Abstract:
The rate constant changes of ionic reactions due to the electrostatic polyelectrolyte effect can be described in some detail. For second-order reactions between ions of equal charge sign, it is shown that the inhomogeneous distribution of reactive ions is equivalent to 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 constant with polymer concentration may be explained in terms of the theories of polyelectrolyte solutions, even when the electrostatic effect may be coupled with more specific interactions.
