SOLUTION THERMODYNAMICS APPLICATIONS

In this chapter we shall consider some thermodynamic properties of solutions in which a polymer is the solute and some low molecular weight species is the solvent. Our special interest is in the application of solution thermodynamics to problems of phase equilibrium. 

McGraw-HiU, New York, 1987. Sandler, S.I., Chemical and Engineeiing Thermodynamics, 2d ed., Wiley, New York, 1989. Smith, J.M., H.C. Van Ness, and M.M. Abbott, Introduction to Chemical Engineeiing Theimodynamics, 5th ed., McGraw-Hill, New York, 1996. Van Ness, H.C., and M.M. Abbott, Classical Theimodynamics of Nonelectrolyte Solutions With Applications to Phase Equi-lihiia, McGraw-Hill, New York, 1982. 

We present a molecular theory of hydration that now makes possible a unification of these diverse views of the role of water in protein stabilization. The central element in our development is the potential distribution theorem. We discuss both its physical basis and statistical thermodynamic framework with applications to protein solution thermodynamics and protein folding in mind. To this end, we also derive an extension of the potential distribution theorem, the quasi-chemical theory, and propose its implementation to the hydration of folded and unfolded proteins. Our perspective and current optimism are justified by the understanding we have gained from successful applications of the potential distribution theorem to the hydration of simple solutes. A few examples are given to illustrate this point. 

With applications to protein solution thermodynamics in mind, we now present an alternative derivation of the potential distribution theorem. Consider a macroscopic solution consisting of the solute of interest and the solvent. We describe a macroscopic subsystem of this solution based on the grand canonical ensemble of statistical thermodynamics, accordingly specified by a temperature, a volume, and chemical potentials for all solution species including the solute of interest, which is identified with a subscript index 1. The average number of solute molecules in this subsystem is... 

Cobble, J. W. "Thermodynamic Properties of High Temperature Aqueous Solutions. VI. Applications of Entropy Correspondence to Thermodynamics and Kinetics" J. Am. 

Valle-Rie tra Project Evolution in the Chemical Process Industries Van Ness and Abbott Classical Thermodynamics of Nonelectrolyte Solutions with Applications to Phase Equilibria Van Winkle Distillation Volk Applied Statistics for Engineers Walas Reaction Kinetics for Chemical Engineers y ... 

Kerrick D. M. and Darken L. S. (1975). Statistical thermodynamic models for ideal oxide and silicate solid solutions, with applications to plagioclase. Geochim. Cosmochim. Acta, 39 1431-1442. 

The fundamental physical laws governing motion of and transfer to particles immersed in fluids are Newton s second law, the principle of conservation of mass, and the first law of thermodynamics. Application of these laws to an infinitesimal element of material or to an infinitesimal control volume leads to the Navier-Stokes, continuity, and energy equations. Exact analytical solutions to these equations have been derived only under restricted conditions. More usually, it is necessary to solve the equations numerically or to resort to approximate techniques where certain terms are omitted or modified in favor of those which are known to be more important. In other cases, the governing equations can do no more than suggest relevant dimensionless groups with which to correlate experimental data. Boundary conditions must also be specified carefully to solve the equations and these conditions are discussed below together with the equations themselves. 

H. C. Van Ness and M. M. Abbott, Classical Thermodynamics of onelectrolxte Solutions With Applications to Phase Eauilibria, McGraw-Hill Book Co., New York, 1982. 

As mentioned above, the primary focus of this chapter is on osmotic pressure and its basis in solution thermodynamics. We consider both classical and statistical thermodynamic interpretations of osmotic pressure. The next three sections are devoted to this. The last two sections describe osmotic effects in charged systems and a few applications of osmotic phenomena. 

The use of a dissolved salt in place of a liquid component as the separating agent in extractive distillation has strong advantages in certain systems with respect to both increased separation efficiency and reduced energy requirements. A principal reason why such a technique has not undergone more intensive development or seen more than specialized industrial use is that the solution thermodynamics of salt effect in vapor-liquid equilibrium are complex, and are still not well understood. However, even small amounts of certain salts present in the liquid phase of certain systems can exert profound effects on equilibrium vapor composition, hence on relative volatility, and on azeotropic behavior. Also extractive and azeotropic distillation is not the only important application for the effects of salts on vapor-liquid equilibrium while used as examples, other potential applications of equal importance exist as well. 

Maron, S. H., Nakajima, N. A theory of the thermodynamic behavior of non electrolyte solutions. II. Application to the system benzene-rubber. J. Polymer Sci. 40, 59-71... 

Van Ness, H. C. Abbott, M. M., "Classical Thermodynamics of Non Electrolyte Solutions with Applications to Phase Equilibria," McGraw-Hill Book Company (1982). 

Walther J. V. and Orville P. M. (1983) The extraction-quench technique for determination of the thermodynamic properties of solute complexes. Application to quartz solubility in fluid mixtures. Am. Mineral. 68, 731-741. 

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