Transactions of the Faraday Society · 1971 · 55 citations · 0 references
Natural SciencesBiochemistryChemistryChemical KineticsPhysical ChemistrySpectroscopyBiophysical KineticsCatalytic Reaction KineticsChemical Reaction KineticsChemical ThermodynamicsElectrical ConductivitySolution ChemistryArrhenius KineticsConductanceDiffusion TheoryRate ConstantsReaction Rate CoefficientsSolvent Effects On Reaction MechanismsSolvent Effects On Reaction RatesSolvent Effects On Reactivity
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.