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Physical chemistry of electrolyte solutions in topics in physical chemistry
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journal of MOLECULAR
LIQUIDS ELSEVIER
Journal of Molecular Liquids 81 (1999) 87-88
Book Review J.M.G. Barthel, H. Krienke, W. Kunz: Physical Chemistry of Electrolyte Solutions in Topics in Physical Chemistry, Vol. 5, Eds. H. Baumgartel, E.U. Franck, W. Gri~nbein (on behalf of Deutsche Bunsengesellschaft fiir Physikalische Chemic). Dr. Dietrich Steinkopff Verlag, Darmstadt and Springer Verlag, New York, 1998. ISBN 3-7985-1076-8
The experimental investigation and theoretical description of electrolyte solutions have made considerable progress during the last years. Therefore, a presentation of the material in a comprehensive monograph was overdue. A group of three authors headed by one of the leading experts in the field has now presented an extremely competent description of the developments and the achievements of theory and experimental practice. The book consists of 6 chapters, the additional 7th chapter (appendix) presents lists of symbols, tables, etc. Chapter 1 (Ion Association and Solvation in Electrolyte Solutions) is an introduction to the modern concepts of descriptions of interactions between ions and solvents. It gives a classification of ions and solvents. The principles of particle interactions and the concepts for the description of ions and dipoles in homogeneous dielectric media are shown. Expressions such as the reaction field are explained. Results of selected experimental studies and a variety of crystallographic and thermodynamic data complete this chapter. Chapter 2 (Transport and Relaxation Phenomena in Electrolyte Solutions) constitutes a similarly presented introduction to transport properties. It starts with the definition of fluxes and currents. Then diffusion and migration, conductivity and transference numbers, hydrodynamic properties and viscosity, and the motion of special particles in a viscous continuum are described. The method of dielectric polarization at higher frequencies is explained. The theoretical description is coupled with a presentation of relaxation spectra of i) pure solvents, ii) mixtures, iii) electrolyte solutions. The influence of ionic equilibria and redox equilibria on the basis of the Marcus theory is discussed. As an alternative method, ultrasonic absorption is explained. Chapter 3 (Electrolyte Solutions at Low to Moderate Concentrations) is an introduction to the "chemical model" of electrolyte solutions. This model describes ion pair formation on the basis of molecular distribution functions in a mean force potential field. It presents equations for the most relevant thermodynamic properties (activity coefficient, osmotic coefficient, etc) including kinetic phenomena (kinetic salt effect, solvent effect, etc). The model is suited to describe the properties at lower concentrated electrolytes. Chapter 4 (Towards Higher Concentrations: The Description of Equilibrium Properties) presents the description of electrolytes by methods of statistical mechanics. This is still based on the concept of particles in a continuum, the so-called McMillan-Mayer level. General relations for the spatial molecular distribution functions are derived. Coulombic systems, charged spheres, and charged hard spheres are studied and discussed on the basis of integral equation theories. Ion association is treated with the hypernetted chain integral equation 0167-7322/99/$ - see front matter © 1999 Elsevier Science B.V. All rights reserved. PII S0167-7322(99) 00035-5
88 theory. The theoretical calculations are compared to results of neutron and X-ray scattering experiments. In chapter 5 (Refined Electrolyte Theory: Models on the BO Level), the solvent is no longer treated as a continuum. The drawback of this much more fundamental approach is that exact solutions of the equations can only be obtained for the simplest systems. Computer simulations have to be worked out to make the theory transparent (molecular dynamical and Monte Carlo methods). The following systems are treated: classical systems with long range forces, ions in apolar solvents, molecular correlation functions for systems with anisotropic interactions, mixtures of charged and dipolar hard spheres. A comparison between the BornOppenheimer and the McMillan-Mayer level concludes this chapter. Chapter 6 (Dynamical and Transport Properties at Molar Concentrations) is the extension of the concept of advanced statistical mechanics to dynamical problems. This chapter starts with an introduction to the principles of molecular dynamics on the Born-Oppenheimer level, followed by the Langevin dynamics, the Smoluchowski dynamics, and the continuity equation approach. This chapter presents trends, not the completely developed theory and is thus an outlook to the future. With this publication, the publishers present a new volume of the very successful publication series of the Deutsche Bunsengesellschaft filr Physikalische Chemie. Written on a very high level, the book is an outstanding, most advanced theoretical and experimental description of electrolyte solutions. Certainly, chapter 1 and 2 help the reader to understand the next chapters. But nevertheless, chapter 4 and 5 demand profound knowledge of advanced statistical mechanics. Chapter 6, however, rewards the reader for the efforts of the preceding chapters: from the top of the mountain he can look into the fascinating surrounding landscape. Chapter 3 must be mentioned separately because it is a very substantial review of the chemical model of electrolyte solutions, an approach which is strongly influenced by one of the authors. But not only because of its contents, this book is outstanding. It is prepared in an exceptionally careful way. This is due to the work of the authors as well as to that of the publisher. Thus, the high quality of the previous volumes is continued by this publication. It is a book which every chemical or physical library must have in its book-shelves. It is also strongly recommended for any reader of physical chemistry as well as for the advanced student. Last but not least, any scientist interested in the field will feel happy to have it in his textbook collection. W. Plieth, Dresden
