Spectra and Decay of Trichloromethyl Radicals in Aqueous Solution

Trichloromethyl radicals (λmax < 230 nm, ε230 nm = 2300 ± 450 M−1 cm−1) are formed by the pulse radiolysis of aqueous carbon tetrachloride solutions. At concentrations of the order of 10−4M and pH 5.5–12.4, CCl3 disappears by a second-order process with 2k = (7.4 ± 1.8) × 108 M−1 s−1 and without detectable hydrolysis. Both CCl3 and CHCl2 are believed to be formed by the pulse radiolysis of aqueous chloroform solutions but at wavelengths greater than 230 nm only absorption attributable to CCl3 was observed.