Chemical Energy and Exergy: An Introduction to Chemical Thermodynamics for Engineers
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Table of contents
- Cover
- CONTENTSvii
- PREFACEv
- CHAPTER 1. THERMODYNAMIC STATE VARIABLES1
- 1.1. Thermodynamic systems1
- 1.2. Variables of the state2
- 1.3. Extensive and intensive variables3
- 1.4. Partial molar quantities3
- 1.5. The extent of a chemical reaction5
- CHAPTER 2. CONSERVATION OF ENERGY9
- 2.1. Energy as a physical quantity of the state9
- 2.2. Conservation of energy10
- 2.3. Internal energy U with independent variables T, V, and ξ11
- 2.4. Enthalpy H with independent variables T, p, and ξ12
- 2.5. Enthalpy and heat of reaction15
- 2.6. Enthalpy of pure substances16
- CHAPTER 3. ENTROPY AS A STATE PROPERTY19
- 3.1. Introduction to entropy19
- 3.2. Reversible and irreversible processes21
- 3.3. The creation of entropy and uncompensated heat23
- 3.4. The creation of entropy and thermodynamic potentials25
- 3.5. Affinity of irreversible processes26
- 3.6. Entropy of pure substances30
- 3.7. Entropy of heat transfer31
- 3.8. Entropy of gas expansion33
- 3.9. Entropy of mixing34
- CHAPTER 4. AFFINITY IN IRREVERSIBLE PROCESSES37
- 4.1. Affinity in chemical reactions37
- 4.2. Affinity and heat of reaction38
- 4.3. The average heat of reaction40
- 4.4. The average affinity of reaction41
- CHAPTER 5. CHEMICAL POTENTIAL45
- 5.1. Thermodynamic potentials in open systems45
- 5.2. The partial molar quantity of energy and the chemical potential46
- 5.3. Chemical potentials and the affinity of reaction47
- 5.4. Chemical potentials and thermodynamic energy functions48
- 5.5. Chemical potentials in homogeneous mixtures: the Gibbs-Duhem equation49
- 5.6. Chemical potentials of substances in ideal mixtures49
- 5.7. Activity and activity coefficient51
- 5.8. Chemical potentials of pure substances52
- 5.9. Thermodynamic potentials in ideal mixtures53
- 5.10. The unitary and mixing terms of thermodynamic potentials54
- CHAPTER 6. UNITARY AFFINITY AND EQUILIBRIUM57
- 6.1. Affinity and equilibrium in chemical reactions57
- 6.2. The unitary affinity58
- 6.3. Equilibrium constants and concentration units59
- 6.4. Equilibrium constants as a function of pressure and temperature60
- CHAPTER 7. GASES, LIQUIDS, AND SOLIDS63
- 7.1. Perfect and ideal gases63
- 7.2. Non-ideal gases65
- 7.3. Liquids and solids66
- 7.4. The state equation and thermodynamic functions of condensed substances67
- CHAPTER 8. SOLUTIONS71
- 8.1. Ideal and non-ideal solutions71
- 8.2. Perfect solutions and ideal solutions72
- 8.3. Reference systems for thermodynamic unitary quantity75
- 8.4. Thermodynamic excess functions in non-ideal solutions76
- 8.5. Units of the concentration77
- 8.6. Osmotic pressure78
- 8.7. Electrolytic solutions80
- CHAPTER 9. ELECTROCHEMICAL ENERGY83
- 9.1. Electrochemical potential of charged particles83
- 9.2. Transfer of charged particles between two condensed phases85
- 9.3. Electrode and electrode potential86
- 9.4. Electrochemical cells89
- 9.5. Equilibrium electrode potential of electronic transfer reactions92
- 9.6. Equilibrium electrode potential of ionic transfer reactions94
- 9.7. Chemical potential of hydrated ions95
- CHAPTER 10. EXERGY97
- 10.1. The concept of exergy97
- 10.2. Exergy and heat99
- 10.3. Exergy and pressure100
- 10.4. Thermal exergy of high temperature substances101
- 10.5. Thermal exergy of low temperature substances104
- 10.6. Exergy in mixing substances105
- 10.7. Chemical exergy of substances107
- 10.8. Standard chemical exergy of substances110
- 10.9. Total exergy of substances112
- 10.10. Exergy and affinity112
- CHAPTER 11. EXERGY DIAGRAM115
- 11.1. Efficiency in the use of energy115
- 11.2. Exergy balance diagram117
- 11.3. Exergy vector diagram120
- 11.4. Principles in exergy vector diagrams123
- 11.5. Exergy transfer between two processes125
- 11.6. Exergy vectors of heating-cooling processes126
- 11.7. Exergy vectors of compression-expansion processes128
- 11.8. Exergy vectors of separating-mixing processes129
- 11.9. Exergy vectors of chemical reactions129
- 11.10. Exergy transfer in chemical reactions131
- 11.11. Exergy vector diagrams of methanol synthesis134
- 11.12. Exergy vectors for electrochemical reactions137
- LIST OF SYMBOLS141
- REFERENCES145
- INDEX147
This book is a beginners introduction to chemical thermodynamics for engineers.
