Solvent effects on the reactivity of solvated electrons with NO3,s-in C1 to C4 alcohols

The rate constants k2(es- + NO3,s-) in pure C1 to C4 alcohol solvents at 298 K increase with increasing viscosity and decreasing permittivity. Thus the reactivity increases with decreasing diffusivity and increasing coulombic repulsion, so the Debye-Smoluchowski model does not apply. The effective reaction radius κRr increases with decrease of effective trap depth Er/τ of the electrons in the solvent: κRr Cτ(Er/τ)pτ. Values of κRr and Er/τ change with temperature, and values of pτ fall into four categories: ∼0.0 for water and methanol; ∼1.3 for primary alcohols; 0.6 for secondary alcohols; 1.8 for tert-butanol. The C-H groups participate in the es- + NO3,s- reaction. (author). 30 refs., 5 figs