Preface 

xvi  


xxvi  

List of Important Equations 


xxix  

Converting the Earth's Resources into Useful Products 


1  (56) 


2  (1) 


3  (3) 

Balanced Chemical Reaction Equations 


6  (5) 

Example 1.1 Balanced Chemical Reaction Equation: Nitric Acid Synthesis 



Example 1.2 Balanced Chemical Reaction Equations: Adipic Acid Synthesis 



GenerationConsumption Analysis 


11  (7) 

Example 1.3 GenerationConsumption Analysis: The LeBlanc Process 



Example 1.4 GenerationConsumption Analysis: The Solvay Process 



Example 1.5 GenerationConsumption Analysis: Ammonia Synthesis 



A First Look at Material Balances and Process Economics 


18  (39) 

Mass, Moles, and Molar Mass 


19  (1) 


20  (4) 

Example 1.6 Atom Economy: LeBlanc versus Solvay 



Example 1.7 Atom Economy: Improved Synthesis of 4ADPA 




24  (2) 

Example 1.8 Process Economy: The Solvay Process 



Process Capacities and Product Values 


26  (1) 

Case Study: SixCarbon Chemistry 


27  (10) 


37  (2) 

ChemiStory: Changing Salt into Soap 


39  (1) 


40  (1) 

References and Recommended Readings 


41  (1) 


41  (16) 

Process Flows: Variables, Diagrams, Balances 


57  (112) 


58  (1) 


59  (8) 

A Brief Review of Dimensions and Units 


59  (2) 

Mass, Moles, and Composition 


61  (2) 


63  (1) 

Volume, Density, and Concentration 


64  (2) 


66  (1) 

Chemical Process Flow Sheets 


67  (8) 

InputOutput Flow Diagrams 


68  (1) 


69  (2) 

Process Flow Diagrams (PFD) 


71  (3) 

Modes of Process Operation 


74  (1) 

Process Flow Calculations 


75  (29) 


76  (2) 

Material Balance Equations 


78  (3) 

A Systematic Procedure for Process Flow Calculations 


81  (1) 

Helpful Hints for Process Flow Calculations 


82  (2) 


84  (20) 

Example 2.1 Mixers: Battery Acid Production 



Example 2.2 Reactors: Ammonia Synthesis 



Example 2.3 Separators: Fruit Juice Concentration 



Example 2.4 Splitters: Fruit Juice Processing 



Example 2.5 Elements as Components: Ibuprofen Analysis 



Example 2.6 Separation with Accumulation: Air Drying 



Example 2.7 Reaction with Accumulation: Light from a Chip 



Degree of Freedom Analysis 


104  (8) 

Example 2.8 DOF Analysis: Ammonia Synthesis 



Example 2.9 DOF Analysis: Light from a Chip 



Example 2.10 DOF Analysis: Battery Acid Production 



Example 2.11 DOF Analysis: Eat Your Greens! 



Process Flow Calculations with Multiple 


112  (57) 


112  (9) 

Example 2.12 Multiple Process Units: Toxin Accumulation 



Example 2.13 Multiple Process Units: Adipic Acid Manufacture from Glucose 



Synthesizing Block Flow Diagrams 


121  (3) 

Example 2.14 Synthesizing Block Flow Diagrams: Adipic Acid Process 




124  (1) 

Degree of Freedom Analysis for Block Flow Diagrams with Multiple Process Units 


125  (2) 

Example 2.15 DOF Analysis: Adipic Acid Production 



Case Study: Evolution of a Greener Process 


127  (9) 


136  (1) 

ChemiStory: Guano and the Guns of August 


137  (4) 


141  (1) 

References and Recommended Readings 


141  (1) 


142  (27) 

Mathematical Analysis of Material Balance Equations and Process Flow Sheets 


169  (94) 


170  (1) 

The Material Balance EquationAgain 


170  (30) 

Conservation of Mass and the Material Balance Equation 


171  (5) 

Example 3.1 Decomposition Reactions 



General Forms of the Differential Material Balance Equations 


176  (6) 

Example 3.2 Mass Balances: Sugar Dissolution 



Example 3.3 Mass Balances: Glucose Consumption in a Fermentor 



Example 3.4 Mole Balances: Manufacture of Urea 



Example 3.5 Mole Balances: Urea Manufacture from Cheaper Reactants 



Degree of Freedom Analysis 


182  (4) 

Example 3.6 DOF Analysis: Urea Synthesis from Cheaper Reactants 



Example 3.7 Differential Material Balance Equation with Multiple Chemical Reactions at Steady State: Benzene into Catechol 



