The Kirkwood-Buff Theory of Solutions
With Selected Applications to Solvation and Proteins
- 1st Edition - October 1, 2023
- Imprint: Elsevier Science
- Author: Arieh Ben-Naim
- Language: English
- Paperback ISBN:9 7 8 - 0 - 4 4 3 - 2 1 9 1 5 - 3
- eBook ISBN:9 7 8 - 0 - 4 4 3 - 2 1 9 1 6 - 0
The Kirkwood-Buff Theory of Solutions: With Selected Applications to Solvation and Proteins presents the Kirkwood-Buff (KB) Theory of solution in a simple and didactic manner, m… Read more
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The Kirkwood-Buff Theory of Solutions: With Selected Applications to Solvation and Proteins presents the Kirkwood-Buff (KB) Theory of solution in a simple and didactic manner, making it understandable to those with minimal background in thermodynamics. Aside from the fact that the KB Theory may be the most important and useful theory of solutions, it is also the most general theory that can be applied to all possible solutions, including aqueous solutions of proteins and nucleic acids. Introductory chapters give readers grounding in the necessary chemical thermodynamics and statistical mechanics, but then move to a systematic derivation of Kirkwood-Buff theory and its inversion.
Originally published in 1951, the KB theory was dormant for over 20 years. It became extremely useful after the publication of the "Inversion of the KB theory" by the author Arieh Ben-Naim in 1978. The book explains all necessary concepts in statistical mechanics featured in the theory in a simple and intuitive way. Researchers will find the theory useful in solving any problem in mixtures or solutions in any phase. Some examples of applications of the KB theory, to water, aqueous solutions, protein folding, and self-association of proteins, are provided in the book.
- Presents an authoritative accounting of the Kirkwood-Buff (KB) Theory of solution as well as the derivation of the inversion of the Kirkwood-Buff Theory
- Provides a grounding in the necessary chemical thermodynamics and statistical mechanics
- Features useful examples of the applications of KB Theory to water, aqueous solutions, protein folding, and self-association of proteins
- Written by world-renowned expert Arieh Ben-Naim, who himself developed the "inversion" of Kirkwood-Buff theory
Advanced undergraduate and graduate-level students in physical chemistry, chemical engineering, and chemical physics. It will also appeal to academic and industrial researchers seeking to acquire a molecular-level understanding of the thermodynamic properties of solutions and soft matter systems. Students and researchers in the adjacent fields of materials science, biophysical chemistry, biochemistry, and molecular biology
Chapter 1: Introduction to the connection between Thermodynamics and Statistical Thermodynamics 1.1 Statistical Thermodynamics and Thermodynamics 1.2 The basic postulates of Statistical Thermodynamics1.2.1 The first postulate; average over time equals average over ensembles 1.2.2 The second postulate; equal probability of all energy states of an isolated system 1.2.3 The Boltzmann definition of entropy1.3 Some useful ensembles, the associated fundamental function and thermodynamics 1.3.1 The isolated system; the E, V, N ensemble 1.3.2 The isothermal isochoric system; the T, V, N ensemble 1.3.3 The isothermal isobaric system; the T, P, N ensemble 1.3.4 The open system; the T, V, or the grand ensemble 1.3.5 The generalized "partition function" 1.3.6 Summary 1.4 Averages and fluctuations 1.5 Classical limit of statistical thermodynamics 1.6 Thermodynamics of ideal gases 1.6.1 Mixture of ideal gases
Chapter 2: Molecular distribution functions and Thermodynamic quantities 2.1 The singlet distribution function in the canonical ensemble2.2 The Pair Distribution Function in the canonical ensemble2.3 The Pair Correlation Function 2.4 Some features of the pair correlation function 2.5 MDFs functions in the grand ensemble 2.6 The Pair potential of mean force (PMF) 2.7 The pair correlation functions in mixtures 2.8 Thermodynamic quantities expressed in terms of MDFs2.8.1 Internal energy and MDFs 2.8.2 The pressure and MDFs 2.8.3 The chemical potential and MDFs 2.8.4 The entropy and MDFs 2.8.5 The compressibility equation
