Effects on the micellar solubilization of organic compounds by surfactant micelles. I. Length of carboxylic side chains in aromatic acids

Abstract

The semiequilibrium dialysis method has been used to determine solubilization equilibrium constants and activity coefficients of benzoic, phenylacetic, and hydrocinnamic acids (solubilizate) in micelles of the cationic surfactant hexadecylpyridinum chloride (cetylpyridinium chloride) in 0.1M HCl aqueous solutions. Methods described previously were employed to infer the concentrations of monomeric organic solute and surfactant on both sides of the dialysis cell. Values of the apparent solubilization constant K of the neutral acids have been correlated with mole fractions of the acid in the micelle X_A, where K=X_A/[monomeric acid]. The activity coefficients of both acid and surfactant were obtained, consistent with the Gibbs-Duhem equation. The solubilization constants of all three acids are nearly the same, indicating that there is no significant effect owing to the presence of one or more methylene groups between the carboxylate and the phenyl groups of benzoic acid. The solubilization constants also decrease appreciably, and the activity coefficients of the acids increase, as the mole fraction of the acid in the micelle increases.