Rate and mechanism of the reaction of hydroxyl radicals with formic and deuteriated formic acids

Journal Article · Wed Nov 09 00:00:00 EST 1988 · Journal of the American Chemical Society; (USA)

DOI:https://doi.org/10.1021/ja00231a032· OSTI ID:5296085

Singleton, D L; Paraskevopoulos, G; Irwin, R S; Jolly, G S; McKenney, D J

Rate constants for the reactions of hydroxyl radicals with the monomer and dimer of formic acid and deuteriated formic acids have been determined in the temperature range 297-445 K by a laser photolysis-resonance absorption technique. Hydroxyl radicals were generated by photolysis of formic acid at 222 nm with a KrCl excimer laser and were monitored by time-resolved resonance absorption. In each case the rate constant of the monomer of formic acid was much larger than that of the dimer, and a large isotope effect was observed when the carboxylic, but not the formyl, hydrogen was substituted by deuterium. A two-channel mechanism is proposed, one involving formation of a hydrogen-bonded adduct followed by transfer of the carboxylic hydrogen to the hydroxyl radical, and the other, direct abstraction of a formyl hydrogen. 31 refs., 2 figs. 1 tab.

• OSTI ID: 5296085
• Journal Information: Journal of the American Chemical Society; (USA), Vol. 110:23; ISSN 0002-7863
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
FORMIC ACID
CHEMICAL REACTIONS
HYDROXYL RADICALS
DEUTERIUM
EXPERIMENTAL DATA
LABELLED COMPOUNDS
TRACER TECHNIQUES
CARBOXYLIC ACIDS
DATA
HYDROGEN ISOTOPES
INFORMATION
ISOTOPE APPLICATIONS
ISOTOPES
LIGHT NUCLEI
MONOCARBOXYLIC ACIDS
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
ORGANIC ACIDS
ORGANIC COMPOUNDS
RADICALS
STABLE ISOTOPES
400201* - Chemical & Physicochemical Properties
400202 - Isotope Effects
Isotope Exchange
& Isotope Separation