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The Gibbs and Butler Equations and the Surface Activity of Dilute Aqueous Solutions of Strong and Weak Linear Polyelectrolyte-Surfactant Mixtures: The Roles of Surface Composition and Polydispersity.
Penfold, Jeffrey; Thomas, Robert K.
Afiliación
  • Penfold J; Rutherford-Appleton Laboratory, Chilton, Didcot, Oxfordshire OX11 0RA, U.K.
  • Thomas RK; Physical and Theoretical Chemistry Laboratory, South Parks Road, Oxford OX1 3QZ, U.K.
J Phys Chem B ; 128(33): 8084-8102, 2024 Aug 22.
Article en En | MEDLINE | ID: mdl-39140373
ABSTRACT
In a previous paper, we applied a combination of direct measurements of both surface tension and surface excess in conjunction with the Gibbs equation to explain features of the adsorption and surface tension of mixtures of surfactants and strong linear polyelectrolytes at the air-water interface. This paper extends that model by including (i) the restrictions of the Butler equation for the behavior of the surface tension of mixed systems and (ii) the surface behavior of surfactant and linear weak polyelectrolyte mixtures, for which the inclusion of measurements of the surface excess and composition is shown to be particularly important. In addition, a closer examination of earlier data at higher concentrations provides evidence that the surface layering that is often observed in polyelectrolyte-surfactant systems is also an average equilibrium phenomenon and is driven by particular aggregation patterns that occur in some systems and not in others. Although the successful application of the Gibbs and Butler equations indicates that strong polyelectrolyte-surfactant systems can be described in terms of an average equilibrium over wide ranges of concentration, we have identified two concentration ranges where polydispersity in either polyelectrolyte molecular weight or composition results in significant time dependence of the surface behavior.

Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: J Phys Chem B Asunto de la revista: QUIMICA Año: 2024 Tipo del documento: Article País de afiliación: Reino Unido Pais de publicación: Estados Unidos

Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: J Phys Chem B Asunto de la revista: QUIMICA Año: 2024 Tipo del documento: Article País de afiliación: Reino Unido Pais de publicación: Estados Unidos