New Thermodynamics for Evaluating the Surface-phase Enrichment in the Lower Surface Tension Component
Corresponding Author
Prof. M. Soledade C. S. Santos
Centro de Química e Bioquímica, Faculdade de Ciências, Universidade de Lisboa, 1749-016 Lisboa (Portugal), Fax: (+) 351-217-500-088
Centro de Química e Bioquímica, Faculdade de Ciências, Universidade de Lisboa, 1749-016 Lisboa (Portugal), Fax: (+) 351-217-500-088===Search for more papers by this authorProf. João Carlos R. Reis
Centro de Ciências Moleculares e Materiais, Faculdade de Ciências, Universidade de Lisboa, 1749-016 Lisboa (Portugal)
Search for more papers by this authorCorresponding Author
Prof. M. Soledade C. S. Santos
Centro de Química e Bioquímica, Faculdade de Ciências, Universidade de Lisboa, 1749-016 Lisboa (Portugal), Fax: (+) 351-217-500-088
Centro de Química e Bioquímica, Faculdade de Ciências, Universidade de Lisboa, 1749-016 Lisboa (Portugal), Fax: (+) 351-217-500-088===Search for more papers by this authorProf. João Carlos R. Reis
Centro de Ciências Moleculares e Materiais, Faculdade de Ciências, Universidade de Lisboa, 1749-016 Lisboa (Portugal)
Search for more papers by this authorGraphical Abstract
Skin deep: Did you know there is a superficial alcohol content of 87 vol % in a 40 vol % alcoholic drink? Standard chemical potentials are introduced for surface-phase components, and quasi-exact expressions are worked out to compute ideal surface tensions and surface-phase compositions of real liquid mixtures.
Abstract
Regarding the surface phase of liquid mixtures as a thermodynamic phase, ideal surface phases are designed so that at fixed bulk-phase composition, real and ideal surface phases have the same chemical composition and identical limiting slopes for the dependence of surface tension on mole fraction. Standard chemical potentials are introduced for surface phase components, and quasi-exact expressions are worked out to compute ideal surface tensions and surface-phase compositions of real liquid mixtures. Guidelines for choosing molecular models to estimate the molar surface area of pure constituents are given. Ideal and excess surface tensions are calculated by using literature data for aqueous ethanol solutions at 298 K. These results show treatment based on Butler’s equations grossly overestimate predicted surface tensions, thus leading to lower ethanol content in the surface phase. These inaccuracies are ascribed to the use of molar surface areas in model equations that are too small.
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