Effect of polyelectrolytes upon the kinetics of ionic reactions. Part 6: Some general aspects

Abstract

The rate constant changes of ionic reactions duc to the electrostatic polyelectrolyte effect can be described in some detail. For second-order reactions betvween ions of equal charge sign, it is shown that the inhomogeneous distribution of reactive ions is equivalent lo a primary salt effect;; the primary salt effect cannot explain the results at high macroion concentration. An expression is derived for this case taking into account the probability of site occupancy by both reactive partners. For first-order reactions, the overall change in rate constanl with polymer concentrtlion may be explained in terms of the theories of polyelectrolyte solutions, even when the electrostatic effect may be coupled with more specific interactions.