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The Thermodynamics of Long-Tail Surfactant Aggregation Driven by Water Addition in Ethanol

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Abstract

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.

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Acknowledgments

Support from The National Natural Science Foundation of China (Grant No. 21273040) is gratefully acknowledged.

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Authors and Affiliations

  1. Institute of Colloid and Interface Chemistry, College of Chemistry and Chemical Engineering, Fuzhou University, Fuzhou, Fujian, 350108, People’s Republic of China

    Jianxi Zhao, Wenjing Dong & Xinzhi Xu

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  1. Jianxi Zhao
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  2. Wenjing Dong
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  3. Xinzhi Xu
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Correspondence to Jianxi Zhao.

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Zhao, J., Dong, W. & Xu, X. The Thermodynamics of Long-Tail Surfactant Aggregation Driven by Water Addition in Ethanol. J Solution Chem 45, 126–139 (2016). https://doi.org/10.1007/s10953-015-0426-x

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