This book is written by Y.V.C. Rao

What is Chemical Engineering Thermodynamics?

Chemical Engineering Thermodynamics deals with the basic concepts of thermodynamics and their applications. It not only introduces thermodynamic potentials as partial Legendre transforms of internal energy, but also deals with a number of advanced methods used for predicting thermodynamic properties, fugacity, fugacity coefficients and vapor-liquid equilibrium (VLE) data using generalized equations of state and the UNIFAC methods.

The book will serve as a core textbook for the course on chemical engineering thermodynamics for undergraduate students of chemical engineering and chemical technology, and also as a reference book for graduate students and practising engineers.

About Author

Prof. Y V C Rao obtained his B.Tech. degree in Chemical Engineering from Andhra University, Visakhapatnam, and his M.Tech. and Ph.D. degrees in Chemical Engineering from the Indian Institute of Technology, Kanpur. At IIT Kanpur, Prof. Rao has been teaching thermodynamics at all levels - core, undergraduate, professional and postgraduate - since 1973. He has published several research papers in national and international journals in the areas of thermodynamics, molecular energy transfer and shock waves, and presented several papers in national and international conferences. In addition to this book, he has published three other books on thermodynamics. Prof. Rao was a Fulbright visiting research scholar at the Columbia University, New York, and is a Fellow of the Institution of Engineers and the Indian Institute of Chemical Engineers.

Content of the book

Preface

Nomenclature

I. INTRODUCTION :

1. What is Thermodynamics?

2. Macroscopic and Microscopic Approaches

3. International System of Units :

i. Base Units

ii. Derived Units

iii. Multiples and Submultiples of SI Units

iv. Convention for Writing Quantities and Units

4. Summary

Review Questions

Problems

II. BASIC CONCEPTS AND DEFINITIONS :

1. System

2. Property

3. Energy

4. Equilibrium

5. Reversible Process

6. Work

7. Heat

8. State Postulate

9. Temperature Scale

10. International Practical Temperature Scale

11. Summary

Review Questions

Problems

III. P-v-T RELATIONS OF FLUIDS

1. Phase

2. Graphical Representation of P-v-T behavior

3. Mathematical Representation of P-v-T Behavior :

i. Ideal Gas Law

ii. Van Der Waals Equation of State

iii. Beattie-Bridgman Equation of State

iv. Benedict-Webb-Rubin Equation of State

v. Redlich-Kwong Equation of State

vi. Virial Equation of State

vii. Law of Corresponding States

4. Generalized Compressibility Factor Correlation

5. Generalized Equations of State :

i. Generalized Redlich-Kwong Equation of State

ii. Soave-Redlich-Kwong Equation of State

iii. Peng-Robinson Equation of State

iv. Lee-Kesler Method

v. Generalized Virial Coefficient Correlation

6. Summary

Review Questions

Problems

IV. FIRST LAW OF THERMODYNAMICS AND ITS APPLICATIONS :

1. First law of thermodynamics

2. Consequences of the First Law of Thermodynamics

3. Control-mass Analysis :

i. Constant Volume (Isometric) Process

ii. Constant Pressure (Isobaric) Process

iii. Adiabatic Process :

