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In fluid (liquid, gas, and/or supercritical) mixtures at elevated pressures, the simultaneous occurrence of vapour-liquid, liquid-liquid, and sometimes also various solid-fluid equilibria can lead to rather complicated phase behaviour. The book begins with a qualitative, richly illustrated overview of the experimentally known fluid phase diagram classes, which also introduces some high-pressure phenomena like retrograde behaviour or barotropic inversion. The following chapters deal with the thermodynamic principles and with the equations needed to compute phase diagrams (phase envelopes, critical curves, etc.). The equations and algorithms discussed in this book cover not only fluid phase equilibria, but also solid-fluid equilibria. Two chapters on equations of state and mixing rules provide an introduction to the theory behind these functions as well as some selection criteria. The final chapter deals with global phase diagrams, a tool for the systematic exploration of complex fluid phase behaviour. The appendix contains numerical methods, which readers wanting to create or optimize their own thermodynamic program code will find useful.
1 Introduction. 1.1 What are fluids? 1.2 Why should you read this book? 1.3 What is the scope of this book? 1.4 Do you have to read the whole book? 1.5 Some conventions. 2 Phenomenology of phase diagrams. 2.1 Basic considerations. 2.2 Experimentally known binary phase diagram classes. 2.3 Phase diagrams of polymer solutions. 2.4 Rational nomenclature of phase diagram classes. 2.5 Phase diagram types of ternary mixtures. 3 Experimental observation of phase equilibria. 3.1 Warning. 3.2 Overview. 3.3 Synthetic methods. 3.4 Analytic methods. 3.5 Transient methods. 4 Thermodynamic variables and functions. 4.1 Fundamentals. 4.2 Energy functions and the equation of state. 4.3 Residual, excess, and partial molar quantities. 4.4 Jacobian determinants. 4.5 Variables of historical interest. 5 Stability and equilibrium . 5.1 Criteria of equilibrium. 5.2 Thermodynamic stability criteria and 2nd Law. 5.3 Phase equilibria of pure substances. 5.4 Critical points of pure fluids. 5.5 Phase equilibria of binary mixtures. 5.6 Critical curves. 5.7 3-phase curves. 5.8 Isochoric thermodynamics. 5.9 Heat effects of phase transitions. 6 Solid-fluid equilibrium. 6.1 Thermodynamic functions of solids. 6.2 Equilibrium of a pure solid and a mixed fluid phase. 6.3 Remarks on phase diagrams of binary mixtures. 6.4 Impure solids. 7 Equations of state for pure fluids. 7.1 Fundamentals. 7.2 The ideal gas. 7.3 Cubic equations of state. 7.4 Equations of state based on molecular theory. 7.5 Reference equations of state. 7.6 The corresponding-states principle. 7.7 Near-critical behaviour. 8 Equations of state for mixtures. 8.1 Fundamentals. 8.2 1-fluid theory. 8.3 Combining rules. 8.4 n-fluid theories. 8.5 The mean-density approximation. 8.6 Advanced theory. 8.7 GE-based mixing rules. 8.8 Fuzzy components. 9 Global phase diagrams. Appendix: A Algebraic and numeric methods. B Proofs. C Equations of state.
Students of chemical engineering, chemical engineers and physical chemists specializing in fluids, companies involved in chemical engineering (separation processes, high-pressure operations) or in producing software for chemical engineers