General Forms of the Integral Material Balance Equations 


186  (7) 

Example 3.8 Integral Equation: Blending and Shipping 



Example 3.9 Integral Equation with Unsteady Flow: Jammin' with Cherries 




193  (7) 

Example 3.10 Integral Equation with Unsteady Flow and Chemical Reaction: Controlled Drug Release 



Example 3.11 Differential Equation with Unsteady Flow and Chemical Reaction: Glucose Utilization in a Fermentor 



Linear Equations and Chemical Reactions (Optional Section) 


200  (13) 

Linear Equations, Linear Independence, Solution Existence, and Solution Uniqueness 


201  (3) 

Using Matrices to Balance Chemical Reactions 


204  (3) 

Example 3.12 Balancing Chemical Equations with Matrix Math: Adipic Acid 



Using Matrices in GenerationConsumption Analysis 


207  (3) 

Example 3.13 GenerationConsumption Analysis Using Matrix Math: Nitric Acid Synthesis 



Using Matrices to Find Linearly Independent Chemical Equations 


210  (3) 

Linear Models of Process Flow Sheets (Optional Section) 


213  (1) 

Linear Models of Single Process Units 


214  (49) 

Example 3.14 Linear Model of a Mixer: Sweet Mix 



Example 3.15 Linear Model of a Splitter: Sweet Split 



Example 3.16 Linear Model of a Reactor: GlucoseFructose Isomerization 



Example 3.17 Linear Model of a Reactor: Multiple Reactions 



Example 3.18 Linear Model of a Separator: Sweet Solutions 




226  (8) 

Example 3.19 Linear Models with Multiple Process Units and Recycle: Taking an old Plant out of Mothballs 



Case Study: Manufacture of Nylon6,6 


234  (10) 


244  (2) 

ChemiStory: Of Toothbrushes and Hosiery 


246  (3) 


249  (1) 

References & Recommended Reading 


249  (1) 


249  (14) 

Synthesis of Reactor Flow Sheets and Selection of Reactor Process Conditions 


263  (102) 


264  (7) 

Industrially Important Chemical Reactions 


264  (2) 

Heuristics for Selecting Chemical Reactions 


266  (1) 

A Brief Review: GenerationConsumption Analysis and Atom Economy 


266  (3) 

Example 4.1 GenerationConsumption and Atom Economy: Improved Synthesis of Ibuprofen 




269  (2) 

Reactor Material Balance Equations 


271  (11) 

Reactors with Known Reaction Stoichiometry 


271  (7) 

Example 4.2 ContinuousFlow SteadyState Reactor with Known Stoichiometry: Combustion of Natural Gas 



Example 4.3 Batch Reactor with Known Reaction Stoichiometry: Ibuprofen Synthesis 



Example 4.4 Semibatch Reactor with Known Reaction Stoichiometry: Ibuprofen Synthesis 



Reactors with Unknown Reaction Stoichiometry 


278  (4) 

Example 4.5 Material Balance Equation with Elements: Combustion of Natural Gas 



Example 4.6 Mass Rates of Reaction: Microbial Degradation of Soil Contaminants 



Stream Composition and System Performance Specifications for Reactors 


282  (22) 

Stream Composition Specification: Excess and Limiting Reactants 


284  (3) 

Example 4.7 Excess Reactants: A Badly Maintained Furnace 



System Performance Specification: Fractional Conversion 


287  (3) 

Example 4.8 Fractional Conversion: Ammonia Synthesis 



Example 4.9 Effect of Conversion on Reactor Flows: Ammonia Synthesis 



Fractional Conversion and Its Effect on Reactor Flow Sheet Synthesis: Recycle 


290  (4) 

Example 4.10 Low Conversion and Recycle: Ammonia Synthesis 



Fractional Conversion and Its Effect on Reactor Flow Sheet Synthesis: Recycle and Purge 


294  (4) 

Example 4.11 Recycle with Purge: Ammonia Synthesis 



System Performance Specifications: Selectivity and Yield 


298  (6) 

Example 4.12 Selectivity and Yield Definitions: Acetaldehyde Synthesis 



Example 4.13 Using Selectivity in Process Flow Calculations: Acetaldehyde Synthesis 



Why Reactors Aren't Perfect: Chemical Equilibrium and Chemical Kinetics 


304  (61) 

The Chemical Reaction Equilibrium Constant Ka 


304  (3) 

Example 4.14 Deriving Equations for Ka: Three Cases 




307  (7) 

Example 4.15 Calculating Ka: Ethyl Acetate Synthesis 



Example 4.16 Chemical Equilibrium Considerations in Selection of Reaction Pathway: Safer Routes to Dimethyl Carbonate 



Chemical Reaction Equilibrium and Reactor Performance 


314  (9) 

Example 4.17 Reactor Performance and Ka: Ammonia Synthesis 



Example 4.18 Equilibrium Conversion as a Function of T and P: Ammonia Synthesis 



Example 4.19 Multiple Chemical Equilibria and Reactor T: NOx Formation. 



