Gibbs Energy and Helmholtz Energy: Liquids, Solutions and Vapours
CHAPTER 4: Excess Molar Gibbs Energies: Related Properties and Formalisms Using DISQUAC
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Published:08 Sep 2021
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Special Collection: 2021 ebook collection
J. A. González, in Gibbs Energy and Helmholtz Energy: Liquids, Solutions and Vapours, ed. E. Wilhelm and T. M. Letcher, The Royal Society of Chemistry, 2021, pp. 183-204.
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In this chapter, it is shown that DISQUAC is a useful tool to describe phase diagrams (vapour–liquid, solid–liquid and liquid–liquid equilibria). Special attention is paid to the fact that DISQUAC is a mean field theory with a critical exponent for the order parameter equal to 0.5. Concentration–concentration structure factors [SCC(0)] and Kirkwood–Buff integrals (Gij) have been determined, using DISQUAC, for a number of mixtures of the type 1-alkanol or polar compound + heptane or 1-alkanol + polar compound. It is found that 1-alkanol + di-n-propyl ether (DPE) or + dimethyl carbonate (DMC) or + ethanenitrile (EtN) systems are characterized by homocoordination. In DPE solutions, this is mainly due to the alcohol self-association. Homocoordination in systems with DMC or EtN arises from dipolar interactions between like molecules. 1-Alkanol + tertiary amide mixtures are characterized by heterocoordination, i.e. by interactions between unlike molecules. Discussion of the results is conducted not only in terms of SCC(0) and Gij values, but also taking into account different thermophysical properties (liquid–liquid equilibria, calorimetric data) and models. This procedure should be considered as a standard method, needed to obtain conclusions of greater soundness.