Contents

Preface

Notes to Students

Acknowledgments

About the Authors

Glossary

Notation

Unit I First and Second Laws

Chapter 1 Basic Concepts

1.1 Introduction

1.2 The Molecular Nature of Energy, Temperature, and Pressure

Example 1.1 The energy derived from intermolecular potentials

Example 1.2 Intermolecular potentials for mixtures

1.3 The Molecular Nature of Entropy

1.4 Basic Concepts

1.5 Real Fluids and Tabulated Properties

Example 1.3 Introduction to steam tables

Example 1.4 Interpolation

Example 1.5 Double interpolation

Example 1.6 Double interpolation using different tables

Example 1.7 Double interpolation using Excel

Example 1.8 Quality calculations

Example 1.9 Constant volume cooling

1.6 Summary

1.7 Practice Problems

1.8 Homework Problems

Chapter 2 The Energy Balance

2.1 Expansion/Contraction Work

2.2 Shaft Work

2.3 Work Associated with Flow

2.4 Lost Work versus Reversibility

Example 2.1 Isothermal reversible compression of an ideal gas

2.5 Heat Flow

2.6 Path Properties and State Properties

Example 2.2 Work as a path function

2.7 The Closed-System Energy Balance

Example 2.3 Internal energy and heat

2.8 The Open-System, Steady-State Balance

Example 2.4 Pump work for compressing H2O

2.9 The Complete Energy Balance

2.10 Internal Energy, Enthalpy, and Heat Capacities

Example 2.5 Enthalpy change of an ideal gas: Integrating CPig(T)

Example 2.6 Enthalpy of compressed liquid

Example 2.7 Adiabatic compression of an ideal gas in a piston/cylinder

2.11 Reference States

Example 2.8 Acetone enthalpy using various reference states

2.12 Kinetic and Potential Energy

Example 2.9 Comparing changes in kinetic energy, potential energy, internal energy, and enthalpy

Example 2.10 Transformation of kinetic energy into enthalpy

2.13 Energy Balances for Process Equipment

2.14 Strategies for Solving Process Thermodynamics Problems

2.15 Closed and Steady-State Open Systems

Example 2.11 Adiabatic, reversible expansion of an ideal gas

Example 2.12 Continuous adiabatic, reversible compression of an ideal gas

Example 2.13 Continuous, isothermal, reversible compression of an ideal gas

Example 2.14 Heat loss from a turbine

2.16 Unsteady-State Open Systems

Example 2.15 Adiabatic expansion of an ideal gas from a leaky tank

Example 2.16 Adiabatically filling a tank with an ideal gas

Example 2.17 Adiabatic expansion of steam from a leaky tank

2.17 Details of Terms in the Energy Balance

2.18 Summary

2.19 Practice Problems

2.20 Homework Problems

Chapter 3 Energy Balances for Composite Systems

3.1 Heat Engines and Heat Pumps – The Carnot Cycle

Example 3.1 Analyzing heat pumps for housing

3.2 Distillation Columns

Example 3.2 Start-up for a distillation column

3.3 Introduction to Mixture Properties

3.4 Ideal Gas Mixture Properties

3.5 Mixture Properties for Ideal Solutions

Example 3.3 Condensation of a vapor stream

3.6 Energy Balance for Reacting Systems

Example 3.4 Stoichiometry and the reaction coordinate

Example 3.5 Using the reaction coordinates for simultaneous reactions

Example 3.6 Reactor energy balances

3.7 Reactions in Biological Systems

3.8 Summary

3.9 Practice Problems

3.10 Homework Problems

Chapter 4 Entropy

4.1 The Concept of Entropy

4.2 The Microscopic View of Entropy

Example 4.1 Entropy change and “lost work” in a gas expansion

Example 4.2 Stirling’s approximation in the Einstein solid

4.3 The Macroscopic View of Entropy

Example 4.3 Adiabatic, reversible expansion of steam

Example 4.4 A Carnot cycle based on steam

Example 4.5 Ideal gas entropy changes in an adiabatic, reversible expansion

Example 4.6 Ideal gas entropy change: Integrating CPig(T)