Chemical Reaction Kinetics and Reactor Performance (Optional Section) 


323  (4) 

Example 4.20 Reaction Kinetics and Reactor Performance: Vegetable Processing 



Case Study: Hydrogen and Methanol 


327  (8) 


335  (2) 

ChemiStory: Quit Bugging Me 


337  (3) 


340  (1) 

References and Recommended Readings 


340  (1) 


341  (24) 

Selection of Separation Technologies and Synthesis of Separation Flow Sheets 


365  (130) 


366  (13) 

Physical Property Differences: The Basis for All Separations 


366  (1) 

Example 5.1 Physical Property Differences: Separating Salt From Sugar 




367  (2) 

Classification of Separation Technologies 


369  (4) 

Heuristics for Selecting and Sequencing Separation Technologies 


373  (6) 

Example 5.2 Selection of Separation Technology: Separating Benzene from Toluene 



Example 5.3 Selection of Separation Technology: Cleaning up OffGas from a Printing Press 



Example 5.4 Sequencing of Separation Technologies: Aromatics and Acid 



Separator Material Balance Equations 


379  (7) 

Example 5.5 Semibatch Mechanical Separation: Filtration of Beer Solids 



Example 5.6 RateBased Separation: Membranes for Kidney Dialysis 



Stream Composition and System Performance Specifications for Separators 


386  (12) 

Example 5.7 Defining Separator Performance Specifications: Separating Benzene from Toluene 



Example 5.8 Purity and Recovery Specifications in Process Flow Calculations: Separating Benzene and Toluene 



Example 5.9 Fractional Recovery in RateBased Separations: Membranes for Kidney Dialysis 



Recycling in Separation Flow Sheets 


394  (4) 

Example 5.10 Separation with Recycle: Separating Sugar Isomers 



Why Separators Aren't Perfect: Entrainment and Equilibrium 


398  (5) 

Entrainment: Incomplete Mechanical Separation 


398  (3) 

Example 5.11 Accounting for Entrainment: Coffee Making 



Phase Equilibrium and the Equilibrium Stage 


401  (2) 

An Exhausting (but Not Exhaustive) Look at Phase Equilibrium 


403  (20) 


404  (1) 

SingleComponent Phase Equilibrium 


405  (3) 

Multicomponent Phase Equilibrium 


408  (15) 

Example 5.12 Using Raoult's Law: Dew Point and Bubble Point Temperatures of HexaneHeptane Mixtures 



EquilibriumBased Separations 


423  (72) 


425  (4) 

Example 5.13 Process Flow Calculations with LiquidSolid Equilibrium Data: Potassium Nitrate Crystallization 



Example 5.14 Entrainment Effects in EquilibriumBased Separations: Separation of Benzene and Naphthalene by Crystallization 



Evaporation, Condensation, and Equilibrium Flash 


429  (5) 

Example 5.15 Process Flow Calculations with Raoult's Law: Dehumidification of Air by Condensation 



Example 5.16 Process Flow Calculations with Raoult's Law: Equilibrium Flash of a Hexane/Heptane Mixture 



Example 5.17 VaporLiquid Separations with Nonideal Solutions: Equilibrium Flash Separation of EthanolWater Mixture 




434  (3) 

Example 5.18 The Power of Multistaging: Distillation versus Equilibrium Flash for Hexane/Heptane Separation 



Absorption, Adsorption, and Extraction 


437  (9) 

Example 5.19 Process Flow Calculations Using GasLiquid Equilibrium Data: Cleaning up Dirty Air by Absorption 



Example 5.20 Process Flow Calculations Using Adsorption Isotherms: Monoclonal Antibody Purification 



Example 5.21 Process Flow Calculations Using LiquidLiquid Distribution Coefficients: Cleanup of Wastewater Stream by Solvent Extraction 



Example 5.22 Process Flow Calculations Using Triangular Phase Diagrams: Separating Acetic Acid from Water 



