988
Tongue
English
Weight
447 KB
Volume
20
Category
Article
ISSN
0538-8066

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✦ Synopsis

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 a t total pressures (using Ar diluent gas) between 25-50 Torr. The kinetic data for dimethylether lk,). diethylether ( k o ) , and dipropylether tk,) were used to derive the Arrhenius expressions k , = (6.7 5 1.5) x 10 l2 exp[-(300 t 70i/T] cm'3 molecule k, = (5.6 2 1.7) x s ' exp[(270 ? 100i/T] cm3 molecule-' s-' and k , = (11 -t 3) x 10 ~' ' exp[(l50 t 8 0 ) / T ] cmd molecule s ' At 296 K, the measured rate constants (in units of em3 molecule-' s-'i were:

k , = 124.9 t 2.21, k, = (136 i 9), and k , = (180 t 22). Room temperature rate constants for the OH reactions with several other aliphatic ethers were also measured. These were tin the above units): di-n-butylether, (278 ? 361; di-n-pentylether, (347 * 20); ethyleneoxide, (0.95 i 0.05); propyleneoxide, (4.95 * 0.52); and tetrahydrofuran.

(

). The results are discussed in terms of the mechanisms for these reactions and are compared to previous literature data

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