Characterization of a Reverse Micellar System by 1H NMR

The H-1 NMR spectrum of IgepalCO520 in ternary mixtures containing water and cyclohexane shows a complex dependence on water content. This is in part because of rapid exchange between surfactant molecules within the micelles and free surfactant dissolved in the continuous phase. The analysis of this two-state system is further complicated by the fact that the chemical shifts of both free and micellar surfactants vary with micelle size. We demonstrate that the relative quantities of free and micellar surfactants can be determined from the NMR spectra if the data are compared within sample sets of constant micelle size but differing global composition. By fixing micelle size, the spectra of both surfactant states remain constant within a given series and only the relative populations of the free and micellar species chance with overall composition. This method of analysis allows for the determination of free surfactant concentration as a function of micelle size. Results are presented for the water/IgepalCO520/cyclohexane system and indicate that the free surfactant concentration is far from negligible and strongly dependent on micelle size. The free surfactant concentration increases with decreasing micelle size, reflecting the lower stability of the smaller micelles. Similar behavior can be expected for other reverse micellar systems based on non-ionic surfactants.