2008/01/01 by Masashi Hojo · 1 citation
Physics and Astronomy · Chemical Engineering · #Spectroscopy and Quantum Chemical Studies #Chemical and Physical Properties in Aqueous Solutions
paper · pdf · doi:10.1351/pac200880071539
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 N 1 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 > ~10 8 ) is destroyed due to any spatial barriers (such as ions, molecules, surface) or elevated temperature.