Protolytic equilibrium in lyophilic nanosized dispersions: Differentiating influence of the pseudophase and salt effects

Abstract

The so-called apparent ionization constants of various acids (mainly indicator dyes) in versatile organized solutions are analyzed. Aqueous micellar solutions of colloidal surfactants and related lyophilic colloidal systems display a strong differentiating influence on the acidic strength of indicators located in the dispersed pseudophase, i.e., non-uniform changes of pKa on going from water to the given system. This concept allows the influence of such media on acid-base properties of dissolved reagents to be rationalized. It is demonstrated that the differentiating phenomenon is the main reason for limitation of the common electrostatic model of acid-base interactions, and is the principal hindrance to exact evaluations of the interfacial electrical potentials of ionic micelles by means of acid-base indicators. Salt effects, i.e., the influence of supporting electrolytes on the apparent ionization constants of acid-base indicators in the Stern region of ionic micelles, are considered. These salt effects can be conventionally divided into two kinds, namely, general (normal) and special (specific) effects. While the first type adds up to screening of the surface charge, the second one consists in micellar transitions caused by hydrophobic counterions.