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Chemical Thermodynamics

Book Description

Aimed at providing undergraduate and postgraduate students with an understanding of this subject, the book brings out the thermodynamic interrelationships by explaining its essential elements. It begins with the fundamentals and progresses to advanced concepts to enable students to appreciate the application of thermodynamics in different areas of chemistry.

Table of Contents

  1. Cover
  2. Title Page
  3. Contents
  4. Dedication
  5. Preface
  6. List of Symbols
  7. Chapter 1: Introduction
    1. 1.a. Scope and Limitations of Thermodynamics
    2. 1.b. The Language and Methods of Thermodynamics
    3. 1.c. Thermodynamic Equilibrium
    4. 1.d. Thermodynamic Processes and Paths
    5. 1.e. State Functions
    6. 1.f. Thermometry
    7. l.g.l. Heat
    8. l.g.2. Work
    9. l.g.3. Energy
    10. 1.h. 1. Work of Expansion
    11. 1.h.2. Reversible and Irreversible Processes— Maximum Work
    12. 1 .h.3. Maximum Work in a Reversible Isothermal Expansion of an Ideal Gas
    13. Questions
  8. Chapter 2: The First Law of Thermodynamics
    1. 2.a. Principle of Conservation of Energy
    2. 2.b.l. Mathematical Formulation of the First Law
    3. 2.b.2. Heat Changes at Constant Volume and Constant Pressure
    4. 2.c. Heat Capacity
    5. 2.d.l. Energy Content of an Ideal Gas
    6. 2.d.2. The Joule-Thomson Effect
    7. 2.e. Some Relations Between Cp and Cv
    8. 2.f. Calculation of AU, AH, q and w for Ideal Gases
    9. 2.g. 1. Temperature Changes in Reversible Adiabatic Processes
    10. 2.g.2. Pressure-Volume Relationships in Reversible Adiabatic Changes
    11. 2.g.3. Relationship Between Pressure and Temperature in Reversible Adiabatic Changes
    12. 2.h. Comparison of Isothennal and Adiabatic Processes
    13. 2.i. Adiabatic Irreversible Expansion
    14. 2.j.1. Calculation of Thermodynamic Quantities for Real Gases
    15. 2.j.2. Isothermal Changes of Real Gases
    16. 2.j.3. Adiabatic Reversible Expansion of a Real Gas
    17. 2.j.4. Irreversible Isothermal Expansion of a Real Gas
    18. 2.j.5. Adiabatic Irreversible Expansion
    19. Questions
  9. Chapter 3: Thermochemistry
    1. 3.a. Heat Changes in Chemical Reactions
    2. 3.b. Standard States and Conventions
    3. 3.c.1. Heat (Enthalpy ) of Formation
    4. 3.c.2. Heat (Enthalpy ) of Combustion
    5. 3.c.3. Thermochemical Laws
    6. 3.c.4. Phase Changes
    7. 3.c.5. Heat (Enthalpy ) of Solution
    8. 3.c.6. Heat (Enthalpy ) of Neutralisation
    9. 3.c.7. Heats (Enthalpies) of Formation of Atoms and Ions
    10. 3.c.8. Born-Haber Cycle
    11. 3.c.9. Bond Energy(Enthalpy)
    12. 3.d. Kirchhoff's Equation
    13. 3.e. Explosions and Flames
    14. Questions
  10. Chapter 4: The Second Law of Thermodynamics
    1. 4.a. The Need for a Second Law
    2. 4.b.l. Statements
    3. 4.b.2. The Efficiency of a Heat Engine
    4. 4.c. Heat Pump and Refrigerator
    5. 4.d. The Thermodynamic Scale of Temperature
    6. 4.e.1. Entropy
    7. 4.e.2. The Evaluation of Entropy Changes
    8. 4.f. Dependence of Entropy on Variables of a System
    9. 4.g. ∆s for Phase Changes
    10. 4.h. Temperature-Entropy Diagram
    11. 4.i. Irreversible Processes
    12. 4.j. Entropy of Mixing
    13. 4.k.1. The Significance of Entropy
    14. 4.k.2. Degradation of Energy
    15. 4.k.3. Entropy as a Measure of Disorder
    16. 4.k.4 Entropy of the Universe
    17. Questions
  11. Chapter 5: Free Energy and Work Function
    1. 5.a.1. Entropy as a Criterion for Spontaneity
    2. 5.a.2. Definition of New State Functions
    3. 5.b. Variation in A and G with Volume, Temperature and Pressure
    4. 5.c. Conditions for Equilibrium and Spontaneity
    5. 5.d. Thermodynamic Formulae—Maxwell Relations
    6. 5.e. Thermodynamic Equations of State
    7. 5.f. Standard Free Energies
    8. 5.g. The Gibbs-Helmholtz Equation
    9. Questions
  12. Chapter 6: The Third Law of Thermodynamics
    1. 6.a. The Nernst Heat Theorem
    2. 6.b. Calculation of Entropy
    3. 6.c. Entropy of Real Gases
    4. 6.d. Applications of the Third Law
    5. 6.e. Entropy Changes in Chemical Reactions
    6. Questions
  13. Chapter 7: Statistical Thermodynamics
    1. 7.a. The Statistical Method
    2. 7.b. The Language of Statistical Thermodynamics
    3. 7.c. Statistical Thermodynamic Formulation of the Boltzmann Equation
    4. 7.d. Negative Temperature
    5. 7.e.1. Partition Function and Thermodynamic Functions
    6. 7.e.2. Molar Partition Function
    7. 7.f. Entropy and the Third Law
    8. 7.g.1. Separation of the Partition Function According to Forms of Energy
    9. 7.g.2. Kinetic Theory of Gases and the Translational Kinetic Energy
