Concise Chemical Thermodynamics Third Edition Concise Chemical Thermodynamics Third Edition A. PETERS CRC Press Taylor & Francis Group 6000 Broken Sound Parkway NW, Suite 300 Boca Raton, FL 33487-2742 © 2010 by Taylor and Francis Group, LLC CRC Press is an imprint of Taylor & Francis Group, an Informa business No claim to original U. Government works Printed in the United States of America on acid-free paper 10 9 8 7 6 5 4 3 2 1 International Standard Book Number-13: 978-1-4398-1333-1 (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.
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xv Symbols and Abbreviations.1 The Realm of Thermodynamics.2 Nature’s Driving Forces.2 Setting the Scene: Basic Ideas.1 System and Surroundings.2 Functions of State.3 Mechanical Work and Expanding Gases.4 The Absolute Temperature Scale.3 Forms of Energy and Their Interconversion.4 Forms of Renewable Energy. The First Law of Thermodynamics.1 Statement of the First Law.1 Reversible Expansion of an Ideal Gas.2 Constant-Volume Processes.3 Constant-Pressure Processes.2 A New Function: Enthalpy.1 Relationship between ΔH and ΔU.3 Uses and Conventions of ΔH.1 Enthalpy Change of Reaction.2 Standard Enthalpies of Formation.3 The Many Uses of Δf H0 Data. 35 v vi Contents Chapter 3.2 Differential Scanning Calorimetry.2 Concepts of Heat Capacity.1 Combustion and Flame Temperatures.2 Variation of Reaction Enthalpies with Temperature.1 Average Bond Dissociation Energies.2 Exothermicity: A Possible Criterion.1 Spontaneous Exothermic Processes.2 Spontaneous Processes Involving No Heat Change.3 The Second Driving Force.1 Measurement of Entropy.1 The Second Law of Thermodynamics.2 Reversibility and Entropy.1 Isothermal Expansion of Gases.2 Reversible Transfer of Heat.3 An Irreversible Change.3 Changes in Entropy with Temperature.4 An Adiabatic Compression.1 The Third Law of Thermodynamics.2 ΔS for Phase Changes.3 The Direction of Time. Free Energy: The Arbiter.1 Processes in Isolated Systems.2 Gibbs Free Energy, G.3 Gibbs Free Energy and Maximum Work.4 Some Processes in Terms of Gibbs Free Energy.3 Endothermic Chemical Processes.4 Exothermic Chemical Process.5 Standard Free Energy Changes.2 Variation of G with Gas Pressure.2 Pressure and Chemical Potential for Ideal Gases.3 Chemical Potential for Real Gases.3 The Active Mass of Pure Liquids and Solids.4 Activity of Materials in Solution.2 Solutes or Minor Components.5 A Summing Up: Activity as a Unifying Concept.6 Practical Aspects of Activity.7 Equilibrium and the Reaction Isotherm.
Equilibrium Experiments and Their Interpretation.1 The Reaction Isochore Equation.1 Le Chatelier Up to Date.2 Applications of the Isochore Equation.2 The Decomposition of the Compound Fe(OH)3.3 The High-Temperature Dissociation of Water Vapor.3 The Clapeyron Equation.3 Standard Electrode Potentials.4 Variation of Cell Electromotive Force with Activity.2 Analysis of Electromotive Force Data to Find E 0.5 Variation of Electromotive Force with Temperature. Free Energy and Industrial Processes.1 Free Energies as a Function of Temperature.1 The Gibbs-Helmholtz Equation.2 The Integrated Form of the Gibbs-Helmholtz Equation.3 Tabulated Forms of Free Energy.2 The Synthesis of Ethanol.2 Use of Activity Coefficients.2 Electrolysis of Alumina.3 Thermal Reduction of Magnesia.4 Titanium and the Kroll Process.5 Silicon Metal Production.1 Calculation of an Adiabatic Flame Temperature.2 Precipitation of Carbide and Nitride Phases from Dilute Solution in Alloy Steel.3 CVD Production of Ultrapure Silicon.4 Processing of Wastes from the Aluminum Electrolytic Furnace.5 Production of Metallurgical-Grade Silicon in an Arc (Oven) Furnace. 203 Suggested Further Reading. 211 Preface This is the third edition of a book that was first published by Dr.
The book was successful for many years and in 1994 I took up the task of writ- ing a revised second edition, which was published in 1996. Although the subject has not changed basically since the two most important publications of Gibbs in 1876 and 1878, I believe that it is necessary for a thermodynamic textbook to be up to date. Today’s students are comfortable with computers. As a result, I have written a number of new problems with the use of programs such as Mathcad or Excel in mind.
Students should graph data, explore expressions and fit experimental data, and plot functions that describe physical behavior. Also, for professionals and students who are taking graduate courses in thermo- dynamics, very good and user-friendly software are now available for their thermo- dynamic calculations. FactSage and HSC Chemistry are two of them. They were also used in the preparation of the third edition of this book.
