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

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400800* -- Combustion
Pyrolysis
& High-Temperature Chemistry
54 ENVIRONMENTAL SCIENCES
540120 -- Environment
Atmospheric-- Chemicals Monitoring & Transport-- (1990-)
ALKOXY RADICALS
COMBUSTION PRODUCTS
DATA
EMISSION SPECTROSCOPY
EXPERIMENTAL DATA
FLUORESCENCE SPECTROSCOPY
INFORMATION
KINETICS
LASERS
MEASURING METHODS
MEDIUM TEMPERATURE
METHOXY RADICALS
NUMERICAL DATA
RADICALS
REACTION KINETICS
SPECTROSCOPY