Thermodynamic Data: Systematics and Estimation PDF
Preview Thermodynamic Data: Systematics and Estimation
Ad vances in Physical Geochemistry Volume 10 Editor-in-Chief Surendra K. Saxena Editorial Board L. Barron P.M. Bell N.D. Chaterjee R. Kretz D.H. Lindsley Y. Matsui A. Navrotsky R.C. Newton G.Ottonello L.L. Perchuk R. Powell R. Robie A.B. Thompson B.l. Wood Advances in Physical Geochemistry Series Editor: Surendra K. Saxena Volume 1 R.C. Newton/A. Navrotsky/BJ. Wood (editors) Thermodynamics of Minerals and Melts 1981. xii, 304 pp. 66 iIlus. ISBN 0-387-90530-8 Volume 2 S.K. Saxena (editor) Advances in Physical Geochemistry, Volume 2 1982. x, 353 pp. 113 illus. ISBN 0-387-90644-4 Volume 3 S.K. Saxena (editor) Kinetics and Equilibrium in Mineral Reactions 1983. vi, 273 pp. 99 illus. ISBN 0-387-90865-X Volume 4 A.B. Thompson/D.C. Rubie (editors) Metamorphic Reactions: Kinetics, Textures, and Deformation 1985. xii, 291 pp. 81 illus. ISBN 0-387-96077-5 Volume 5 J.V. Walther/BJ. Wood (editors) Fluid-Rock Interactions during Metamorphism 1986. x, 211 pp. 59 illus. ISBN 0-387-96244-1 Volume 6 S.K. Saxena (editor) Chemistry and Physics of Terrestrial Planets 1986. x, 405 pp. 94 illus. ISBN 0-387-96287-5 Volume 7 S. Ghose/J.M.D. Cohe/E. Salje (editors) Structural and Magnetic Phase Transitions in Minerals 1988. xiii, 272 pp. 117 illus. ISBN 0-387-96710-9 Volume 8 J. Ganguly (editor) Diffusion, Atomic Ordering, and Mass Transport: Selected Topics in Geochemistry 1991. xiv, 584 pp. 170 illus. ISBN 0-387-97287-0 Volume 9 L.L. Perchuk/1. Kushiro (editors) Physical Chemistry of Magmas 1991. 352 pp. 137 illus. ISBN 0-387-97500-4 Volume 10 S.K. Saxena (editor) Thermodynamic Data: Systematics and Estimation 1992. xiv, 367 pp. 126 illus. ISBN 0-387-97696-5 Surendra K. Saxena Editor Thermodynamic Data Systematics and Estimation With Contributions by F. Baccarin A.B. Belonoshko M. Blander S.L. Chaplot N. Choudhury S. Usha-Devi G. Fiquet D.G. Fraser S. Ghose P. Gillet A. Della Giusta CM. Gramaccioli G. Grimvall A.F. Guillermet K. Heinzinger E. Ito A.G. Kalinichev Y.H. Kim M.H. Manghnani L.C Ming A. Dal Negro D.R. Neuville G. Ottonello T. Pilati K.R. Rao K. Refson P. Richet CR. Stover V.S. Urusov J.-A. Xu With 126 Illustrations Springer-Verlag New York Berlin Heidelberg London Paris Tokyo Hong Kong Barcelona Budapest Surendra K. Saxena Planetary Geochemistry Program Institute of Geology Uppsala University Box 555 S-75122 Uppsala Sweden Library of Congress Cataloging-in-Publication Data Thermodynamic data: systematics and estimation / Surendra K. Saxena. p. cm.-(Advances in physical geochemistry; v. 10) Includes bibliographical references and index. ISBN -13 :978-1-4612-7692-0 e-ISBN -13 :978-1-4612-2842-4 DOl: 10.1007/978-1-4612-2842-4 1. Geochemistry. 2. Thermodynamics. I. Saxena, Surendra Kumar, 1936- . II. Series. QE515.T433 1992 551.9-dc20 91-31481 Printed on acid-free paper © 1992 Springer-Verlag New York Inc. Softcover reprint of the hardcover 1st edition 1992 All rights reserved. This work may not be translated or copied in whole or in part without the written permission of the publisher (Springer-Verlag New York Inc., 175 Fifth Avenue, New York, NY 10010, USA), except for brief excerpts in connection with reviews or scholarly analysis. Use in connection with any form of information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar methodology now known or hereafter developed is forbidden. The use of general descriptive names, trade names, trademarks, etc., in this publication, even if the former are not especially identified, is not to be taken as a sign that such names, as understood by the Trade Marks and Merchandise Marks Act, may accordingly be used freely by anyone. Production managed by Christin R. Ciresi; manufacturing supervised by Robert Paella. Typeset by Asco Trade Typesetting Ltd., Hong Kong. 9 8 7 6 5 4 3 2 1 Preface With the rapid development of fast processors, the power of a mini-super computer now exists in a