This book is intended to be the text for a course in thermodynamics for undergraduate
students in chemical engineering. It has been used in this manner at the University
of Delaware for more than twenty years, originally as a course for third-year
students and currently for sophomores. I had two objectives in writing the first edition
of this book, which have been retained in the succeeding editions. The first was
to develop a modern applied thermodynamics text, especially for chemical engineering
students, that was relevant to other parts of the curriculum, specifically courses
in separations processes, chemical reactor analysis, and process design. The other
objective was to organize and present material in sufficient detail, and in such a way
that the student obtained a good understanding of the principles of thermodynamics,
and a proficiency in applying these principles to the solution of a large variety of
energy flow and equilibrium problems.
Since the first two editions largely met these goals, and the principles of thermodynamics
have not changed in the last decade, this edition is similar in structure to
the earlier ones. However, there have been three important changes in engineering
education in the recent decades. The first is the availability of powerful desktop computers.
The second is greater concerns about safety and the environment. The third
is the application of chemical engineering principles to new technology areas such
as biotechnology, polymers, solid-state processing, etc. In the current edition of this
text I have made changes to address each of these issues.
Author(s): Stanley I. Sandler
Edition: 3
Publisher: John Wiley & Sons. Inc.
Year: 1999
Language: English
Pages: XX; 772
City: New York
Title Page
Preface
Dedication
About the Author
Table of Contents
Notation
Special Notation
General Notation
Subscripts
Superscripts
Chapter 1 - INTRODUCTION
1.1 The Central Problems of Thermodynamics
1.2 A System of Units
1.3 The Equilibrium State
1.4 Pressure, Temperature, and Equilibrium
1.5 Heat, Work, and the Conservation of Energy
1.6 Specification of the Equilibrium State; Intensive and Extensive Variables; Equations of State
1.7 A Summary of Important Experimental Observations
1.8 A Comment on the Development of Thermodynamics
Problems
Chapter 2 - CONSERVATION OF MASS AND ENERGY
2.1 A General Balance Equation and Conserved Quantities
2.2 Conservation of Mass
2.3 Conservation of Energy
2.4 The Thermodynamic Properties of Matter
2.5 Applications of the Mass and Energy Balances
2.6 Conservation of Momentum
2.7 The Microscopic Equations of Change for Thermodynamics and Fluid Mechanics (Optional)
Problems
Chapter 3 - ENTROPY: AN ADDITIONAL BALANCE EQUATION
3.1 Entropy: A New Concept
3.2 The Entropy Balance and Reversibility
3.3 Heat, Work, Engines, and Entropy
3.4 Entropy Changes of Matter
3.5 Applications of the Entropy Balance
3.6 Liquefaction
3.7 Power Generation and Refrigeration Cycles
3.8 The Thermodynamics of Mechanical Explosions
3.9 The Microscopic Entropy Balance (Optional)
Problems
Chapter 4 - THE THERMODYNAMIC PROPERTIES OF REAL SUBSTANCES
4.1 Some Mathematical Preliminaries
4.2 The Evaluation of Thermodynamic Partial Derivatives
4.3 The Ideal Gas and Absolute-Temperature Scales
4.4 The Evaluation of Changes in the Thermodynamic Properties of Real Substances Accompanying a Change of State
4.5 An Example Involving the Change of State of a Real Gas
4.6 The Principle of Corresponding States
4.7 Generalized Equations of State
4.8 The Third Law of Thermodynamics
4.9 More About Thermodynamic Partial Derivatives (Optional)
Appendix A4.1 A Program for Thermodynamic PropertiesCalculations Using the Peng-Robinson Cubic Equationof State, PR1
Problems
Chapter 5 - EQUILIBRIUM AND STABILITY IN ONE-COMPONENT SYSTEMS
5.1 The Criteria for Equilibrium
5.2 Stability of Thermodynamic Systems
5.3 Phase Equilibria: Application of the Equilibrium and StabilityCriteria to the Equation of State
5.4 The Molar Gibbs Free Energy and Fugacity of a PureComponent
5.5 The Calculation of Pure Fluid-Phase Equilibrium: The Computationof Vapor Pressure from an Equation of State
