This edition first published 2014
© 2014 John Wiley & Sons, Ltd
Registered office
John Wiley & Sons Ltd, The Atrium, Southern Gate, Chichester, West Sussex, PO19 8SQ, United Kingdom
For details of our global editorial offices, for customer services and for information about how to apply for permission to reuse the copyright material in this book please see our website at www.wiley.com.
The right of the author to be identified as the author of this work has been asserted in accordance with the Copyright, Designs and Patents Act 1988.
All rights reserved. No part of this publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording or otherwise, except as permitted by the UK Copyright, Designs and Patents Act 1988, without the prior permission of the publisher.
Wiley also publishes its books in a variety of electronic formats. Some content that appears in print may not be available in electronic books.
Designations used by companies to distinguish their products are often claimed as trademarks. All brand names and product names used in this book are trade names, service marks, trademarks or registered trademarks of their respective owners. The publisher is not associated with any product or vendor mentioned in this book.
Limit of Liability/Disclaimer of Warranty: While the publisher and author have used their best efforts in preparing this book, they make no representations or warranties with respect to the accuracy or completeness of the contents of this book and specifically disclaim any implied warranties of merchantability or fitness for a particular purpose. It is sold on the understanding that the publisher is not engaged in rendering professional services and neither the publisher nor the author shall be liable for damages arising herefrom. If professional advice or other expert assistance is required, the services of a competent professional should be sought.
The advice and strategies contained herein may not be suitable for every situation. In view of ongoing research, equipment modifications, changes in governmental regulations, and the constant flow of information relating to the use of experimental reagents, equipment, and devices, the reader is urged to review and evaluate the information provided in the package insert or instructions for each chemical, piece of equipment, reagent, or device for, among other things, any changes in the instructions or indication of usage and for added warnings and precautions. The fact that an organization or Website is referred to in this work as a citation and/or a potential source of further information does not mean that the author or the publisher endorses the information the organization or Website may provide or recommendations it may make. Further, readers should be aware that Internet Websites listed in this work may have changed or disappeared between when this work was written and when it is read. No warranty may be created or extended by any promotional statements for this work. Neither the publisher nor the author shall be liable for any damages arising herefrom.
Library of Congress Cataloging-in-Publication Data
Poirier, Bill, author.
A conceptual guide to thermodynamics / Bill Poirier.
pages cm
Includes index.
ISBN 978-1-118-84053-5 (pbk.)
1. Thermodynamics. I. Title.
QC311.P757 2014
536′.7--dc23
2014024539
A catalogue record for this book is available from the British Library.
ISBN: 9781118840535
To students everywhere
Thank you for your interest in A Conceptual Guide to Thermodynamics. This book is itself a new concept of sorts, which merits some explanation.
First, a description of what this book is not. It is not a textbook; the discussion is insufficiently complete to serve as the primary text for an undergraduate thermodynamics course, and there are no problems or exercises. Neither is it a popular science or lay person’s introduction; the primary intended audience is science and engineering students. Nor is it a history of thermodynamics; though that is itself a fascinating subject, you will find little such discussion here. It is definitely not a book written to impress academic colleagues; they will not be impressed.
What this book is is a conceptual and practical guide—a companion to your primary thermodynamics textbook, meant to supplement and clarify the latter. The goal is to simultaneously improve both your fundamental understanding of the material (the “conceptual” part) and your homework and exam performance (the “practical” part), to better “get you through” your thermodynamics course. Culling from over a decade of experience teaching undergraduate physical chemistry thermodynamics at Texas Tech University, this book was written from top to bottom with the practical needs of you, the student, foremost in mind.
But why should you buy this (fairly inexpensive) supplement in addition to the (no doubt much more expensive) required textbook you have likely already purchased? There are several reasons. First, some textbooks (and some lecturers) may give short shrift to the explication of core thermodynamics concepts such as equilibrium and entropy. The likely reason is clear: there is much material to cover, and they do not want to get bogged down in lengthy explanations and potentially confusing subtleties. Some of the problems arising in this field are indeed profound and intractable; several of its brilliant but frustrated early founders ended their own lives (see Appendix A) … That said, I have learned over my years of teaching thermodynamics that dedicating a modest amount of time during the early stages to a careful (but not too rigorous) discussion of the key concepts—if done succinctly and clearly—can lead to major practical benefits for students later on.
