SOLVENT STRUCTURE EFFECTS ON SOLVATED ELECTRON REACTIONS IN MIXED-SOLVENTS - POSITIVE-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 = kappa-RTfr(r)/1.5-eta-r(d) where kappa is the probability that a reactant encounter pair will react, R is the gas constant, T is the temperature, f is a factor that reflects the effect of electrostatic interaction between the reactants on their probability of attaining the closeness of approach r(r) at which reaction occurs, eta is the solvent viscosity, and r(d) is the effective radius of the reactant entities 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 k2, activation energies E2, and pre-exponential factors A2 of reactions of solvated electrons e(s)- with H(s)+, Ag(s)+, Cu(s)2+, and Al(s)3+ ions vary with the composition of 1-propanol/water and 2-propanol/water mixed solvents. Plots of k2-eta/fT against solvent composition are nonlinear and change with the solvent pair and with reactant pair. Measured molar conductivities LAMBDA-0(H(s)+, ClO4,s-), LAMBDA-0(Ag(s)+, ClO4,s-), LAMBDA-0(Cu(s)2+, 2ClO4,s-), and LAMBDA-0(Al(s)3+, 3ClO4,s-) indicate that the values of r(d) for the mutual diffusion of the cations and anions have a minimum near 90 mol% water, and that the values in pure propanol-1 or -2 (150-190 pm) are larger than those in pure water solvent (26 pm for H(s)+, 70 pm for the metal ions). The liquid structure influences both the rate of diffusion and the probability of reaction of a reactant encounter pair.