Essentials of Chemical Reaction Engineering

Preface xv

About the Author xxxi





Chapter 1: Mole Balances 1

1.1 The Rate of Reaction, -rA 4

1.2 The General Mole Balance Equation 8

1.3 Batch Reactors (BRs) 10

1.4 Continuous-Flow Reactors 12

1.5 Industrial Reactors 23



Chapter 2: Conversiona and Reactor Sizing 33

2.1 Definition of Conversion 34

2.2 Batch Reactor Design Equations 34

2.3 Design Equations for Flow Reactors 37

2.4 Sizing Continuous-Flow Reactors 40

2.5 Reactors in Series 49

2.6 Some Further Definitions 60



Chapter 3: Rate Laws 71

3.1 Basic Definitions 72

3.2 The Rate Law 74

3.3 The Reaction Rate Constant 85

3.4 Molecular Simulations 95

3.5 Present Status of Our Approach to Reactor Sizing and Design 99



Chapter 4: Stoichiometry 111

4.1 Batch Systems 113

4.2 Flow Systems 119

4.3 Reversible Reactions and Equilibrium Conversion 132



Chapter 5: Isothermal Reactor Design: Conversion 147

5.1 Design Structure for Isothermal Reactors 148

5.2 Batch Reactors (BRs) 152

5.3 Continuous-Stirred Tank Reactors (CSTRs) 160

5.4 Tubular Reactors 170

5.5 Pressure Drop in Reactors 177

5.6 Synthesizing the Design of a Chemical Plant 199



Chapter 6: Isothermal Reactor Design: Moles and Molar Flow Rates 217

6.1 The Molar Flow Rate Balance Algorithm 218

6.2 Mole Balances on CSTRs, PFRs, PBRs, and Batch Reactors 218

6.3 Application of the PFR Molar Flow Rate Algorithm to a Microreactor 222

6.4 Membrane Reactors 227

6.5 Unsteady-State Operation of Stirred Reactors 236

6.6 Semibatch Reactors 237



Chapter 7: Collection and Analysis of Rate Data 255

7.1 The Algorithm for Data Analysis 256

7.2 Determining the Reaction Order for Each of Two Reactants Using the Method of Excess 258

7.3 Integral Method 259

7.4 Differential Method of Analysis 263

7.5 Nonlinear Regression 271

7.6 Reaction-Rate Data from Differential Reactors 276

7.7 Experimental Planning 283



Chapter 8: Multiple Reactions 293

8.1 Definitions 294

8.2 Algorithm for Multiple Reactions 297

8.3 Parallel Reactions 300

8.4 Reactions in Series 309

8.5 Complex Reactions 319

8.6 Membrane Reactors to Improve Selectivity in Multiple Reactions 327

8.7 Sorting It All Out 332

8.8 The Fun Part 332



Chapter 9: Reaction Mechanisms, Pathways, Bioreactions, and Bioreactors 349

9.1 Active Intermediates and Nonelementary Rate Laws 350

9.2 Enzymatic Reaction Fundamentals 359

9.3 Inhibition of Enzyme Reactions 372

9.4 Bioreactors and Biosynthesis 380



Chapter 10: Catalysis and Catalytic Reactors 419

10.1 Catalysts 419

10.2 Steps in a Catalytic Reaction 425

10.3 Synthesizing a Rate Law, Mechanism, and Rate-Limiting Step 441

10.4 Heterogeneous Data Analysis for Reactor Design 457

10.5 Reaction Engineering in Microelectronic Fabrication 467

10.6 Model Discrimination 472

10.7 Catalyst Deactivation 475

10.8 Reactors That Can Be Used to Help Offset Catalyst Decay 485



Chapter 11: Nonisothermal Reactor Design-The Steady-State Energy Balance and Adiabatic PFR Applications 515

11.1 Rationale 516

11.2 The Energy Balance 517

11.3 The User-Friendly Energy Balance Equations 525

11.4 Adiabatic Operation 531

11.5 Adiabatic Equilibrium Conversion 541

11.6 Reactor Staging with Interstage Cooling or Heating 546

11.7 Optimum Feed Temperature 550



Chapter 12: Steady-State Nonisothermal Reactor Design-Flow Reactors with Heat Exchange 565

12.1 Steady-State Tubular Reactor with Heat Exchange 566

12.2 Balance on the Heat-Transfer Fluid 569

12.3 Algorithm for PFR/PBR Design with Heat Effects 572

12.4 CSTR with Heat Effects 592

12.5 Multiple Steady States (MSS) 602

12.6 Nonisothermal Multiple Chemical Reactions 609

12.7 Radial and Axial Variations in a Tubular Reactor 624

12.8 Safety 632



Chapter 13: Unsteady-State Nonisothermal Reactor Design 661

13.1 The Unsteady-State Energy Balance 662

13.2 Energy Balance on Batch Reactors (BRs) 664

13.3 Batch and Semibatch Reactors with a Heat Exchanger 679

13.4 Nonisothermal Multiple Reactions 690



Appendix A: Numerical Techniques 715

A.1 Useful Integrals in Reactor Design 715

A.2 Equal-Area Graphical Differentiation 716

A.3 Solutions to Differential Equations 718

A.4 Numerical Evaluation of Integrals 719

A.5 Semilog Graphs 721

A.6 Software Packages 721





Appendix B: Ideal Gas Constant and Conversion Factors 723



Appendix C: Thermodynamic Relationships Involving the Equilibrium Constant 727



Appendix D: Software Packages 733



D.1 Polymath 733

D.2 Wolfram 735

D.3 MATLAB 735

D.4 Excel 736

D.5 COMSOL (http://www.umich.edu/~elements/5e/12chap/comsol.html) 736

D.6 Aspen 737

D.7 Visual Encyclopedia of Equipment-Reactors Section 738

D.8 Reactor Lab 738





Appendix E: Rate-Law Data 739



Appendix F: Nomenclature 741



Appendix G: Open-Ended Problems 745



G.1 Design of Reaction Engineering Experiment 745

G.2 Effective Lubricant Design 745

G.3 Peach Bottom Nuclear Reactor 745

G.4 Underground Wet Oxidation 746

G.5 Hydrodesulfurization Reactor Design 746

G.6 Continuous Bioprocessing 746

G.7 Methanol Synthesis 746

G.8 Cajun Seafood Gumbo 746

G.9 Alcohol Metabolism 747

G.10 Methanol Poisoning 748



Appendix H: Use of Computational Chemistry Software Packages 749

H.1 Computational Chemical Engineering 749



Appendix I: How to Use the CRE Web Resources 751

I.1 CRE Web Resources Components 751

I.2 How the Web Can Help Your Learning Style 754

I.3 Navigation 755



Index 757



Web Chapters (available on companion Web site)


Chapter 14: Mass Transfer Limitations in Reacting Systems

Chapter 15: Diffusion and Reaction

Chapter 16: Residence Time Distributions of Chemical Reactors

Chapter 17: Predicting Conversion Directly from the Residence Time Distribution

Chapter 18: Models for Nonideal Reactors