INTRODUCTION TO CHEMICAL THERMODYNAMICS INTRODUCTION TO CHEMICAL THERMODYNAMICS Rose Marie O. Mendoza ARCLER P r e ss www.arclerpress.com Introduction to Chemical Thermodynamics Rose Marie O. Mendoza Arcler Press 2010 Winston Park Drive, 2nd Floor Oakville, ON L6H 5R7 Canada www.arclerpress.com Tel: 001-289-291-7705 001-905-616-2116 Fax: 001-289-291-7601 Email: [email protected] e-book Edition 2020 ISBN: 978-1-77407-393-3 (e-book) This book contains information obtained from highly regarded resources. Reprinted material sources are indicated and copyright remains with the original owners. Copyright for images and other graphics remains with the original owners as indicated. A Wide variety of references are listed. Reasonable efforts have been made to publish reliable data. Authors or Editors or Publish- ers are not responsible for the accuracy of the information in the published chapters or conse- quences of their use. The publisher assumes no responsibility for any damage or grievance to the persons or property arising out of the use of any materials, instructions, methods or thoughts in the book. The authors or editors and the publisher have attempted to trace the copyright holders of all material reproduced in this publication and apologize to copyright holders if permission has not been obtained. If any copyright holder has not been acknowledged, please write to us so we may rectify. Notice: Registered trademark of products or corporate names are used only for explanation and identification without intent of infringement. © 2020 Arcler Press ISBN: 978-1-77407-254-7 (Softcover) Arcler Press publishes wide variety of books and eBooks. For more information about Arcler Press and its products, visit our website at www.arclerpress.com ABOUT THE AUTHOR Dr. Rose obtained her PhD in Chemical Engineering from the University of the Philippines-Diliman in 2013. She is also a Professor in the Graduate School Department under the Master of Engineering Program at Adamson University since 2006, and is a Visiting Research Fellow at the Department of Environmental Engineering and Science, and the Department of Environmental Resource Management in Chia Nan University of Pharmacy and Science, Tainan Taiwan since 2010. She is now taking up her Post Doctorate Degree in Green Power: Hydrogen Generation and Fuel Cell Development at the University of Philippines-Diliman under the Department of Mining, Metallurgy and Materials Engineering and the University of California, Merced, USA under the Department of Mechanical Engineering. TABLE OF CONTENTS List of Figures ........................................................................................................xi List of Abbreviations ...........................................................................................xiii Preface........................................................................ ........................................xv Chapter 1 Introduction to Thermodynamics ..............................................................1 1.1. Introduction ........................................................................................2 1.2. History of Thermodynamics ................................................................5 1.3. The Four Laws of Thermodynamics ....................................................10 1.4. Applications of Thermodynamics ......................................................15 1.5. Thermal Efficiency ............................................................................16 Review Questions ...................................................................................17 References ...............................................................................................18 Chapter 2 Chemical Thermodynamics And Its Origin ..............................................21 2.1. Introduction ......................................................................................22 2.2. History of Chemical Thermodynamics...............................................25 2.3. Human Chemical Thermodynamics ..................................................29 2.4. Objectives of Chemical Thermodynamics .........................................31 2.5. Limitations of Classic Thermodynamics ............................................32 Review Questions ....................................................................................38 References ...............................................................................................39 Chapter 3 Principles of Chemical Thermodynamics ................................................41 3.1. Introduction ......................................................................................42 3.2. Thermodynamics Equilibrium ...........................................................45 3.3. Principles of Thermodynamics ..........................................................48 3.4. Kinetic Theory of Gases ....................................................................58 Review Questions ....................................................................................62 Chapter 4 Chemical Thermodynamics Laws ............................................................63 4.1. Introduction ......................................................................................64 4.2. Systems And Surroundings ................................................................65 4.3. Internal Energy ..................................................................................68 4.4. Difference Between First And Second Law Of Thermodynamics ........69 4.5. The Zeroth Law Of Thermodynamics .................................................72 4.6. The First Law Of Thermodynamics ....................................................73 4.7. The Second Law Of Thermodynamics ...............................................75 4.8. The Third Law Of Thermodynamics ...................................................78 4.9. Conclusion .......................................................................................78 Review Questions ....................................................................................79 References ...............................................................................................80 Chapter 5 Chemical Energy And Chemical Thermodynamics ..................................81 5.1. Introduction ......................................................................................82 5.2. Chemical Energy ...............................................................................85 5.3. Chemical Thermodynamics ...............................................................91 Review Questions ....................................................................................98 References ...............................................................................................99 Chapter 6 Thermodynamic Equilibrium In System .................................................101 6.1. Introduction ....................................................................................102 6.2. Types Of Thermodynamic Equilibrium ............................................104 6.3. Thermodynamic Stability ................................................................108 6.4. Thermodynamic Vs. Kinetic Stability ...............................................110 6.5. Thermodynamic Equilibrium Constant ............................................111 6.6. Theoretical Analysis On Thermodynamic Stability Of Chignolin ......112 6.7. Approach To Thermodynamic Equilibrium.......................................115 Review Questions ..................................................................................117 References .............................................................................................118 Chapter 7 Thermodynamics Of Chemical Mixtures ...............................................123 7.1. Introduction ....................................................................................124 7.2. Mixtures .........................................................................................125 7.3. Saturated States ...............................................................................127 7.4. Introduction To Calculations In Mixing ...........................................128 viii 7.5. Case Of Ideal Mixtures ..................................................................131 7.6. The Entropy In The Process Of Mixing .............................................134 Review Questions ..................................................................................140 References .............................................................................................141 Chapter 8 Chemical Thermodynamics And Biological Systems .................................................................................................143 8.1. Introduction ....................................................................................144 8.2. Role Of Chemical Thermodynamics In Living Organisms ................148 8.3. Biotechnology And Chemical Thermodynamics ..............................152 8.4. Scientific Applications of Chemical Thermodynamics in Biological Systems ...................................................................153 8.5. Some Real-Life Applications of Chemical Thermodynamics ............155 Review Questions ..................................................................................160 References .............................................................................................161 Chapter 9 Applications of Chemical Thermodynamics ..........................................165 9.1. Introduction ....................................................................................166 9.2. Application of Thermodynamics In Electrical Appliances ................167 9.3. Application of Thermodynamics In Thermal Machines And Heat Engines .........................................................................173 9.4. Application of Thermodynamics In Biotechnology ..........................176 9.5. Application of Thermodynamics In Food Processing ........................178 9.6. Conclusion .....................................................................................182 Review Questions ..................................................................................183 References .............................................................................................184 Chapter 10 Future of Chemical Engineering As A Product of Chemical Thermodynamics ...................................................................185 10.1. Introduction ..................................................................................186 10.2. Grand Challenges In Chemical Engineering ..................................187 10.3. Importance of Chemical Engineering ............................................195 10.4. Application of Chemical Engineering ............................................197 10.5. Significance of Chemical Engineering Thermodynamics ................198 Review Questions ..................................................................................202 References .............................................................................................203 Index .....................................................................................................205 ix LIST OF FIGURES Figure 1.1: Basic principles of the thermodynamics Figure 1.2: History of the thermodynamics Figure 1.3: The zeroth law of the thermodynamics Figure 1.4: The first of the thermodynamics Figure 1.5: The second law of thermodynamics Figure 2.1: The graph shows that during a chemical reaction, free energy decreases until the reactions reach equilibrium. In simple words, the curve moves based on the conditions of the reaction Figure 2.2: Josiah Willard Gibbs: His work on the thermodynamics applications was helpful in changing physical chemistry into a deductive science Figure 2.3: Barometer, one of the human thermodynamic instrument Figure 3.1: Graph shows the Carnot cycle Figure 3.2: Mechanical equilibrium Figure 3.3: Thermal equilibrium Figure 3.4: Types of systems Figure 3.5: Water enthalpy formation Figure 3.6: Gibbs free energy for spontaneous and non-spontaneous reactions Figure 3.7: Movement of gas particles Figure 4.1: Systems and surroundings in the chemical reaction process Figure 4.2: Transformation of electrical energy into light energy and heat energy Figure 4.3: Basic functioning of the first law of thermodynamics Figure 4.4: Process of entropy in the second law of thermodynamics Figure 5.1: Basic thermodynamics systems Figure 5.2: Basic thermodynamics Engine Figure 5.3: Enthalpy graph Figure 5.4: Entropy system xi Figure 6.1: Zeroth law of thermodynamics: an example in equilibrium Figure 6.2: An example of mechanical equilibrium Figure 6.3: An example of thermal equilibrium Figure 6.4: An example of chemical equilibrium: Pentacene 6-methyl equilibrium Figure 7.1: Solutions form an integral part of the chemical mixtures Figure 7.2: The mixtures may be found in natural form as in that of sugar and tea Figure 7.3: In gypsum, some substance may be found in saturated forms Figure 7.4: A separation of gases depicted in a system Figure 8.1: The involvement of the chemical thermodynamics in the biological systems have explained many phenomenon like that of metabolism Figure 8.2: The functions that take place inside a leaf are capable of denoting and explaining the Laws of Chemical Thermodynamics that are used in the biological systems Figure 8.3: Application of chemical thermodynamics in biological systems on scientific level has helped in the detection of many serious diseases Figure 8.4: The understand of the chemical thermodynamics at biological level helps in explaining the changes that takes place in the genetic codes Figure 8.5: Melting of ice explains the application of chemical thermodynamics in relation with the Biological systems in daily life Figure 9.1: Nicolas Léonard Sadi Carnot, the Father of thermodynamics Figure 9.2: Application of thermodynamics in refrigeration Figure 9.3: Representation of Carnot Heat Engine Figure 9.4: Application of thermodynamics in studying cell behavior xii