Multistaged Separations Using Material Separating Agents (Optional) 


446  (5) 

Example 5.23 The Power of Multistaging: Recovery of Acetic Acid from Wastewater 



Case Study: Scrubbing Sour Gas 


451  (6) 


457  (1) 

ChemiStory: How Sweet It Is 


458  (3) 


461  (1) 

References and Recommended Readings 


462  (1) 


462  (33) 

Process Energy Calculations and Synthesis of Safe and Efficient Energy Flow Sheets 


495  (126) 


496  (8) 


496  (3) 

Energy Distribution: Electricity, Heating Fluids, and Cooling Fluids 


499  (1) 

Energy Transfer Equipment 


500  (2) 

A Brief Review of EnergyRelated Dimensions and Units 


502  (2) 

Process Energy Calculations: The Basics 


504  (3) 

The Energy Balance Equation 


504  (1) 

System Energy, Energy Flows, Specific Energy 


505  (2) 

Putting a Number on Energy: Energy Data and Model Equations 


507  (14) 

Two Forms of Energy: Kinetic and Potential 


508  (3) 

Example 6.1 Kinetic and Potential Energy: Toddler Troubles 



Example 6.2 Change in Potential Energy: Snow Melt 



Example 6.3 Change in Kinetic Energy of a Stream: Thomas Edison or Rube Goldberg? 



A Third Kind of Energy and a Convenience Function: Internal Energy and Enthalpy 


511  (1) 

Using Tables and Graphs to Find U and H 


512  (9) 

Example 6.4 Using Steam Tables to Find H: Several Cases 



Example 6.5 Using Steam Tables: Pumping Water, Compressing Steam 



Example 6.6 Comparing Kinetic, Potential, and Internal Energy: Frequent Flyer 



Example 6.7 Using EnthalpyComposition Graphs: AmmoniaWater Mixtures 



Using Model Equations to Find U and H 


521  (15) 

Example 6.8 Enthalpy Calculations: Enthalpy of Vaporization of Water at High Pressure 



Example 6.9 Enthalpy Calculations: Enthalpy of Reaction at High Temperature 




535  (1) 

Energy Flows: Heat and Work 


536  (2) 

The Energy Balance EquationAgain 


538  (2) 

Process Energy Calculations 


540  (20) 

A Systematic Procedure for Process Energy Calculations 


540  (1) 

Helpful Hints for Process Energy Calculations 


541  (1) 


542  (18) 

Example 6.10 Potential Energy into Work: Water over the Dam 



Example 6.11 Integral Energy Balance with a Closed System: Unplugging the Frozen Pipes 



Example 6.12 Temperature Change with Dissolution: Caustic Tank Safety 



Example 6.13 Simultaneous Energy and Material Balances: Mel and Dan's Lemonade Stand 



Example 6.14 Energy Balance with Equilibrium Flash: Separation of Hexane and Heptane 



Example 6.15 Energy Balance with Chemical Reaction: Adiabatic Flame Temperature 



Example 6.16 Energy Balance with Multiple Reactions: Synthesis of Acetaldehyde 



Example 6.17 UnsteadyState Heat Loss: Cooling a Batch of Sterilized Broth 



A Process Energy Sampler (Optional Section) 


560  (61) 

Work and the Engineering Bernoulli Equation 


560  (3) 

Example 6.18 The Engineering Bernoulli Equation: Sizing a Pump 



Heat and the Synthesis of Heat Exchange Networks 


563  (4) 

Example 6.19 Heat Exchanger Sizing: Steam Heating of Methanol Vapor 



Energy Conversion Processes 


567  (12) 

Example 6.20 Converting Reaction Energy to Heat: Furnace Efficiency 



Example 6.21 Converting Reaction Energy to Work: Heat Engine Analysis 



Example 6.22 Converting Reaction Energy to Work: Hydrogen Fuel Cells 



Chemical Energy and Chemical Safety: Explosions 


579  (5) 

Example 6.23 Estimating Explosive Potential: Trinitrotoluene 



Case Study: Energy Management in a Chemical Reactor 


584  (5) 


589  (2) 

ChemiStory: Get the Lead Out! 


591  (4) 


595  (1) 

References and Recommended Readings 


595  (1) 


596  (25) 
Appendix A Mathematical Methods 

621  (20) 
Appendix B Physical Properties 

641  (32) 
Appendix C Answers to Select Problems 

673  (8) 
Glossary 

681  
Index 

1  