Thermochemistry of aqueous micellar systems

Surfactants tend to aggregate above a certain concentration, called the critical micelle concentration, into large clusters or micelles. With modern calorimetric and other related techniques it is now possible to measure precisely and rapidly the thermodynamic properties of liquid systems over a wide range of concentration and temperature. An overview is given of data obtained in our laboratory for heat capacities, enthalpies, entropies and free energies of aqueous sodium decanoate, octylammonium hydrobromide, nonyl and decyltrimethylammonium bromide. The thermodynamic functions of micellization are derived and interpreted with a phase—sepa— ration model. The closely related microemulsions are also briefly dis— cussed.