IONIC RADIUS AND IONIC EFFICIENCY

1. It has been shown in preceding papers that when we separate solutions of electrolytes from pure water by collodion membranes the ions with the same sign of charge as the membrane increase while the ions with the opposite sign of charge diminish the rate of diffusion of water from the side of pure water to the side of solution; and that the accelerating and depressing effects of these ions on the rate of diffusion of water increase with their valency. 2. It is shown in this paper that aside from the valency a second quantity of the ion plays a rôle in this effect, namely the radius, which in a monatomic ion means the distance between the central positive nucleus and the outermost ring or shell of electrons of the ion. In monatomic, monovalent anions the radius increases in the order Cl< Br< I (being largest in I), while for monatomic, monovalent cations it increases in the order Li< Na< K< Rb (being largest in Rb). 3. It is shown that the accelerating as well as the depressing effect of the anions mentioned increases directly with the order of magnitude of their radius and that the efficiency is greatest in the case of I which has the largest radius; while the accelerating as well as the depressing effect of cations increases inversely with the order of magnitude of their radius, Li with the smallest radius having the greatest efficiency. 4. This is intelligible on the assumption that the action of the ions is electrostatic in character, in the case of cations due to the electrostatic effect of the excess charge of their positive nucleus, and in the case of anions due to the excess charge of their captured electron. The electrostatic effect of the positive nucleus of a cation on the membrane (or any other body) will be the greater the smaller the ionic radius of the cation; and the electrostatic effect of an excess electron will be the greater the further its distance from its own positive nucleus. 5. It is suggested that this rule may possibly include polyatomic, monovalent ions (e.g. NO(3), CNS, etc.) when we replace these polyatomic ions by monatomic models in which the radius is calculated in such a way as to give the model the same electrostatic effect which the polyatomic ion possesses. 6. These conclusions are in harmony with the fact that the efficiency of ions increases also with their valency. 7. It is suggested that these rules concerning the influence of the ionic radius can possibly be demonstrated in other phenomena, depending on the electrostatic effect of ions.