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  • 1. THERMODYNAMICSAND CHEMISTRY SECOND EDITIONHOWARD DEVOE

2. Thermodynamicsand ChemistrySecond Edition Version 4, March 2012Howard DeVoeAssociate Professor of Chemistry EmeritusUniversity of Maryland, College Park, Maryland 3. The rst edition of this book was previously published by Pearson Education, Inc. It wascopyright 2001 by Prentice-Hall, Inc.The second edition, version 4 is copyright 2012 by Howard DeVoe.This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivsLicense, whose full text is at http://creativecommons.org/licenses/by-nc-nd/3.0You are free to read, store, copy and print the PDF le for personal use. You are not allowedto alter, transform, or build upon this work, or to sell it or use it for any commercial purposewhatsoever, without the written consent of the copyright holder.The book was typeset using the LTEX typesetting system and the memoir class. Most ofAthe gures were produced with PSTricks, a related software program. The fonts are AdobeTimes, MathTime, Helvetica, and Computer Modern Typewriter.I thank the Department of Chemistry and Biochemistry, University of Maryland, CollegePark, Maryland (http://www.chem.umd.edu) for hosting the Web site for this book. Themost recent version can always be found online at http://www.chem.umd.edu/thermobookIf you are a faculty member of a chemistry or related department of a college or uni-versity, you may send a request to hdevoe@umd.edu for a complete Solutions Manualin PDF format for your personal use. In order to protect the integrity of the solutions,requests will be subject to verication of your faculty status and your agreement not toreproduce or transmit the manual in any form. 4. S HORT C ONTENTSBiographical Sketches 15Preface to the Second Edition 16From the Preface to the First Edition 171 Introduction192 Systems and Their Properties273 The First Law 564 The Second Law1025 Thermodynamic Potentials1356 The Third Law and Cryogenics1507 Pure Substances in Single Phases1648 Phase Transitions and Equilibria of Pure Substances 1939 Mixtures22310 Electrolyte Solutions28611 Reactions and Other Chemical Processes 30312 Equilibrium Conditions in Multicomponent Systems 36713 The Phase Rule and Phase Diagrams41914 Galvanic Cells 450Appendix A Denitions of the SI Base Units4714 5. S HORT C ONTENTS5Appendix B Physical Constants 472Appendix C Symbols for Physical Quantities473Appendix D Miscellaneous Abbreviations and Symbols477Appendix E Calculus Review480Appendix F Mathematical Properties of State Functions 482Appendix G Forces, Energy, and Work 487Appendix H Standard Molar Thermodynamic Properties505Appendix I Answers to Selected Problems 508Bibliography512Index 521Thermodynamics and Chemistry, second edition, version 4 2012 by Howard DeVoe. Latest version: www.chem.umd.edu/thermobook 6. C ONTENTSBiographical Sketches 15Preface to the Second Edition 16From the Preface to the First Edition 171 Introduction191.1 Units . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19 1.1.1 Amount of substance and amount . . . . . . . . . . . . . . . . . . 211.2 Quantity Calculus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 221.3 Dimensional Analysis . . . . . . . . . .. . . . . . . . . . . . . . . . . . 24Problem . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 262 Systems and Their Properties272.1 The System, Surroundings, and Boundary . . . .. . . . . . . . . . . . . . 27 2.1.1 Extensive and intensive properties . . . . . . . . . . . . . . . . . . 282.2 Phases and Physical States of Matter . . . . . . .. . . . . . . . . . . . . . 30 2.2.1 Physical states of matter . . . . . . . . .. . . . . . . . . . . . . . 30 2.2.2 Phase coexistence and phase transitions .. . . . . . . . . . . . . . 31 2.2.3 Fluids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32 2.2.4 The equation of state of a uid . . . . . .. . . . . . . . . . . . . . 33 2.2.5 Virial equations of state for pure gases . . . . . . . . . . . . . . . . 34 2.2.6 Solids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 362.3 Some Basic Properties and Their Measurement . . . . . . . . . . . . . . . 36 2.3.1 Mass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36 2.3.2 Volume . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37 2.3.3 Density . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . 38 2.3.4 Pressure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38 2.3.5 Temperature . . . . . . . . . . . . . . .. . . . . . . . . . . . . . 402.4 The State of the System . . . . . . . . . . . . . . . . . . . . . . . . . . . 45 2.4.1 State functions and independent variables. . . . . . . . . . . . . . 45 2.4.2 An example: state functions of a mixture . . . . . . . . . . . . . . 46 2.4.3 More about independent variables . . . . . . . . . . . . . . . . . . 476 7. C ONTENTS 7 2.4.4 Equilibrium states . . . . . . . . . . . . . . . . . . . . . . . . . . 