Robert DeHoff - Thermodynamics in Materials Science - 2ed

Esta é uma pré-visualização de arquivo. Entre para ver o arquivo original

Thermodynamics
in
Materials
Science
Thermodynamics
in
Materials
Science
Robert DeHoff
Second Edition
CRC Press
Taylor & Francis Group
6000 Broken Sound Parkway NW, Suite 300
Boca Raton, FL 33487-2742
© 2006 by Taylor & Francis Group, LLC
CRC Press is an imprint of Taylor & Francis Group, an Informa business
No claim to original U.S. Government works
Version Date: 20110713
International Standard Book Number-13: 978-1-4200-0585-1 (eBook - PDF)
This book contains information obtained from authentic and highly regarded sources. Reasonable efforts 
have been made to publish reliable data and information, but the author and publisher cannot assume 
responsibility for the validity of all materials or the consequences of their use. The authors and publishers 
have attempted to trace the copyright holders of all material reproduced in this publication and apologize to 
copyright holders if permission to publish in this form has not been obtained. If any copyright material has 
not been acknowledged please write and let us know so we may rectify in any future reprint.
Except as permitted under U.S. Copyright Law, no part of this book may be reprinted, reproduced, transmit-
ted, or utilized in any form by any electronic, mechanical, or other means, now known or hereafter invented, 
including photocopying, microfilming, and recording, or in any information storage or retrieval system, 
without written permission from the publishers.
For permission to photocopy or use material electronically from this work, please access www.copyright.
com (http://www.copyright.com/) or contact the Copyright Clearance Center, Inc. (CCC), 222 Rosewood 
Drive, Danvers, MA 01923, 978-750-8400. CCC is a not-for-profit organization that provides licenses and 
registration for a variety of users. For organizations that have been granted a photocopy license by the CCC, 
a separate system of payment has been arranged.
Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are used 
only for identification and explanation without intent to infringe.
Visit the Taylor & Francis Web site at
http://www.taylorandfrancis.com
and the CRC Press Web site at
http://www.crcpress.com
Ankita Mangal
Ankita Mangal
Ankita Mangal
Ankita Mangal
Ankita Mangal
Ankita Mangal
Ankita Mangal
Ankita Mangal
Ankita Mangal
Ankita Mangal
Ankita Mangal
Ankita Mangal
Ankita Mangal
Ankita Mangal
Ankita Mangal
Ankita Mangal
Ankita Mangal
Ankita Mangal
Ankita Mangal
Ankita Mangal
Ankita Mangal
Ankita Mangal
Ankita Mangal
Ankita Mangal
Ankita Mangal
	Cover Page
	Half Title Page
	Title Page
	Copyright Page
	Preface to the Second Edition
	Preface to the First Edition
	About the Author
	Table of Contents
	Chapter 1. Why Study Thermodynamics?
	1.1 The Power and Breadth of Thermodynamics
	1.2 The Generic Question Addressed by Thermodynamics
	1.3 Thermodynamics Is Limited to Systems in Equilibrium
	1.4 The Thermodynamic Basis for Equilibrium Maps
	1.4.1 The Principles
	1.4.2 The Strategies
	1.4.3 Databases
	1.4.4 Maps of Equilibrium States
	1.5 Three Levels of the Thermodynamic Apparatus
	1.6 Summary
	Chapter 2. The Structure of Thermodynamics
	2.1 A Classification of Thermodynamic Systems
	2.2 Classification of Thermodynamic Variables
	2.2.1 State Functions
	2.2.2 Process Variables
	2.2.3 Extensive and Intensive Properties
	2.3 Classification of Relationships
	2.4 Criterion for Equilibrium
	2.5 Summary
	Chapter 3. The Laws of Thermodynamics
	3.1 The First Law of Thermodynamics
	3.2 The Second Law of Thermodynamics
	3.3 Intuitive Meaning of Entropy Production
	3.4 Relation between Entropy Transfer and Heat Absorbed
	3.5 Combined Statement of the First and Second Laws
	3.6 The Third Law of Thermodynamics
	3.7 Summary
	References
	Chapter 4. Thermodynamic Variables and Relations
	4.1 Classification of Thermodynamic Relationships
	4.1.1 The Laws of Thermodynamics
	4.1.2 Definitions in Thermodynamics
	4.1.2.1 Enthalpy, H
	4.1.2.2 Helmholtz Free Energy, F
	4.1.2.3 Gibbs Free Energy, G
	4.1.3 Coefficient Relations
	4.1.4 Maxwell Relations
