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Determination of the mechanism of the oxidation of the trichloromethyl radical by the photolysis of chloral in the presence of oxygen
Author(s) -
Ohta Tomohiro,
Mizoguchi Isao
Publication year - 1980
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550121005
Subject(s) - chemistry , photochemistry , chloral , carbon monoxide , photodissociation , oxygen , radical , reaction mechanism , hydrogen atom , organic chemistry , catalysis , alkyl
The photooxidation of chloral was studied by infrared spectroscopy under steady‐state conditions with irradiation of a blackblue fluorescent lamp (300 nm < λ < 400 nm, λ max = 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: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:The ratio of the initial rates of CO and CO 2 formation gave k 7 / k 6 = 4.23 M −1 , and the lower limit of reaction (5) was found to be 3.7 × 10 8 M −1 sec −1 .