Liquids and Liquid Mixtures, Third Edition explores the equilibrium properties of liquids and liquid mixtures and relates them to the properties of the constituent molecules using the methods of statistical thermodynamics. Topics covered include the critical state, fluid mixtures at high pressures, and the statistical thermodynamics of fluids and mixtures.
This book consists of eight chapters and begins with an overview of the liquid state and the thermodynamic properties of liquids and liquid mixtures, including vapor pressure and heat capacities. The discussion then turns to the thermodynamics of and inequalities at the critical point; measurement of thermodynamic functions in the critical region; experimental values of the critical exponents; and scaling of the free energy. The change of thermodynamic functions with composition is the subject of the next two chapters, followed by an analysis of fluid mixtures at high pressures. The final chapter is devoted to the statistical thermodynamics of fluids and mixtures, paying particular attention to the thermodynamic properties in terms of the forces between the molecules; the balance of intermolecular potentials between like and unlike molecules; and phase behavior.
This monograph will be of interest to students and researchers in the fields of chemistry and chemical engineering.

Contenu

Preface to the Third Edition
1 Introduction
1.1 The Liquid State
2 The Thermodynamic Properties
2.1 Summary of Thermodynamic Relations
2.2 Vapor Pressure
2.3 Mechanical Properties
2.4 Heat Capacities
2.5 Adiabatic Properties
2.6 Residual and Configurational Properties
2.7 van der Waals's Equation
3 The Critical State
3.1 Thermodynamics of the Critical Point
3.2 Inequalities at the Critical Point
3.3 The Measurement of Critical Constants
3.4 Experimental Values of the Critical Exponents
3.5 Scaling the Free Energy
4 The Thermodynamics of Liquid Mixtures
4.1 Introduction
4.2 Partial Molar Quantities
4.3 The Ideal Mixture
4.4 Thermodynamics of Non-ideal Mixtures
4.5 Tests for Consistency
4.6 Azeotropy
4.7 Fields and Densities
4.8 Thermodynamics of Partially Miscible Liquids
4.9 Exponents at the Critical Point of a Binary Mixture
4.10 Tricritical Points
5 Excess Thermodynamic Functions
5.1 Introduction
5.2 The Experimental Determination of Excess Functions
5.3 Mixtures of Condensed Gases
5.4 Liquefied Natural-Gas Mixtures
5.5 Mixtures of the Higher Hydrocarbons
5.6 Mixtures Containing Halides
5.7 Mixtures Containing Fluorocarbons
5.8 Mixtures Containing Polar Liquids
5.9 Aqueous Mixtures
5.10 Mixtures of Quantum Liquids
6 Fluid Mixtures at High Pressures
6.1 Introduction
6.2 Gas-Liquid Critical States of Binary Mixtures
6.3 High-Pressure Phase Equilibria: Type I Mixtures
6.4 High-Pressure Phase Equilibria: Type II and Type VI Mixtures
6.5 High-Pressure Phase Equilibria: Type III Mixtures
6.6 High-Pressure Phase Equilibria: Type IV and Type V Mixtures
7 The Statistical Thermodynamics of Fluids
7.1 Intermolecular Forces
7.2 Molecular Distribution Functions
7.3 Molecular Correlation Functions
7.4 The Measurement and Calculation of Correlation Functions
7.5 The Principle of Corresponding States
7.6 Perturbation Theories: Spherical Molecules
7.7 Perturbation Theories: Non-Spherical Molecules
8 The Statistical Thermodynamics of Mixtures
8.1 Introduction
8.2 Ideal and Random Mixtures
8.3 Mixtures of Spheres
8.4 The van der Waals Approximation
8.5 Perturbation Theories of Mixtures of Spherical Molecules
8.6 Excess Functions of Simple Mixtures
8.7 Mixtures of Alkanes
8.8 Perturbation Theories of Mixtures of Non-Spherical Molecules
8.9 Phase Equilibria at High Pressures
8.10 Conclusions
General Index
Index of Systems