lap-top box. Quite sophisticated techniques are be coming accessible to geoscientists, thus making disciplinary boundaries fade. Chemists and physicists are no longer shying away from computational mineral ogical and material science problems "too complicated to handle." Geoscientists are willing to delve into quantitative physico-chemical methods and open those "black boxes" they had shunned for several decades but with which had learned to live. I am proud to present yet another volume in this series which is designed to break the disciplinary boundaries and bring the geoscientists closer to their chemist and physicist colleagues in achieving a common goal. This volume is the result of an international collaboration among many physical geochemists (chemists, physicists, and geologists) aiming to understand the nature of material. The book has one common theme: namely, how to determine quantitatively through theory the physico-chemical parameters of the state of a solid or fluid. The book begins with a study of fluids in the first three chapters. Chapter 1 by Kalinichev and Heinzinger provides us with an extensive review of the current methods for simulating the pressure-volume-temperature (P-V-T) of fluids. After reviewing the various techniques, the authors focus on the Monte Carlo simulation method and provide useful data on aqueous fluids. Fluids are also the topic of discussion in the next two chapters. Both deal with the tech nique of molecular dynamics. In Chapter 2, Fraser and Refson use the tech nique to simulate the high P-V-T properties of fluids, and in Chapter 3, Belonoshko and Saxena do the same. The two chapters differ in using different types of intermolecular potentials, and it is interesting to compare the results. Such comparisons are instructive in providing us with insight into the operation of these new tools of theory. In Chapter 4, Richet, Gillet, and Fiquet review the current information on VI Preface linking the macroscopic and microscopic properties of minerals. The latter section p'repares the reader for the study of the last five chapters of the book. The authors begin with the experimental methods of obtaining the heat capacity of solids and then follow through with a review of the empirical methods of estimation and calculations. The next chapter, also by Richet in coauthorship with Neuville, reviews the latest work on the thermodynamics of silicate melts. The authors have chosen the configurational heat capacity of the melts as their theme. This property of materials is of paramount importance in geochemical and industrial applications because it not only constrains the phase-equilibrium relations, but is also related to viscosity via the configurational entropy. Chapter 5 provides an excellent opportunity for an interested reader to start his or her study of this rapidly developing branch of physical chemistry. V.S. Urusov presents in Chapter 6 the energetics of binary solid solutions. His analysis of the various energy contributions arising from the mixing of compo nents with different volumes and crystal structures lays the foundation for a quantitative treatment of solid solution behavior. Such attempts are now begin ning to meet with considerable success, of which Chapter 7 is an excellent example. Ottonello, Della Giusta, Dal Negro, and Baccarin show how a con strained ionic model simulation of crystal structures of pure components and of their solution in a multicomponent chemical system can be performed with a surprising degree of accuracy. Chapters 8 through 11 are devoted to the estimation of the thermodynamic properties of a solid. In the first of these contributions, Gramaccioli and Pilati review the current approaches to calculating the energetics of crystals. Their review outlines the problems encountered in rigorous calculations and presents useful simplifications and computer techniques that lead to improved calcula tions of energy with minimum errors. In Chapter 9, Blander