5.6 The Specification of the Equilibrium Thermodynamic State of aSystem of Several Phases: The Gibbs Phase Rule for a One-Component System
5.7 Thermodynamic Properties of Phase Transitions
Problems
Chapter 6 - THE THERMODYNAMICS OF MULTICOMPONENT MIXTURES
6.1 The Thermodynamic Description of Mixtures
6.2 The Partial Molar Gibbs Free Energy and the Generalized Gibbs-Duhem Equation
6.3 A Notation for Chemical Reactions
6.4 The Equations of Change for a Multicomponent System
6.5 The Heat of Reaction and a Convention for the Thermodynamic Properties of Reacting Mixtures
6.6 The Experimental Determination of the Partial Molar Volume and Enthalpy
6.7 Criteria for Phase Equilibrium in Multicomponent Systems
6.8 The Criteria for Chemical Equilibrium, and Combined Chemical andPhase Equilibrium
6.9 The Specification of the Equilibrium Thermodynamic State of a Multicomponent, Multiphase System; the Gibbs Phase Rule
6.10 Some Concluding Remarks
Problems
Chapter 7 - THE ESTIMATION OF THE GIBBS FREE ENERGY AND FUGACITY OF A COMPONENT IN A MIXTURE
7.1 The Ideal Gas Mixture
7.2 The Partial Molar Gibbs Free Energy and Fugacity
7.3 The Ideal Mixture and Excess Mixture Properties
7.4 The Fugacity of Species in Gaseous, Liquid, and Solid Mixtures
7.5 Several Correlative Liquid Mixture (Activity Coefficient) Models
7.6 Two Predictive Activity Coefficient Models
7.7 A Corresponding States Principle for Mixtures; The Pseudocritical Constant Method
7.8 The Fugacity of Species in Nonsimple Mixtures
7.9 Some Comments on Reference and Standard States
7.10 A Combined Equation-of-State-Excess Gibbs Free EnergyModels
7.11 Electrolyte Solutions
7.12 Concluding Remarks
Appendix A7.1 A Statistical Mechanical Interpretation of the Entropy ofMixing in an Ideal Mixture
Appendix A7.2 A Program for Multicomponent Vapor-Liquid Equilibrium Calculations Using the Peng-Robinson Cubic Equation of State, VLMU
Appendix A7.3 Multicomponent Excess Gibbs Free Energy (Activity Coefficient) Models
Appendix A7.4 A Program for the Prediction of Activity Coefficients and Low Pressure Vapor-Liquid Equilibrium Using theUNIFAC Model, UNIFAC
Problems
Chapter 8 - PHASE EQUILIBRIUM IN MIXTURES
8.1 Vapor-Liquid Equilibria Using Activity Coefficient Models
Problems for Section 8.1
8.2 Vapor-Liquid Equilibria Using Equations of State
Problems for Section 8.2
8.3 The Solubility of a Gas in a Liquid
Problems for Section 8.3
8.4 The Solubility of a Liquid in a Liquid and Vapor-Liquid-Liquid Equilibrium
Problems for Section 8.4
8.5 The Solubility of a Solid in a Liquid, Gas, or Supercritical Fluid
Problems for Section 8.5
8.6 The Partitioning of a Solute Among Two Coexisting Liquid Phases; The Distribution Coefficient
Problems for Section 8.6
8.7 Freezing-Point Depression of a Solvent Due to the Presence of a Solute; the Freezing Point of Liquid Mixtures
Problems for Section 8.7
8.8 Osmotic Equilibrium and Osmotic Pressure
Problems for Section 8.8
8.9 The Phase Behavior Modeling of Chemicals in the Environment
Problems for Section 8.9
8.10 The Phase Behavior of Solid Mixtures
Problems for Section 8.10
8.11 Concluding Remarks
Additional Phase Equilibrium Problems
Chapter 9 - CHEMICAL EQUILIBRIUM AND THE BALANCE EQUATIONS FOR CHEMICALLY REACTING SYSTEMS
9.1 Chemical Equilibrium in a Single-Phase System
9.2 Heterogeneous Chemical Reactions
9.3 Chemical Equilibrium When Several Reactions Occur in a Single Phase
9.4 Combined Chemical and Phase Equilibrium
9.5 The Balance Equations for a Tank-Type Chemical Reactor
9.6 The Balance Equations for a Thbular Reactor
9.7 Overall Reactor Balance Equations and the Adiabatic Reaction Temperature
9.8 The Thermodynamics of Chemical Explosions
9.9 Introduction to Electrochemical Processes
9.10 Coupled Chemical Reactions
Appendix A9.1 A Program for the Calculation of Chemical EquilibriumConstants As a Function of Temperature, CHEMEQ
Problems
Appendices
Appendix I Conversion Factors for SI Units
Appendix II The Molar Heat Capacities of Gases in the Ideal Gas (Zero Pressure) State
Appendix III The Thermodynamic Properties of Water and Steam
Appendix IV Enthalpies and Free Energies of Formation
Appendix V Heats of Combustion
Index
