Critical micelle concentration of surfactants in aqueous buffered and unbuffered systems

Critical micelle concentration (CMC) of sodium dodecyl sulphate (SDS), lithium perfluorooctanesulfonate (LPFOS), hexadecyltrimethylammonium bromide (HTAB), tetradecyltrimethylammonium bromide (TTAB), and sodium cholate (SC), surfactants commonly used as pseudostationary phases in micellar electrokinetic chromatography (MEKC), have been determined by means of three different methods: MEKC, spectrophotometry, and conductometry. Determinations have been performed in water, and also in different concentrations of phosphate buffer at pH 7.0. CMC values ranging from 8.08 (water) to 1.99 (50 mM phosphate buffer) mM for SDS, from 7.16 (water) to 2,81 (30 mM phosphate buffer) mM for LPFOS, from 3.77 (water) to 1.93 (20 mM phosphate buffer) mM for TTAB, from 0.91 (water) to ∼0.34 (20 mM phosphate buffer) for HTAB, and around 13 mM (20 mM phosphate buffer) for SC, are obtained. The effect of the electrolyte concentration on the CMC, as well as the linear relationship between the electrolyte counter-ion concentration and the CMC are discussed. This linear relationship provides an easy way for users to estimate the CMC of a MEKC system, at a given electrolyte concentration. A comparison between experimental methods, as well as a discussion about the suitability of a given method for the determination of the CMC for a given surfactant system is also provided.