Example 4.7 Entropy generation and “lost work”

Example 4.8 Entropy generation in a temperature gradient

4.4 The Entropy Balance

Example 4.9 Entropy balances for steady-state composite systems

4.5 Internal Reversibility

4.6 Entropy Balances for Process Equipment

Example 4.10 Entropy generation by quenching

Example 4.11 Entropy in a heat exchanger

Example 4.12 Isentropic expansion in a nozzle

4.7 Turbine, Compressor, and Pump Efficiency

4.8 Visualizing Energy and Entropy Changes

4.9 Turbine Calculations

Example 4.13 Various cases of turbine outlet conditions

Example 4.14 Turbine efficiency calculation

Example 4.15 Turbine inlet calculation given efficiency and outlet

4.10 Pumps and Compressors

Example 4.16 Isothermal reversible compression of steam

Example 4.17 Compression of R134a using P-H chart

4.11 Strategies for Applying the Entropy Balance

4.12 Optimum Work and Heat Transfer

Example 4.18 Minimum heat and work of purification

4.13 The Irreversibility of Biological Life

4.14 Unsteady-State Open Systems

Example 4.19 Entropy change in a leaky tank

Example 4.20 An ideal gas leaking through a turbine (unsteady state)

4.15 The Entropy Balance in Brief

4.16 Summary

4.17 Practice Problems

4.18 Homework Problems

Chapter 5 Thermodynamics of Processes

5.1 The Carnot Steam Cycle

5.2 The Rankine Cycle

Example 5.1 Rankine cycle

5.3 Rankine Modifications

Example 5.2 A Rankine cycle with reheat

Example 5.3 Regenerative Rankine cycle

5.4 Refrigeration

Example 5.4 Refrigeration by vapor compression cycle

5.5 Liquefaction

Example 5.5 Liquefaction of methane by the Linde process

5.6 Engines

5.7 Fluid Flow

5.8 Problem-Solving Strategies

5.9 Summary

5.10 Practice Problems

5.11 Homework Problems

Unit II Generalized Analysis of Fluid Properties

Chapter 6 Classical Thermodynamics — Generalizations for any Fluid

6.1 The Fundamental Property Relation

6.2 Derivative Relations

Example 6.1 Pressure dependence of H

Example 6.2 Entropy change with respect to T at constant P

Example 6.3 Entropy as a function of T and P

Example 6.4 Entropy change for an ideal gas

Example 6.5 Entropy change for a simple nonideal gas

Example 6.6 Accounting for T and V impacts on energy

Example 6.7 The relation between Helmholtz energy and internal energy

Example 6.8 A quantum explanation of low T heat capacity

Example 6.9 Volumetric dependence of CV for ideal gas

Example 6.10 Application of the triple product relation

Example 6.11 Master equation for an ideal gas

Example 6.12 Relating CP to CV

6.3 Advanced Topics

6.4 Summary

6.5 Practice Problems

6.6 Homework Problems

Chapter 7 Engineering Equations of State for PVT Properties

7.1 Experimental Measurements

7.2 Three-Parameter Corresponding States

7.3 Generalized Compressibility Factor Charts

Example 7.1 Application of the generalized charts

7.4 The Virial Equation of State

Example 7.2 Application of the virial equation

7.5 Cubic Equations of State

7.6 Solving the Cubic Equation of State for Z

Example 7.3 Peng-Robinson solution by hand calculation

Example 7.4 The Peng-Robinson equation for molar volume

Example 7.5 Application of the Peng-Robinson equation

7.7 Implications of Real Fluid Behavior

Example 7.6 Derivatives of the Peng-Robinson equation

7.8 Matching the Critical Point

Example 7.7 Critical parameters for the van der Waals equation

7.9 The Molecular Basis of Equations of State: Concepts and Notation

Example 7.8 Estimating molecular size

Example 7.9 Characterizing molecular interactions

7.10 The Molecular Basis of Equations of State: Molecular Simulation

Example 7.10 Computing molecular collisions in 2D

Example 7.11 Equations of state from trends in molecular simulations

7.11 The Molecular Basis of Equations of State: Analytical Theories

Example 7.12 Deriving your own equation of state

7.12 Summary

7.13 Practice Problems

7.14 Homework Problems

Chapter 8 Departure Functions

8.1 The Departure Function Pathway

8.2 Internal Energy Departure Function

Example 8.1 Internal energy departure from the van der Waals equation

8.3 Entropy Departure Function

8.4 Other Departure Functions

8.5 Summary of Density-Dependent Formulas

8.6 Pressure-Dependent Formulas

8.7 Implementation of Departure Formulas

Example 8.2 Real entropy in a combustion engine

Example 8.3 Compression of methane using the virial equation

Example 8.4 Computing enthalpy and entropy departures from the Peng-Robinson equation