In the textbook efforts have been made to visualize as clearly as possible the main concepts of thermodynamic quantities such as enthalpy and entropy, thus making them more perceivable. Furthermore, intricate formulae in thermodynamics have been discussed as functionally unified sets of formulae to understand their meaning rather than to mathematically derive them in detail.
In this textbook, the affinity of irreversible processes, defined by the second law of thermodynamics, has been treated as the main subject, rather than the equilibrium of chemical reactions. The concept of affinity is applicable in general not only to the processes of chemical reactions but also to all kinds of irreversible processes.
This textbook also includes electrochemical thermodynamics in which, instead of the classical phenomenological approach, molecular science provides an advanced understanding of the reactions of charged particles such as ions and electrons at the electrodes.
Recently, engineering thermodynamics has introduced a new thermodynamic potential called exergy, which essentially is related to the concept of the affinity of irreversible processes. This textbook discusses the relation between exergy and affinity and explains the exergy balance diagram and exergy vector diagram applicable to exergy analyses in chemical manufacturing processes.
This textbook is written in the hope that the readers understand in a broad way the fundamental concepts of energy and exergy from chemical thermodynamics in practical applications. Finishing this book, the readers may easily step forward further into an advanced text of their specified line.
- Visualizes the main concepts of thermodynamics to show the meaning of the quantities and formulae.
- Focuses mainly on the affinity of irreversible processes and the related concept of exergy.
- Provides an advanced understanding of electrochemical thermodynamics.
In the textbook efforts have been made to visualize as clearly as possible the main concepts of thermodynamic quantities such as enthalpy and entropy, thus making them more perceivable. Furthermore, intricate formulae in thermodynamics have been discussed as functionally unified sets of formulae to understand their meaning rather than to mathematically derive them in detail.
In this textbook, the affinity of irreversible processes, defined by the second law of thermodynamics, has been treated as the main subject, rather than the equilibrium of chemical reactions. The concept of affinity is applicable in general not only to the processes of chemical reactions but also to all kinds of irreversible processes.
This textbook also includes electrochemical thermodynamics in which, instead of the classical phenomenological approach, molecular science provides an advanced understanding of the reactions of charged particles such as ions and electrons at the electrodes.
Recently, engineering thermodynamics has introduced a new thermodynamic potential called exergy, which essentially is related to the concept of the affinity of irreversible processes. This textbook discusses the relation between exergy and affinity and explains the exergy balance diagram and exergy vector diagram applicable to exergy analyses in chemical manufacturing processes.
This textbook is written in the hope that the readers understand in a broad way the fundamental concepts of energy and exergy from chemical thermodynamics in practical applications. Finishing this book, the readers may easily step forward further into an advanced text of their specified line.
- Visualizes the main concepts of thermodynamics to show the meaning of the quantities and formulae.
- Focuses mainly on the affinity of irreversible processes and the related concept of exergy.
- Provides an advanced understanding of electrochemical thermodynamics.