RESUMO
The Gibbs Adsorption Isotherm equation is a two-dimensional analogous of the Gibbs-Duhem equation, and it is one of the cornerstones of interface science. It is also widely used to estimate the surface excess concentration (SEC) for surfactants and other compounds in aqueous solution, from surface tension measurements. However, in recent publications some authors have cast doubt on this method. In the present work, we review some of the best available surface tension experimental data, and compare estimations of the SEC, using the Gibbs isotherm method (GIM), to direct measurements reported in the literature. This is done for both nonionic and ionic surfactants, with and without added salt. Our review leads to the conclusion that the GIM has a very solid agreement with experiments, and that it does estimate accurately the SEC for surfactant concentrations smaller than the critical micellar concentration (CMC).
RESUMO
Onsager's irreversible thermodynamics is used to perform a systematic deduction of the kinetic equations governing the opening and collapse of transient pores in spherical vesicles. We show that the edge tension has to be determined from the initial stage of the pore relaxation and that in the final state the vesicle membrane is not completely relaxed, since the surface tension and the pressure difference are about 25% of its initial value. We also show that the pore life-time is controlled by the solution viscosity and its opening is driven by the solution leak-out and the surface tension drop. The final collapse is due to a non-linear interplay between the edge and the surface tensions together with the pressure difference. We also discuss the connection with previous models.
