book

Chemical Thermodynamics

Name: Chemical Thermodynamics
Author: J. Rajaram
ISBN: 9789332520172

by J. Rajaram

June 2013

Intermediate to advanced

684 pages

15h 57m

English

Pearson India

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Cover
Title Page
Contents
Dedication
Preface
List of Symbols
Chapter 1: Introduction
1.a. Scope and Limitations of Thermodynamics1.b. The Language and Methods of Thermodynamics1.c. Thermodynamic Equilibrium 1.d. Thermodynamic Processes and Paths1.e. State Functions 1.f. Thermometryl.g.l. Heatl.g.2. Workl.g.3. Energy1.h. 1. Work of Expansion1.h.2. Reversible and Irreversible Processes— Maximum Work1 .h.3. Maximum Work in a Reversible Isothermal Expansion of an Ideal Gas Questions
Chapter 2: The First Law of Thermodynamics
2.a. Principle of Conservation of Energy2.b.l. Mathematical Formulation of the First Law2.b.2. Heat Changes at Constant Volume and Constant Pressure 2.c. Heat Capacity2.d.l. Energy Content of an Ideal Gas 2.d.2. The Joule-Thomson Effect2.e. Some Relations Between Cp and Cv2.f. Calculation of AU, AH, q and w for Ideal Gases2.g. 1. Temperature Changes in Reversible Adiabatic Processes2.g.2. Pressure-Volume Relationships in Reversible Adiabatic Changes2.g.3. Relationship Between Pressure and Temperature in Reversible Adiabatic Changes2.h. Comparison of Isothennal and Adiabatic Processes2.i. Adiabatic Irreversible Expansion2.j.1. Calculation of Thermodynamic Quantities for Real Gases2.j.2. Isothermal Changes of Real Gases2.j.3. Adiabatic Reversible Expansion of a Real Gas 2.j.4. Irreversible Isothermal Expansion of a Real Gas2.j.5. Adiabatic Irreversible Expansion Questions
Chapter 3: Thermochemistry
3.a. Heat Changes in Chemical Reactions 3.b. Standard States and Conventions3.c.1. Heat (Enthalpy ) of Formation 3.c.2. Heat (Enthalpy ) of Combustion 3.c.3. Thermochemical Laws3.c.4. Phase Changes3.c.5. Heat (Enthalpy ) of Solution3.c.6. Heat (Enthalpy ) of Neutralisation3.c.7. Heats (Enthalpies) of Formation of Atoms and Ions3.c.8. Born-Haber Cycle3.c.9. Bond Energy(Enthalpy)3.d. Kirchhoff's Equation3.e. Explosions and Flames Questions
Chapter 4: The Second Law of Thermodynamics
4.a. The Need for a Second Law4.b.l. Statements4.b.2. The Efficiency of a Heat Engine4.c. Heat Pump and Refrigerator4.d. The Thermodynamic Scale of Temperature 4.e.1. Entropy4.e.2. The Evaluation of Entropy Changes 4.f. Dependence of Entropy on Variables of a System4.g. ∆s for Phase Changes 4.h. Temperature-Entropy Diagram4.i. Irreversible Processes4.j. Entropy of Mixing4.k.1. The Significance of Entropy4.k.2. Degradation of Energy4.k.3. Entropy as a Measure of Disorder4.k.4 Entropy of the Universe Questions