Chapter 3: The Kirkwood-Buff Theory and its Inversion 3.1 The relationship between the KBI and the cross fluctuations in the Grand Ensemble 3.2 The relationship between thermodynamic quantities and the KBIs 3.3 Inversion of the Kirkwood-Buff Theory 3.3.1 Two-component systems 3.3.2 Three-component systems 3.4 Some recent developments 3.5 Some concluding remarks
Chapter 4: Characterization of "Ideal Solutions" using the KBIs 4.1 Ideal-gas mixtures 4.2 Symmetrical Ideal solutions 4.3 Dilute ideal solutions 4.4 Small deviation from ideal solutions 4.5 Some examples of SI solutions
Chapter 5: A few applications of the KBT 5.1 The unusual negative temperature dependence of the molar volume of water 5.1.1 The Wada Two-Structure Model (TSM) for water5.1.2 Application of an exact two-structure model (TSM)5.2 The outstanding large and negative entropy of solvation of inert solute in water 5.2.1 Introduction to aqueous solutions of inert gases 5.2.2 Early theories of aqueous solutions of inert gases 5.2.3 The facts and the main problem 5.2.4 Application of the mixture-model approach to reformulating the problem 5.2.5 Formulation of the problem of stabilization of the structure of water within the MM approach 5.2.6 The application of the Kirkwood-Buff theory 5.3 Applications of the KBT to systems at chemical equilibrium 5.3.1 The simplest case of an isomerization equilibrium 5.3.2 An isomerization equilibrium in a solvent 5.3.3 Dissociation equilibrium in a solvent 5.3.4 Completely dissociated solutes 5.3.5 Conclusion
Chapter 6: Solute and solvent effects on chemical equilibria6.1 Some simple examples 6.2 Generalization to multi-component systems 6.3 Some limiting ideal solutions 6.3.1 The limit of , and and finite 6.3.2 The limit but is finite 6.3.3 The symmetric ideal solution
Chapter 7: Solvation, Preferential Solvation and KBIs 7.1 Solvation process and solvation thermodynamics 7.1.1 Solvation of a solute S in pure S 7.1.2 Solvation of a solute S in a DI solution in a solvent W7.2 Preferential solvation and relative affinities 7.2.1 Definition of local composition and PS in liquid mixtures7.2.2 Preferential solvation in three-component systems 7.2.3 Preferential solvation in two-component systems
Chapter 8: Application of the KBT to solutions of Biomolecules 8.1 Definitions, notations, and the source of difficulties in the application of the KBT 8.2 Biopolymer solutions viewed as a mixture of conformers8.3 Solvation of molecules with internal rotations 8.4 Application of the KBT to Some Aspects of Protein folding 8.4.1 Introduction to the Protein Folding Problem (PFP)8.4.2 Le Chatelier Principle and the protein folding process.8.4.3 Pressure denaturation (PD) 8.4.4 Solute denaturation (SD) 8.4.5 Conclusion8.5 Application of the KBT to Some Aspects of Self-assembly of Proteins 8.5.1. Introduction to the problem of self-assembly of proteins8.5.2. Le Chatelier Principle formulated for the self-assembly of proteins 8.5.3. Temperature effect on self-assembly 8.5.4. Pressure effect on self-assembly 8.5.5. Solute effect on self-assembly 8.5.6. Conclusion
Appendix A: Long-range behavior of the pair correlation function in liquids and liquid mixtures Appendix B: An inequality due to the stability condition for the chemical equilibrium
- Edition: 1
- Published: October 1, 2023
- Imprint: Elsevier Science
- Language: English
AB
Arieh Ben-Naim
Arieh Ben-Naim is Emeritus Professor of physical chemistry who retired in 2003 from the Department of Chemistry, Hebrew University of Jerusalem, Israel. He has made major contributions over 40 years to the theory of the structure of water, aqueous solutions, and hydrophobic-hydrophilic interactions. He is mainly concerned with theoretical and experimental aspects of the general theory of liquids and solutions. In recent years, he has advocated the use of information theory to better understand and advance statistical mechanics and thermodynamics. He has authored more than 230 journal papers and 30 books
Affiliations and expertise
Professor Emeritus, Department of Physical Chemistry, The Institute of Chemistry, Hebrew University of Jerusalem, IsraelRead The Kirkwood-Buff Theory of Solutions on ScienceDirect