Mass action model for solute distribution between water and micelles. Partial molar volumes of butanol and pentanol in dodecyl surfactant solutions

The densities of 1-butanol and 1-pentanol were measured in aqueous solutions of dodecyltrimethylammonium bromide and dodecyldimethylamine oxide and the partial molar volumes at infinite dilution of the alcohols in aqueous surfactants solutions were obtained. The observed trends of this quantity as a function of the surfactant concentration were rationalized using a mass-action model for the alcohol distribution between the aqueous and the micellar phase. At the same time, the model was revised to account for the alcohol effect on the surfactant micellization equilibrium. The partial molar volume of alcohols in the aqueous and in the micellar phases and the ratios between the binding constant and the aggregation number were calculated. These thermodynamic quantities are nearly the same in the two surfactants analyzed in this paper but differ appreciably from those in sodium dodecylsulfate. The apparent molar volume of surfactants in some hydroalcoholic solutions at fixed alcohol concentration were also calculated. In the micellization region the trend of this quantity as a function of the surfactant concentration shows a hump, which depends on the alcohol concentration and on the alcohol alkyl chain length. The alcohol extraction from the aqueous to the micellar phase due to the addition of the surfactant can account for the observed trends.