nels WVIe, LOOP APPLICATIONS IN MATERIALS SYSTEMS DYNAMIC FIRST EDITION: DONALD L. JOHNSON Professor Emeritus of Mechanical Engineering, Metallurgy Program, University of Nebraska-Lincoln, Lincoln, Nebraska GLENN B. STRACHER Professor of Geology, East Georgia College, University System of Georgia, Swainsboro, GeorgiaA Publication of The Minerals, Metals & Materials Society 420 Commonwealth Drive Warrendale, Pennsylvania 15086 (412) 776-9000 The Minerals, Metals & Materials Society is not responsible for statements or opinions and is absolved of liability due to misuse of information contained in this publication. Printed in the United States of America Library of Congress Catalog Number 94-073747 ISBN Number 0-87339-270-1 Authorization to photocopy items for inter- nal or personal use, or the internal or per- sonal use of specific clients, is granted by The Minerals, Metals & Materials Society for us- cers registered with the Copyright Clearance Center (CCQ) Transactional Reporting Serv- ice, provided that the base fee of $3.00 per gnaale Meine Nols copy is paid directly to Copyright Clearance Center, 27 Congress Street, Salem, Massa- chusetts 01970. For those organizations that have been granted a photocopy license by Copyright Clearance Center, a separate sys- tem of payment has been arranged. If you are interested in purchasing a copy of this book, or if you would like to receive the latest TMS publications catalog, please telephone 1-800-759-4867.CONTENTS Preface .... Systems and Unit Notation .. Symbols for Partial Molar Mixing Properties ..... Table of Physical Constants and Conversion Factors .... 1 INTRODUCTION 1.1 The Science of Thermodynamics... 1.2 Systems, Surroundings, and Phases ..... 1.3. Macroscopic State of a System... 1.4 Equilibrium. 1.5 Adiabatic and Diathermic Boundaries 1.6 _ Irreversible and Reversible Processes .. 1.7 Path Independent Properties, Change in State, and Cyclic Processes 1.8 Equation of State and the Condition of Exactness 1.9 Path Dependent Processes: Work and Heat..... Roe eee 1.10 Discussion Questions ..... 1,11 Exercise Problems ..... 2 THE FIRST LAW OF THERMODYNAMICS AND ENTHALPY 2.1 Internal Energy and the First Law of Thermodynamics 2.2 Enthalpy: a State Function 2.3. Heat Capacity ..... 2.4 Enthalpy (Heat) of Transformation 2.5 Standard State Enthalpy..... 2.6 Enthalpy (Heat) of Formation and Reaction ...THERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS 2.7 Introduction to the Thermodynamic Loop (TL)... 2.8 Discussion Questions... 2.9 Exercise Problems ... 3. THE SECOND AND THIRD LAWS OF THERMODYNAMICS 3.1. Thermodynamic Efficiency, the Second Law and Entrop: 3.2 Entropy of Reaction and the Third Law 47 3.3. TL Analysis: Temperature Dependence 3.4 Stability Criteria: Entropy... 3.5 Alternate Definition of Entropy ..... 3.6 Discussion Questions 3.7 Exercise Problems 4 GIBBS FREE ENERGY 4,1 Stability Criteria... 4.2 Standard States: Gibbs Free Energy of Formation and Reaction... 4.3. Methods for Determination of AG? 44 TLAnalysis Incorporating Pressure Dependence -70 4.5 Useful Thermodynamic Relations ..... 4.6 Discussion Questions... 4.7 Exercise Problems ... 5 HETEROGENEOUS EQUILIBRIA: VARIABLE GAS PHASE COMPOSITION 5.1 Ideal Gas Mixtures, Dalton’s Law, and Gibbs Free Energy of a Gas 5.2. TL Analysis and Ellingham Diagram: 5.3. Discussion Questions ... 5.4 Exercise Problems .... vi6 HETEROGENEOUS EQUILIBRIA: VARIABLE COMPOSITION IN CONDENSED PHASES 6.1 Gas Partial Pressure and Fugacity 6.2 Thermodynamic Activity .... 6.3 Solutions and Partial Molar Properties .. 6.4 Solution Models... 6.5 Excess Thermodynamic Properties and Alternate Solution Models 6.6 TL Analysis of Solutions in Heterogeneous Reactions 6.7 The Gibbs-Duhem Equation 6.8 Chemical Potential ... 6.9 Discussion Questions... 6.10 Exercise Problems ... 7 ANALYSIS AND APPLICATIONS: BINARY PHASE DIAGRAMS 7.1 Eutectic Systems: No Solid Solubilit 7.2 Eutectic Systems: Terminal Solid Solubility... 7.3 Chemical Potential: Phases at Equilibrium ... 7.4 — Univariant Equilibrium: Clapeyron Equation 7.5 Pressure Effect on Phase Boundaries 7.6 Gibbs Phase Rule... 7.1 Discussion Questions 7.8 Exercise Problems ... 8 ACTIVITY QUOTIENT AND EQUILIBRIUM CONSTANT: APPLICATIONS 8.1 TL Derivation of the Activity Quotient and Equilibrium Constant .... 