	4.2 General Strategy for Deriving Thermodynamic Relations
	4.2.1 Entropy and Volume Relations to T and P
	4.2.2 Energy Functions Expressed in Terms of T and P
	4.2.3 The General Procedure
	4.2.4 Application to an Ideal Gas
	4.2.5 Applications to Solids and Liquids
	4.3 Summary
	References
	Chapter 5. Equilibrium in Thermodynamic Systems
	5.1 Intuitive Notions of Equilibrium
	5.2 Thermodynamic Formulation of a General Criterion for Equilibrium
	5.3 Mathematical Formulation of the General Conditions for Equilibrium
	5.4 Application of the General Strategy for Finding Conditions for Thermodynamic Equilibrium: The Unary Two-Phase System
	5.5 Alternate Formulations of the Criterion for Equilibrium
	5.6 Summary
	References
	Chapter 6. Statistical Thermodynamics
	6.1 Microstates, Macrostates, and Entropy
	6.2 Conditions for Equilibrium in Statistical Thermodynamics
	6.2.1 Evaluation of Entropy
	6.2.2 Evaluation of the Isolation Constraints
	6.2.3 The Constrained Maximum in the Entropy Function
	6.2.4 Calculation of the Macroscopic Properties from the Partition Function
	6.3 Applications of the Algorithm
	6.3.1 A Model with Two Energy Levels
	6.3.2 Einstein’s Model of a Crystal
	6.3.3 Monatomic Gas Model
	6.4 Alternate Statistical Formulations
	6.5 Summary
	References
	Chapter 7. Unary Heterogeneous Systems
	7.1 Structure of Unary Phase Diagrams in ðP; T Þ Space
	7.1.1 Chemical Potential and the Gibbs Free Energy
	7.1.2 Chemical Potential Surfaces and the Structure of Unary Phase Diagrams
	7.1.3 Calculation of Chemical Potential Surfaces
	7.1.4 Competing Equilibria: Metastability
	7.1.5 Phase Stability Calculations
	7.2 The Clausius – Clapeyron Equation
	7.3 Integration of the Clausius – Clapeyron Equation
	7.3.1 Vaporization and Sublimation Curves
	7.3.2 Phase Boundaries between Condensed Phases
	7.4 Triple Points
	7.5 Computer Calculations of (P, T) Unary Phase Diagrams
	7.6 Alternate Representations of Unary Phase Diagrams
	7.7 Summary
	Chapter 8. Multicomponent Homogeneous Nonreacting Systems: Solutions
	8.1 Partial Molal Properties
	8.1.1 Definition of Partial Molal Properties
	8.1.2 Consequences of the Definition of Partial Molal Properties
	8.1.3 The Mixing Process
	8.1.4 Molar Values of the Properties of Mixtures
	8.2 Evaluation of Partial Molal Properties
	8.2.1 Partial Molal Properties from Total Properties
	8.2.2 Graphical Determination of Partial Molal Properties
	8.2.3 Evaluation of the PMPs of One Component from Measured Values of PMPs of the Other
	8.3 Relationships Among Partial Molal Properties
	8.4 Chemical Potential in Multicomponent Systems
	8.5 Fugacities, Activities, and Activity Coefficients
	8.5.1 Properties of Ideal Gas Mixtures
8.5.2 Mixtures of Real Gases: Fugacity
	8.5.3 Activity and the Behavior of Real Solutions
	8.5.4 Use of the Activity Coefficient to Describe the Behavior of Real Solutions
	8.6 The Behavior of Dilute Solutions
	8.7 Solution Models
	8.7.1 Regular Solution Models
	8.7.2 Modeling Real Solutions
	8.7.3 Atomistic Models for Solution Behavior
	8.8 Summary
	References
	Chapter 9. Multicomponent Heterogeneous Systems
	9.1 The Description of Multiphase Multicomponent Nonreacting Systems
	9.2 Conditions for Equilibrium
	9.3 The Gibbs Phase Rule
	9.4 The Structure of Phase Diagrams
	9.4.1 Phase Diagrams Plotted in Thermodynamic Potential Space
	9.4.2 Unary Systems
	9.4.3 Binary Phase Diagrams
	9.4.4 Ternary Phase Diagrams
	9.5 The Interpretation of Phase Diagrams
	9.5.1 The Lever Rule for Tie Lines
	9.5.2 The Lever Rule for Tie Triangles
	9.6 Applications of Phase Diagrams in Materials Science
	9.7 Summary
	References
	Chapter 10. Thermodynamics of Phase Diagrams
	10.1 Free Energy – Composition (G-X) Diagrams
	10.1.1 Reference States for G – X Curves
	10.1.2 The Common Tangent Construction and Two Phase Equilibrium
	10.1.3 Two-Phase Fields on Binary Phase Diagrams
	10.1.4 Three-Phase Equilibria
	10.1.5 Intermediate Phases
	10.1.6 Metastable Phase Diagrams
	10.2 Thermodynamic Models for Binary Phase Diagrams
	10.2.1 Ideal Solution Models for Phase Diagrams
	10.2.2 Regular Solution Model for Phase Diagrams
	10.2.3 The Midrib Curve
	10.2.4 Pattern of Regular Solution Phase Diagrams with Two Phases