a. Examples of Irreversible Adiabatic Processes

iv. Constant Internal Energy Process

v. Constant Temperature (Isothermal) Process

vi. Polytropic Process

4. Control-mass Analysis of Transient Flow Processes :

i. Charging of a Tank

ii. Discharging of a Tank

5. Control-volume Analysis

6. Throttling process

7. Control-volume Analysis of Transient Flow Processes :

i. Charging of a Tank

ii. Discharging of a Tank

8. Chemically Reacting Systems :

i. Notation for a Chemical Reaction

ii. Standard Enthalpy Change of a Chemical Reaction

iii. Standard Enthalpy of Formation

iv. Standard Enthalpy Change of Combustion

v. Effect of Temperature on the Standard Enthalpy Change of a Reaction

vi. Adiabatic Flame Temperature

9. Summary

Review Questions

Problems

V. SECOND LAW OF THERMODYNAMICS AND ITS APPLICATIONS :

1. Limitations of the First Law of Thermodynamics

2. Heat Engine and Heat Pump/Refrigerator

3. Second Law of Thermodynamics :

i. Kelvin-Planck Statement

ii. Clausius Statement

4. Criterion for Irreversibility

5. Carnot Cycle and Carnot Theorems

6. Thermodynamic Temperature Scale

7. Clausius Inequality

8. Entropy and its Calculation :

i. Entropy Change for an Ideal Gas

ii. Entropy Change for Mixing of Non-identical Ideal Gases

9. Principle of Entropy Increase

10. Second Law of Thermodynamics for a Control-volume

11. Isentropic Efficiency

12. Summary

Review Questions

Problems

VI. THERMODYNAMIC POTENTIALS :

1. Postulates

2. Intensive Properties

3. Criteria of Equilibrium :

i. Criterion of Thermal Equilibrium

ii. Criterion of Mechanical equilibrium

iii. Criterion of Chemical Equilibrium

4. Euler Relation

5. Gibbs-Duhem Relation

6. Legendre Transformation

7. Internal Energy

8. Enthalpy

9. Helmholtz Free Energy

10. Gibbs Free Energy

11. Energy Minimum Principle

12. Summary

Review Questions

Problems

VII. THERMODYNAMIC PROPERTY RELATIONS :

1. Mathematical Preliminaries

2. Maxwell Relations

3. Internal Energy :

i. Partial Derivatives Method

ii. Jacobian Method

4. Enthalpy :

i. Partial Derivatives Method

5. Entropy :

i. Partial Derivatives Method

ii. Jacobian Method

6. Difference between Heat Capacities

7. Joule-Thomson Coefficient

8. General Derivatives

9. Bridgman Table

10. Clapeyron Equation and Latent Heat of Vaporization

11. Summary

Review Questions

Problems

VIII. Thermodynamic Properties of Real Gases :

1. Thermodynamic Properties of an Ideal Gas

2. Departure Functions

3. Evaluation of Departure Functions from Equations of State

4. Evaluation of Departure Functions from Generalized Equations of State

5. Evaluation of Departure Functions from Compressibility Factor Correlation

6. Departure Functions from Virial Coefficient Correlation

7. Thermodynamic Property Tables and Diagrams

8. Summary

Review Questions

Problems

IX. MULTICOMPONENT MIXTURES :

1. Partial Molar Properties

2. Chemical Potential

3. Fugacity and Fugacity Coefficient

4. Estimation of Fugacity Coefficient for Pure Gases :

i. Fugacity Coefficient through Equation of State

ii. Fugacity Coefficient through Generalized Equations of State

iii. Fugacity Coefficient through Compressibility Factor Correlation

iv. Fugacity Coefficient through virial Coefficient Correlation

5. Thermodynamic Properties of Real Gas Mixtures :

i. Mixing Rules

ii. Prediction of P-v-T Properties of Real Gas Mixtures

iii. Prediction of Departure Functions for Real Gas Mixtures

iv. Fugacity and Fugacity Coefficient for Real Gas Mixtures

6. Fugacity of a Component in a Mixture

7. Fugacity of Liquid and Solid

8. Summary

Review Questions

Problems

X. Stability and Phase Transition in Thermodynamic Systems :

1. Stability Criteria

2. Phase Transition in a Pure Substance

3. Gibbs Phase Rule

4. Vapor Pressure of a Pure Substance

5. Summary

Review Questions

Problems

XI. PROPERTIES OF SOLUTIONS :

1. Ideal Solution

2. Phase Equilibrium in Ideal Solutions

3. Phase Diagram for Ideal Solutions

4. Phase Equilibrium Problems

5. Excess Properties

6. Gibbs-Duhem Relation

7. Excess Gibbs Free Energy Models :

i. Margules Equation

ii. Redlich-Kister Equation

iii. Wohl's Equation

iv. Van Laar Equation

v. Wilson and NRTL Equations :

a. Wilson Equation

b. Non-random Two Liquid (NRTL) Equation

6. UNIversal QUAsi Chemical (UNIQUAC) Equation

8. Prediction of Activity Coefficients-Group Contribution Methods :

i. ASOG Method

ii. UNIquac Functional Group Activity Coefficient (UNIFAC) Method

9. Henry's Law

10. Summary

Review Questions

Problems

XII. VAPOR-LIQUID EQUILIBRIUM :

1. Basic Equation for vapor-liquid equilibrium

2. Reduction of VLE data

3. VLE at Low to Moderate Pressure-Excess Gibbs Free Energy Models

4. Azeotropic Data

5. VLE at High Pressures

6. Multicomponent Vapor-Liquid Equilibria

7. Bubble Point and Dew Point Calculations

8. Thermodynamic Consistency Test of VLE Data

9. Descriptive Vapor-Liquid Equilibrium :

i. Retrograde Condensation

ii. VLE Diagrams for Binary Mixtures

10. Summary

Review Questions

Problems

XIII. DILUTE SOLUTION LAWS :

1. Nernst's Law

2. Lowering of Vapor Pressure

3. Depression of Freezing Point

4. Elevation of Boiling Point

5. Osmotic Pressure

6. Solubility of a Solid or Gas in a Liquid

7. Summary

Review Questions

Problems

XIV. CHEMICAL REACTION EQUILIBRIUM :

1. The Standard Gibbs Free Energy Change and Equilibrium Constant

2. Effect of Temperature on Equilibrium Constant

3. Homogeneous Gas Phase Reactions

4. Effect of Operating Conditions on Degree of Conversion at Equilibrium

5. Adiabatic Reaction Temperature

6. Equilibrium with Simultaneous Reactions

7. Homogeneous Liquid Phase Reactions

8. Heterogeneous Reactions

9. Summary

Review Questions

Problems

The book will serve as a core textbook for the course on chemical engineering thermodynamics for undergraduate students of chemical engineering and chemical technology, and also as a reference book for graduate students and practising engineers.

