THERMODYNAMICS Second Edition

THERMODYNAMICS Second Edition

N. A. Gokcen, Sc.D. Albany, Oregon

R. G. Reddy, Ph.D. The University of Alabama

Tuscaloosa, Alabama

Springer Science+Business Media, LLC

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Additional material to this book can be downloaded from http://extras.springer.comISBN 978-1-4899-1375-3 ISBN 978-1-4899-1373-9 (eBook)DOI 10.1007/978-1-4899-1373-9

© Springer Science+Business Media New York 1996Originally published by Plenum Press, New York in 1996Softcover reprint of the hardcover 1st edition 1996

All rights reserved

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No part of this book may be reproduced, stored in a retrieval system, or transmittedin any form or by any means, electronic, mechanical, photocopying, microfilming,recording, or otherwise, without written permission from the Publisher

The first edition of this book was published by Techscience, Inc., Hawthorne,California, 1975

To

Emel Gokcen

and

Rama Reddy

with devotion and dedication

PREFACE

This edition of Thermodynamics is a thoroughly revised, streamlined, and cor­rected version of the book of the same title, first published in 1975. It is intended for students, practicing engineers, and specialists in materials sciences, metallur­gical engineering, chemical engineering, chemistry, electrochemistry, and related fields. The present edition contains many additional numerical examples and prob­lems. Greater emphasis is put on the application of thermodynamics to chemical, materials, and metallurgical problems. The SI system has been used through­out the textbook. In addition, a floppy disk for chemical equilibrium calculations is enclosed inside the back cover. It contains the data for the elements, oxides, halides, sulfides, and other inorganic compounds.

The subject material presented in chapters III to XIV formed the basis of a thermodynamics course offered by one of the authors (R.G. Reddy) for the last 14 years at the University of Nevada, Reno. The subject matter in this book is based on a minimum number of laws, axioms, and postulates. This procedure avoids unnecessary repetitions, often encountered in books based on historical sequence of development in thermodynamics. For example, the Clapeyron equation, the van't Hoff equation, and the Nernst distribution law all refer to the Gibbs energy changes of relevant processes, and they need not be presented as radically different relationships.

The manuscript and galley proofs were corrected not only by the authors, but also by Dr. J.A. Sommers, whose diligent efforts are gratefully acknowl­edged. Criticisms and suggestions during the past two decades from Professors E.F. Westrum, Jr., Y.K. Rao, D.A. Stevenson, G.R. St. Pierre, A.E. Morris, D.C. Lynch, L. Brewer, and Dr. M. Blander are also acknowledged. Help rendered by Professors SJ. Louis, F.C. Harris, Jr., and their students in developing the software package for thermodynamic calculations is greatly appreciated. They are not re­sponsible for the content of the text, and the responsibility rests entirely with the authors who welcome further comments and criticism from readers.

Finally, we thank our families for their patience, support, and encouragement throughout the preparation of this book.

N.A. Gokcen Albany, Oregon

R.G. Reddy Tuscaloosa, Alabama

vii

CONTENTS

CHAPTER I. INTRODUCTION AND DEFINITIONS ........... . Introduction .......................................... . Terms and Symbols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 Thermodynamic State of a System . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 Boundaries of a System . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 Work and Energy ....................................... 8 Equilibrium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9 Objectives of Thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9 Problems. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

CHAPTER II. DIFFERENTIATION, INTEGRATION, AND SPECIAL FUNCTIONS. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 11 Differentials and Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 11 Second Derivatives ...................................... 14 Useful Differentials. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 14 Maxima, Minima and Inflection Points . . . . . . . . . . . . . . . . . . . . . . . .. 15 L'Hopital's Theorem . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 16 Homogeneous Functions .................................. 17 Euler's Theorem on Homogeneous Functions .................... 17 Homogeneous Thermodynamic Functions. . . . . . . . . . . . . . . . . . . . . .. 18 Integrals. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 20 Exact Differentials. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 21 Line Integrals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 23 A Graphical Example. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 24 Cross Differentials. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 25 Lagrange's Method of Undetermined Multipliers . . . . . . . . . . . . . . . . .. 26 Change of Independent Variables . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 27 Representation of Data. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 28 Determinants .......................................... 31

ix

x Contents

Useful Series .......................................... 32 Problems. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 33

