Abstract
An attempt is made to derive a model for thermodynamic properties of water and water mixtures that incorporates the effect of strong orientation dependent hydrogen bonding interactions in the mean-field approximation. The theoretical analysis presented permits us to describe the physically important features of the liquid/vapour interfaces of aqueous mixtures with the aid of four phenomenological parameters, E11, E12 and ΔS11, ΔS12, determined in bulk solution. The parameters E11 and E12 are the energies of hydrogen bond formation between water molecules or water molecules and a second component. ΔS11 and ΔS12 are corresponding entropies of bond formation. The theory provides relations for the contribution of hydrogen bonding to bulk and surface equilibrium properties: surface free energy of water, excess energies and free energies of mixing and excess surface free energy of the mixture. An accurate description of experimental data for the system water-dimethylsulphoxide is obtained.
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