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

Journal Article · Thu Oct 18 00:00:00 EDT 1990 · Journal of Physical Chemistry; (USA)

DOI:https://doi.org/10.1021/j100384a028· OSTI ID:6043430

Bogan, D J; Kaufman, M; Hand, C W; Sanders, W A; Brauer, B E ^[1]

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1. Naval Research Lab., Washington, DC (USA) Catholic Univ. of America, Washington, DC (USA)

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.

• OSTI ID: 6043430
• Journal Information: Journal of Physical Chemistry; (USA), Vol. 94:21; ISSN 0022-3654
• Country of Publication: United States
• Language: English

Related Subjects

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-)