High-Pressure Fluid Phase Equilibria

Phenomenology and Computation


  • Ulrich Deiters, University of Cologne
  • Thomas Kraska, University of Cologne

The book begins with an overview of the phase diagrams of fluid mixtures (fluid = liquid, gas, or supercritical state), which can show an astonishing variety when elevated pressures are taken into account; phenomena like retrograde condensation (single and double) and azeotropy (normal and double) are discussed. It then gives an introduction into the relevant thermodynamic equations for fluid mixtures, including some that are rarely found in modern textbooks, and shows how they can they be used to compute phase diagrams and related properties. This chapter gives a consistent and axiomatic approach to fluid thermodynamics; it avoids using activity coefficients. Further chapters are dedicated to solid-fluid phase equilibria and global phase diagrams (systematic search for phase diagram classes). The appendix contains numerical algorithms needed for the computations. The book thus enables the reader to create or improve computer programs for the calculation of fluid phase diagrams.
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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


Book information

  • Published: April 2012
  • Imprint: ELSEVIER
  • ISBN: 978-0-444-56347-7

Table of Contents

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
A Algebraic and numeric methods
B Proofs
C Equations of state