48 2.4.5 Steady states . . . . . . . .. . . . . . . . . . . . . . . . . . . . . 502.5 Processes and Paths . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 502.6 The Energy of the System . . . . .. . . . . . . . . . . . . . . . . . . . . 52 2.6.1 Energy and reference frames. . . . . . . . . . . . . . . . . . . . . 53 2.6.2 Internal energy . . . . . . .. . . . . . . . . . . . . . . . . . . . . 53Problems . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . 553 The First Law 563.1 Heat, Work, and the First Law . . . . . . . . . . . . . . . . . . . . . . . . 56 3.1.1 The concept of thermodynamic work . . . . . .. . . . . . . . . . 57 3.1.2 Work coefcients and work coordinates . . . . .. . . . . . . . . . 59 3.1.3 Heat and work as path functions . . . . . . . . .. . . . . . . . . . 60 3.1.4 Heat and heating . . . . . . . . . . . . . . . . . . . . . . . . . . . 61 3.1.5 Heat capacity . . . . . . . . . . . . . . . . . . .. . . . . . . . . . 62 3.1.6 Thermal energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . 623.2 Spontaneous, Reversible, and Irreversible Processes . . . . . . . . . . . . . 64 3.2.1 Reversible processes . . . . . . . . . . . . . . . . . . . . . . . . . 64 3.2.2 Irreversible processes . . . . . . . . . . . . . . . . . . . . . . . . . 66 3.2.3 Purely mechanical processes . . . . . . . . . . .. . . . . . . . . . 663.3 Heat Transfer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67 3.3.1 Heating and cooling . . . . . . . . . . . . . . .. . . . . . . . . . 67 3.3.2 Spontaneous phase transitions . . . . . . . . . .. . . . . . . . . . 693.4 Deformation Work . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . 69 3.4.1 Gas in a cylinder-and-piston device . . . . . . .. . . . . . . . . . 70 3.4.2 Expansion work of a gas . . . . . . . . . . . . .. . . . . . . . . . 72 3.4.3 Expansion work of an isotropic phase . . . . . . . . . . . . . . . . 73 3.4.4 Generalities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 743.5 Applications of Expansion Work . . . . . . . . . . . . .. . . . . . . . . . 75 3.5.1 The internal energy of an ideal gas . . . . . . . .. . . . . . . . . . 75 3.5.2 Reversible isothermal expansion of an ideal gas .. . . . . . . . . . 75 3.5.3 Reversible adiabatic expansion of an ideal gas . . . . . . . . . . . . 75 3.5.4 Indicator diagrams . . . . . . . . . . . . . . . . . . . . . . . . . . 77 3.5.5 Spontaneous adiabatic expansion or compression . . . . . . . . . . 78 3.5.6 Free expansion of a gas into a vacuum . . . . . .. . . . . . . . . . 793.6 Work in a Gravitational Field . . . . . . . . . . . . . . . . . . . . . . . . . 803.7 Shaft Work . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . 82 3.7.1 Stirring work . . . . . . . . . . . . . . . . . . .. . . . . . . . . . 83 3.7.2 The Joule paddle wheel . . . . . . . . . . . . . . . . . . . . . . . . 843.8 Electrical Work . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86 3.8.1 Electrical work in a circuit . . . . . . . . . . . . . . . . . . . . . . 86 3.8.2 Electrical heating . . . . . . . . . . . . . . . . . . . . . . . . . . . 88 3.8.3 Electrical work with a galvanic cell . . . . . . . . . . . . . . . . . 893.9 Irreversible Work and Internal Friction . . . . . . . . . . . . . . . . . . . . 913.10 Reversible and Irreversible Processes: Generalities . . .. . . . . . . . . . 95Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . 97Thermodynamics and Chemistry, second edition, version 4 2012 by Howard DeVoe. Latest version: www.chem.umd.edu/thermobook 8. C ONTENTS 84 The Second Law 1024.1 Types of Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1024.2 Statements of the Second Law . . . . . . . . . . . . . . . . . . . . . . . . 1034.3 Concepts Developed with Carnot Engines . . . . . . . . . . . . . . . . . . 106 4.3.1 Carnot engines and Carnot cycles . . . . . . . . . . . . . . .. . . 106 4.3.2 The equivalence of the Clausius and KelvinPlanck statements. . . 109 4.3.3 The efciency of a Carnot engine . . . . . . . . . . . . . . .. . . 111 4.3.4 Thermodynamic temperature . . . . . . . . . . . . . . . . . . . . . 1144.4 Derivation of the Mathematical Statement of the Second Law . . . . . . . 116 4.4.1 The existence of the entropy function . . . . . . . . . . . . . . . . 116 4.4.2 Using reversible processes to dene the entropy . . . . . . . . . . . 120 4.4.3 Some properties of the entropy . . . . . . . . . . . . . . . . .. . . 1234.5 Irreversible Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124 4.5.1 Irreversible adiabatic processes . . . . . . . . . . . . . . . .. . . 124 4.5.2 Irreversible processes in general . . . . . . . . . . . . . . . . . . . 1254.6 Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126 4.6.1 Reversible heating . . . . . . . . . . . . . . . . . . . . . . .. . . 127 4.6.

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