Theory of Solutions
This chapter is concerned with a few aspects of the theory of solutions that are either of fundamental character or useful in the study of aqueous solutions. We begin by generalizing some concepts and relationships from the theory of pure liquids and proceed with aspects that are specific to mixtures and solutions. The terms “mixture” and “solution” are used here almost synonymously. The latter is traditionally used when one component (the solute) is dissolved in the other (the solvent). Perhaps one of the most useful concepts in the theory of solution is the concept of ideal solutions. These were defined originally in terms of experimental observations, such as Raoult’s or Henry’s laws. We shall develop the theoretical background that led to such ideal behaviors. In section 6.7 we present the Kirkwood-Buff theory of solution—an important tool for the study of simple solutions as well as some aspects of aqueous solutions. The concept of solvation, though traditionally used in the context of extremely dilute solutions, is introduced beginning in section 6.13 and applied to any molecule (not necessarily a solute) in any fluid (not necessarily a solvent). This concept enters whenever we study processes such as chemical equilibrium, adsorption, allosteric effect, and so on, in the liquid state.
KeywordsActivity Coefficient Thermodynamic Quantity Partial Molar Volume Pair Correlation Function Preferential Solvation
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