Molecular theory of solutions - Ben-Naim, Arieh (Oxford University Press, 2006)
Master and use copy. Digital master created according to Benchmark for Faithful Digital Reproductions of Monographs and Serials, Version 1. Digital Library Federation, December 2002
Includes bibliographical references (pages 372-377) and index
List of abbreviations -- 1 Introduction -- 1.1 Notation regarding the microscopic description of the system -- 1.2 The fundamental relations between statistical thermodynamics and thermodynamics -- 1.3 Fluctuations and stability -- 1.4 The classical limit of statistical thermodynamics -- 1.5 The ideal gas and small deviation from ideality -- 1.6 Suggested references on general thermodynamics and statistical mechanics -- 2 Molecular distribution functions -- 2.1 The singlet distribution function -- 2.2 The pair distribution function -- 2.3 The pair correlation function -- 2.4 Conditional probability and conditional density -- 2.5 Some general features of the radial distribution function -- 2.5.1 Theoretical ideal gas -- 2.5.2 Very dilute gas -- 2.5.3 Slightly dense gas -- 2.5.4 Lennard-Jones particles at moderately high densities -- 2.6 Molecular distribution functions in the grand canonical ensemble -- 2.7 Generalized molecular distribution functions -- 2.7.1 The singlet generalized molecular distribution function -- 2.7.2 Coordination number -- 2.7.3 Binding energy -- 2.7.4 Volume of the Voronoi polyhedron -- 2.7.5 Combination of properties -- 2.8 Potential of mean force -- 2.9 Molecular distribution functions in mixtures -- 2.10 Potential of mean force in mixtures
3 Thermodynamic quantities expressed in terms of molecular distribution functions -- 3.1 Average values of pairwise quantities -- 3.2 Internal energy -- 3.3 The pressure equation -- 3.4 The chemical potential -- 3.4.1 Introduction -- 3.4.2 Insertion of one particle into the system -- 3.4.3 Continuous coupling of the binding energy -- 3.4.4 Insertion of a particle at a fixed position: The pseudo-chemical potential -- 3.4.5 Building up the density of the system -- 3.4.6 Some generalizations -- 3.4.7 First-order expansion of the coupling work -- 3.5 The compressibility equation -- 3.6 Relations between thermodynamic quantities and generalized molecular distribution functions -- 4 The Kirkwood-Buff theory of solutions -- 4.1 Introduction -- 4.2 General derivation of the Kirkwood-Buff theory -- 4.3 Two-component systems -- 4.4 Inversion of the Kirkwood-Buff theory -- 4.5 Three-component systems -- 4.6 Dilute system of S in A and B -- 4.7 Application of the KB theory to electrolyte solutions -- 5 Ideal solutions -- 5.1 Ideal-gas mixtures -- 5.2 Symmetrical ideal solutions -- 5.2.1 Very similar components: A sufficient condition for SI solutions -- 5.2.2 Similar components: A necessary and sufficient condition for SI solutions -- 5.3 Dilute ideal solutions -- 5.4 Summary
6 Deviations from ideal solutions -- 6.1 Deviations from ideal-gas mixtures -- 6.2 Deviations from SI Behavior -- 6.3 Deviations from dilute ideal solutions -- 6.4 Explicit expressions for the deviations from IG, SI, and DI behavior -- 6.4.1 First-order deviations from ideal-gas mixtures -- 6.4.2 One-dimensional model for mixtures of hard "spheres" -- 6.5 The McMillan-Mayer theory of solutions -- 6.6 Stability condition and miscibility based on first-order deviations from SI solutions -- 6.7 Analysis of the stability condition based on the Kirkwood-Buff theory -- 6.8 The temperature dependence of the region of instability: Upper and lower critical solution temperatures -- 7 Solvation thermodynamics