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

Typeset version

 

TY  - JOUR
  - 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
DA  - 2003/NaN
ER  - 
@article{V16399756,
   = {Moriarty,  Jennie and Sidebottom,  Howard and Wenger,  John and Mellouki,  Abdelwahid and 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},
  pages = {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.}},
  issn = {1089-5639},
   = {http://dx.doi.org/10.1021/jp021267i},
  source = {IRIS}
}
AUTHORSMoriarty, Jennie,Sidebottom, Howard,Wenger, John,Mellouki, Abdelwahid,Le Bras, Georges
YEAR2003
MONTHUnknown
JOURNAL_CODEThe Journal of Physical Chemistry A
TITLEKinetic Studies on the Reactions of Hydroxyl Radicals with Cyclic Ethers and Aliphatic Diethers
STATUSValidated
TIMES_CITED()
SEARCH_KEYWORD
VOLUME107
ISSUE10
START_PAGE1499
END_PAGE1505
ABSTRACTRate 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.
PUBLISHER_LOCATION
ISBN_ISSN1089-5639
EDITION
URLhttp://dx.doi.org/10.1021/jp021267i
DOI_LINK
FUNDING_BODY
GRANT_DETAILS