Solvated electrons at elevated temperatures in different alcohols: Temperature and molecular structure effects

The absorption spectra of solvated electrons in pentanol, hexanol and octanol are measured from 22 to 200, 22 to 175 and 50 to150 °C, respectively, at a fixed pressure of 15 MPa, using nanosecond pulse radiolysis technique. The results show that the peak positions of the absorption spectra have a red-shift (shift to longer wavelengths) as temperature increases, similar to water and other alcohols. Including the above mentioned data, a compilation of currently available experimental data on the energy of absorption maximum (Emax) of solvated electrons changed with temperature in monohydric alcohols, diols and triol is presented. Emax of solvated electron is larger in those alcohols that have more OH groups at all the temperatures. The molecular structure effect, including OH numbers, OH position and carbon chain length, is investigated. For the primary alcohols with same OH group number and position, the temperature coefficient increases with increase in chain length. For the alcohols with same chain length and OH numbers, temperature coefficient is larger for the symmetric alcohols than the asymmetric ones.