ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Ultraviolet absorption spectra have been characterized for the acetyl-h3 and acetyl-d3 radicals, which were generated by the flash photolysis of the corresponding acetones. The spectra are broad and intense, with values of the extinction coefficient at the respective maxima estimated as: εCH3CO(215) = (1.0 ± 0.1) × 104 L/mol·cm and εCD3CO(207.5) = (1.0 ± 0.05) × 104 L/mol·cm. Rate constants for the reactions of mutual interaction were estimated as: k4H = 3.5 × 1010 L/mol·s and k4D = 3.4 × 1010 L/mol·s. Rate constants for the reactions of cross interaction were estimated as: k3H = 8.6 × 1010 L/mol·s and k3D = 5.2 × 1010 L/mol·s. The related values of the cross interaction ratios k3H/(k2Hk4H)1/2 = 2.6 and k3D/(k2Dk4D)1/2 = 1.6 do not differ significantly from the statistical value of 2. The participation of the radical displacement reactions was estimated in terms of the fractions k3bH/k3H = 0.38 and k3bD/k3D = 0.47.Corroborative spectra were obtained from the flash photolysis of methyl ethyl ketone and biacetyl, and the relative rates of the competing primary processes were estimated from the relative peak heights of the acetyl and methyl radicals in each system.
Additional Material:
9 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550131206
