Contents
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
1.5 Real Fluids and Tabulated Properties
Example 1.3 Introduction to steam tables
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
2.1 Expansion/Contraction Work
2.4 Lost Work versus Reversibility
Example 2.1 Isothermal reversible compression of an ideal gas
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
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
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
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
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
Example 4.9 Entropy balances for steady-state composite systems
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
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
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
Chapter 5 Thermodynamics of Processes
Example 5.2 A Rankine cycle with reheat
Example 5.3 Regenerative Rankine cycle
Example 5.4 Refrigeration by vapor compression cycle
Example 5.5 Liquefaction of methane by the Linde process
5.8 Problem-Solving Strategies
Unit II Generalized Analysis of Fluid Properties
Chapter 6 Classical Thermodynamics — Generalizations for any Fluid
6.1 The Fundamental Property Relation
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
Chapter 7 Engineering Equations of State for PVT Properties
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
7.6 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
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
8.5 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
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
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
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
10.6 Relating VLE to Distillation
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
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
11.5 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
Example 11.13 Osmotic pressure of BSA
Example 11.14 Osmotic pressure and electroporation of E. coli
Chapter 12 Van Der Waals Activity Models
12.1 The van der Waals Perspective for Mixtures
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
Example 12.3 Deriving activity models involving volume fractions
Example 12.4 Scatchard-Hildebrand versus van Laar theory for methanol + benzene
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
Chapter 13 Local Composition Activity Models
Example 13.1 VLE prediction using UNIFAC activity coefficients
Example 13.2 Local compositions in a two-dimensional lattice
Example 13.3 Application of Wilson’s equation to VLE
Example 13.4 Combinatorial contribution to the activity coefficient
Example 13.5 Calculation of group mole fractions
Example 13.6 Detailed calculations of activity coefficients via UNIFAC
Example 13.7 Calculation of activity coefficients using COSMO-RS/SAC
13.7 The Molecular Basis of Solution Models
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
Example 14.4 The binary LLE algorithm using MAB and SSCED models
14.5 VLLE with Immiscible Components
Example 14.5 Steam distillation
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
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
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
Chapter 16 Advanced Phase Diagrams
16.1 Phase Behavior Sections of 3D Objects
16.2 Classification of Binary Phase Behavior
Chapter 17 Reaction Equilibria
Example 17.1 Computing the reaction coordinate
17.2 Reaction Equilibrium Constraint
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
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
Chapter 18 Electrolyte Solutions
18.1 Introduction to Electrolyte Solutions
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
18.6 Thermodynamic Network for Electrolyte Equilibria
18.7 Perspectives on Speciation
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
Example 18.8 Dissociation and solubility of fluconazole
Example 18.9 Alkaline dry-cell battery
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
18.22 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
Chapter 19 Molecular Association and Solvation
19.1 Introducing the Chemical Contribution
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
19.6 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)
19.11 Fitting the Constants for an Associating Equation of State
Appendix A Summary of Computer Programs
A.1 Programs for Pure Component Properties
A.2 Programs for Mixture Phase Equilibria
A.4 Notes on Excel Spreadsheets
B.2 Solutions to Cubic Equations
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.3 Activity Coefficient (Gamma-Phi) Methods
Appendix D Models for Process Simulators
Appendix E Themodynamic Properties
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.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)