Cover -- Related Titles -- Title page -- Copyright page -- Contents -- Preface -- Acknowledgments -- List of Important Symbols and Abbreviations -- 1: Introduction -- 1.1 The Importance of Liquids -- 1.2 Solids, Gases, and Liquids -- 1.3 Outline and Approach -- 1.4 Notation -- References -- Further Reading -- 2: Basic Macroscopic and Microscopic Concepts: Thermodynamics, Classical, and Quantum Mechanics -- 2.1 Thermodynamics -- 2.1.1 The Four Laws -- 2.1.2 Quasi-Conservative and Dissipative Forces -- 2.1.3 Equation of State -- 2.1.4 Equilibrium -- 2.1.5 Auxiliary Functions -- 2.1.6 Some Derivatives and Their Relationships -- 2.1.7 Chemical Content -- 2.1.8 Chemical Equilibrium -- 2.2 Classical Mechanics -- 2.2.1 Generalized Coordinates -- 2.2.2 Hamilton's Principle and Lagrange's Equations -- 2.2.3 Conservation Laws -- 2.2.4 Hamilton's Equations -- 2.3 Quantum Concepts -- 2.3.1 Basics of Quantum Mechanics -- 2.3.2 The Particle-in-a-Box -- 2.3.3 The Harmonic Oscillator -- 2.3.4 The Rigid Rotator -- 2.4 Approximate Solutions -- 2.4.1 The Born-Oppenheimer Approximation -- 2.4.2 The Variation Principle -- 2.4.3 Perturbation Theory -- References -- Further Reading -- 3: Basic Energetics: Intermolecular Interactions -- 3.1 Preliminaries -- 3.2 Electrostatic Interaction -- 3.3 Induction Interaction -- 3.4 Dispersion Interaction -- 3.5 The total Interaction -- 3.6 Model Potentials -- 3.7 Refinements -- 3.7.1 Hydrogen Bonding -- 3.7.2 Three-Body Interactions -- 3.7.3 Accurate Empirical Potentials -- 3.8 The Virial Theorem -- References -- Further Reading -- 4: Describing Liquids: Phenomenological Behavior -- 4.1 Phase Behavior -- 4.2 Equations of State -- 4.3 Corresponding States -- 4.3.1 Extended Principle -- References -- Further Reading -- 5: The Transition from Microscopic to Macroscopic: Statistical Thermodynamics -- 5.1 Statistical Thermodynamics.

5.1.1 Some Concepts -- 5.1.2 Entropy and Partition Functions -- 5.1.3 Fluctuations -- 5.2 Perfect Gases -- 5.2.1 Single Particle -- 5.2.2 Many Particles -- 5.2.3 Pressure and Energy -- 5.3 The Semi-Classical Approximation -- 5.4 A Few General Aspects -- 5.5 Internal Contributions -- 5.5.1 Vibrations -- 5.5.2 Rotations -- 5.5.3 Electronic Transitions -- 5.6 Real Gases -- 5.6.1 Single Particle -- 5.6.2 Interacting Particles -- 5.6.3 The Virial Expansion: Canonical Method -- 5.6.4 The Virial Expansion: Grand Canonical Method -- 5.6.5 Critique and Some Further Remarks -- References -- Further Reading -- 6: Describing Liquids: Structure and Energetics -- 6.1 The Structure of Solids -- 6.2 The Meaning of Structure for Liquids -- 6.2.1 Distributions Functions -- 6.2.2 Two Asides -- 6.3 The Experimental Determination of g(r) -- 6.4 The Structure of Liquids -- 6.5 Energetics -- 6.6 The Potential of Mean Force -- References -- Further Reading -- 7: Modeling the Structure of Liquids: The Integral Equation Approach -- 7.1 The Vital Role of the Correlation Function -- 7.2 Integral Equations -- 7.2.1 The Yvon-Born-Green Equation -- 7.2.2 The Kirkwood Equation -- 7.2.3 The Ornstein-Zernike Equation -- 7.2.4 The Percus-Yevick Equation -- 7.2.5 The Hyper-Netted Chain Equation -- 7.2.6 The Mean Spherical Approximation -- 7.2.7 Comparison -- 7.3 Hard-Sphere Results -- 7.4 Perturbation Theory -- 7.4.1 The Gibbs-Bogoliubov Inequality -- 7.4.2 The Barker-Henderson Approach -- 7.4.3 The Weeks-Chandler-Andersen Approach -- 7.5 Molecular Fluids -- 7.6 Final Remarks -- References -- Further Reading -- 8: Modeling the Structure of Liquids: The Physical Model Approach -- 8.1 Preliminaries -- 8.2 Cell Models -- 8.3 Hole Models -- 8.3.1 The Basic Hole Model -- 8.3.2 An Extended Hole Model -- 8.4 Significant Liquid Structures -- 8.5 Scaled-Particle Theory -- References.