8.2 — Effect of Temperature and Pressure at Equilibrium 8.3 TLAnalysis and K,,: Example Problems 8.4 The Nernst Equation... viiTHERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS 8.5 Discussion Questions... 8.6 Exercise Problems .... APPENDIX A TABLES OF THERMODYNAMIC DATA Table A.1 Table A.2 Table A.3A Table A.3B Table A.4 Table A.S Table A.6 APPENDIX B Table B.1 Table B.2 APPENDIX C Table C.1 APPENDIX D Table D.1 Table D.2 APPENDIX E viii Figure E.1 Figure E.2 Standard Heats of Formation, Standard Entropies, Melting and Boiling Points .. Heats of Transformation and Fusion Heat Capacities .... Heat Capacities .... Standard Gibbs Free Energy Changes of Selected Reactions Vapor Pressures Over Pure Condensed Phases ........ 172 Activity of Carbon in Austenite Between 800-1200°C TABLES OF SELECTED PHYSICAL CONSTANTS Density, Molecular Mass, Volume Thermal Expansion and Isothermal Compressibility Coefficients .... Standard Molar Volumes, Volume Thermal Expansion and Isothermal Compressibility Coefficients .... ELECTROMOTIVE FORCE SERIES Half Cell Reactions and Standard Potentials PROPERTIES AT VAPOR-LIQUID EQUILIBRIUM Saturated Water Vapor-Liquid Equilibrium ..... Potassium Vapor-Liquid Equilibrium .. FIGURES Isothermal Transformation (I-T) Diagram for AISI 1050 Steel... Ellingham Diagram for OxidesFigure E.3_ Ellingham Diagram for Sulfides ... Figure E.4 Log P,/? vs. 10*/T Diagram for Select Metal Nitride Systems... Figure E.5 Standard Gibbs Free Energy of Formation and Reversible Decomposition Voltage of Select Chlorides as a Function of Temperature ... Figure E.6 AI-Si Eutectic Phase Diagram: No Solid Solubility .. Figure E.7 Ag-Cu Eutectic Phase Diagram: Terminal Solid Solubility ... Figure E.8 Bi-Pb Phase Diagram Figure E.9 Pb-Sb Phase Diagram ..... Figure E.10 NaAISi,O,-SiO, Eutectic Phase No Solid Solubility .. Figure E.11 Diamond-Graphite Univariant P-T Phase Diagram..... jagram: APPENDIX F REFERENCES FOR THERMODYNAMIC DAT, APPENDIX G ADDITIONAL REFERENCESPREFACE This book is intended for use in an initial one-semester course in “materi- als” thermodynamics, although it could be used for self-study or as a supple- ment to a text selected for a two-semester undergraduate-graduate sequence. Each chapter is designed so that the student can learn to use thermodynamics as a problem solving tool for a broad range of materials applications. The book is written from notes developed in a course entitled “Thermodynamics of Alloys.” Although this course was originally designed as an elective in mechanical engineering at the University of Nebraska-Lincoln, the broader perspective of thermodynamics of materials has emerged as a result of student contacts in earth science, mechanical, chemical, and corrosion engincering, and electrical materials, For many scientists and engineers, thermodynamics may be most useful for applications where quickly obtained numerical estimates are all that is needed. Such a situation may prevail for those working in materials-related areas where the generation of thermodynamic data is not an objective in itself. The earth scientist, for example, may need to interpret the stability of mineral assem- blages in a rock by using thermodynamic data available in the literature. On the other hand, metallurgists and chemists as well as mechanical, electrical, and materials engineers may be concerned with elevated temperature phase equilibria, phase transformations, and environmental reactions. For the corro- sion and chemical engineer, the concept of potential (EMF) is very important in corrosion control as it relates to the Nernst Equation and associated “Pourbaix” diagrams. Fundamentals of classical thermodynamics are briefly reviewed and sys- tematically introduced into problem solving using “thermodynamic loop” or TL analysis. This concept, derived from Kirchhoff’s law, is analogous to cy- clic analysis used to evaluate engine performance in mechanical systems. Vir- tually all material thermodynamic applications can be analyzed by TL analy- sis. TL analysis is a method of organization whereby the known state of a system is combined with thermodynamic properties of materials obtainable from the literature to calculate system properties in another state. TL analysis isa powerful analytical tool because it divides