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Equilibrium Adsorption of Surfactants at the Gas–Liquid Interface

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Interfacial Processes and Molecular Aggregation of Surfactants

Part of the book series: Advances in Polymer Science ((POLYMER,volume 218))

Abstract

Theories on equilibrium adsorption of surfactants at the gas-liquid interface have been reviewed andvalidated. For the adsorption of nonionic surfactants, the thermodynamic approach of Butler has been used,in conjunction with the Lucassen-Reynders dividing surface, to describe the adsorption layer state and adsorptionisotherm as a function of partial molar area. Applying the Butler–Lucassen–Reynders modelingapproach provides the generalized adsorption isotherm and equation of state, which is capable of describingthe effect of the surfactant orientational states and aggregation at the interface. For Langmuirian andFrumkinian surfactant adsorption, the Butler–Lucassen–Reynders modeling approach produces thesame predictions for surface tension as described by the well-known Langmuir and Frumkin adsorption isotherms.The adsorption of ionic surfactants and ionic–nonionic surfactant mixtures has been described followingthe traditional approach with the Gibbs dividing surface and Gibbs adsorption isotherm, and the Gouy-Chapmanelectrical double layer electrostatics. The developed theories have been validated through comparison withthe experimental data on surface tension. Regression analysis by minimizing the reduced chi-square hasbeen used to best fit the models to the experimental data to obtain the model free parameters. For thesurfactant homologous series of octaethyleneglycol-n-alkyl ethers C n H2n+1O(CH2CH2)8H,the negative sign of the intermolecular interaction parameter obtained in the regression analysis of surfacetension has not been resolved by the model for the surfactant orientational state at the interface. Forthe surfactant series, the surface aggregation model gives physically consistent fitting and parameters.The models for adsorption of ionic surfactants have been validated using the surface tension of a seriesof sodium n-hexadecylsulfates with the sulfate group located at the differentpositions in the hydrocarbon chain, a homologue series of sodium alkyl sulfates, and a seriesof alkali dodecylsulfates. Improved adsorption models for ionic surfactants have been developed throughfundamental modeling of the adsorption processes and the molecular interactions in the adsorption layers.The improved predictions reduce the required number of free parameters and agree with the surface tensionand surface potential data better than the conventional models.

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Authors and Affiliations

  1. Division of Chemical Engineering, School of Engineering, The University of Queensland, Brisbane, 4072, Queensland, Australia

    Stoyan I. Karakashev & Anh V. Nguyen

  2. Department of Metallurgical Engineering, University of Utah, 135 South 1460 East, 84112, Salt Lake City, UT, USA

    Jan D. Miller

Authors
  1. Stoyan I. Karakashev
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  2. Anh V. Nguyen
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  3. Jan D. Miller
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Corresponding author

Correspondence to Jan D. Miller .

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Ranga Narayanan

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© 2008 Springer-Verlag Berlin Heidelberg

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Karakashev, S.I., Nguyen, A.V., Miller, J.D. (2008). Equilibrium Adsorption of Surfactants at the Gas–Liquid Interface. In: Narayanan, R. (eds) Interfacial Processes and Molecular Aggregation of Surfactants. Advances in Polymer Science, vol 218. Springer, Berlin, Heidelberg. https://doi.org/10.1007/12_2008_161

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