About Author

Prof. Y V C Rao obtained his B.Tech. degree in Chemical Engineering from Andhra University, Visakhapatnam, and his M.Tech. and Ph.D. degrees in Chemical Engineering from the Indian Institute of Technology, Kanpur. At IIT Kanpur, Prof. Rao has been teaching thermodynamics at all levels - core, undergraduate, professional and postgraduate - since 1973. He has published several research papers in national and international journals in the areas of thermodynamics, molecular energy transfer and shock waves, and presented several papers in national and international conferences. In addition to this book, he has published three other books on thermodynamics. Prof. Rao was a Fulbright visiting research scholar at the Columbia University, New York, and is a Fellow of the Institution of Engineers and the Indian Institute of Chemical Engineers.

Content of the book

Preface

Nomenclature

I. INTRODUCTION :

1. What is Thermodynamics?

2. Macroscopic and Microscopic Approaches

3. International System of Units :

i. Base Units

ii. Derived Units

iii. Multiples and Submultiples of SI Units

iv. Convention for Writing Quantities and Units

4. Summary

Review Questions

Problems

II. BASIC CONCEPTS AND DEFINITIONS :

1. System

2. Property

3. Energy

4. Equilibrium

5. Reversible Process

6. Work

7. Heat

8. State Postulate

9. Temperature Scale

10. International Practical Temperature Scale

11. Summary

Review Questions

Problems

III. P-v-T RELATIONS OF FLUIDS

1. Phase

2. Graphical Representation of P-v-T behavior

3. Mathematical Representation of P-v-T Behavior :

i. Ideal Gas Law

ii. Van Der Waals Equation of State

iii. Beattie-Bridgman Equation of State

iv. Benedict-Webb-Rubin Equation of State

v. Redlich-Kwong Equation of State

vi. Virial Equation of State

vii. Law of Corresponding States

4. Generalized Compressibility Factor Correlation

5. Generalized Equations of State :

i. Generalized Redlich-Kwong Equation of State

ii. Soave-Redlich-Kwong Equation of State

iii. Peng-Robinson Equation of State

iv. Lee-Kesler Method

v. Generalized Virial Coefficient Correlation

6. Summary

Review Questions

Problems

IV. FIRST LAW OF THERMODYNAMICS AND ITS APPLICATIONS :

1. First law of thermodynamics

2. Consequences of the First Law of Thermodynamics

3. Control-mass Analysis :

i. Constant Volume (Isometric) Process

ii. Constant Pressure (Isobaric) Process

iii. Adiabatic Process :