Further Reading -- 9: Modeling the Structure of Liquids: The Simulation Approach -- 9.1 Preliminaries -- 9.2 Molecular Dynamics -- 9.3 The Monte Carlo Method -- 9.4 An Example: Ammonia -- References -- Further Reading -- 10: Describing the Behavior of Liquids: Polar Liquids -- 10.1 Basic Aspects -- 10.2 Towards a Microscopic Interpretation -- 10.3 Dielectric Behavior of Gases -- 10.3.1 Estimating μ and α -- 10.4 Dielectric Behavior of Liquids -- 10.5 Water -- 10.5.1 Models of Water -- 10.5.2 The Structure of Liquid Water -- 10.5.3 Properties of Water -- References -- Further Reading -- 11: Mixing Liquids: Molecular Solutions -- 11.1 Basic Aspects -- 11.1.1 Partial and Molar Quantities -- 11.1.2 Perfect Solutions -- 11.2 Ideal and Real Solutions -- 11.2.1 Raoult's and Henry's Laws -- 11.2.2 Deviations -- 11.3 Colligative Properties -- 11.4 Ideal Behavior in Statistical Terms -- 11.5 The Regular Solution Model -- 11.5.1 The Activity Coefficient -- 11.5.2 Phase Separation and Vapor Pressure -- 11.5.3 The Nature of w and Beyond -- 11.6 A Slightly Different Approach -- 11.6.1 The Solubility Parameter Approach -- 11.6.2 The One- and Two-Fluid Model -- 11.7 The Activity Coefficient for Other Composition Measures -- 11.8 Empirical Improvements -- 11.9 Theoretical Improvements -- References -- Further Reading -- 12: Mixing Liquids: Ionic Solutions -- 12.1 Ions in Solution -- 12.1.1 Solubility -- 12.2 The Born Model and Some Extensions -- 12.3 Hydration Structure -- 12.3.1 Gas-Phase Hydration -- 12.3.2 Liquid-Phase Hydration -- 12.4 Strong and Weak Electrolytes -- 12.5 Debye-Hückel Theory -- 12.5.1 The Activity Coefficient and the Limiting Law -- 12.5.2 Extensions -- 12.6 Structure and Thermodynamics -- 12.6.1 The Correlation Function and Screening -- 12.6.2 Thermodynamic Potentials -- 12.7 Conductivity -- 12.7.1 Mobility and Diffusion.

