Determination of Critical Micelle Concentration of Ionic and Non‐Ionic Surfactants by Streaming Potential Measurements

A capillary electrophoresis system capable of measuring streaming potentials was used for the determination of critical micelle concentration (CMC) of anionic, cationic, zwitterionic and non-ionic surfactants. The CMC values of anionic surfactant sodium dodecyl sulphate (SDS), cationic surfactant cetyltrimethylammonium bromide (CTAB), zwitterionic surfactant 3-((3-cholamidopropyl) dimethylammonio)-1-propanesulfonate (CHAPS) and non-ionic surfactant polyethylene glycol p-(1,1,3,3-tetramethylbutyl)-phenyl ether (Triton X-100) in water or salt solutions were determined by determining the abrupt change in the trend of streaming potential change with the surfactant concentration. The CMC values were 8.23, 0.93, 5.80 and 0.16 mM, respectively. This method was also used to demonstrate how the CMCs of SDS and CTAB change differently with temperature. The CMC of SDS decreased from 10°C to 25°C and then increased from 25°C to 40°C, whereas CTAB only increased linearly within 10°C-40°C. The capillary wall zeta potentials in surfactant solutions can be calculated from the measured streaming potential, conductivity and solution viscosity. Surface charge densities were calculated using the zeta potentials obtained. The surface charge densities of SDS were calculated to be 5.6-0.8 C/m² when SDS solutions with concentrations of 2-20 mM zeta potentials were used. The calculated zeta potentials and surface charge densities reached a plateau at about 8 mM, which coincided with the CMC of SDS determined in the present study and the literature values. The CMC values obtained from streaming potential measurement are comparable to values obtained with other CMC determination techniques such as surface tension and conductometric measurements.