Interactions in Mixed Micellar Systems of an Amphoteric Chelating Surfactant and Ionic Surfactants

Mixtures of ionic surfactants and the chelating surfactant 2-dodecyldiethylenetriaminepentaacetic acid (4-C₁₂-DTPA) have been examined in terms of interactions in mixed micellar systems. The amphoteric 4-C₁₂-DTPA is zwitterionic with a negative net charge at the studied pH levels. The investigated ionic surfactants were the cationic dodecyltrimethylammonium chloride (DoTAC), the anionic sodium dodecyl sulfate (SDS), and the zwitterionic dimethyldodecylamine-N-oxide (DDAO). The surfactants all have the same hydrophobic chain lengths, and the results are evaluated in terms of headgroup interactions. 4-C₁₂-DTPA interacts with different ionic surfactants by accepting or donating protons to the aqueous solution to increase the attractive interactions between the two surfactants; i.e., the protonation equilibrium of 4-C₁₂-DTPA is shifted in different directions depending on whether there are predominant repulsions between positively or negatively charged groups in the mixed micelles. This was monitored by measuring pH vs concentration in the mixed systems. By measuring the pH, it was also possible to study the shift in the protonation equilibrium at increasing concentration, as the composition in the micelles approaches the composition in the total solution. Following the approach of Rubingh’s regular solution theory, the interaction parameter β for mixed micelle formation was calculated from the cmc values determined by NMR diffusometry. Synergism in mixed micelle formation and negative β parameters were found in all of the investigated systems. As expected, the most negative β parameter was found in the mixture with DoTAC, followed by DDAO and SDS. The self-diffusion in the 4-C₁₂-DTPA/DoTAC system was also discussed. The self-diffusion coefficient vs concentration plots show two distinctly different curves, depending on the surfactant that is present in excess.