12.8 Conductivity Continued -- 12.8.1 Association -- 12.9 Final Remarks -- References -- Further Reading -- 13: Mixing Liquids: Polymeric Solutions -- 13.1 Polymer Configurations -- 13.2 Real Chains in Solution -- 13.2.1 Temperature Effects -- 13.3 The Flory-Huggins Model -- 13.3.1 The Entropy -- 13.3.2 The Energy -- 13.3.3 The Helmholtz Energy -- 13.3.4 Phase Behavior -- 13.4 Solubility Theory -- 13.5 EoS Theories -- 13.5.1 A Simple Cell Model -- 13.5.2 The FOVE Theory -- 13.5.3 The LF Theory -- 13.5.4 The SS Theory -- 13.6 The SAFT Approach -- References -- Further Reading -- 14: Some Special Topics: Reactions in Solutions -- 14.1 Kinetics Basics -- 14.2 Transition State Theory -- 14.2.1 The Equilibrium Constant -- 14.2.2 Potential Energy Surfaces -- 14.2.3 The Activated Complex -- 14.3 Solvent Effects -- 14.4 Diffusion Control -- 14.5 Reaction Control -- 14.6 Neutral Molecules -- 14.7 Ionic Solutions -- 14.7.1 The Double-Sphere Model -- 14.7.2 The Single-Sphere Model -- 14.7.3 Influence of Ionic Strength -- 14.7.4 Influence of Permittivity -- 14.8 Final Remarks -- References -- Further Reading -- 15: Some Special Topics: Surfaces of Liquids and Solutions -- 15.1 Thermodynamics of Surfaces -- 15.2 One-Component Liquid Surfaces -- 15.3 Gradient Theory -- 15.4 Two-Component Liquid Surfaces -- 15.5 Statistics of Adsorption -- 15.6 Characteristic Adsorption Behavior -- 15.6.1 Amphiphilic Solutes -- 15.6.2 Hydrophobic Solutes -- 15.6.3 Hydrophilic Solutes -- 15.7 Final Remarks -- References -- Further Reading -- 16: Some Special Topics: Phase Transitions -- 16.1 Some General Considerations -- 16.2 Discontinuous Transitions -- 16.2.1 Evaporation -- 16.2.2 Melting -- 16.3 Continuous Transitions and the Critical Point -- 16.3.1 Limiting Behavior -- 16.3.2 Mean Field Theory: Continuous Transitions -- 16.3.3 Mean Field Theory: Discontinuous Transitions.

16.3.4 Mean Field Theory: Fluid Transitions -- 16.4 Scaling -- 16.4.1 Homogeneous Functions -- 16.4.2 Scaled Potentials -- 16.4.3 Scaling Lattices -- 16.5 Renormalization -- 16.6 Final Remarks -- References -- Further Reading -- Appendix A: Units, Physical Constants, and Conversion Factors -- Basic and Derived SI Units -- Physical Constants -- Conversion Factors for Non-SI Units -- Prefixes -- Greek Alphabet -- Standard Values -- Appendix B: Some Useful Mathematics -- B.1 Symbols and Conventions -- B.2 Partial Derivatives -- B.3 Composite, Implicit, and Homogeneous Functions -- B.4 Extremes and Lagrange Multipliers -- B.5 Legendre Transforms -- B.6 Matrices and Determinants -- B.7 Change of Variables -- B.8 Scalars, Vectors, and Tensors -- B.9 Tensor Analysis -- B.10 Calculus of Variations -- B.11 Gamma Function -- B.12 Dirac and Heaviside Function -- B.13 Laplace and Fourier Transforms -- B.14 Some Useful Integrals and Expansions -- Further Reading -- Appendix C: The Lattice Gas Model -- C.1 The Lattice Gas Model -- C.2 The Zeroth Approximation or Mean Field Solution -- C.3 The First Approximation or Quasi-Chemical Solution -- C.3.1 Pair Distributions -- C.3.2 The Helmholtz Energy -- C.3.3 Critical Mixing -- C.4 Final Remarks -- References -- Appendix D: Elements of Electrostatics -- D.1 Coulomb, Gauss, Poisson, and Laplace -- D.2 A Dielectric Sphere in a Dielectric Matrix -- D.3 A Dipole in a Spherical Cavity -- Further Reading -- Appendix E: Data -- References -- Appendix F: Numerical Answers to Selected Problems -- Index.