Reaction Rates in Ionic Solutions

Smoluchowski's method of evaluating the fundamental frequency factor for the rate of a reaction like the coagulation of colloid suspension by employing a purely diffusional treatment is extended to include the electrostatic effects arising from the presence of net charges. The introduction of the concept of a diffuse ionic cloud and the potential calculated therefrom leads to the following results: (a) The wellestablished Bronsted‐Debye primary salt effect formula is derived. (b) The so‐called “solvent” term of the Christiansen‐Scatchard equation arising from the self potential of the ions is also derived but appears as the linear approximation of an exponential expression. The conspicuous absence of quantum theory in evaluating the absolute rate of a kinetic reaction merits attention. V. K. LaM