	10.2.5 Diagrams with Three or More Phases
	10.2.6 Modeling Phase Diagrams with Line Compounds
	10.3 Thermodynamic Models for Three Component Systems
	10.4 Calculation of Phase Diagrams in Potential Space
	10.5 Computer Calculations of Phase Diagrams
	10.6 Summary
	References
	Chapter 11. Multicomponent Multiphase Reacting Systems
	11.1 Reactions in the Gas Phase
	11.1.1 Univariant Reactions in the Gas Phase
	11.1.2 Multivariant Reactions in the Gas Phase
	11.2 Reactions in Multiphase Systems
	11.3 Patterns of Behavior in Common Reacting Systems
	11.3.1 Richardson – Ellingham Charts for Oxidation
	11.3.2 Oxidation in CO/CO2 and H2/H2O Mixtures
	11.4 Predominance Diagrams and Multivariant Equilibria
	11.4.1 Pourbaix High Temperature Oxidation Diagrams
	11.4.2 Predominance Diagrams with Two Compositional Axes
	11.4.3 Interpretation of Predominance Diagrams
	11.5 Compounds as Components in Phase Diagrams
	11.6 Summary
	References
	Chapter 12. Capillarity Effects in Thermodynamics
	12.1 The Geometry of Surfaces
	12.2 Surface Excess Properties
	12.3 Conditions for Equilibrium in Systems with Curved Interfaces
	12.4 Surface Tension: The Mechanical Analogue of Surface Free Energy
	12.5 Capillarity Effects on Phase Diagrams
	12.5.1 Phase Boundary Shifts in Unary Systems
	12.5.2 Vapor Pressure in Equilibrium with Curved Surfaces
	12.5.3 Effect of Curvature upon the Melting Temperature
	12.5.4 Effect of Curvature on Chemical Potential in Unary Systems
	12.5.5 Phase Boundary Shifts in Binary Systems
	12.5.6 Local Equilibrium and the Application of Capillarity Shifts
	12.6 The Equilibrium Shape of Crystals: The Gibbs –Wulff Construction
	12.7 Equilibrium at Triple Lines
	12.8 Adsorption at Surfaces
	12.8.1 Measures of Adsorption
	12.8.2 The Gibbs Adsorption Equation
	12.9 Summary
	References
	Chapter 13. Defects in Crystals
	13.1 Point Defects in Elemental Crystals
	13.1.1 Conditions for Equilibrium in a Crystal with Vacant Lattice Sites
	13.1.2 The Concentration of Vacancies in an Elemental Crystal at Equilibrium
	13.1.3 Interstitial Defects and Divacancies
	13.2 Point Defects in Stoichiometric Compound Crystals
	13.2.1 Frenkel Defects
	13.2.2 Schottky Defects
	13.2.3 Combined Defects in Binary Compounds
	13.2.4 Multivariate Equilibrium among Defects in a Stoichiometric Compound Crystal
	13.3 Nonstoichiometric Compound Crystals
	13.3.1 Equilibrium in Compound Crystals with a Variety of Defects
	13.3.2 Illustration of the Conditions for Equilibrium for Alumina
	13.4 Impurities in Nonstoichiometric Compounds
	13.5 Summary
	References
	Chapter 14. Equilibrium in Continuous Systems: Thermodynamic Effects of External Fields
	14.1 Thermodynamic Densities and the Description of Nonuniform Systems
	14.2 Conditions for Equilibrium in the Absence of External Fields
	14.3 Conditions for Equilibrium in the Presence of External Fields
	14.3.1 Potential Energy of a Continuous System
	14.3.2 Conditions for Equilibrium
	14.3.3 Equilibrium in a Gravitational Field
	14.3.4 Equilibrium in a Centrifugal Field
	14.3.5 Equilibrium in an Electrostatic Field
	14.4 The Gradient Energy in Nonuniform Systems
	14.5 Summary
	References
	Chapter 15. Electrochemistry
	15.1 Equilibrium within an Electrolyte Solution
	15.1.1 Equilibrium in Weak Electrolytes
	15.1.2 Equilibrium in a Strong Electrolyte
	15.2 Equilibrium in Two-Phase Systems Involving an Electrolyte
	15.3 Equilibrium in an Electrochemical Cell
	15.3.1 Conditions for Equilibrium in a General Galvanic Cell
	15.3.2 Temperature Dependence of the Electromotive Force of a Cell
	15.3.3 The Standard Hydrogen Electrode
	15.4 Pourbaix Diagrams
	15.4.1 The Stability of Water
	15.4.2 Pourbaix Diagram for Copper
	15.5 Summary
	References
	Appendices
	Appendix A. Fundamental Physical Constants and Conversion Factors
	Appendix B. Properties of Selected Elements
	Appendix C. Phase Transformations for the Elements
	Appendix D. Properties of Some Random Solutions
	Appendix E. Properties of Selected Compounds
	Appendix F. Interfacial Energies of Selected Elements
	Appendix G. Electrochemical Series
	Appendix H. The Carnot Cycle
	Appendix I. Answers to Homework Problems
	Back Cover