CHAPTER III. THE FIRST LAW OF THERMODYNAMICS . . . . . .. 37 Work of Compression and Expansion . . . . . . . . . . . . . . . . . . . . . . . . .. 38 Heat. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 39 Reversible Processes in Closed Systems . . . . . . . . . . . . . . . . . . . . . . .. 40 Application of the First Law to Ideal Gases . . . . . . . . . . . . . . . . . . .. 40 Energy of Ideal Gases .................................... 40 Heat Capacity. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 42 Processes with Ideal Gases. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 42 Simple Kinetic Theory of Ideal Gases. . . . . . . . . . . . . . . . . . . . . . . . .. 45 Real Gases, Liquids and Solids . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 47 Compressibility Factor. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 47 van der Waals Equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 48 Other Equations of State. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 51 Liquids and Solids. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 53 Enthalpy and Heat Capacity. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 53 Heat Capacity of Solids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 54 Empirical Representation of Heat Capacity . . . . . . . . . . . . . . . . . . . . .. 57 Relationship between C~ and H~ - H~98 ....................... 57 Enthalpy Change of Phase Transformations ........... : . . . . . . . . .. 58 Thermochemistry ...................................... 60 Variation of /}., HI- with Temperature . . . . . . . . . . . . . . . . . . . . . . . . .. 63 Bond Energies ......................................... 65 Adiabatic Flame Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 66 Problems. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 67

CHAPTER IV. THE SECOND LAW OF THERMODYNAMICS. . . .. 71 The Second Law of Thermodynamics. . . . . . . . . . . . . . . . . . . . . . . . .. 71 Carnot Engine. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 72 Carnot Theorem . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . .. 74 Kelvin Temperature Scale. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 75 Carnot Engine with an Ideal Gas . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 77 Refrigeration Engine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 79 Spontaneous Processes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 79 Reversible Cyclic Processes .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 79 Entropy Change in Reversible Processes . . . . . . . . . . . . . . . . . . . . . . .. 83 Entropy Change in Irreversible Processes .. . . . . . . . . . . . . . . . . . . . .. 83 Method of Caratheodory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 85 The Second Law of Thermodynamics. . . . . . . . . . . . . . . . . . . . . . . . .. 87 Problems. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 88

Contents Xl

CHAPTER V. ENTROPY AND RELATED FUNCTIONS . . . . . . . .. 89 Entropy Change ........................................ 89 Entropy of Mixing of Ideal Gases ............................ 91 Entropy of Phase Change and Chemical Reactions . . . . . . . . . . . . . . . .. 92 Entropy, Randomness and Probability. . . . . . . . . . . . . . . . . . . . . . . . .. 93 Thermodynamic Equations of State . . . . . . . . . . . . . . . . . . . . . . . . . .. 94 Difference Between C p and C v . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 96 Variation of C p and C v with P and V ......................... 97 Joule-Kelvin Expansion of Gases. . . . . . . . . . . . . . . . . . . . . . . . . . . .. 97 Problems. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 99

CHAPTER VI. HELMHOLTZ AND GIBBS ENERGIES. . . . . . . . .. 101 Introduction and Definitions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 101 Partial Differential Relations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 103 Isothermal Changes in A and G . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 104 Criteria for Reversibility and Irreversibility . . . . . . . . . . . . . . . . . . . . .. 105 Examples. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 107 Problems. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 108

CHAPTER VII. THE THIRD LAW OF THERMODYNAMICS . . . . .. 109 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 109 The Third Law of Thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . .. 111 Entropy from Statistical Mechanics .......................... '. 113 Entropies of Supercooled Liquids ............................ 114 Consequences of the Third Law. . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 115 Thermal Evaluation of Entropy . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 116 Problems. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 117

