Pulse Radiolysis Study of Alcohols in Aqueous Solution

Authors: M. Simic, P. Neta, E. Hayon

A detailed pulse radiolysis study of aqueous solutions of methanol, ethanol, isopropyl alcohol, n-, iso-, and t-butyl alcohols, neopentanol, and eyelohexanol has been carried out. Optical absorption spectra of some of the transients have been measured down to 210 nm. Similar spectra were obtained in liquid methanol, ethanol, and isopropyl alcohol. Absorption maxima of transients have been obtained in aqueous solutions of n-BuOH (at 222 nm), i-BuOH (at 225 nm), t-BuOH (at 225 nm), neopentanol (at 238 nm), and cyclohexanol (at 230 nm). In alkaline solutions, disassociation of the alpha-hydroaxyalkyl radicals (ROH) takes place, and the absorption spectra of the transients are considerably broadened, the disassciated form of the transients (RO-) exhibit higher extinction coefficients and lower decay rate constants as compared to the undisassociated form. In oxygenated solutions absorption spectra with λ(max) ~240-250 nm have been observed and are suggested to be due to the organic peroxy radicals (O2ROH).

https://doi.org/10.1021/j100845a038