Wednesday, June 30, 2010

Chemical Engineering Thermodynamics


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







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