CHAPTER VIII. PHASE EQUILIBRIA . ...................... 119 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 119 Two-Phase Equilibrium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 119 Vaporization Equilibria ................................... 121 Variation of Vapor Pressure with Total Pressure at Constant Temperature.. 124 Representation of Phase Equilibria. . . . . . . . . . . . . . . . . . . . . . . . . . .. 125 Components. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 126 Variables of State and Degrees of Freedom . . . . . . . . . . . . . . . . . . . . .. 130 Partial (Molar) Gibbs Energy, or Chemical Potential. . . . . . . . . . . . . . .. 130 Conditions of Phase Equilibrium . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 131 Phase Rule. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 133 Other Definitions of G i ................................... 135 Useful Partial (Molar) Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 136 G i and Criterion of Equilibrium ............................. 136 Problems. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 136

Xll Contents

CHAPTER IX. FUGACITY AND ACTIVITY. . . . . . . . . . . . . . . . . .. 139 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 139 Fugacity of Pure Gases. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 140 Alternative Equations for Fugacity . . . . . . . . . . . . . . . . . . . . . . . . . . .. 141 Variation of Fugacity with Temperature ........................ 142 Definition of Activity. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 143 Raoult's Law .......................................... 144 Henry's Law. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 145 Problems. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 149

CHAPTER X. SOLUTIONS . ............................. 151 Part I Ideal Solutions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 151 Equilibrium Between an Ideal Solution and Its Vapor . . . . . . . . . . . . . .. 152 Constant Pressure Binary Equilibrium Diagrams .... . . . . . . . . . . . . .. 156 Equilibria Between Pure Immiscible Solids and Ideal Liquid Solutions . .. 157 Relative Positions of Liquidus and Solidus Lines . . . . . . . . . . . . . . . . .. 158 Depression of Freezing Point ............................... 159 Elevation of the Boiling Point. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 160 Determination of Molecular Weights .......................... 160 Ideal Solubilities of Gases ................................. 161 Part II Real Solutions .................................. 162 Definition of Real Solutions .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 162 Equilibrium Between a Real Solution and Its Vapor

at Constant Temperature. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 162 Equilibrium Between a Real Solution and Its Vapor

at Constant Pressure. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 166 Variation of Activity and Activity Coefficients with Composition

in Binary Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 170 Variation of Activities in Binary Solutions with Pressure and Temperature. 172 Dilute Solutions ........................................ 172 Molar, Partial Molar, and Excess Thermodynamic Properties of Solutions . 173 Problems. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 177

CHAPTER XI. PARTIAL (MOLAR) PROPERTIES . ............ 179 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 179 Partial (Molar) Properties of Binary Systems. . . . . . . . . . . . . . . . . . . .. 180 Excess Gibbs Energy; Binary Systems . . . . . . . . . . . . . . . . . . . . . . . .. 182 Representation of GE . . • . • • • • . • . • . . • . . . . • • . . • • • . . • . . . . . . •• 183 Alternative Equations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 187 Regular Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 189 Maximum, Minimum, and Critical Points in (11.43) . . . . . . . . . . . . . . .. 190 Spinodal Points. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 192 Theoretical Derivation of (11.40) . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 192

Contents xiii

Effect of Temperature on G E and gi . . . . . . . . . . . . . . . . . . . . . . . . . .. 195 Equations with Henrian Reference States ....................... 199 Wagner Interaction Parameters .............................. 200 Problems . ............................................ 201

