By I M Kolthoff
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69, 1096 (1926); Z. anorg. allgem. , 160, 5 (1927). 1 ION ACTIVITY 53 Objections to the theory of Sv. Arrhenius. 2. The Arrhenius theory assumes (a) solution dissociate into ions. that strong electrolytes in This reaction is reversible and may be represented, in the case of sodium chloride, by the following equation : NaCl The mass + Na+ action law should be valid for this equilibrium, so that [Na+][Cl~] [NaCl] where _ " ' K stands trolyte. was + Cl~. Soon for the dissociation constant of the strong elecafter the publication of the ARRHENIUS theory it K was by no means constant, but rather inwith markedly increasing concentration.
Therefore If we wish to prepare a strongly acid solution, we have but to more concentrated solution of the acid. 01 N) may be prepared from hydrochloric acid. dilute a a pH On the other hand, when it is a matter of preparing solutions in which the pH varies between 3 and 7 this simple dilution method is no longer sufficiently accurate. When we prepare, for ex; ample, a hydrochloric acid solution of pH 6, we subject a normal solution to a millionfold dilution. Naturally such a solution can not be used with confidence.
In the preceding table is compiled a number of values found in the literature. 4. K a and Kb Neutralization curves of ampholytes. When a strong acid is added to a solution of an ampholyte, the concentration of A+ ions increases while the [A~~] diminishes. AMPHOTERIC SUBSTANCES 41 If a large enough excess of acid is present, the [A~] becomes so small as to be insignificant compared with the ampholyte cation concentration. In such a case, we may regard the ampholyte merely as a weak base, and can calculate the remainder of the neutralization curve on this basis.