1992 Volume 65 Issue 4 Pages 1038-1040
The reactivities of the transient UV-band with a peak at 330 nm produced in irradiated liquid carbon tetrachloride with various alcohols have been measured using the absolute technique of pulse radiolysis. The obtained bimolecular rate constants have been compared with those previously determined for the reaction of chlorine atoms with various alcohols using the competitive scavenging method. The values of reaction rate constants of the UV-band are nearly twice those of chlorine atoms. Similar kinetic isotope effects were observed for deuterated methanol and 2-methyl-2-propanol. However, the dependence on the structure of the alcohols, which is characteristic for hydrogen abstraction from alcohols by chlorine atoms, has not been established by the reaction of the UV-band. These results strongly suggest that the assignment of the UV-band to chlorine atoms is not plausible, and instead, support the assignment to parent cations.
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