CHAPTER XII. GIBBS ENERGY CHANGE OF REACTIONS. . . .. 203 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 203 Feasibility of Chemical Reactions ..... . . . . . . . . . . . . . . . . . . . . . .. 204 Equilibria in Real Gas Mixtures. . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 209 Equilibria Involving Condensed Phases. . . . . . . . . . . . . . . . . . . . . . . .. 211 Determination of Standard Gibbs Energy Changes. . . . . . . . . . . . . . . .. 212 Method I-Determination of I'l. GO from Equilibrium Constant. . . . . . . .. 212 Method II-Thermal Data ................................. 214 Method III-Electromotive Force (emf) Method .................. 214 Method IV-Spectroscopic Data and Mechanics of Molecules ......... 215 Thermodynamic Equations ................................. 215 Tabulation of Thermodynamic Data . . . . . . . . . . . . . . . . . . . . . . . . . .. 216 Use of Tables . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 224 Other Thermodynamic Tables and Compilations .................. 228 Use of Tabular Data in Experimental Work . . . . . . . . . . . . . . . . . . . . .. 229 Complex Equilibria. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 238 Generalized Reactions and Their Equilibrium Constants . . . . . . . . . . . .. 240 Problems. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 244

CHAPTER XIII. SOLUTIONS OF ELECTROLYTES . ........... 247 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 247 Activity and Activity Coefficient . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 248 Debye-Htickel Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 250 Concentrated Electrolytes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 256 Determination of Activities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 257 Weak Electrolytes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 262 Temkin Rule. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 264 Problems. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 265

CHAPTER XIV. REVERSIBLE GALVANIC CELLS. . . . . . . . . . . .. 267 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 267 Properties of Reversible Cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 268 Single Electrode Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 268 Convention in Notation ................................... 269 Reaction Isotherm and emf . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 271 Standard emf of Half-cells ................................. 272 Variation of emf with Temperature and Pressure. . . . . . . . . . . . . . . . . .. 276 Ionization Constant of Water. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 277

xiv Contents

Cells with Solid Electrolytes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 280 Problems. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 282

CHAPTER XV. PHASE DIAGRAMS. . . . . . . . . . . . . . . . . . . . . . .. 285 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 285 Binary Phase Diagrams ................................... 285 Erroneous Diagrams ..................................... 288 Lever Rule . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 290 Molar Gibbs Energy of Mixing-Composition Diagrams ............ 291 !1G Diagrams for Other Phases .............................. 294 !1G Diagrams for Complex Systems .......................... 298 Calculation of Phase Diagrams from Thermodynamic Data . . . . . . . . . .. 299 Ternary Phase Diagrams. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 302 Tielines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 309 Thermodynamic Consideration . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 309 Second Order Transitions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 313 Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 314 Problems. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 314 Selected Binary Phase Diagrams . ........................... 315

CHAPTER XVI. SPECIAL TOPICS ........................ 323 Part I Surface Tension . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 323 Properties of Surfaces .................................... 323 Criteria for Equilibrium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 324 Gibbs Adsorption Equation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 325 Vapor Pressure of Droplets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 326 Part II Gravitational Electric and Magnetic Fields. . . . . . . . . . . . .. 327 Gravitational Field. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 327 Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 328 Centrifugal Force ....................................... 329 Electric and Magnetic Fields . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 329 Part ill Long-Range Order . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 330 Ordering and Clustering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 331 Order-Disorder in Binary Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 331 Long-Range Order Parameter . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 333 Gorsky and Bragg-Williams (GBW) Approximation. . . . . . . . . . . . . . .. 334 Heat Capacity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 336 Problems. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 338

APPENDIX I. GENERAL REFERENCES . . . . . . . . . . . . . . . . . . .. 339

APPENDIX II. TABLES OF THERMODYNAMIC DATA FOR EXAMPLES AND PROBLEMS IN TEXT. . . . ... . . . . . . . . . . . . . .. 341

Contents xv

APPENDIX III. THERMODYNAMIC SIMULATOR (TSIM) FOR THERMODYNAMIC CALCULATIONS ...................... 371

APPENDIX IV. ESTIMATION OF ACTIVITIES IN MULTICOMPONENT IONIC SOLUTIONS. . . . . . . . . . . . . . . . . . .. 373

APPENDIX V. STABILITY DIAGRAMS ..................... 381

APPENDIX VI. LIST OF SYMBOLS. . . . . . . . . . . . . . . . . . . . . . .. 387

INDEX .............................................. 393

1 G

roup

IA

-,

-H

1.

