Theoretical studies of polyelectrolyte “catalysis” of ionic reactions. Part 1.—Interionic reactions between oppositely charged species

Using an activated-complex theory proposed by Brönsted and Bjerrum, and polyelectrolyte theories proposed by Manning and Lifson–Katchalsky, the “catalytic” influence of polyelectrolytes on ionic reactions between oppositely charged species is discussed. The reaction rates of some inter-ionic reactions, i.e., ammonium cyanate-urea conversion, carbamoylation reactions of polyethylenimine and its low molecular weight analogues with cyanate ions, and cyanide addition reaction of coenzyme model compounds, are successfully explained by the theories. From the comparison, it is concluded that the decelerating effect of polyelectrolytes on ionic reactions between oppositely charged ionic species can be accounted for in terms of the so-called “primary salt effect” earlier proposed for simple electrolyte systems, without using the “accumulation effect”.