Customer Reviews

Molecular Theory of Solutions

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This is an important book that provides a clear account of the molecular theory of solutions and mixtures based mainly on the Kirkwood-Buff theory that was developed many years ago. The theory could not have been fully exploited until Ben-Naim developed methods to calculate the Kirkwood-Buff (KB) integrals from experimental data rather than from the pair correlation functions.

The KB integrals, as well as some derived quantities, provide information about the local properties of the system, as opposed to their global properties described by the excess thermodynamic functions that were and are commonly used. Ben-Naim also introduced a new measure of the thermodynamics of solvation that does not depend on hypothetical standard states that were traditionally part of solution chemistry. The book is written very clearly and the arguments are carefully presented and illustrated with examples. It is strongly recommended for both the beginning graduate student and experienced scientist with interests in solutions.

This is an excellent book that highly succeeds in explaining a difficult subject! Thermodynamics of solution mixtures has a long history and much has been written on this topic. I am amongst those of you that have been confused from time to time by the various definitions of excess functions, activity coefficients and reference states. In "Molecular Theory of Solutions", Ben-Naim introduces the reader to the elementary statistical mechanics of liquids and solution mixtures. A central theme of the book is the Kirkwood-Buff (KB) theory of solution, which, as originally shown by Ben-Naim, can be used to extract (local) molecular properties from (global) thermodynamic properties. Ben-Naim next uses KB theory to derive a thermodynamic formalism for ideal- and nonideal solutions. I was intrigued when first reading this newly derived formalism. Being educated to calculate "deviations from Raoult" (just numbers, nothing more), suddenly nonideality acquired a very clear microscopic significance. Beautiful! I highly recommend this book to anybody interested in the subject, in particular to those of you that teach it.

This book is very important and necessary for the chemistry and biochemistry. The special interest presents a new definition of solvation. In the traditional definition one needs to specify the standard state for the solute in the ideal gas and liquid phase. It is the reason of some confusion concerning the "standard state" that exists in the literature. The confusion arises from the fact that the solvation Gibbs energy Äìs* is determined experimentally in a similar way as one of the conventional standard Gibbs energy of solvation. The latter does involve a choice of standard state. Moreover in all the conventional processes the standard quantities apply only to very dilute solutions of solute in the system, i.e. it could be studied only in the concentration range when Henry's law is obeyed. This is a very severe restriction on the applicability of the standard quantities. In Ben-Naim's definition of a new process of solvation there is no need to specify any standard state for the solvation. This is quite clear from the definition of the solvation process. In addition the process of Ben-Naim's solvation and the corresponding thermodynamic quantities can be defined for the concentrated solutions and pure liquids.