0079

3 Li

6.94

1

11

Na

22.9

898

19

K

39.0

983

37

Rb

85.4

678

55

Cs

132.

905

87

Fr

(223

)

Pe

rio

dic

tab

le o

f th

e e

lem

en

ts

2 •

New

not

atio

n P

revi

ous

IUPA

C 'o

rm

IIA

~CAS_~""

4 Be

9.01

218

12

3

4 5

6 7

8 9

10

M9

iliA

-...

IV A

V

A

VIA

V

ilA

Vill

A

2U

05

II

IB

IVB

V

B

VIB

V

IIB

,.-V

III--,

20

2

1

22

2

3

24

2

5

26

2

7

28

Ca

Sc

Ti

V

Cr

Mn

Fe

Co

Ni

40.0

8 44

.955

9 47

.88

50.9

415

51.9

96

54.9

380

55.8

47

58.9

332

58.6

9

38

3

9

40

41

4

2

43

44

4

5

46

Sr

Y

Zr

Nb

Mo

Tc

Ru

Rh

Pd

87.6

2 88

.905

9 91

.224

92

.906

4 95

.94

(98)

10

1.07

10

2.90

6 10

6.42

56

5

7

72

13

74

1

5

16

1

1

18

Sa

La*

Hf

Ta

W

Re

Os

Ir P

t 13

7.33

13

8.90

6 'I' 1

78.4

9 18

0.94

8 18

3.8S

18

6.20

7 19

0.2

192.

22

195.

08

88

8

9 ! 1

04

a

10

5 a

1

06

a

10

1 a

Ra

Ac AUn~

Unp

U

nli

Uns

m

.02

5

227.

028

( (2

61)

(262

) (2

631

(262

)

* La

nth

an

ide

se

rie

s

.to. A

cti

nid

e

seri

es

• • •

11

12

IB

liB

29

3

0

Cu

Zn

63.5

46

65.3

9

41

4

8

A9

Cd

107.

868

112.

41

79

8

0

Au

Hg

196.

967

200.

59

18

Vill

A

13

14

15

16

17 ~

IIIB

IV

B

VB

V

IB

VIIB

H

e il

iA

IVA

V

A

VIA

V

ilA

4.00

260

5 6

7 8

9 1

0

8 C

N

0

F N

e.

10.8

1 12

.011

14

.006

7 15

.999

4 18

.998

4 20

.179

.

13

1

4

15

16

1

1

18

AI

Si

P S

CI

Ar

26.9

815

28.0

855

30.9

738

32.0

6 35

.453

39

.948

31

32

3

3

34

35

3

6

Ga

Ge

As

Se

Sr

Kr

69.7

2 72

.59

74.9

216

78.9

6 79

.904

83

.80

49

5

0

51

52

53

5

4

In

Sn

Sb

Te

I X

e 11

4.82

11

8.71

12

1.15

12

7.60

12

6.90

5 1 J

1.2

9

81

8

2

83

8

4

85

8

6

TI

Pb

Bi

Po

At

Rn

204.

383

207.

2 20

8.98

0 (2

09)

(210

) (2

22)

No

le:

Alo

mic

ma

sse

s sh

ow

n h

ere

are

the

196

31U

PA

C v

alu

es

(ma

xim

um

of

six

sig

nifi

can

t fig

ure

s).

a S

ymb

Ols

ba

sed

on

IU

PA

C s

yste

ma

tic n

am

es.

Rep

rodu

ced

by

perm

issi

on f

rom

Ad

van

ced

Ino

rgan

ic C

hem

istr

y, f

ifth

editi

on,

by

F.

A.

Cot

ton

and

G.

Wilk

inso

n,

Wile

y-In

ters

cien

ce (

1988

).