a problem into parts and graphi- cally structures it in such a manner as to provide the student with a clearly depicted solution path. In addition, TL analysis eliminates some of the need for memorizing detailed formulas because it can be used to derive them. Ex- tensive use of TL analysis is a unique feature of this book. The first chapter introduces thermodynamics as a science and defines im- portant terms. The thermodynamic loop is introduced in the second chapter. Example applications in the second chapter include constant and variable tem- perature enthalpy calculations and supercooling. The Second and Third Laws of Thermodynamics are introduced in the third chapter and the concept of entropy as a stability criterion is discussed. Example applications include con- stant and variable temperature calculations and supercooling. Finally, ther- modynamic efficiency is defined graphically from a temperature-entropy (T- S) diagram. The fourth chapter is devoted to Gibbs free energy, stability crite- tia, and introduction of the Ellingham diagram. Example TL applications in- clude variable temperature and pressure equilibrium calculations for closed xiTHERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS systems, The chapter includes the application of free energy stability criteria to the same supercooling problems presented in Chapters 2 and 3. A compari- son with entropy stability criteria illustrates the simplicity of Gibbs free en- ergy calculations in analyzing reactions at equilibrium. Chapter 4 concludes with numerous thermodynamic relations that are used later in the book. The fifth and sixth chapters further develop the analysis of systems at equilibrium. Chapter 5 covers systems open with respect to gaseous phases (variable gas composition), applications of the Ellingham diagram, and illustrations of tech- niques for calculating gas phase equilibria over pure condensed phases. These techniques are expanded in Chapter 6 to include variable condensed phase compositions. Chapter 6 begins by defining fugacity, thermodynamic activ- ity, and partial properties in terms of volume and then builds upon these con- cepts to define other common mixing properties. Discussion is limited to two- component systems. Partial properties are the basis upon which ideal, dilute, and regular solution models are subsequently derived. The chapter concludes with several problems including alloy oxidation, application of the Gibbs- Duhem equation, and development of Sievert’s law. Chapter 7 is devoted to the analysis of binary phase diagrams. There is a wealth of untapped informa- tion in phase diagrams and the intent of this chapter is to illustrate the utility of the TL concept in extracting, at the very least, useful estimates of partial molar properties from liquidus, solidus, and solvus equilibria. These estimates are incorporated into such applications as prediction of purity, carburizing potential, and analysis of reactions. In addition, techniques are developed for estimating the effect of pressure on phase boundaries. Finally, phase rule con- cepts are introduced. Chapter 8 introduces the concept of the equilibrium con- stant and illustrates its utility in more complex three component systems. The equilibrium constant, K,q, is generally not required to solve any of the prob- lems presented in this book. Experience has shown that the student or casual user often employs it improperly. In this connection, reliance upon computer programs to solve thermodynamic problems is left to the reader who has mas- tered basic concepts. The chapter concludes with a discussion of corrosion cell polarity. Numerous people helped the authors during the development and prepa- ration of the final draft and its accompanying solutions manual. Sincere ap- preciation goes to Dr. Russell C. Nelson, Department of Mechanical Engi- neering, University of Nebraska-Lincoln, for his review and critique of manu- script drafts. Thanks also goes to Dr. Dana J. Medlin, Department of Metallur- gical and Materials Engineering, Colorado School of Mines, for helpful com- ments on the initial draft. The authors are especially grateful to Janet L. Stracher for valuable and untiring assistance with the preliminary preparation of fig- ures and graphs and for final editing of the solutions