Supercritical Fluids: Fundamentals for Application PDF
Preview Supercritical Fluids: Fundamentals for Application
Supercritical Fluids Fundamentals for Application NATO ASI Series Advanced Science Institutes Series A Series presenting the results of activities sponsored by the NA TO Science Committee, which aims at the dissemination of advanced scientific and technological knowledge, with a view to strengthening links between scientific communities. The Series is published by an international board of publishers in conjunction with the NATO Scientific Affairs Division A Life Sciences Plenum Publishing Corporation B Physics London and New York C Mathematical Kluwer Academic Publishers and Physical Sciences Dordrecht, Boston and London D Behavioural and Social Sciences E Applied Sciences F Computer and Systems Sciences Springer-Verlag G Ecological Sciences Berlin, Heidelberg, New York, London, H Cell Biology Paris and Tokyo I Global Environmental Change NATO-PCO-DATA BASE The electronic index to the NATO ASI Series provides full bibliographical references (with keywords and/or abstracts) to more than 30000 contributions from international scientists published in all sections of the NATO ASI Series. Access to the NATO-PCO-DATA BASE is possible in two ways: - via online FILE 128 (NATO-PCO-DATA BASE) hosted by ESRIN, Via Galileo Galilei, 1-00044 Frascati, Italy. - via CD-ROM "NATO-PCO-DATA BASE" with user-friendly retrieval software in English, French and German (©WTV GmbH and DATAWARE Technologies Inc. 1989). The CD-ROM can be ordered through any member of the Board of Publishers or through NATO-PCO, Overijse, Belgium. Series E: Applied Sciences -Vol. 273 Supercritical Fluids Fundamentals for Application edited by Erdogan Kiran Department of Chemical Engineering, University of Maine, Orono, Maine, U.S.A. and Johanna M. H. Levelt Sengers Thermophysics Division, National Institute of Standards and Technology, Gaithersburg, Maryland, U.S.A. Springer-Science+Business Media, B.V. Proceedings of the NATO Advanced Study Institute on Supercritical Fluids - Fundamentals for Application Kemer, Antalya, Turkey July 18-31,1993 A C.I.P. Catalogue record for this book is available from the Library of Congress ISBN 978-90-481-4427-3 ISBN 978-94-015-8295-7 (eBook) DOl 10.1007/978-94-015-8295-7 Printed on acid-free paper All Rights Reserved © 1994 Springer Science+Business Media Dordrecht Originally published by K1uwer Academic Publishers in 1994. Softcover reprint of the hadcover 1s t edition 1994 No part of the material protected by this copyright notice may be reproduced or utilized in any form or by any means, electronic or mechanical, including photo copying, recording or by any information storage and retrieval system, without written permission from the copyright owner. CONTENTS ix Preface Organizing Committee and the List of Contributors xiii Part L Critical Behavior, Phase Equilibria, ThermodynamiLS Critical behavior of fluids: Concepts and applications J. M. H. Levelt Sengers 3 The classical theory of critical points R. A. Heidemann 39 Understanding phase diagrams Th. W. de Loos 65 Physico-chemical properties and phase equilibria of pure fluids and fluid mixtures at high pressures G. M. Schneider 91 Multiphase equilibria in near-critical solvents C. J. Peters 117 Equations of state for phase equilibrium computations S. I. Sandler 147 Mixing rules for the estimation of vapor-liquid equilibrium of highly non-ideal mixtures using cubic equations of state H.Orbey 177 Part IL Fluctuations, Crossover effects, Transport Properties Thermodynamics and fluctuation solution theory with some applications to systems at near-or supercritical conditions J. P. O'Connell 191 vi Effects of critical fluctuations on the thennodynamic and transport properties of supercritical fluids J. V. Sengers 231 On correlating the transport properties of supercritical fluids V. Vesovic 273 Part IlL Integral Equations Approach Introduction to integral equation approximations with application to near-critical and supercritical fluids Peter T. Cummings 287 On the non-solution region of the hypemetted chain and related equations for ionic and simple fluids E. Lomba 313 Critical behavior in modem liquid state theories A. Meroni 325 Integral equations for the microstructures of supercritical fluids L. L. Lee and H. D. Cochran 365 Part