Supercritical fluids which are neither gas nor liquid, but can be compressed gradually from low to high density, are gaining increasing importance as tunable solvents and reaction media in the chemical process industry. By adjusting the pressure, or more strictly the density, the properties of these fluids are customized and manipulated for the particular process at hand, be it a physical transformation, such as separation or solvation, or a chemical transformation, such as a reaction or reactive extraction. Supercritical fluids, however, differ from both gases and liquids in many respects. In order to properly understand and describe their properties, it is necessary to know the implications of their nearness to criticality, to be aware of the complex types of phase separation (including solid phases) that occur when the components of the fluid mixture are very different from each other, and to develop theories that can cope with the large differences in molecular size and shape of the supercritical solvent and the solutes that are present.
Table of ContentsPreface. Part I: Critical Behavior, Phase Equilibria, Thermodynamics. Critical behavior of fluids: Concepts and applications; J.M.H. Levelt Sengers. The classical theory of critical points; R.A. Heidemann. Understanding phase diagrams; Th.W. de Loos. Physico-chemical properties and phase equilibria of pure fluids and fluid mixtures at high mixtures; G.M. Schneider. Multiphase equilibria in near-critical solvents; C.J. Peters. Equations of state for phase equilibrium computations; S.I. Sandler. Mixing rules for the estimation of vapor-liquid equilibrium of highly non-ideal mixtures using cubic equations of state; H. Orbey. Part II: Fluctuations, Crossover Effects, Transport Properties. Thermodynamics and fluctuation solution theory with some applications to systems at near or supercritical conditions; J.P. O'Connell. Effects of critical fluctuations on the thermodynamic and transport properties of supercritical fluids; J.V. Sengers. On correlating the transport properties of supercritical fluids; V. Vesovic. Part III: Integral Equations Approach. Introduction to integral equation approximations with application to near-critical and supercritical fluids; P.T. Cummings. On the non-solution region of the hypernetted chain and related equations for ionic and simple fluids; E. Lomba. Critical behavior in modern liquid state theories; A. Meroni. Integral equations for the microstructures of supercritical fluids; L.L. Lee, H.D. Cochran. Part IV: Computer Simulations. Molecular simulation of near-critical and supercritical fluids; P.T. Cummings. Molecular simulation of phase equilibria; A.Z. Panagiotopoulos. Solute--solute interactions: Theory and simulations; P.G. Debenedetti. Part V: Chemistry, Reactions Spectroscopy. Reactions in supercritical fluids; A.A. Clifford. Kinetics and selectivity of chemical processes in fluid phases; M. Buback. Absorption spectroscopy in fluid phases; M. Buback. Spectroscopy and chemistry in supercritical fluids; S.M. Hosdle, M. Poliakoff. Part VI: Polymers. Polymer formation, modifications and processing in or with supercritical fluids; E. Kiran. Optimizing properties of polymer systems; L.A. Kleintjens. Copolymer solution behavior in supercritical fluids; M.A. McHugh. Density-tuned phase behavior of polyolefin solutions in supercritical olefins: Toward macromolecular separations; M. Radosz. Part VII: Applications: Chromatography, Particle Formation, Extractions. Current challenges in thermodynamics of supercritical fluid chromatography; M. Roth. Effect of phase behavior on supercritical fluid chromatographic and extraction performance; S.H. Page, J.F. Morrison, M.L. Lee. Scale-up of supercritical fluid chromatography (SFC); G.H. Brunner, D. Upmoor. Fundamentals of solids extraction by supercritical fluids; A. Akgerman, G. Madras. Extraction and destruction of waste with supercritical water; G.H. Brunner. Predicting oxide solubilities in supercritical water; J.I. Brand. Supercritical fluids as particle formation media; P.G. Debenedetti. Interfacial tension in binary systems containing a dense gas; S. Peter, A. Blaha-Schnabel, H. Schiemann, E. Weidner. Applications of fluid mixtures and supercritical solvents: a survey; G.M. Schneider. Part VIII: Discussion Sessions and Tutorials. Future directions -- a summary of the final discussions. Theory.