All popular features of the previous editions are retained while new ones have been added. The main body of the text remains largely unchanged. I have added new material to several chapters. In Chapter 1, there is an extensive outlook on the world’s current energy consumption and the role of renewable energy in the future.
In Chapter 6, an example of an exothermic reaction is added. In the so-called Mond process for extracting and purifying nickel, the “battle” between enthalpy and entropy is explained as a function of temperature. In Chapter 7, it is shown how a plot of the Gibbs energy for a reaction mixture versus the extent of reaction is cal- culated with the help of Mathcad. Students are asked to do this themselves in some additional problems.
In Chapter 9, the Lambda sensor, which reduces vehicle emis- sions, is explained electrochemically with the Nernst law. In Chapters 10 and 11, the production of silicon in an arc (oven) furnace is described and calculated in detail with the aid of the professional FactSage software. After working many years with this book, I have seen students making the same mistakes over and over again in some problems. Therefore, these problems have been reworked and more hints are given.
Furthermore, new problems have been added to several chapters. The list of suggested readings has also been updated. A solutions manual that contains solutions to all exercises in the text is available as a PDF file for instructors only. I also used the opportunity to correct old typographical mistakes, and if read- ers should detect some in this new edition, please do not hesitate to contact me at: a.
I would like to thank two of my students: Marc Linssen, for preparing a usable Word file from the e-book version of the second edition, and especially Jurrie Noordijk, who did a great job by retyping all tables, preparing numerous figures, and retyping all formulas with MathType. ix x Preface I am very glad to know Prof. Klaus Hack, who is the managing director of GTT Technologies (Gesellschaft für Technische Thermochemie und –physik mbH) and professor at the Rheinisch-Westfälische Technische Hochschule in Aachen, Germany. He helped me with the preparation of Chapters 10 and 11 by providing data from the Scientific Group Thermodata Europe database, and with the computa- tions by the FactSage program.
I also am grateful for the discussions via e-mail about things I was not sure of. I also wish to thank Annti Rone and Satu Mansikka from Ouotec Research Oy company in Finland. They provided me with the latest HSC Chemistry software pro- gram for free. I used this program for numerous calculations in the third edition and I can recommend it to all instructors who teach and students who follow courses in thermodynamics.
For providing me with a photo of a silicon arc furnace for the cover of the third edition, I would like to thank Dr. Rolf Degel, general sales manager of SMS Siemag AG in Düsseldorf, Germany. And last, but not least, I would like to thank CRC Press, which has contributed to this new edition. Ir Toon Peters Heerlen, The Netherlands Preface to the Second Edition I switched to higher professional education in 1989, having worked as a secondary school teacher for four years.
I started to work as a chemistry teacher in the higher laboratory education of the Hogeschool Den Haag, where I was requested to teach thermodynamics. Since a suitable course book was not available, I was at liberty to introduce a book of my own choice on thermodynamics. This choice was easily made after comparing a number of books: The first edition of Concise Chemical Thermodynamics explained thermodynamics in a simple way without slipping into complicated mathematical deductions. In addition, the book stood out due to the many practical examples that were used to illustrate the possible applications of ther- modynamics in many disciplines.
Owing to a pending merger of the higher laboratory education of the Hogeschool Den Haag with another Hogeschool, I switched to the higher laboratory education of the Hogeschool Heerlen, now Hogeschool Limburg, in 1990. Here, again, I was asked to teach thermodynamics and was allowed to choose my own course book. As my experience with Dr. Warn’s book was extremely positive, I naturally introduced his book at my new school.
However, I had noticed that the book had not been updated since the first edition. After having used the book for five years, I had drawn up a list of suggestions and improvements which I sent to the publisher in 1994. It appeared that the publisher had intended to have the book revised for some time and was looking for a suitable candidate for the job. When I was asked to do this, I consented.
I have tried to bring the book up to date and, where necessary, to introduce improvements. Without the help of a number of people, I would not have been able to complete this task success- fully. I would like to thank Prof. Ir Erik Cordfunke and Ir Robert de Boer of the Netherlands Energy Research Foundation at Petten, who provided data for Chapters 1 and 9.
I am very grateful to Dr. Klaus Hack of GTT Technologies at Herzogenrath, Germany, who not only provided data for Chapter 11 and Appendix III but also allowed me to use the computer program MicroTherm. Furthermore, I would like to thank my colleague, Mrs. Sis Achten, whom I often bothered with English-language problems.
Finally, I would like to thank one of my students, Sjef Cremers, for typing and checking all the data used in Appendix III. Last, but not least, I would like to thank everyone at Chapman & Hall who have contributed to this new edition. Ir Toon Peters Heerlen, The Netherlands xi Preface to the First Edition Thermodynamics, like classical music, is an acquired taste. The initiation must be sensitively carried out; otherwise, the mathematical rigor, like the formal structure of the music, acts to discourage a deeper relationship.
It is sad but true that some stu- dents, both of thermodynamics and of Bach, never recover from the initial shock. In this, we are all losers.