High Pressure Phase Behaviour of Multicomponent Fluid Mixtures

The high pressure phase behaviour of binary fluid mixtures has been extensively studied during the last three decades. There is ample experimental data for a wide variety of binary mixtures and extensive methods for prediction have been developed. In contrast, the investigation of ternary and other multicomponent fluids is in its infancy. Experimental ternary mixture critical data are very rare and theoretical studies have been limited to data correlation rather than genuine prediction. The phase behaviour of ternary and other multicomponent fluid mixtures has many novel aspects which are not manifested in binary mixtures. The properties of ternary mixtures are also likely to be more difficult to characterize experimentally. It is in this context that calculated phase diagrams have an important role in leading the discovery of new phenomena and guiding experimental work.

The criteria for phase equilibria of multicomponent fluids with particular emphasis on the critical state are examined in this book, and models for predicting fluid equilibria (e.g., different equations of state) are compared. Particular attention is paid to the critical state of ternary mixtures which has hitherto been largely neglected. The problems associated with predicting ternary equilibria are discussed, and some novel aspects of ternary critical phenomena are illustrated.

The books also describes a novel type of critical transition which appears to be a common feature of the equilibria of ternary mixtures. Extensive phase diagrams of a wide range of ternary mixtures including systems containing carbon dioxide, water, nitrogen and tetrafluoromethane as one or more component are presented. The theoretical treatment is detailed in the appendix and a computation of known experimental critical points is also included.

1. Survey of the High Pressure Phase Behaviour of Fluids. Introduction. Phase Behaviour of Binary Fluids. Phase Behaviour of Ternary and Multicomponent Fluids. 2. The Thermodynamics of Phase Equilibria. Criteria for Equilibrium. Coexistent Phases. The Phase Rule. Criteria for Phase Stability. Critical Phases. Consequences for Phase Equilibria Calculations. 3. Models for High Pressure Multicomponent Equilibria. The Phase Integral. Computer Simulation. Conformal Solution Theory. Perturbation Theories. Equations of State. Mixing Rules for Multicomponent Equilibria. An Analytic Description of Attractive Forces in Binary Fluid Mixtures. Equations of State Calculations. 4. Procedure for Determining the Phase Behaviour of Ternary Mixtures: Comparison of Experiment with Theory for Gas-Liquid Critical Temperatures. Determining Stable Ternary Critical Points. Strategies for Ternary Phenomena. Gas-Liquid Critical Properties of Ternary Mixtures. Computing Options for Ternary Calculations. 5. Novel Higher Order Critical Phenomena in Ternary Mixtures. Tricritical Phenomena. Higher-Order Critical Transitions in Ternary Mixtures. 6. Phase Behaviour of Ternary Carbon Dioxide and n-Alkane Mixtures. Methane + n-Hexane + Carbon Dioxide. Ethane + n-Hexane + Carbon Dioxide. Propane + n-Hexane + Carbon Dioxide. n-Butane + n-Hexane + Carbon Dioxide. n-Pentane + n-Hexane + Carbon Dioxide. n-Heptane + n-Hexane + Carbon Dioxide. n-Octane + n-Hexane + Carbon Dioxide. n-Oxtane + n-Hexane + Carbon Dioxide. n-Nonane + n-Hexane + Carbon Dioxide. n-Decane + n-Hexane + Carbon Dioxide. 7. Ternary Tetrafluoromethane and n-Alkane Mixtures. Methane + Ethane + Tetrafluoromethane. n-Propane + i-Butane + Tetrafluoromethane. n-Propane + n-Butane + Tetrafluoromethane. n-Propane + n-Pentane + Tetrafluoromethane. 8. Ternary Mixtures Containing Nitrogen. Methane + Ethane + Nitrogen. Methane + n-Pentane + Nitrogen. Ethane + Nitrogen + Water. n-Pentane + Nitrogen + Water. 9. Ternary Mixtures Containing Water and n-Alkanes. Ethane + Propane + Water. Ethane + n-Pentane + Water. Ethane + n-Hexane + Water. n-Pentane + n-Hexane + Water. Ethane + Carbon Dioxide + Water. Appendix A. Appendix B. Subject Index. Author Index. The book contains extensive references.