Direct kinetic study of radical transformation reaction Me sub 2 COH + Ph sub 2 CO yields Me sub 2 CO + Ph sub 2 COH

Journal Article · Thu Feb 07 00:00:00 EST 1991 · Journal of Physical Chemistry; (United States)

DOI:https://doi.org/10.1021/j100156a036· OSTI ID:5200375

Demeter, A; Berces, T ^[1]

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1. Central Research Inst. for Chemistry, Budapest (Hungary)

Reaction Me{sub 2}COH + Ph{sub 2}CO {yields} Me{sub 2}CO + Ph{sub 2}COH (5) was studied by laser flash photolysis under such experimental conditions where the changes in the concentrations of ketyl radicals with reaction time were controlled by this radical transformation process. Diphenylketyl radical concentration profiles were obtained by monitoring transient absorption at 540 nm and the rate coefficient k{sub 5} was extracted from that part of the concentration trajectory which was determined solely by reaction 5. Thus, k{sub 5} = (3.6 {plus minus} 0.6) {times} 10{sup 5} dm{sup 3} mol{sup {minus}1} s{sup {minus}1} was determined at 298 K in acetonitrile, which is higher than the two recently reported values derived from quantum yields measured under steady-state conditions. A reaction mechanism for the radical transformation process (5) is proposed in which hydrogen-bonded species formed from ketyl radical and benzophenone participate.

• OSTI ID: 5200375
• Journal Information: Journal of Physical Chemistry; (United States), Vol. 95:3; ISSN 0022-3654
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
BENZOPHENONE
PHOTOLYSIS
ABSORPTION SPECTROSCOPY
ARRHENIUS EQUATION
CHEMICAL REACTION KINETICS
EXPERIMENTAL DATA
LASERS
MEDIUM TEMPERATURE
CHEMICAL REACTIONS
DATA
DECOMPOSITION
EQUATIONS
INFORMATION
KETONES
KINETICS
NUMERICAL DATA
ORGANIC COMPOUNDS
PHOTOCHEMICAL REACTIONS
REACTION KINETICS
SPECTROSCOPY
400500* - Photochemistry