Chapter 5: Free Energy and Work Function
5.a.1. Entropy as a Criterion for Spontaneity5.a.2. Definition of New State Functions5.b. Variation in A and G with Volume, Temperature and Pressure5.c. Conditions for Equilibrium and Spontaneity5.d. Thermodynamic Formulae—Maxwell Relations 5.e. Thermodynamic Equations of State 5.f. Standard Free Energies5.g. The Gibbs-Helmholtz EquationQuestions
Chapter 6: The Third Law of Thermodynamics
6.a. The Nernst Heat Theorem 6.b. Calculation of Entropy 6.c. Entropy of Real Gases6.d. Applications of the Third Law6.e. Entropy Changes in Chemical ReactionsQuestions
Chapter 7: Statistical Thermodynamics
7.a. The Statistical Method7.b. The Language of Statistical Thermodynamics7.c. Statistical Thermodynamic Formulation of the Boltzmann Equation7.d. Negative Temperature7.e.1. Partition Function and Thermodynamic Functions7.e.2. Molar Partition Function 7.f. Entropy and the Third Law7.g.1. Separation of the Partition Function According to Forms of Energy7.g.2. Kinetic Theory of Gases and the Translational Kinetic Energy 7.g.3. Molar Entropy of an Ideal Monoatomic Gas (Translational Entropy)7.g.4. Diatomic Molecules—Rotational Partition Function7.g.5. Partition Function and Vibrational Energy7.g.6. Electronic Partition Function 7.g.7. Total or Combined Partition Function 7.h. Calculation of Equilibrium Constants by Using Partition Functions7.i.1. Heat Capacity7.i.2. Equipartition of Energy7.i.3. Heat Capacities from the Classical Theory7.i.4. Quantum Statistical Theory of Specific Heat7.i.5. Diatomic Molecules7.i.6. Rotational Heat Capacity for the Hydrogen Molecule7.i.7. Vibrational Contribution7.j. Heat Capacity of Solids7.k.1. Quantum Statistics7.k.2. Fermi-Dirac Statistics 7.k.3. Bose-Einstein StatisticsQuestions
Chapter 8: Partial Molar Properties
8.a. Systems of Variable Composition8.b.l. Molarity and Mol Fraction8.b.2. Molality and Mol Fraction8.c. Partial Molar Quantities8.d.l. Chemical Potential (μ) and the Gibbs-Duhem Equations8.d.2. Mixtures of Gases8.e. Alternative Definitions of Chemical Potential8.f. Variation of Chemical Potential with T and P8.g. Determination of Partial Molar Properties8.h. Differential and Integral Heats (Enthalpies) of Solution8.i. Determination of Partial Molar Properties from Apparent Molar Properties Questions
Chapter 9: Phase Equilibria
9.a. Chemical Potential and Phase Equilibria 9.b. Single Component Systems9.c. The Clausius-Clapeyron Equation9.d. Thermodynamic Derivation of the Phase Rule9.e. Applications of the Phase Rule to a Few SystemsQuestions
Chapter 10: Fugacity and Activity
10.a. Fugacity10.b.1. Methods of Detennining the Fugacity of a Real Gas10.b.2. Variation of Fugacity with Pressure10.b.3. Variation of Fugacity with Temperature10.c. Ideal Solutions and Raoult's Law 10.d. Thermodynamics of Mixing 10.e.1. Dilute Solutions10.e.2. Composition of the Vapour in Equilibrium with a Liquid 10.e.3. Deviations from Raoult's Law10.e.4. Henry's Law and the Solubility of Gases10.f. Nernst Distribution Law 10.g.1. Colligative Properties10.g.2. Lowering of Vapour Pressure 10.g.3. Elevation of the Boiling Point10.g.4. Depression of the Freezing Point10.g.5. Osmosis and Osmotic Pressure10.g.6. Association and Dissociation in Solution 10.h.l. Activity10.h.2. Choice of Standard States 10.h.3. Dependence of Activity on Temperature and Pressure10.h.4. The Activity Coefficient10.h.5. Determination of Activity and Activity Coefficients of Non-electrolytes10.h.6. Determination of the Activity of One Component from That of the Other Questions
Chapter 11: Chemical Equilibrium
11.a. The Law of Mass Action11.b. Free Energy Criterion and Reversible Reactions11.c. Free Energy and the Equilibrium Constant 11.d. Equilibrium in Ideal Gas Systems 11.e. Significance of the Equilibrium Constant11.f.1. Application of the Law of Mass Action to a Few Chemical Equilibria11.f.2. Homogeneous Equilibria11.f.3. Heterogeneous Equilibria11.g.1. Effect of External Factors on Chemical Equilibria11.g.2. Effect of Pressure on Chemical Equilibria11.g.3. Effect of Temperature on Chemical Equilibria 11.h. The Reaction Isotherm Questions
Chapter 12: Aqueous Solutions of Electrolytes
12 a. Fugacity and Activity of Electrolytes12.b.l. Mean Ionic Activity12.b.2. Mean Ionic Activity Coefficient 12.b.3. Determination of the Activities and Activity Coefficients of Strong Electrolytes12.c. Ionic Strength12.d.1. Activity Coefficients from Solubility Measurements12.d.2. Results of Activity Coefficient Measurements12.d.3. Activity Coefficients from Debye-Huckel Theory12.e.1. Applications of the Debye-Huckel Limiting Law12.e.2. Verification of the Limiting Law 12.f. Thermodynamics of Ions in SolutionQuestions
Appendix A: Thermodynamic Properties of Systems Under the Influence of Various Fields
Appendix B: Non-equilibrium Thermodynamics or Thermodynamics of Irreversible Processes
Appendix C: A Molecular Approach to Internal Energy and Enthalpy
Appendix D: A Few pplications of Quantum Statistics
Appendix E: Tables: List of Tables A to H
Endnotes
Bibliography
Copyright
Back Cover

Content preview from Chemical Thermodynamics

Chapter 5 Free Energy and Work Function

5.a.1. Entropy as a Criterion for Spontaneity

In an isolated system the internal energy is constant and any spontaneous change is accompanied by an increase in entropy. The system being isolated, cannot transfer its energy in the form of work. In order that no work of expansion occurs, it is seen that the volume of an isolated system should also be constant. Thus an isolated system may be defined as one of constant U and V and so any spontaneous change is accompanied by an increase in entropy. If we take the system and the surroundings together, we can consider it to be an isolated system and apply the criterion that the entropy of the universe must increase for any spontaneous process. Alternatively, ...

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Chemical Thermodynamics

by J. Rajaram

Chapter 5

Free Energy and Work Function

5.a.1. Entropy as a Criterion for Spontaneity

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