manual. We also thank Bob Makowski, Janet Urbas, Dane Semonian, and the staff at The Minerals, Metals and Materials Society of the American Institute of Mining, Metallurgical and Petroleum Engineers for their guidance through the entire project. Finally, the authors wish to thank their families for their patience and encouragement during the many long hours devoted to writing this book. DONALD L, JOHNSON GLENN B. STRACHER xiiSYSTEMS AND UNITS The standardization of physical quantities is necessary so that measure- ments based on these quantities or combinations of them mean the same thing in various disciplines. Quantities chosen as standards represent the basic units of measurement, Basic units are selected so as to represent the smallest num- ber of physical quantities from which all others may be derived. Derived units then, are simply combinations of the basic units. Because of the variety of units used, conversions are presented in this section. The Fourteenth Conference on Weights and Measures in 1971 adopted three classes of units intemationally accepted today: (1) base units in Table SI-1, (2) derived units in Table SI-2, and (3) supplementary units (NBS Publication 330, 1972). The symbols for derived units are obtained by expressing the base and/or supplementary units with the mathematical symbols for division and multiplication. For example, the derived SI unit for force is kg-m/s? (to which is assigned the name Newton, symbolized by a capital N). Likewise, the de- rived SI unit for power is [(kg-m/s)-m]/s = (Newton-m)/s = joule/s (where joule is symbolized by a capital J). The SI system excludes using units such as the dyne (1 dyne = 10-5 N) and the erg (1 erg = 10°7 J), disapproves of using the torr [1 torr = 1 mm Hg = (101.325/760) kPa] and the calorie (1 thermochemical calorie = 4.184 J), and tolerates using the bar (1 bar = 10° Pa) and the standard atmosphere (1 atm = 101.325 kPa). Because of past and currently widespread use of the calorie, bar, and standard atmosphere by engineers and scientists, these units will be used on occasion throughout this book. U.S. Customary Units In addition to the SI system of units, the U.S. customary or British system of units is commonly used today in the United States, Great Britain, and else- where. Conversion factors between SI and U.S. customary units, given in Table CF-1, may be useful. Table SI-1: SI (Systéme International) Base Units Quantity Name. Symbol Length meter m Mass kilogram kg Time second s Thermodynamic temperature kelvin K Amount of substance mole mol Electric current ampere I xiiiTHERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS. Table SI-2: Derived SI Units Quantity SI Formula Special Symbol Special Name Area m? A _— Volume (solids) m3 Vv — Volume (liquids) 10-3 m3 L liter Density A — _— Force kg-m/s? N Newton Pressure, stress N/m? Pa pascal Pressure 101.325 kPa atm atmosphere Pressure 10° Pa _ bar Work, energy Nm J joule Power Js Ww watt Linear velocity m/s = = Linear acceleration —_m/s? _— — Electric charge Is ie coulomb Electromotive force W/I ¥ volt Table CF-1: SI and U.S. Customary Equivalents Quantity SI Unit USS. Customary Equivalent Length 25.40 mm in Length 0.3048 m ft Area 645.2 mm? in? Area 0.0929 m2 fe Volume 16.39 cm? in Volume 0.02832 m3 fe Volume liquid 0.9464 L gt (quart) Volume liquid 3.785 L gal (gallon) Mass 0.4536 kg Ib mass Mass 14.59 kg slug Mass 907.2 kg ton Force 4.448N Ib; Force 4.448 KN kip Pressure, stress 47,88 Pa Ib/ft? Pressure, stress 6.895 kPa Iby/in? (psi) Pressure, stress 6.895 MPa 1000 Iby/in? (ksi) Pressure 101,325 Pa = 1 atm ed Pressure 10° Pa= 1 bar _- Work, energy 1.3563 ft-lby Heat, energy 1054.8 J BTU (British thermal unit) Power 1,356 watts ft-lb/s Power 745.7 watts hp xivBoe RRER RERERS CHOPS ORE FAG SSE UAAESNYVO OTS SEY 38 aH? SYSTEMS, UNITS, AND NOTATION NOTATION Pressure Partial Pressure of Gas Component i Molar Volume Specific Volume (mass basis) Length Liter Density Temperature Transformation Temperature Fusion Temperature, Pure Component Degrees Centigrade Degrees Fahrenheit Degrees Kelvin Degrees Rankine or Ideal Gas Joules Kilojoules General State Function Mass Gram Kilogram Pound Mass Pound Force Work/Mol or Work/Unit Volume Heat (Transfer)/Mol Heat (Transfer)/Unit Mass Molar Potential Energy Molar Kinetic