Pure and Applied Chemistry

Abstract: The paper reviews ion aggregation in ionic solution in solvents of low and high permittivity. Although higher ion aggregates from 1:1 type electrolytes in low-pemittivity media (ε_r < 10) are widely accepted, only a few chemists have recognized the higher ion aggregation in the higher-permittivity media. However, we have clarified that the chemical interaction, such as coordination, can operate between simple anions and cations in nonaqueous solvents (20 < ε_r < 65) of low solvation ability. Acids (HA) and their conjugate base anions (A^-) may react with each other to form homoconjugated species, such as A^-(HA)₂, in acetonitrile or benzonitrile (i.e., solvents possessing poor hydrogen-bonding donor and acceptor abilities). An analytical method of conductivity data for 1:1 electrolytes has been developed and successfully applied to very complicated systems, in which the ion pair (1:1), triple ions (2:1 and 1:2), and the quadrupole (2:2 association) are involved in a solution at the same time. After observing the direct reaction of some anions (e.g., Cl^-) and cations (e.g., Li⁺) toward a certain species, we interpreted comprehensively the salt effects in chemical equilibria, based on distinct chemical interactions and not merely a vague term, "medium effect". The mechanism of salt effects on solvolysis reactions of the S_N1 type in organic-aqueous mixed solvents has been elucidated. We discussed that a reaction manner similar to that in nonaqueous solution can take place even in some "aqueous" solution if the huge network of hydrogen-bonding of bulk water (the number of water, n_w > ~10⁸) is destroyed due to any spatial barriers (such as ions, molecules, surface) or elevated temperature.