Second, a principal advantage of this approach is that the core concepts are pretty much the same across all of the many disciplines that (with good reason!) require thermodynamics training as part of their degree plans. Thus, students of chemistry, physics, biology, geosciences, and the engineering fields, may all benefit from this book, even though the application of this fundamental science varies greatly from field to field. To this end, discipline-specific material is mostly avoided here, in favor of instruction designed to convey the general logic of how to solve thermodynamics problems. In this context, memorization per se does not really help so much, though many students are naturally inclined to fall back on this tried-and-true companion. In contrast, a conceptual understanding offers something that most students ultimately find to be far more valuable—a sense of how to approach any given problem, as opposed to that uncomfortable state of having “no clue where to begin.”
Third, in its role as a true “supplement” to your primary textbook, this book provides explicit references to the latest editions of all of the major thermodynamics texts used by each of the various disciplines listed above. A comprehensive list is provided on p. xv of this book, in the Textbook Guide section. In that section, also, terminology and notation differences between your primary text and this supplement are “translated” for your convenience. Moreover, at the start of each chapter, you will find a map that directs you to the page numbers in your primary text where corresponding material is presented. You will also find the occasional textbook-specific commentary sprinkled throughout this book. All of this is to make it as beneficial and easy for you to use as possible.
Among the range of individuals who would find this book useful, then, one might encounter:
I am extraordinarily grateful for the substantial help and encouragement I have received from various individuals, in the course of putting together this book. I must thank Texas Tech University, and especially Carol Korzeniewski, the Chair of Chemistry and Biochemistry, for supporting my faculty development leave in the fall of 2011. Much of this book was designed during this “sabbatical” period, and might not have been possible—or at least severely delayed—without it. I must also thank Gérard Parlant and the Centre national de la recherche scientifique at the Université Montpellier 2, for acting as my hosts during this period (and particularly Odile Eisenstein, for the use of her office). My wife, Anne, is also to be commended for her copious patience and understanding—particularly considering the other ways we might have spent our time in the sud de France. I thank David Tannor and Michael New for the style files used to typeset the earliest versions of the manuscript, and also Peter Wilson and Piet van Oostrum—respective authors of the changepage and fancyhdr packages, used extensively for the later versions. Of course, I am grateful to the many colleagues, educators, formal reviewers, and editors who read through those preliminary drafts, and provided much useful feedback. Above all, however, I must fervently acknowledge the many students who have urged me over the years to write such a book—without their ardor and persistent arm-twisting, it never would have happened.
Saint Mathieu de Tréviers, France Bill Poirier
December, 2011
As this book nears completion, it has become clear that I must acknowledge by name those tireless volunteers who have reviewed the entire book manuscript; their copious and insightful “notes” have resulted in an immeasurably superior final product. To Joseph Ellis, Thomas Gibson, Jeremy Maddox, Jason L. McAfee, Michele S. McAfee, Corey Petty, and Caroline Taylor, you have earned my eternal gratitude. I would also be remiss not to acknowledge two specific editors at John Wiley & Sons, who bent over backwards and went the extra mile, time and again; this book certainly would not have happened without the many efforts taken on its behalf by Sarah Higginbotham and Sarah Keegan.
The quotation on p. 78 is reprinted with permission from Y. A. Çengel and M. A. Boles, Thermodynamics: An Engineering Approach, seventh edition. Copyright © 2011 by McGraw-Hill Education. The quotations on pp. 79 and 99 are from RAFF, LIONEL M., PRINCIPLES OF PHYSICAL CHEMISTRY, 1st Edition, © 2001, pp, 170, 144. Reprinted by permission of Pearson Education, Inc., Upper Saddle River, NJ.
This book was fueled not so much by caffeine as by YES; may they make it into the Rock and Roll Hall of Fame.
Vienna, Austria Bill Poirier
October, 2013