Thermodynamics Of Dilute Aqueous Solutions

This book deals with a subject that has been studied since the beginning of physical chemistry. Despite the thousands of articles and scores of books devoted to solvation thermodynamics, I feel that some fundamen tal and well-established concepts underlying the traditional approach to this subject are not satisfactory and need revision. The main reason for this need is that solvation thermodynamics has traditionally been treated in the context of classical (macroscopic) ther modynamics alone. However, solvation is inherently a molecular pro cess, dependent upon local rather than macroscopic properties of the system. Therefore, the starting point should be based on statistical mechanical methods. For many years it has been believed that certain thermodynamic quantities, such as the standard free energy (or enthalpy or entropy) of solution, may be used as measures of the corresponding functions of solvation of a given solute in a given solvent. I first challenged this notion in a paper published in 1978 based on analysis at the molecular level. During the past ten years, I have introduced several new quantities which, in my opinion, should replace the conventional measures of solvation thermodynamics. To avoid confusing the new quantities with those referred to conventionally in the literature as standard quantities of solvation, I called these "nonconventional," "generalized," and "local" standard quantities and attempted to point out the advantages of these new quantities over the conventional ones.

This book provides a thorough discussion of the thermodynamics of aqueous solutions and presents tools for analyzing and solving scientific and practical problems arising in this area. It also presents methods that can be used to deal with ionic and nonionic aqueous solutions under sub- or supercritical conditions. Illustrations and tables give examples of procedures employed to predict thermodynamic quantities of the solutions, and an appendix summarizing statistical mechanical equations used to describe the systems is also provided. High-Temperature Aqueous Solutions: Thermodynamic Properties contains essential information for physical chemists, geochemists, geophysicists, chemical technicians, and scientists involved in electric power generation.

Solution Thermodynamics and its Application to Aqueous Solutions: A Differential Approach, Second Edition introduces a differential approach to solution thermodynamics, applying it to the study of aqueous solutions. This valuable approach reveals the molecular processes in solutions in greater depth than that gained by spectroscopic and other methods. The book clarifies what a hydrophobe, or a hydrophile, and in turn, an amphiphile, does to H2O. By applying the same methodology to ions that have been ranked by the Hofmeister series, the author shows that the kosmotropes are either hydrophobes or hydration centers, and that chaotropes are hydrophiles. This unique approach and important updates make the new edition a must-have reference for those active in solution chemistry. Unique differential approach to solution thermodynamics allows for experimental evaluation of the intermolecular interaction Incorporates research findings from over 40 articles published since the previous edition Numerical or graphical evaluation and direct experimental determination of third derivatives, enthalpic and volumetric AL-AL interactions and amphiphiles are new to this edition Features new chapters on spectroscopic study in aqueous solutions as well as environmentally friendly and hostile water aqueous solutions