Moriarty, Jennie,Sidebottom, Howard,Wenger, John,Mellouki, Abdelwahid,Le Bras, Georges;

2003

Unknown

The Journal of Physical Chemistry A

Kinetic Studies on the Reactions of Hydroxyl Radicals with Cyclic Ethers and Aliphatic Diethers

Validated

()

107

10

1499

1505

Rate coefficients for the reactions of hydroxyl radicals with a series of cyclic ethers and aliphatic diethers have been determined at 298 +- 2 K. Experiments were performed using a photolytic relative rate method at atmospheric pressure and the absolute rate technique of pulsed laser photolysislaser induced fluorescence. The temperature dependence of the rate coefficients for the cyclic ethers was also studied over the temperature range 263372 K. The rate coefficients show significant deviations from simple structureactivity relationships. The reactivity of the aliphatic diethers toward hydroxyl radicals is discussed in terms of the initial formation of a hydrogen-bonded adduct which then undergoes an intramolecular H atom transfer via five-, six-, and seven-membered-ring structures. The reactivity of cyclic ethers is also discussed in relation to adduct formation. However, because of steric restrictions, it is unlikely that the hydrogen-bonded adducts readily undergo H atom transfer via ring formation.

1089-5639

http://dx.doi.org/10.1021/jp021267i