Pulse radiolytic induced transient electrical conductance in liquid solutions. Part 4.—The radiolysis of methanol, ethanol, 1-propanol and 2-propanol

Abstract

The rate constants and Arrhenius activation energies for the reaction of ROH⁺₂ with RO^– in the liquid state have been measured for R = CH₃, C₂H₅, 1-C₃H₇ and 2-C₃H₇. The values at 25°C are 7.05 × 10¹⁰, 3.0; 4.59 × 10¹⁰, 4.3; 2.40 × 10¹⁰, 5.9; and 1.50 × 10¹⁰ l. mol^–1 s^–1 and 7.3 kcal mol^–1 respectively. Evidence is presented that, for all the solvents studied (a) the rate coefficients for ROH⁺₂+ e⁺_s are nearly the same as the above, (b) the rate data (including the effect of traces of water) are adequately accounted for by diffusion theory, (c)λ(e^–_s)≈λ(RO^–) and (d)g(free-ions)≈ 2.