Simultaneous adsorption at the liquid/solid and liquid/gas interfaces.
Physical adsorption from binary or higher-order liquid mixtures on solids is often accompanied by adsorption phenomena at the liquid/gas interface. As long as the adsorption effects are comparable, both interfaces have to be included in the respective thermodynamic equations. A purely phenomenological thermodynamic description in terms of excess quantities is given of the simultaneous adsorption from multicomponent liquid mixtures at the liquid/solid and liquid/gas interfaces. In order to illustrate the thermodynamic procedure, the individual and simultaneous adsorption excess isotherms of three binary liquid mixtures at the liquid/Teflon and liquid/vapor interfaces are calculated from experimental surface-tension and contact-angle data taken from the literature. Special attention is focused on the estimation of error in calculated adsorption isotherms. A line of approach is given to find the confidence limits of adsorption isotherms that cover the entire mole fraction scale. The isotherms as well as their confidence limits are presented and discussed.