Abstract
A natural extension of the Langmuir isotherm to the entire surface composition range (surface coverage θ≤1) in binary liquid mixtures [Pineiro (2001)] provides the key to the integration of the Gibbs adsorption equation, the calculation of the absolute surface concentrations, and the bulk activity coefficients of both components. This treatment shows that it is possible using the surface tension data as a function of the mole fraction to obtain separately the adsorption of the solvent and the amphiphile. This information makes possible a new way to express Traube's rule in terms of the infinite dilution activity coefficient. The new surface equation of state, called the Langmuir–Gibbs equation, establishes a clear and direct correspondence between the energy of adsorption and the energy of micellization. The surface equation of state brings a better fit to binary systems, both ideal and non-ideal, compared with the Szyszkowsky-Langmuir equation.
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