Abstract
AbstractThe photooxidation of chloral was studied by infrared spectroscopy under steady‐state conditions with irradiation of a blackblue fluorescent lamp (300 nm < λ < 400 nm, λmax = 360 nm) at 296 ± 2 K. The products were hydrogen chloride, carbon monoxide, carbon dioxide, and phosgen. The kinetic results reveal that the reaction proceeds via chain reaction of the Cl atom: equation image The results lead to the conclusion that mechanism (B) is confirmed to be more likely than mechanism (A), which was favored at one time by Heicklen for the mechanism of the oxidation of trichloromethyl radicals by oxygen molecules: equation image The ratio of the initial rates of CO and CO2 formation gave k7/k6 = 4.23M−1, and the lower limit of reaction (5) was found to be 3.7 × 108M−1 sec−1.
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