Example 8.5 Enthalpy departure for the Peng-Robinson equation

Example 8.6 Gibbs departure for the Peng-Robinson equation

Example 8.7 U and S departure for the Peng-Robinson equation

8.8 Reference States

Example 8.8 Enthalpy and entropy from the Peng-Robinson equation

Example 8.9 Liquefaction revisited

Example 8.10 Adiabatically filling a tank with propane

8.9 Generalized Charts for the Enthalpy Departure

8.10 Summary

8.11 Practice Problems

8.12 Homework Problems

Chapter 9 Phase Equilibrium in a Pure Fluid

9.1 Criteria for Phase Equilibrium

9.2 The Clausius-Clapeyron Equation

Example 9.1 Clausius-Clapeyron equation near or below the boiling point

9.3 Shortcut Estimation of Saturation Properties

Example 9.2 Vapor pressure interpolation

Example 9.3 Application of the shortcut vapor pressure equation

Example 9.4 General application of the Clapeyron equation

9.4 Changes in Gibbs Energy with Pressure

9.5 Fugacity and Fugacity Coefficient

9.6 Fugacity Criteria for Phase Equilibria

9.7 Calculation of Fugacity (Gases)

9.8 Calculation of Fugacity (Liquids)

Example 9.5 Vapor and liquid fugacities using the virial equation

9.9 Calculation of Fugacity (Solids)

9.10 Saturation Conditions from an Equation of State

Example 9.6 Vapor pressure from the Peng-Robinson equation

Example 9.7 Acentric factor for the van der Waals equation

Example 9.8 Vapor pressure using equal area rule

9.11 Stable Roots and Saturation Conditions

9.12 Temperature Effects on G and f

9.13 Summary

9.14 Practice Problems

9.15 Homework Problems

Unit III Fluid Phase Equilibria in Mixtures

Chapter 10 Introduction to Multicomponent Systems

10.1 Introduction to Phase Diagrams

10.2 Vapor-Liquid Equilibrium (VLE) Calculations

10.3 Binary VLE Using Raoult’s Law

10.4 Multicomponent VLE Raoult’s Law Calculations

Example 10.1 Bubble and dew temperatures and isothermal flash of ideal solutions

Example 10.2 Adiabatic flash

10.5 Emissions and Safety

10.6 Relating VLE to Distillation

10.7 Nonideal Systems

10.8 Concepts for Generalized Phase Equilibria

10.9 Mixture Properties for Ideal Gases

10.10 Mixture Properties for Ideal Solutions

10.11 The Ideal Solution Approximation and Raoult’s Law

10.12 Activity Coefficient and Fugacity Coefficient Approaches

10.13 Summary

10.14 Practice Problems

10.15 Homework Problems

Chapter 11 An Introduction to Activity Models

11.1 Modified Raoult’s Law and Excess Gibbs Energy

Example 11.1 Gibbs excess energy for system 2-propanol + water

11.2 Calculations Using Activity Coefficients

Example 11.2 VLE predictions from the Margules equation

Example 11.3 Gibbs excess characterization by matching the bubble point

Example 11.4 Predicting the Margules parameter with the MAB model

11.3 Deriving Modified Raoult’s Law

11.4 Excess Properties

11.5 Modified Raoult’s Law and Excess Gibbs Energy

11.6 Redlich-Kister and the Two-Parameter Margules Models

Example 11.5 Fitting one measurement with the two-parameter Margules equation

Example 11.6 Dew pressure using the two-parameter Margules equation

11.7 Activity Coefficients at Special Compositions

Example 11.7 Azeotrope fitting with bubble-temperature calculations

11.8 Preliminary Indications of VLLE

11.9 Fitting Activity Models to Multiple Data

Example 11.8 Fitting parameters using nonlinear least squares

11.10 Relations for Partial Molar Properties

Example 11.9 Heats of mixing with the Margules two-parameter model

