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The thermodynamics of the micellization of long-tail surfactants, including docosyl-, eicosyl-, and octodecyl-trimethylammobium bromide (C22TABr, C20TABr, and C18TABr), docosylethoxyldimethyl-ammonium bromide (C22(OH)DABr), and docosylbenzyldimethyl-ammobium bromide (C22BzDABr), have been studied using static light scattering measurements in ethanol following addition of water. The water content was found to influence the thermodynamics of micellization. In this study, the surfactants examined were at mmol·L−1 concentrations in ethanol and thereby the critical water content inducing aggregation was always smaller than 50 wt%. All the thermodynamic functions are negative over the concentration range investigated. The micellization is mainly enthalpy- and partly entropy-driven. With continuously increasing water content, the entropic contribution to the driving force increases. The critical water contents leading to the transition from mainly enthalpy-driven to mainly entropy-driven behavior are 66.9 wt% (C22BzDABr), 73.2 wt% (C22TABr), and 77.1 wt% (C22(OH)DABr), respectively. Enthalpy–entropy compensation occurs during the micellization processes. The compensation temperatures T c are close to the general values for surfactants in aqueous solution.
Journal of Solution Chemistry – Springer Journals
Published: Jan 12, 2016
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