Theoretical studies of polyelectrolyte “catalysis” of ionic reactions. Part 2.–Interionic reactions between similarly charged species

Abstract

Using an activated-complex theory proposed by Brönsted and Bjerrum, and a polyelectrolyte theory proposed by Manning, the “catalytic” accelerating influence of polyelectrolytes on interionic reactions between similarly charged species is discussed. The reaction rates of [+m, +n]-type interionic reactions (m > n, m 2, n 1), for example, electron-transfer reaction between Fe²⁺ and Co-complex, and bromoacetate-thiosulphate ion reaction, are successfully explained by the theories. Furthermore, in the case of [+m, +m](m 2)-type interionic reactions, most experimental results are in agreement with the theories. Thus the accelerating effect of polyelectrolytes on ionic reactions between similarly charged ionic species can be accounted for in terms of of the so-called “primary salt effect” as with the decelerating effect of polyelectrolytes on interionic reactions between oppositely charged species.