11.11 Distillation and Relative Volatility of Nonideal Solutions

Example 11.10 Suspecting an azeotrope

11.12 Lewis-Randall Rule and Henry’s Law

Example 11.11 Solubility of CO2 by Henry’s Law

Example 11.12 Henry’s constant for CO2 with the MAB/SCVP+ model

11.13 Osmotic Pressure

Example 11.13 Osmotic pressure of BSA

Example 11.14 Osmotic pressure and electroporation of E. coli

11.14 Summary

11.15 Practice Problems

11.16 Homework Problems

Chapter 12 Van Der Waals Activity Models

12.1 The van der Waals Perspective for Mixtures

12.2 The van Laar Model

Example 12.1 Infinite dilution activity coefficients from the van Laar theory

12.3 Scatchard-Hildebrand Theory

Example 12.2 VLE predictions using the Scatchard-Hildebrand theory

12.4 The Flory-Huggins Model

Example 12.3 Deriving activity models involving volume fractions

Example 12.4 Scatchard-Hildebrand versus van Laar theory for methanol + benzene

Example 12.5 Polymer mixing

12.5 MOSCED and SSCED Theories

Example 12.6 Predicting VLE with the SSCED model

12.6 Molecular Perspective and VLE Predictions

12.7 Multicomponent Extensions of van der Waals’ Models

Example 12.7 Multicomponent VLE using the SSCED model

Example 12.8 Entrainer selection for gasohol production

12.8 Flory-Huggins and van der Waals Theories

12.9 Summary

12.10 Practice Problems

12.11 Homework Problems

Chapter 13 Local Composition Activity Models

Example 13.1 VLE prediction using UNIFAC activity coefficients

13.1 Local Composition Theory

Example 13.2 Local compositions in a two-dimensional lattice

13.2 Wilson’s Equation

Example 13.3 Application of Wilson’s equation to VLE

13.3 NRTL

13.4 UNIQUAC

Example 13.4 Combinatorial contribution to the activity coefficient

13.5 UNIFAC

Example 13.5 Calculation of group mole fractions

Example 13.6 Detailed calculations of activity coefficients via UNIFAC

13.6 COSMO-RS Methods

Example 13.7 Calculation of activity coefficients using COSMO-RS/SAC

13.7 The Molecular Basis of Solution Models

13.8 Summary

13.9 Important Equations

13.10 Practice Problems

13.11 Homework Problems

Chapter 14 Liquid-Liquid and Solid-Liquid Phase Equilibria

14.1 The Onset of Liquid-Liquid Instability

Example 14.1 Simple vapor-liquid-liquid equilibrium (VLLE) calculations

Example 14.2 LLE predictions using Flory-Huggins theory: Polymer mixing

14.2 Stability and Excess Gibbs Energy

14.3 Binary LLE by Graphing the Gibbs Energy of Mixing

Example 14.3 LLE predictions by graphing

14.4 LLE Using Activities

Example 14.4 The binary LLE algorithm using MAB and SSCED models

14.5 VLLE with Immiscible Components

Example 14.5 Steam distillation

14.6 Binary Phase Diagrams

14.7 Plotting Ternary LLE Data

14.8 Critical Points in Binary Liquid Mixtures

Example 14.6 Liquid-liquid critical point of the Margules one-parameter model

Example 14.7 Liquid-liquid critical point of the Flory-Huggins model

14.9 Numerical Procedures for Binary, Ternary LLE

14.10 Solid-Liquid Equilibria

Example 14.8 Variation of solid solubility with temperature

Example 14.9 Eutectic behavior of chloronitrobenzenes

Example 14.10 Eutectic behavior of benzene + phenol

Example 14.11 Precipitation by adding antisolvent

Example 14.12 Wax precipitation

14.11 Summary

14.12 Practice Problems

14.13 Homework Problems

Chapter 15 Phase Equilibria in Mixtures by an Equation of State

15.1 Mixing Rules for Equations of State

