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Mixed Micellization of Cationic/Anionic Surfactants: Role of Matching Water Affinities between Oppositely Charged
Li-Sheng Hao1, Kai Xiao1, Yan Hu1
1Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research (Ministry of Education of China), College of Chemistry and Chemical Engineering , Hunan Normal University , Changsha 410081 , China.
Abstract:
To explore the role of matching water affinities between the oppositely charged headgroups, the micellization of cetyltrimethylammonium bromide (CTA+Br-)/sodium dodecanoate (Na+L-) mixed system and the CTA+Br-/sodium dodecylsulfonate (Na+AS-) mixed system has been investigated by the surface tension method and molecular dynamic (MD) simulation. In comparison with the CTA+Br-/Na+L- system, the CTA+Br-/Na+AS- system shows stronger micelle formation ability, smaller critical micelle concentration (cmc), and stronger synergistic effect arising from the higher degree of matching water affinities between the headgroups CTA+ and AS-. To explore the role of matching water affinities between the oppositely charged constituent counterions, the micellization of CTA+X-/Y+L- mixed systems with various counterions has been investigated. The higher degree of matching water affinities between counterions X- and Y+ and the higher degree of mismatching water affinities between headgroups and counterions are unfavorable to the screening effect of counterions on the electrostatic attraction between headgroups CTA+ and L-, leading to stronger micelle formation ability and smaller cmc and vice versa. MD simulation results also indicate that, for the mixed micellization of cationic/anionic surfactants, the role of matching water affinities between oppositely charged headgroups is more important than that between oppositely charged constituent counterions.
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