Effects of solvent structure on electron reactivity and radiolysis yields: 2-propanol/water mixed solvents

Abstract

Reaction of solvated electrons with nitrobenzene, N, is nearly diffusion controlled in both pure solvents; kN ~ 1010 dm3/mol s. The value of kN is approximately proportional to the inverse viscosity η−1 in the pure solvents, and in the mixed solvents at different temperatures. However, on going from zero to 74 mol% water at the same temperature kN is independent of the 40% increase of η. Electron diffusion in the mixed solvents is not a simple function of fluidity.Reaction with the inefficient scavengers tryptophane (kS ~ 109 dm3/mol s) and phenol (kS ~ 107–108 dm3/mol s) correlates inversely with the electron optical absorption energy. The latter is related to the trap depth in the solvent; electrons in deeper traps have less tendency to react with molecules of low electron affinity.Addition of 3 mol% 2-PrOH to water at 296 K increases the value of Gεmax by 16%, although the value in pure 2-PrOH is three-fold smaller than that in pure water. The increase is attributed to an increase in the free ion yield, caused by an increase in the product of the electron thermalization range and the microscopic dielectric constant of the fluid between the ion and electron, averaged over the time that they exist as a correlated pair. Addition of a small amount of alcohol to water increases the orderliness of the water structure.