The reactivity of allyl and propargyl alcohols with solvated electrons: temperature and solvent effects

The rate constants K1 for the reaction of solvated electrons with allyl alcohol in a number of hydroxylic solvents differ by up to two orders of magnitude and decrease in the order tert-butyl alcohol > 2-propanol > l-propanol approximately ethanol > methanol approximately ethylene glycol > water. In methanol and ethylene glycol the rate constants (7 x 107 M-1 s-1 at 298 K) and activation energies (16 kJ/mol) are equal, in spite of a 32-fold difference in solvent viscosity (0.54 and 17.3 cP, respectively) and 3-fold difference in its activation energy (11 and 32 kJ/mol, respectively). The reaction in tert-butyl alcohol is nearly diffusion controlled and has a high activation energy that is characteristic of transport in that liquid (E1 = 31 kJ/mol, E sub(eta) = 39 kJ/mol). The activation energies in the other alcohols are all 16 kJ/mol, and it is 14 kJ/mol in water. They do not correlate with transport properties. The solvent effect is connected primarily with the entropy of activation. The rate constants correlate with the solvated electron trap depth. When the electron affinity of the scavenger is small, a favorable configuration of solvent molecules about the electron/scavenger encounter pair is required for the electron jump to take place. The behavior of the rate parameters for propargyl alcohol is similar to that for allyl alcohol, but k1, A1, and E1 are larger for the former. The ratio k(propargyl)/k(allyl) at 298 K equals 10.5 in water and decreases through the series, reaching 1.3 in tert-butyl alcohol. Rate parameters for several other scavengers are also reported. (author)