a. Examples of Irreversible Adiabatic Processes

iv. Constant Internal Energy Process

v. Constant Temperature (Isothermal) Process

vi. Polytropic Process

4. Control-mass Analysis of Transient Flow Processes :

i. Charging of a Tank

ii. Discharging of a Tank

5. Control-volume Analysis

6. Throttling process

7. Control-volume Analysis of Transient Flow Processes :

i. Charging of a Tank

ii. Discharging of a Tank

8. Chemically Reacting Systems :

i. Notation for a Chemical Reaction

ii. Standard Enthalpy Change of a Chemical Reaction

iii. Standard Enthalpy of Formation

iv. Standard Enthalpy Change of Combustion

v. Effect of Temperature on the Standard Enthalpy Change of a Reaction

vi. Adiabatic Flame Temperature

9. Summary

Review Questions

Problems

V. SECOND LAW OF THERMODYNAMICS AND ITS APPLICATIONS :

1. Limitations of the First Law of Thermodynamics

2. Heat Engine and Heat Pump/Refrigerator

3. Second Law of Thermodynamics :

i. Kelvin-Planck Statement

ii. Clausius Statement

4. Criterion for Irreversibility

5. Carnot Cycle and Carnot Theorems

6. Thermodynamic Temperature Scale

7. Clausius Inequality

8. Entropy and its Calculation :

i. Entropy Change for an Ideal Gas

ii. Entropy Change for Mixing of Non-identical Ideal Gases

9. Principle of Entropy Increase

10. Second Law of Thermodynamics for a Control-volume

11. Isentropic Efficiency

12. Summary

Review Questions

Problems

VI. THERMODYNAMIC POTENTIALS :

1. Postulates

2. Intensive Properties

3. Criteria of Equilibrium :

i. Criterion of Thermal Equilibrium

ii. Criterion of Mechanical equilibrium

iii. Criterion of Chemical Equilibrium

4. Euler Relation

5. Gibbs-Duhem Relation

6. Legendre Transformation

7. Internal Energy

8. Enthalpy

9. Helmholtz Free Energy

10. Gibbs Free Energy

11. Energy Minimum Principle

12. Summary

Review Questions

Problems

VII. THERMODYNAMIC PROPERTY RELATIONS :

1. Mathematical Preliminaries

2. Maxwell Relations

3. Internal Energy :

i. Partial Derivatives Method

ii. Jacobian Method

4. Enthalpy :

i. Partial Derivatives Method

5. Entropy :

i. Partial Derivatives Method

ii. Jacobian Method

6. Difference between Heat Capacities

7. Joule-Thomson Coefficient

8. General Derivatives

9. Bridgman Table

10. Clapeyron Equation and Latent Heat of Vaporization

11. Summary

Review Questions

Problems

VIII. Thermodynamic Properties of Real Gases :

1. Thermodynamic Properties of an Ideal Gas

2. Departure Functions

3. Evaluation of Departure Functions from Equations of State

4. Evaluation of Departure Functions from Generalized Equations of State

5. Evaluation of Departure Functions from Compressibility Factor Correlation

6. Departure Functions from Virial Coefficient Correlation

7. Thermodynamic Property Tables and Diagrams

8. Summary

Review Questions

Problems

IX. MULTICOMPONENT MIXTURES :

1. Partial Molar Properties

2. Chemical Potential

3. Fugacity and Fugacity Coefficient

4. Estimation of Fugacity Coefficient for Pure Gases :

i. Fugacity Coefficient through Equation of State

ii. Fugacity Coefficient through Generalized Equations of State

iii. Fugacity Coefficient through Compressibility Factor Correlation

iv. Fugacity Coefficient through virial Coefficient Correlation

5. Thermodynamic Properties of Real Gas Mixtures :

i. Mixing Rules

ii. Prediction of P-v-T Properties of Real Gas Mixtures

iii. Prediction of Departure Functions for Real Gas Mixtures

iv. Fugacity and Fugacity Coefficient for Real Gas Mixtures

6. Fugacity of a Component in a Mixture

7. Fugacity of Liquid and Solid

8. Summary

Review Questions

Problems

X. Stability and Phase Transition in Thermodynamic Systems :

1. Stability Criteria

2. Phase Transition in a Pure Substance

3. Gibbs Phase Rule

4. Vapor Pressure of a Pure Substance

5. Summary

Review Questions

Problems

XI. PROPERTIES OF SOLUTIONS :

1. Ideal Solution

2. Phase Equilibrium in Ideal Solutions

3. Phase Diagram for Ideal Solutions

4. Phase Equilibrium Problems

5. Excess Properties

6. Gibbs-Duhem Relation

7. Excess Gibbs Free Energy Models :

i. Margules Equation

ii. Redlich-Kister Equation

iii. Wohl's Equation

iv. Van Laar Equation

v. Wilson and NRTL Equations :

a. Wilson Equation

b. Non-random Two Liquid (NRTL) Equation

6. UNIversal QUAsi Chemical (UNIQUAC) Equation

8. Prediction of Activity Coefficients-Group Contribution Methods :

i. ASOG Method

ii. UNIquac Functional Group Activity Coefficient (UNIFAC) Method

9. Henry's Law

10. Summary

Review Questions

Problems

XII. VAPOR-LIQUID EQUILIBRIUM :

1. Basic Equation for vapor-liquid equilibrium

2. Reduction of VLE data

3. VLE at Low to Moderate Pressure-Excess Gibbs Free Energy Models

4. Azeotropic Data

5. VLE at High Pressures

6. Multicomponent Vapor-Liquid Equilibria

7. Bubble Point and Dew Point Calculations

8. Thermodynamic Consistency Test of VLE Data

9. Descriptive Vapor-Liquid Equilibrium :

i. Retrograde Condensation

ii. VLE Diagrams for Binary Mixtures

10. Summary

Review Questions

Problems

XIII. DILUTE SOLUTION LAWS :

1. Nernst's Law

2. Lowering of Vapor Pressure

3. Depression of Freezing Point

4. Elevation of Boiling Point

5. Osmotic Pressure

6. Solubility of a Solid or Gas in a Liquid

7. Summary

Review Questions

Problems

XIV. CHEMICAL REACTION EQUILIBRIUM :

1. The Standard Gibbs Free Energy Change and Equilibrium Constant

2. Effect of Temperature on Equilibrium Constant

3. Homogeneous Gas Phase Reactions

4. Effect of Operating Conditions on Degree of Conversion at Equilibrium

5. Adiabatic Reaction Temperature

6. Equilibrium with Simultaneous Reactions

7. Homogeneous Liquid Phase Reactions

8. Heterogeneous Reactions

9. Summary

Review Questions

Problems