IV. Computer Simulations Molecular simulation of near-critical and supercritical fluids P. T. Cummings 387 Molecular simulation of phase equilibria A. Z. Panagiotopoulos 411 Solute -solute interactions: Theory and simulations P. G. Debenedetti 439 Part V. Chemistry, Reactions and Spectroscopy Reactions in supercritical fluids A. A. Clifford 449 Kinetics and selectivity of chemical processes in fluid phases M. Buback 481 vii Absorption spectroscopy in fluid phases M. Buback 499 Spectroscopy and chemistry in supercritical fluids S. M. Howdle and M. Poliakoff 527 Part VL Polymers Polymer formation, modifications and processing in or with supercritical fluids E. Kiran 541 Optimizing properties of polymer systems L. A. Kleintjens 589 Copolymer solution behavior in supercritical fluids M. A. McHugh 599 Density-tuned phase behavior of poly olefin solutions in supercritical olefins: Toward macromolecular separations M. Radosz 619 Part VIL Applications: Chromatography, Particle Formation, Extractions Current challenges in thermodynamics of supercritical fluid chromatography M. Roth 631 Effect of phase behavior on supercritical fluid chromatographic and extraction performance S. H. Page, J. F. Morrison and M. L. Lee 641 Scale-up of supercritical fluid chromatography (SFC) G. H. Brunner and D. Upnmoor 653 Fundamentals of solids extraction by supercritical fluids A. Akgerman and G. Madras 669 Extraction and destruction of waste with supercritical water G. H. Brunner 697 Predicting oxide solubilities in supercritical water J. I. Brand 707 Supercritical fluids as particle formation media P. G. Debenedetti 719 viii Interfacial tension in binary systems containing a dense gas S. Peter, A. Blaha-Schnabel, H. Schiemann and E. Weidner 731 Applications of fluid mixtures and supercritical solvents: A survey 739 G. M. Schneider Part VIII. Discussion Sessions and Tutorials Future Directions -A summary of the final discussions 761 Theory 761 Experiment 764 Applications 767 Tutorials and Discussion Groups 771 Appendix 1. Posters and Other Presentations 773 Appendix II. List of Participants 779 Index 791 PREFACE This volume comprises the proceedings of the NATO Advanced Study Institute on Supercritical Fluids- Fundamentals for Application held in Kerner, Antalya, Turkey, between July 18-31, 1993. This institute was the first to be concerned with this rapidly growing field of science and technology. The focus was on the fundamentals. Supercritical fluids which are neither gas nor liquid, but can be compressed gradually from low to high density are gaining an ever 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. In recent years, there has been an accelerated search for the industrial utilization of these fluids in extraction, chemical processing, and analytical instrumentation. 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 about 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. Approximative formulations that are accurate in the gas or liquid state may fail. For proper operation in the supercritical regime, the engineer needs to be familiar with a broad field of science, that ranges from fundamental physical theories of molecular interaction and of critical phenomena, to the engineering disciplines of phase behavior, modeling of thermodynamic and transport properties of fluid mixtures, and theory of chemical reactivity and kinetics, all the way to experimentation in an unfamiliar highly compressible medium. Aware of the breadth of disciplines that needs to be drawn upon in proper utilization of the potential of supercritical fluids, we made the decision to organize this NATO Advanced Study Institute, during a visit of Levelt Sengers to the University of Maine as a Distinguished Lecturer in the Chemical Engineering Department in the Spring of 1991. The objective was to bring together the experts in the field to critically review the current state of knowledge and the recent scientific advances in experimental and theoretical methods. The institute indeed brought together many lecturers, students and active researchers from academic, government and industrial organizations from both the NATO and non-NATO countries including several participants from the former Soviet Union. There were a total of 97 participants representing 17 countries. ix
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