sup 1 (n,. pi. *) photochemistry of acetic acid at 200 nm: Further evidence for an exit channel barrier and reaction selectivity

Journal Article · Thu Jan 24 04:00:00 EST 1991 · Journal of Physical Chemistry; (USA)

DOI:https://doi.org/10.1021/j100155a015· OSTI ID:5774460

Hunnicutt, S S; Waits, L D; Guest, J A ^[1]

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1. Univ. of Cincinnati, OH (USA)

Acetic acid was photolyzed at 200 nm at low pressure. The nascent OH photofragment was probed by using laser fluorescence excitation to determine its scalar and vector properties. Doppler spectroscopy was used to determine the OH photofragment mean translational energy (E{sub {tau}}(OH) = 10.4 {plus minus} 1.0 kcal mol{sup {minus}1}). Kinematic arguments are presented to demonstrate that acetic acid decomposes via primary C-O single bond fission, with subsequent CH{sub 3}CO decomposition. Nearly the same mean translational energy is imparted to OH for both 200- and 218-nm photolyses, suggesting the presence of a barrier to product formation in the CH{sub 3}COOH {yields} CH{sub 3}CO + OH exit channel. CD{sub 3}COOH was photolyzed at 200 and 218 nm to explore the possibility that an enol intermediate plays a role in the dissociation mechanism.

• OSTI ID: 5774460
• Journal Information: Journal of Physical Chemistry; (USA), Journal Name: Journal of Physical Chemistry; (USA) Vol. 95:2; ISSN 0022-3654; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400500* -- Photochemistry
ACETIC ACID
CARBOXYLIC ACIDS
CHEMICAL REACTIONS
DATA
DECOMPOSITION
EXPERIMENTAL DATA
HYDROXYL RADICALS
INFORMATION
KINETICS
MEASURING METHODS
MEDIUM TEMPERATURE
MONOCARBOXYLIC ACIDS
NUMERICAL DATA
ORGANIC ACIDS
ORGANIC COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
RADICALS
REACTION KINETICS