Solvent structure effects on solvated electron reactions in mixed solvents: Negative ions in 1-propanol–water and 2-propanol–water

In models of the kinetics of chemical reactions in solution the solvent is commonly assumed to be a uniform continuum. An example is the Smoluchowski–Debye–Stokes–Einstein equation for the rate constant k2 of a bimolecular reaction between charged or polar species: k2 = κRTfrr/1.5ηrd where κ = probability that a reactant encounter pair will react, R = gas constant, T = temperature, f = Coulombic interaction factor, rr = effective radius for reaction, η = solvent viscosity, and rd = effective radius for mutual diffusion. The equation is useful in evaluating effects of bulk-fluid properties on reaction rates. Residual effects are attributed to more specific solvent behaviour. Rate constants and activation energies E2 of reactions of solvated electrons [Formula: see text] with [Formula: see text] and [Formula: see text] ions vary with the composition of 1-propanol–water and 2-propanol–water mixed solvents. Plots of k2η/fT against solvent composition are nonlinear and change with solvent pair and with reactant pair. Measured molar conductivities Λ0(Li+, [Formula: see text]) and Λ0(2Li+, [Formula: see text]) indicate the solvent dependence of rd for the mutual diffusion of Li+ and [Formula: see text] or [Formula: see text]. The liquid structure influences both the rate of diffusion of the reactants and the probability of reaction of a reactant encounter pair.