Thermodynamic consideration of the mixed micelle of surfactants

In conformity with the conclusion obtained previously, the mixed micelle formation of surfactants was treated thermodynamically as the appearance of a macroscopic bulk phase with the aid of the excess thermodynamic quantities similar to those used for the adsorbed film. The composition of surfactant in the mixed micelle and the thermodynamic quantities of micelle formation were found to be evaluated by applying the thermodynamic equations derived. These equations were extended so as to be applicable to any kind of surfactant mixture. It was shown that the critical micelle concentration vs. composition of surfactant curves form a diagram analogous to the phase diagram of binary mixture. Applying the equation to the published data on typical surfactant systems, this thermodynamic approach was proved to be useful to clarify the miscibility of surfactants in the micellar state.