| Autor: |
D. G. L. James, N. Basco, Hiroyuki Adachi |
| Rok vydání: |
1981 |
| Předmět: |
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| Zdroj: |
International Journal of Chemical Kinetics. 13:1251-1276 |
| ISSN: |
0538-8066 |
| DOI: |
10.1002/kin.550131206 |
| Popis: |
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: k = 3.5 × 1010 L/mol·s and k = 3.4 × 1010 L/mol·s. Rate constants for the reactions of cross interaction were estimated as: k = 8.6 × 1010 L/mol·s and k = 5.2 × 1010 L/mol·s. The related values of the cross interaction ratios k/(kk)1/2 = 2.6 and k/(kk)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 k/k = 0.38 and k/k = 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. |
| Databáze: |
OpenAIRE |
| Externí odkaz: |
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