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Adsorption Properties of Surface Chemically Pure Sodium Perfluoro-n-alkanoates at the Air/Water Interface: Counterion Effects within Homologous Series of 1:1 Ionic Surfactants

Lunkenheimer, Klaus, Prescher, Dietrich, Hirte, Rolf, Geggel, Katrina·2015·Langmuir
DOI 10.1021/la503450k
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Abstract

The unusual behavior of saturation adsorption calculated from experimental equilibrium surface tension (σ(e)) versus logarithm of concentration (c) isotherms within the homologous series of aqueous sodium perfluoro-n-alkanoate solutions represents a particular problem in the adsorption of homologous ionic 1:1 amphiphiles at fluid interfaces. Special precautions were taken to guarantee surface-chemical purity for all solutions, avoiding falsifying effects by surface-active trace impurities. Surprisingly, all homologues' adsorption isotherms reveal ideal surface behavior. The minimal surface area demand per molecule adsorbed for shorter-chain homologues slightly decreases with increasing chain lengths but then goes up steeply after having passed a minimum. A similar feature has been observed with the chemically quite different homologous series of the hydrocarbon surfactants of sodium-n-alkylsulfates. Comparing the corresponding 3D saturation concentrations in the boundary layer and in the bulk, it becomes evident that at high bulk concentrations when boundary layer and bulk concentrations are of the same order of magnitude the adsorption behavior may be treated as that of a pseudononionic surfactant. However, under conditions of the homologues' strongest surface activity, adsorption seems to become increasingly governed by electrostatic repulsion, resulting in increasingly greater cross-sectional areas. Deviation from pseudononionic behavior sets in when the Debye length becom…

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  • Surface activity and air-water interface adsorption potential of PFAS are influenced by compound chain length, water chemistry properties such as ionic composition, and the presence of co-occurring PFAS compounds.

    “Prior research for PFAS has shown that surface activity (and air-water interface adsorption potential) is influenced by compound chain length (Psillakis et al., 2009; Baba et al., 2013; Lunkenheimer et al., 2015), water chemistry properties such as ionic composition (Downes et al., 1995), and the presence of co-occurring PFAS compounds (Vecitis et al., 2008).”

    From Assessing the potential contributions of additional retention processes to PFAS retardation in the subsurface (2018) · cites this paper as Lunkenheimer et al., 2015

  • Others have reported similar measurements of strong air-water interface adsorption, measured in terms of surface excess, for PFOS and PFOA.

    “Others have reported similar measurements of strong air-water interface adsorption, measured in terms of surface excess, for PFOS and PFOA (Downes et al., 1995; Vecitis et al., 2008; Lunkenheimer et al., 2015).”

    From Assessing the potential contributions of additional retention processes to PFAS retardation in the subsurface (2018) · cites this paper as Lunkenheimer et al., 2015

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Metadata

Authors
Lunkenheimer, K., Prescher, D., Hirte, R., & Geggel, K.
Affiliations
  • Max-Planck-Institut für Kolloid- und Grenzflächenforschung, Department Adsorption Layers, Am Mühlenberg 1, D-16321 Potsdam, Germany
  • Technische Fachhochschule Wildau, D-15745 Wildau, Germany
Venue
Langmuir
Publisher
American Chemical Society (ACS)
Published
2015-01-14
Volume
31
Issue
3
Pages
970-981
ISSN
  • 0743-7463
  • 1520-5827
DOI
10.1021/la503450k
Cited by
45
References
1
Language
en

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