ISSN 1017-2548(Print)
ISSN 2234-8530(Online)
Volume 27, Number 3
JKCSEZ 27(3)
June 20, 1983 

The rate constants for solvated electrons with benzene in the binary mixture (tetrahydrofuran-water) were measured at a various temperatures(-18℃∼+51℃) by photolysis. From Arrhenius plots of rate constants it was observed that the activation energies were decreased with increasing tetrahydrofuran(THF) content. Decreasing the viscosity of solvent mixtures by adding water, the rate constants were also decreased. It indicates that the reaction of solvated electrons are not controlled by diffusion. The change of activation enthalpy in kcal M-1and the rate constants in M-1sec-1 were 4.90 and 8.80×108 for 30M% of THF, 2.80 and 5.14×108 for 49M% of THF, and -0.30 and 1.43×108 for 75M% of THF, respectively. The slope of the linear plot of activation enthalpies against activation entropies was 244oK, which supports the reaction parameter is the change of activation entropy in the range of the experimental temperature. From the solvent effect on the activation energy, it was found that the step of the reaction, es- ＋ B ↔ B- shifted to the exothermic reaction with increasing THF content.