    10. 7.g.3. Molar Entropy of an Ideal Monoatomic Gas (Translational Entropy)
    11. 7.g.4. Diatomic Molecules—Rotational Partition Function
    12. 7.g.5. Partition Function and Vibrational Energy
    13. 7.g.6. Electronic Partition Function
    14. 7.g.7. Total or Combined Partition Function
    15. 7.h. Calculation of Equilibrium Constants by Using Partition Functions
    16. 7.i.1. Heat Capacity
    17. 7.i.2. Equipartition of Energy
    18. 7.i.3. Heat Capacities from the Classical Theory
    19. 7.i.4. Quantum Statistical Theory of Specific Heat
    20. 7.i.5. Diatomic Molecules
    21. 7.i.6. Rotational Heat Capacity for the Hydrogen Molecule
    22. 7.i.7. Vibrational Contribution
    23. 7.j. Heat Capacity of Solids
    24. 7.k.1. Quantum Statistics
    25. 7.k.2. Fermi-Dirac Statistics
    26. 7.k.3. Bose-Einstein Statistics
    27. Questions
  14. Chapter 8: Partial Molar Properties
    1. 8.a. Systems of Variable Composition
    2. 8.b.l. Molarity and Mol Fraction
    3. 8.b.2. Molality and Mol Fraction
    4. 8.c. Partial Molar Quantities
    5. 8.d.l. Chemical Potential (μ) and the Gibbs-Duhem Equations
    6. 8.d.2. Mixtures of Gases
    7. 8.e. Alternative Definitions of Chemical Potential
    8. 8.f. Variation of Chemical Potential with T and P
    9. 8.g. Determination of Partial Molar Properties
    10. 8.h. Differential and Integral Heats (Enthalpies) of Solution
    11. 8.i. Determination of Partial Molar Properties from Apparent Molar Properties
    12. Questions
  15. Chapter 9: Phase Equilibria
    1. 9.a. Chemical Potential and Phase Equilibria
    2. 9.b. Single Component Systems
    3. 9.c. The Clausius-Clapeyron Equation
    4. 9.d. Thermodynamic Derivation of the Phase Rule
    5. 9.e. Applications of the Phase Rule to a Few Systems
    6. Questions
  16. Chapter 10: Fugacity and Activity
    1. 10.a. Fugacity
    2. 10.b.1. Methods of Detennining the Fugacity of a Real Gas
    3. 10.b.2. Variation of Fugacity with Pressure
    4. 10.b.3. Variation of Fugacity with Temperature
    5. 10.c. Ideal Solutions and Raoult's Law
    6. 10.d. Thermodynamics of Mixing
    7. 10.e.1. Dilute Solutions
    8. 10.e.2. Composition of the Vapour in Equilibrium with a Liquid
    9. 10.e.3. Deviations from Raoult's Law
    10. 10.e.4. Henry's Law and the Solubility of Gases
    11. 10.f. Nernst Distribution Law
    12. 10.g.1. Colligative Properties
    13. 10.g.2. Lowering of Vapour Pressure
    14. 10.g.3. Elevation of the Boiling Point
    15. 10.g.4. Depression of the Freezing Point
    16. 10.g.5. Osmosis and Osmotic Pressure
    17. 10.g.6. Association and Dissociation in Solution
    18. 10.h.l. Activity
    19. 10.h.2. Choice of Standard States
    20. 10.h.3. Dependence of Activity on Temperature and Pressure
    21. 10.h.4. The Activity Coefficient
    22. 10.h.5. Determination of Activity and Activity Coefficients of Non-electrolytes
    23. 10.h.6. Determination of the Activity of One Component from That of the Other
    24. Questions
  17. Chapter 11: Chemical Equilibrium
    1. 11.a. The Law of Mass Action
    2. 11.b. Free Energy Criterion and Reversible Reactions
    3. 11.c. Free Energy and the Equilibrium Constant
    4. 11.d. Equilibrium in Ideal Gas Systems
    5. 11.e. Significance of the Equilibrium Constant
    6. 11.f.1. Application of the Law of Mass Action to a Few Chemical Equilibria
    7. 11.f.2. Homogeneous Equilibria
    8. 11.f.3. Heterogeneous Equilibria
    9. 11.g.1. Effect of External Factors on Chemical Equilibria
    10. 11.g.2. Effect of Pressure on Chemical Equilibria
    11. 11.g.3. Effect of Temperature on Chemical Equilibria
    12. 11.h. The Reaction Isotherm
    13. Questions
  18. Chapter 12: Aqueous Solutions of Electrolytes
    1. 12 a. Fugacity and Activity of Electrolytes
    2. 12.b.l. Mean Ionic Activity
    3. 12.b.2. Mean Ionic Activity Coefficient
    4. 12.b.3. Determination of the Activities and Activity Coefficients of Strong Electrolytes
    5. 12.c. Ionic Strength
    6. 12.d.1. Activity Coefficients from Solubility Measurements
    7. 12.d.2. Results of Activity Coefficient Measurements
    8. 12.d.3. Activity Coefficients from Debye-Huckel Theory
    9. 12.e.1. Applications of the Debye-Huckel Limiting Law
    10. 12.e.2. Verification of the Limiting Law
    11. 12.f. Thermodynamics of Ions in Solution
    12. Questions
  19. Appendix A: Thermodynamic Properties of Systems Under the Influence of Various Fields
  20. Appendix B: Non-equilibrium Thermodynamics or Thermodynamics of Irreversible Processes
  21. Appendix C: A Molecular Approach to Internal Energy and Enthalpy
  22. Appendix D: A Few pplications of Quantum Statistics
  23. Appendix E: Tables: List of Tables A to H
  24. Endnotes
  25. Bibliography
  26. Copyright
  27. Back Cover