CY6116 : Advanced Solution Thermodynamics

Ideal and non-ideal solutions, activity and activity coefficients, mixing and excess properties of liquid-liquid mixtures. Theories of solutions of electrolyte and non-electrolyte liquids: van Laar theory, van der Waals theory, Scatchard-Hildebrand theory, Lattice theory, Prigogine Cell theory, Flory equation of state theory, Prigogine-Flory-Patterson theory, Extended Real Associated Solution model and Kirkwood-Buff theory.

Modern experimental techniques: determination of vapour-liquid equilibrium by static and dynamic methods, heat capacity and heat of mixing by calorimeters, and determination of volumetric, transport, acoustic and optical properties of liquid-liquid mixtures. Thermodynamic relations of excess Gibbs energy, excess entropy, excess enthalpy, excess volume, viscosity deviation, excess heat capacity and excess compressibility. Partial molar properties, their physical significance and methods of their determination. Study of non-ideal behaviour of various types of solutions: nonpolar + nonpolar, polar + nonpolar, polar + polar, and mixtures with hydrogen-bond formation and charge transfer complexes; interpretation in terms of molecular interactions.

Empirical and semi-empirical formulas, theoretical expressions, correlations, group contribution methods and computational models for the prediction of thermodynamic properties of liquids and liquid mixtures.

Text Books:

  1. Prausnitz J. M., Lichtenthaler R.N., Azevedo E.G., Molecular Thermodynamic of Fluid-Phase Equilibria, (Prentice Hall, 3rd edition, 1998).
  2. Rowlinson J.S., Liquid and Liquid Mixtures, (Springer; 1st edition, 1995).
  3. Acree W.E., Thermodynamic Properties of Nonelectrolyte Solutions, (Academic Press, 1984).
  4. Bevan Ott, Juliana Boerio-Goates, Chemical Thermodynamics: Advanced Applications, (Academic Press, 1st edition, 2000).
  5. Prigogine, The Molecular Theory of Solutions, (North Holland Publishing Co. Amsterdam 1957).
  6. Arieh Ben-Naim, Molecular Theory of Solutions, (Oxford University Press, USA, 2006).