Energy Total Energy/Mol Molar Internal Energy Internal Energy (mass basis) Molar Enthalpy Molar Enthalpy Change Standard State Molar Enthalpy Change Standard State Molar Enthalpy of Formation Molar Heat of Transformation Molar Heat of Fusion, Pure Component Molar Heat of Vaporization Molar Heat of Sublimation Molar or Standard Molar Heat of Solution (Alternately, Hi") Enthalpy (mass basis) Molar Entropy Molar Entropy Change xvTHERMODYNAMIC LOOP APPLICATIONS IN MATERIALS SYSTEMS. a ASL BRRRRS > 9 3 ANB 2 £22 Sui Standard State Molar Entropy Change Standard State Molar Entropy of Formation Molar Entropy of Fusion, Pure Component Molar or Standard Molar Entropy of Solution (Alternately, 5i") Entropy (mass basis) Molar Gibbs Free Energy Molar Gibbs Free Energy Change Standard State Molar Gibbs Free Energy Change Standard State Molar Gibbs Free Energy of Formation Molar Gibbs Free Energy of Fusion Molar or Standard Molar Gibbs Free Energy of Solution (Alternately, Gi") Gibbs Free Energy (mass basis) Molar Helmholtz Free Energy or area Constant Pressure Molar Heat Capacity Constant Volume Molar Heat Capacity Constant Pressure Specific Heat Capacity (mass basis) Constant Volume Specific Heat Capacity (mass basis) Activity of Component i Activity Coefficient of Component i Product of Activities Activity Quotient Concentration of Component i Equilibrium Constant Fugacity of Component i Chemical Potential of Component i Uniaxial Stress Uniaxial Strain Solid: e.g., PbS(s) or Liquid: e.g., H,O()) or [H,O] Gas: e.g., No(g) or (N2) Superscript Prime: Used for extensive thermodynamic variables. For example, AH’ is the total enthalpy change of a substance or a reaction. Weight Fraction of Component i Volume Fraction of Component i Gram Mole, or Gram Atom Percent Parts Per Million (mass basis) Parts Per Billion (mass basis) Number of Atoms of Componenti Total Number of Atoms Avogadro’s NumberSYSTEMS, UNITS, AND NOTATION Boltzmann's Constant (R/Nay) Number of Moles of Component i Total Number of Moles Molar Mass Atomic Fraction of Component i in Condensed Phase Atomic Fraction of Component i in Gas Phase Atomic Percent Weight Percent Nonideal Solution Constants Nonideal Solution Constants Coordination Number Phases, Degrees of Freedom, and Components respec- tively: Gibbs Phase Rule Electromotive Force (EMF) Faraday’s Constant: Coulomb/equivalent(eq) Valence (eq/mol) or molar mass/equivalent mass where M/n is equivalent mass Volume Thermal Expansion Coefficient or Polymorphic Phase Isothermal Compressibility Coefficient or Polymorphic Phase Thermodynamic Efficiency SYMBOLS FOR MOLAR PROPERTIES: CHARACTERIZED Va. ie rae Na Np XuXp ve Ts" vm os BY VOLUME* Molar volume of pure components A and B respectively Partial molar volume of A and B respectively Number of moles of A and B respectively Mole fraction of A and B respectively, where Xq = nal(ng + ny), Xp = nga + ng) and X, +Xp = 1.0 Partial molar volume of mixing of A and B respectively, where V," = V, - Va and V," = Vy - Vp Molar volume of mixing where V" =X, V," + Xp 73" Partial molar excess volume of A Total Volume of Mixing where V™"’ = ny Vx" + np Vs" * (1) Identical expressions are used for thermodynamic properties other than volume. 2) Ideal properties are designated by “id” Forexample, 7," is the partial molar volume of mixing of A in liquid solution; reference is pure liquid A. (3) Phase identification is denoted with a superscript. For example, 7," is the partial molar volume of mixing of A in liquid solution; reference is pure liquid A. xviiSYSTEMS, UNITS, AND NOTATION TABLE OF PHYSICAL CONSTANTS AND CONVERSION FACTORS Ideal Gas Constant R =8.3144 joules/(mol-K) = 1.987 calories(mol-K) = 82.057 cm3-atm/(mol-K) = 0.082057 liter-atm/(mol-K) = 0.083144 liter-bar/(mol-K) = 1.987 BTU/(Ib mol R) = 0.73 atm-ft3/(b mol-R) Pressure 1 atmosphere (atm) = 760 mm Hg = 760 torr = 14.696 Ibg/in2 = 1.01325 bar = 101.325 kN/m2 = 101.325 kPa ‘Temperature: K =°C + 273.16 degrees °F = (9/5)°C + 32.00 degrees R =°F +459.67 degrees Energy Equivalents ‘1 calorie = 4.184 joules (J) = 4.184 x 107 ergs = 0.041293 liter-atm = 41.3223 [Link] = 3.0855 ft-lbg = 1.4580 x 10°3 atm-f3 = 3.9683 x 10°3 BTU Avogadro's Number Nay = 6.0232 x 1023/mol Boltzmann's Constant k =RINgy Faraday’s Constant = 95,000 coulomb/equivalent xix