Thermodynamic Approach to the Wetting of Solids by Surface-Active Agents: A Supplementary Approach to the Gibbs Formalism.
The adsorption of a solute on a solid can be followed by contact angle measurements of a drop of the solution on the solid. The Gibbs isotherm model can be used for quantitative interpretation of wettability variations. Its use in linking the wettability to the adsorption isotherm involves assimilating the Gibbs' planes to the surfaces themselves. Within this framework, these interpretations lead to the conclusion that adsorption of surface-active agents is greater on solid-vapor interfaces than on solid-liquid interfaces, for hydrophilic solids. This is not the only approach. Thermodynamics allows other formalisms, the conclusions of which can be completely different. We present a thermodynamic approach which explicitly reveals relationships between surface tensions and contents of surfaces, without referring to the Gibbs' plane. This permits us to explain the behavior of a drop of surfactant solution put on hydrophilic or hydrophobic solids with conclusions different from those reached using the Gibbs approach. We show that all these thermodynamic approaches are linked; they do not dismiss one another but give different views of the same phenomenon. Copyright 2000 Academic Press.
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Laboratoire d'Energétique et Réactivité aux Interfaces (EA 1519), Université Pierre et Marie Curie, Case 39, 4, Place Jussieu, Paris Cedex 05, 75252, France
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