THERMODYNAMICS
AND
CHEMISTRY
SECOND EDITION
HOWARD DEVOE
, Thermodynamics
and Chemistry
Second Edition
Version 7a, December 2015
Howard DeVoe
Associate Professor of Chemistry Emeritus
University of Maryland, College Park, Maryland
,The first edition of this book was previously published by Pearson Education, Inc. It was
copyright ©2001 by Prentice-Hall, Inc.
The second edition, version 7a is copyright ©2015 by Howard DeVoe.
This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivs
License, whose full text is at
http://creativecommons.org/licenses/by-nc-nd/3.0
You are free to read, store, copy and print the PDF file for personal use. You are not allowed
to alter, transform, or build upon this work, or to sell it or use it for any commercial purpose
whatsoever, without the written consent of the copyright holder.
The book was typeset using the LATEX typesetting system and the memoir class. Most of
the figures were produced with PSTricks, a related software program. The fonts are Adobe
Times, MathTime, Helvetica, and Computer Modern Typewriter.
I thank the Department of Chemistry and Biochemistry, University of Maryland, College
Park, Maryland (http://www.chem.umd.edu) for hosting the Web site for this book. The
most recent version can always be found online at
http://www.chem.umd.edu/thermobook
If you are a faculty member of a chemistry or related department of a college or uni-
versity, you may send a request to for a complete Solutions Manual
in PDF format for your personal use. In order to protect the integrity of the solutions,
requests will be subject to verification of your faculty status and your agreement not to
reproduce or transmit the manual in any form.
, S HORT C ONTENTS
Biographical Sketches 15
Preface to the Second Edition 16
From the Preface to the First Edition 17
1 Introduction 19
2 Systems and Their Properties 27
3 The First Law 56
4 The Second Law 101
5 Thermodynamic Potentials 134
6 The Third Law and Cryogenics 149
7 Pure Substances in Single Phases 163
8 Phase Transitions and Equilibria of Pure Substances 192
9 Mixtures 222
10 Electrolyte Solutions 285
11 Reactions and Other Chemical Processes 302
12 Equilibrium Conditions in Multicomponent Systems 366
13 The Phase Rule and Phase Diagrams 418
14 Galvanic Cells 449
Appendix A Definitions of the SI Base Units 470
4
AND
CHEMISTRY
SECOND EDITION
HOWARD DEVOE
, Thermodynamics
and Chemistry
Second Edition
Version 7a, December 2015
Howard DeVoe
Associate Professor of Chemistry Emeritus
University of Maryland, College Park, Maryland
,The first edition of this book was previously published by Pearson Education, Inc. It was
copyright ©2001 by Prentice-Hall, Inc.
The second edition, version 7a is copyright ©2015 by Howard DeVoe.
This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivs
License, whose full text is at
http://creativecommons.org/licenses/by-nc-nd/3.0
You are free to read, store, copy and print the PDF file for personal use. You are not allowed
to alter, transform, or build upon this work, or to sell it or use it for any commercial purpose
whatsoever, without the written consent of the copyright holder.
The book was typeset using the LATEX typesetting system and the memoir class. Most of
the figures were produced with PSTricks, a related software program. The fonts are Adobe
Times, MathTime, Helvetica, and Computer Modern Typewriter.
I thank the Department of Chemistry and Biochemistry, University of Maryland, College
Park, Maryland (http://www.chem.umd.edu) for hosting the Web site for this book. The
most recent version can always be found online at
http://www.chem.umd.edu/thermobook
If you are a faculty member of a chemistry or related department of a college or uni-
versity, you may send a request to for a complete Solutions Manual
in PDF format for your personal use. In order to protect the integrity of the solutions,
requests will be subject to verification of your faculty status and your agreement not to
reproduce or transmit the manual in any form.
, S HORT C ONTENTS
Biographical Sketches 15
Preface to the Second Edition 16
From the Preface to the First Edition 17
1 Introduction 19
2 Systems and Their Properties 27
3 The First Law 56
4 The Second Law 101
5 Thermodynamic Potentials 134
6 The Third Law and Cryogenics 149
7 Pure Substances in Single Phases 163
8 Phase Transitions and Equilibria of Pure Substances 192
9 Mixtures 222
10 Electrolyte Solutions 285
11 Reactions and Other Chemical Processes 302
12 Equilibrium Conditions in Multicomponent Systems 366
13 The Phase Rule and Phase Diagrams 418
14 Galvanic Cells 449
Appendix A Definitions of the SI Base Units 470
4