~
journal of MOLECULAR
LIQUIDS ELSEVIER
Journal of Molecular Liquids 81 (1999) 87-88
Book Review J.M.G. Barthel, H. Krienke, W. Kunz: Physical Chemistry of Electrolyte Solutions in Topics in Physical Chemistry, Vol. 5, Eds. H. Baumgartel, E.U. Franck, W. Gri~nbein (on behalf of Deutsche Bunsengesellschaft fiir Physikalische Chemic). Dr. Dietrich Steinkopff Verlag, Darmstadt and Springer Verlag, New York, 1998. ISBN 3-7985-1076-8
The experimental investigation and theoretical description of electrolyte solutions have made considerable progress during the last years. Therefore, a presentation of the material in a comprehensive monograph was overdue. A group of three authors headed by one of the leading experts in the field has now presented an extremely competent description of the developments and the achievements of theory and experimental practice. The book consists of 6 chapters, the additional 7th chapter (appendix) presents lists of symbols, tables, etc. Chapter 1 (Ion Association and Solvation in Electrolyte Solutions) is an introduction to the modern concepts of descriptions of interactions between ions and solvents. It gives a classification of ions and solvents. The principles of particle interactions and the concepts for the description of ions and dipoles in homogeneous dielectric media are shown. Expressions such as the reaction field are explained. Results of selected experimental studies and a variety of crystallographic and thermodynamic data complete this chapter. Chapter 2 (Transport and Relaxation Phenomena in Electrolyte Solutions) constitutes a similarly presented introduction to transport properties. It starts with the definition of fluxes and currents. Then diffusion and migration, conductivity and transference numbers, hydrodynamic properties and viscosity, and the motion of special particles in a viscous continuum are described. The method of dielectric polarization at higher frequencies is explained. The theoretical description is coupled with a presentation of relaxation spectra of i) pure solvents, ii) mixtures, iii) electrolyte solutions. The influence of ionic equilibria and redox equilibria on the basis of the Marcus theory is discussed. As an alternative method, ultrasonic absorption is explained. Chapter 3 (Electrolyte Solutions at Low to Moderate Concentrations) is an introduction to the "chemical model" of electrolyte solutions. This model describes ion pair formation on the basis of molecular distribution functions in a mean force potential field. It presents equations for the most relevant thermodynamic properties (activity coefficient, osmotic coefficient, etc) including kinetic phenomena (kinetic salt effect, solvent effect, etc). The model is suited to describe the properties at lower concentrated electrolytes. Chapter 4 (Towards Higher Concentrations: The Description of Equilibrium Properties) presents the description of electrolytes by methods of statistical mechanics. This is still based on the concept of particles in a continuum, the so-called McMillan-Mayer level. General relations for the spatial molecular distribution functions are derived. Coulombic systems, charged spheres, and charged hard spheres are studied and discussed on the basis of integral equation theories. Ion association is treated with the hypernetted chain integral equation 0167-7322/99/$ - see front matter © 1999 Elsevier Science B.V. All rights reserved. PII S0167-7322(99) 00035-5
88 theory. The theoretical calculations are compared to results of neutron and X-ray scattering experiments. In chapter 5 (Refined Electrolyte Theory: Models on the BO Level), the solvent is no longer treated as a continuum. The drawback of this much more fundamental approach is that exact solutions of the equations can only be obtained for the simplest systems. Computer simulations have to be worked out to make the theory transparent (molecular dynamical and Monte Carlo methods). The following systems are treated: classical systems with long range forces, ions in apolar solvents, molecular correlation functions for systems with anisotropic interactions, mixtures of charged and dipolar hard spheres. A comparison between the BornOppenheimer and the McMillan-Mayer level concludes this chapter. Chapter 6 (Dynamical and Transport Properties at Molar Concentrations) is the extension of the concept of advanced statistical mechanics to dynamical problems. This chapter starts with an introduction to the principles of molecular dynamics on the Born-Oppenheimer level, followed by the Langevin dynamics, the Smoluchowski dynamics, and the continuity equation approach. This chapter presents trends, not the completely developed theory and is thus an outlook to the future. With this publication, the publishers present a new volume of the very successful publication series of the Deutsche Bunsengesellschaft filr Physikalische Chemie. Written on a very high level, the book is an outstanding, most advanced theoretical and experimental description of electrolyte solutions. Certainly, chapter 1 and 2 help the reader to understand the next chapters. But nevertheless, chapter 4 and 5 demand profound knowledge of advanced statistical mechanics. Chapter 6, however, rewards the reader for the efforts of the preceding chapters: from the top of the mountain he can look into the fascinating surrounding landscape. Chapter 3 must be mentioned separately because it is a very substantial review of the chemical model of electrolyte solutions, an approach which is strongly influenced by one of the authors. But not only because of its contents, this book is outstanding. It is prepared in an exceptionally careful way. This is due to the work of the authors as well as to that of the publisher. Thus, the high quality of the previous volumes is continued by this publication. It is a book which every chemical or physical library must have in its book-shelves. It is also strongly recommended for any reader of physical chemistry as well as for the advanced student. Last but not least, any scientist interested in the field will feel happy to have it in his textbook collection. W. Plieth, Dresden