Pulse Radiolysis Studies. IV. The Solvated Electron in the Aliphatic Alcohols

Some of the physical and chemical properties of the solvated electron in the aliphatic alcohols have been investigated by means of the pulse radiolysis technique. In ethanol the optical absorption spectrum exhibits a maximum at 700 mμ. The decadic molar extinction coefficient at 5461 Å is determined to be εe—sol5461=(1.1±0.4)×104 M—1 cm—1. From this the oscillator strength of the band from 270 mμ to about 980 mμ is estimated to be f=0.7. The radiation chemical yield of the solvated electron in ethanol is found to be 1.0±0.3 per 100 eV of absorbed energy. Absolute rate constants for a number of reactions of the solvated electron in ethanol and methanol have been determined. The diphenylide ion, formed by electron attachment to diphenyl in ethanol, shows a fast first-order decay for which the rate constant has been determined.