Example 15.1 The virial equation for vapor mixtures

15.2 Fugacity and Chemical Potential from an EOS

Example 15.2 K-values from the Peng-Robinson equation

15.3 Differentiation of Mixing Rules

Example 15.3 Fugacity coefficient from the virial equation

Example 15.4 Fugacity coefficient from the van der Waals equation

Example 15.5 Fugacity coefficient from the Peng-Robinson equation

15.4 VLE Calculations by an Equation of State

Example 15.6 Bubble-point pressure from the Peng-Robinson equation

Example 15.7 Isothermal flash using the Peng-Robinson equation

Example 15.8 Phase diagram for azeotropic methanol + benzene

Example 15.9 Phase diagram for nitrogen + methane

Example 15.10 Ethane + heptane phase envelopes

15.5 Strategies for Applying VLE Routines

15.6 Summary

15.7 Practice Problems

15.8 Homework Problems

Chapter 16 Advanced Phase Diagrams

16.1 Phase Behavior Sections of 3D Objects

16.2 Classification of Binary Phase Behavior

16.3 Residue Curves

16.4 Practice Problems

16.5 Homework Problems

Unit IV Reaction Equilibria

Chapter 17 Reaction Equilibria

17.1 Introduction

Example 17.1 Computing the reaction coordinate

17.2 Reaction Equilibrium Constraint

17.3 The Equilibrium Constant

17.4 The Standard State Gibbs Energy of Reaction

Example 17.2 Calculation of standard state Gibbs energy of reaction

17.5 Effects of Pressure, Inerts, and Feed Ratios

Example 17.3 Butadiene production in the presence of inerts

17.6 Determining the Spontaneity of Reactions

17.7 Temperature Dependence of Ka

Example 17.4 Equilibrium constant as a function of temperature

17.8 Shortcut Estimation of Temperature Effects

Example 17.5 Application of the shortcut van’t Hoff equation

17.9 Visualizing Multiple Equilibrium Constants

17.10 Solving Equilibria for Multiple Reactions

Example 17.6 Simultaneous reactions that can be solved by hand

Example 17.7 Solving multireaction equilibria with Excel

17.11 Driving Reactions by Chemical Coupling

Example 17.8 Chemical coupling to induce conversion

17.12 Energy Balances for Reactions

Example 17.9 Adiabatic reaction in an ammonia reactor

17.13 Liquid Components in Reactions

Example 17.10 Oligomerization of lactic acid

17.14 Solid Components in Reactions

Example 17.11 Thermal decomposition of methane

17.15 Rate Perspectives in Reaction Equilibria

17.16 Entropy Generation via Reactions

17.17 Gibbs Minimization

Example 17.12 Butadiene by Gibbs minimization

Example 17.13 Direct minimization of the Gibbs energy with Excel

Example 17.14 Pressure effects for Gibbs energy minimization

17.18 Reaction Modeling with Limited Data

17.19 Simultaneous Reaction and VLE

Example 17.15 The solvent methanol process

Example 17.16 NO2 absorption

17.20 Summary

17.21 Practice Problems

17.22 Homework Problems

Chapter 18 Electrolyte Solutions

18.1 Introduction to Electrolyte Solutions

18.2 Colligative Properties

Example 18.1 Freezing point depression

Example 18.2 Example of osmotic pressure

Example 18.3 Example of boiling point elevation

18.3 Speciation and the Dissociation Constant

18.4 Concentration Scales and Standard States

18.5 The Definition of pH

18.6 Thermodynamic Network for Electrolyte Equilibria

18.7 Perspectives on Speciation

18.8 Acids and Bases

Example 18.4 Dissociation of fluconazole

18.9 Sillèn Diagram Solution Method

Example 18.5 Sillèn diagram for HOAc and NaOAc

Example 18.6 Phosphate salt and strong acid

