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Title: Laser-induced fluorescence study of methoxy radical formation from the reactions of F( sup 2 P) atoms with CH sub 3 OH, CD sub 3 OH, and CH sub 3 OD

Abstract

Kinetic aspects of the formation and consumption of methoxy radicals in the reactions of F({sup 2}P) atoms with CH{sub 3}OH, CH{sub 3}OD, and CD{sub 3}OH have been studied in a flow reactor at 300 K. Laser-induced fluorescence from the transition (A {sup 2}A{sub 1} {yields} X {sup 2}E) was used to monitor the concentration of methoxy. Reaction of F with CH{sub 3}OH forms both CH{sub 3}O (1a) and CH{sub 2}OH (1b) radicals, but CH{sub 2}OH reacts quickly with F{sub 2} to regenerate fluorine atoms (12): F({sup 2}P) + CH{sub 3}OH {yields} HF + CH{sub 3}O (1a); F({sup 2}P) + CH{sub 3}OH {yields} HF + CH{sub 2}OH (1b); F{sub 2} + CH{sub 2}OH {yields} F + FCH{sub 2}OH (12). The effect of this chain reaction sequence is that, in the presence of excess F{sub 2} and CH{sub 3}OH, each F atom initially present leads to one CH{sub 3}O radical. The role of excess F{sub 2} was independently established as follows: methoxy was not observed from the reaction, Cl + CH{sub 3}OH {yields} CH{sub 2}OH + HCl, but appeared when F{sub 2} was added downstream of the CH{sub 3}OH inlet.

Authors:
; ; ; ;  [1]
  1. (Naval Research Lab., Washington, DC (USA) Catholic Univ. of America, Washington, DC (USA))
Publication Date:
OSTI Identifier:
6043430
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry; (USA)
Additional Journal Information:
Journal Volume: 94:21; Journal ID: ISSN 0022-3654
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 54 ENVIRONMENTAL SCIENCES; METHOXY RADICALS; FLUORESCENCE SPECTROSCOPY; COMBUSTION PRODUCTS; EXPERIMENTAL DATA; LASERS; MEASURING METHODS; MEDIUM TEMPERATURE; REACTION KINETICS; ALKOXY RADICALS; DATA; EMISSION SPECTROSCOPY; INFORMATION; KINETICS; NUMERICAL DATA; RADICALS; SPECTROSCOPY; 400800* - Combustion, Pyrolysis, & High-Temperature Chemistry; 540120 - Environment, Atmospheric- Chemicals Monitoring & Transport- (1990-)

Citation Formats

Bogan, D.J., Kaufman, M., Hand, C.W., Sanders, W.A., and Brauer, B.E. Laser-induced fluorescence study of methoxy radical formation from the reactions of F( sup 2 P) atoms with CH sub 3 OH, CD sub 3 OH, and CH sub 3 OD. United States: N. p., 1990. Web. doi:10.1021/j100384a028.
Bogan, D.J., Kaufman, M., Hand, C.W., Sanders, W.A., & Brauer, B.E. Laser-induced fluorescence study of methoxy radical formation from the reactions of F( sup 2 P) atoms with CH sub 3 OH, CD sub 3 OH, and CH sub 3 OD. United States. doi:10.1021/j100384a028.
Bogan, D.J., Kaufman, M., Hand, C.W., Sanders, W.A., and Brauer, B.E. Thu . "Laser-induced fluorescence study of methoxy radical formation from the reactions of F( sup 2 P) atoms with CH sub 3 OH, CD sub 3 OH, and CH sub 3 OD". United States. doi:10.1021/j100384a028.
@article{osti_6043430,
title = {Laser-induced fluorescence study of methoxy radical formation from the reactions of F( sup 2 P) atoms with CH sub 3 OH, CD sub 3 OH, and CH sub 3 OD},
author = {Bogan, D.J. and Kaufman, M. and Hand, C.W. and Sanders, W.A. and Brauer, B.E.},
abstractNote = {Kinetic aspects of the formation and consumption of methoxy radicals in the reactions of F({sup 2}P) atoms with CH{sub 3}OH, CH{sub 3}OD, and CD{sub 3}OH have been studied in a flow reactor at 300 K. Laser-induced fluorescence from the transition (A {sup 2}A{sub 1} {yields} X {sup 2}E) was used to monitor the concentration of methoxy. Reaction of F with CH{sub 3}OH forms both CH{sub 3}O (1a) and CH{sub 2}OH (1b) radicals, but CH{sub 2}OH reacts quickly with F{sub 2} to regenerate fluorine atoms (12): F({sup 2}P) + CH{sub 3}OH {yields} HF + CH{sub 3}O (1a); F({sup 2}P) + CH{sub 3}OH {yields} HF + CH{sub 2}OH (1b); F{sub 2} + CH{sub 2}OH {yields} F + FCH{sub 2}OH (12). The effect of this chain reaction sequence is that, in the presence of excess F{sub 2} and CH{sub 3}OH, each F atom initially present leads to one CH{sub 3}O radical. The role of excess F{sub 2} was independently established as follows: methoxy was not observed from the reaction, Cl + CH{sub 3}OH {yields} CH{sub 2}OH + HCl, but appeared when F{sub 2} was added downstream of the CH{sub 3}OH inlet.},
doi = {10.1021/j100384a028},
journal = {Journal of Physical Chemistry; (USA)},
issn = {0022-3654},
number = ,
volume = 94:21,
place = {United States},
year = {1990},
month = {10}
}