and Stover outline an effective method for the predic tion of high-temperature entropies of vapor molecules and for some classes of solids with a given stoichiometry. The method has great potential for further development to include other solids and fluids. In Chapter 10, Grimvall and Fernandez-Guillermot continue with the theme of predicting entropy. They introduce an entropy Debye temperature that changes atomic masses and arrive at another important approach to predicting the vibrational entropy of solids at intermediate and high temperatures. The next chapter by Ghose reviews the work on the phonon density of states and demonstrates the application of the lattice dynamicals approach to calculate thermodynamic functions for silicates. The book ends with a final chapter by Ming, Manghnani, Kim, Usha-Devi, Xu and Ito who have joined their forces to obtain experimental data on thermal expansion on the spinels. Such data are as yet a rarity because of the experimen tal difficulties of measuring the volumes of solids in-situ at high pressure and temperatures. I thank the editorial staff of Springer-Verlag (Victor Van Beuren, Lorraine Preface vii Walsh and Jessica Downey) for their invaluable support and the production department for the care with which it handled the book. July 9,1991 S.K. Saxena U ppsala, Sweden Contents Preface v Contributors xi 1. Computer Simulations of Aqueous Fluids at High Temperatures and Pressures 1 A.G. KALINICHEV and K. HEINZINGER 2. Estimating Thermodynamic Properties by Molecular Dynamics Simulations: The Properties of Fluids at High Pressures and Temperatures 60 D.G. FRASER and K. REFSON 3. Equations of State of Fluids at High Temperature and Pressure (Water, Carbon Dioxide, Methane, Carbon Monoxide, Oxygen, and Hydrogen) 79 A.B. BELONOSHKO and S.K. SAXENA 4. Thermodynamic Properties of Minerals: Macroscopic and Microscopic Approaches 98 P. RICHET, P. GILLET, and G. FIQUET 5. Thermodynamics of Silicate Melts: Configurational Properties 132 P. RICHET and D.R. NEUVILLE 6. Crystal Chemical and Energetic Characterization of Solid Solution 162 V.S. URUSOV x Contents 7. A Structure Energy Model for C2/c Pyroxenes in the System Na-Mg-Ca-Mn-Fe-AI-Cr-Ti-Si-O 194 G. OTTONELLO, A. DELLA GruSTA, A. DAL NEGRO, and F. BACCARIN 8. Practical Problems in Calculating Thermodynamic Functions for Crystalline Substances from Empirical Force Fields 239 C.M. GRAMACCIOLI and T. PILATI 9. Predictions of the Entropies of Molecules and Condensed Matter 264 M. BLANDER and C.R. STOVER 10. Systematics of Bonding Properties and Vibrational Entropy in Compounds 272 G. GRIMVALL and A. FERNANDEZ GUILLERMET 11. Phonon Density of States and Thermodynamic Properties of Minerals 283 S. GHOSE, N. CHOUDHURY, S.L. CHAPLOT, and K.R. RAO 12. Thermal Expansion Studies of (Mg, FehSi0 -Spinels Using 4 Synchrotron Radiation 315 L.c. MING, M.H. MANGHNANI, Y.H. KIM, S. USHA-DEVI, I-A. Xu, and E. ITO Appendix 335 Index 359 Contributors F. BACCARIN E.N.E.L., Unita Nazionale Geotermica, Via Andrea Pisano 120, 56100 Pisa, Italy A.B. BELONOSHKO Department of Mineralogy and Petrology, Uppsala University, Uppsala S75122, Sweden M. BLANDER Argonne National Laboratory, 9700 South Cass Av enue, Argonne, IL 60439, USA S.L. CHAPLOT Solid State Physics Division, Bhabha Atomic Research Centre, Trombay, Bombay 400085, India N.CHOUDHURY Solid State Physics Division, Bhabha Atomic Research Centre, Trombay, Bombay 400085, India S. USHA-DEVI National Aeronautical Laboratory, Bangalore 560017, India G. FIQUET Laboratorie de Mineralogie Physique, Universite de Rennes 1,35042 Rennes Cede x, France D.G. FRASER Department of Earth Sciences, University of Oxford, Parks Road, Oxford OXI 3PR, United Kingdom S. GHOSE Mineral Physics Group, Department of Geological Sciences, University of Washington, Seattle, WA 948195, USA P. GILLET Laboratoire de Mineralogie Physique, Universite de Rennes 1,35042 Rennes Cedex, France
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