Excess thermodynamic properties complex formations

Whereas it is possible, for materials that are predominantly ionic or metallic, to estimate fairly good enthalpies of formation on the basis of sensible models, the covalent bond in metallic phases has so far defied quantitative description. The situation is even more complex in phases which exhibit a proportion of all three bond types, as occurs for example in most concentrated metallic solutions. Other attempts to predict unknown thermodsmamic values have therefore been based on entirely empirical rules. There seems to exist, for instance, a linear relation between the enthalpies and excess entropies of formation of concentrated solutions independent of bond mechanism. Other investigators are at present engaged in testing various empirical equations for the estimation of the thermodynamic properties of multicomponent solutions from those of the binaries. ... 

The first chapter by J. Jiao and D. J. Burgess discusses the thermodynamic instability of multiple emulsions as a result of the excess of free energy caused by the formation of the emulsion droplets. In multiple emulsions consisting of three distinct liquid phases, counteracting the effect of the Laplace pressure by electrolyte addition to the inner dispersed aqueous phase will increase the destabilization of the system owing to osmotic pressure. In addition the authors discuss the effects of both osmotic and Laplace pressure as well as the interfacial rheological properties of these complex systems and their stability. 

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