Abstract

For single and mixed nonionic surfactants, the Gibbs adsorption isotherm and Gibbs-Duhem equations reveal two possible causes of tension minima in dilute systems: (1) sign change in interfacial excess inventory of a surfactant, and (2) a maximum in chemical potential of a surfactant with respect to its total inventory. Whether either occurs depends on details of solution, adsorption, partitioning and association behavior as linked by the requirement of mass conservation. Specific cases are examined using the Bury-Hartley limit of multiple association equilibria, and also, for mixed surfactants, the more approximate phase-separation limit. A single surfactant in two phases, as in one, can ordinarily have no maximum in chemical potential. With two surfactans, mixed micelles must form in at least one phase to cause a maximum in any of the cases studied.

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