Example 18.7 Distribution of species in glycine solution

18.10 Applications

Example 18.8 Dissociation and solubility of fluconazole

18.11 Redox Reactions

Example 18.9 Alkaline dry-cell battery

18.12 Biological Reactions

Example 18.10 ATP hydrolysis

Example 18.11 Biological fuel cell

18.13 Nonideal Electrolyte Solutions: Background

18.14 Overview of Model Development

18.15 The Extended Debye-Hückel Activity Model

18.16 Gibbs Energies for Electrolytes

18.17 Transformed Biological Gibbs Energies and Apparent Equilibrium Constants

Example 18.12 Gibbs energy of formation for ATP

18.18 Coupled Multireaction and Phase Equilibria

Example 18.13 Chlorine + water electrolyte solutions

18.19 Mean Ionic Activity Coefficients

18.20 Extending Activity Calculations to High Concentrations

18.21 Summary

18.22 Supplement 1: Interconversion of Concentration Scales

18.23 Supplement 2: Relation of Apparent Chemical Potential to Species Potentials

18.24 Supplement 3: Standard States

18.25 Supplement 4: Conversion of Equilibrium Constants

18.26 Practice Problems

18.27 Homework Problems

Chapter 19 Molecular Association and Solvation

19.1 Introducing the Chemical Contribution

19.2 Equilibrium Criteria

19.3 Balance Equations for Binary Systems

19.4 Ideal Chemical Theory for Binary Systems

Example 19.1 Compressibility factors in associating/solvating systems

Example 19.2 Dimerization of carboxylic acids

Example 19.3 Activity coefficients in a solvated system

19.5 Chemical-Physical Theory

19.6 Wertheim’s Theory for Complex Mixtures

Example 19.4 The chemical contribution to the equation of state

19.7 Mass Balances for Chain Association

Example 19.5 Molecules of H2O in a 100 ml beaker

19.8 The Chemical Contribution to the Fugacity Coefficient and Compressibility Factor

19.9 Wertheim’s Theory of Polymerization

Example 19.6 Complex fugacity for the van der Waals model

Example 19.7 More complex fugacity for the van der Waals model

19.10 Statistical Associating Fluid Theory (The SAFT Model)

Example 19.8 The SAFT model

19.11 Fitting the Constants for an Associating Equation of State

19.12 Summary

19.13 Practice Problems

19.14 Homework Problems

Appendix A Summary of Computer Programs

A.1 Programs for Pure Component Properties

A.2 Programs for Mixture Phase Equilibria

A.3 Reaction Equilibria

A.4 Notes on Excel Spreadsheets

A.5 Notes on MATLAB

A.6 Disclaimer

Appendix B Mathematics

B.1 Important Relations

B.2 Solutions to Cubic Equations

B.3 The Dirac Delta Function

Example B.1 The hard-sphere equation of state

Example B.2 The square-well equation of state

Appendix C Strategies for Solving VLE Problems

C.1 Modified Raoult’s Law Methods

C.2 EOS Methods

C.3 Activity Coefficient (Gamma-Phi) Methods

Appendix D Models for Process Simulators

D.1 Overview

D.2 Equations of State

D.3 Solution Models

D.4 Hybrid Models

D.5 Recommended Decision Tree

Appendix E Themodynamic Properties

E.1 Thermochemical Data

E.2 Latent Heats

E.3 Antoine Constants

E.4 Henry’s Constant with Water as Solvent

E.5 Dielectric Constant for Water

E.6 Dissociation Constants of Polyprotic Acids

E.7 Standard Reduction Potentials

E.8 Biochemical Data

E.9 Properties of Water

E.10 Pressure-Enthalpy Diagram for Methane

E.11 Pressure-Enthalpy Diagram for Propane

E.12 Pressure-Enthalpy Diagram for R134a (1,1,1,2-Tetraflouroethane)

Index

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