Elements of Chemical Reaction Engineering

by: Fogler, H. Scott

Elements of Chemical Reaction Engineering

by: Fogler, H. Scott

ISBN 13:
9780135317082
ISBN 10:
0135317088
Edition: 3rd
Format: Hardcover w/CD
Copyright: 01/01/1999
Publisher: Prentice Hall PTR
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Summary

"The fourth edition of Elements of Chemical Reaction Engineering is a completely revised version of the book. It combines authoritative coverage of the principles of chemical reaction engineering with an unsurpassed focus on critical thinking and creative problem solving, employing open-ended questions and stressing the Socratic method. Clear and organized, it integrates text, visuals, and computer simulations to help readers solve even the most challenging problems through reasoning, rather than by memorizing equations."--BOOK JACKET.

PREFACE

1 MOLE BALANCES

(32)

1.1 Definition of the Rate of Reaction, --r(A)

(4)

1.2 The General Mole Balance Equation

(2)

1.3 Batch Reactors

(2)

1.4 Continuous-Flow Reactors

(6)

1.4.1 Continuous-Stirred Tank Reactor

(1)

1.4.2 Tubular Reactor

(3)

1.4.3 Packed-Bed Reactor

(2)

1.5 Industrial Reactors

(9)

Summary

(1)

Questions and Problems

(6)

CD-ROM Material

(1)

Supplementary Reading

(2)

2 CONVERSION AND REACTOR SIZING

(35)

2.1 Definition of Conversion

(1)

2.2 Design Equations

(6)

2.2.1 Batch Systems

(3)

2.2.2 Flow Systems

(3)

2.3 Applications of the Design Equations for Continuous-Flow Reactors

(8)

2.4 Reactors in Series

(8)

2.5 Some Further Definitions

(3)

Summary

(3)

Questions and Problems

(4)

CD-ROM Material

(1)

Supplementary Reading

(1)

3 RATE LAWS AND STOICHIOMETRY

(57)

3.1 Basic Definitions

(15)

3.1.1 The Reaction Rate Constant

(4)

3.1.2 The Reaction Order

(2)

3.1.3 Elementary Rate Laws and Molecularity

(2)

3.1.4 Reversible Reactions

(4)

3.1.5 Nonelementary Rate Laws and Reactions

(2)

3.2 Present Status of Our Approach to Reactor Sizing and Design

(1)

3.3 Stoichiometric Table

(21)

3.3.1 Batch Systems

(3)

3.3.2 Constant-Volume Reaction Systems

(3)

3.3.3 Flow Systems

(2)

3.3.4 Volume Change with Reaction

(3)

3.4 Expressing Concentrations in Terms Other Than Conversion

105

(2)

3.5 Reactions with Phase Change

107

(4)

Summary

111

(3)

Questions and Problems

114

(9)

CD-ROM Material

123

(1)

Supplementary Reading

123

(2)

4 ISOTHERMAL REACTOR DESIGN

125

(98)

4.1 Design Structure for Isothermal Reactors

125

(4)

4.2 Scale-Up of Liquid-Phase Batch Reactor Data to the Design of a CSTR

129

(18)

4.2.1 Batch Operation

129

(8)

4.2.2 Design of CSTRs

137

(10)

4.3 Tubular Reactors

147

(6)

4.4 Pressure Drop in Reactors

153

(21)

4.4.1 Pressure Drop and the Rate Law

153

(1)

4.4.2 Flow Through a Packed Bed

154

(14)

4.4.3 Spherical Packed-Bed Reactors

168

(5)

4.4.4 Pressure Drop in Pipes

173

(1)

4.5 Synthesizing a Chemical Plant

174

(2)

4.6 Using C(A) (liquid) and F(A) (gas) in the Mole Balances and Rate Laws

176

(11)

4.6.1 CSTRs, PFRs, PBRs, and Batch Reactors

177

(5)

4.6.2 Membrane Reactors

182

(5)

4.7 Unsteady-State Operation of Reactors

187

(13)

4.7.1 Startup of a CSTR

189

(1)

4.7.2 Semibatch Reactors

190

(7)

4.7.3 Reactive Distillation

197

(3)

4.8 Recycle Reactors

200

(2)

Summary

202

(2)

ODE Solver Algorithm

204

(1)

Questions and Problems

205

(14)

Journal Critique Problems

219

(1)

Some Thoughts on Critiquing What You Read

220

(1)

CD-ROM Material

220

(2)

Supplementary Reading

222

(1)

5 COLLECTION AND ANALYSIS OF RATE DATA

223

(59)

5.1 Batch Reactor Data

224

(15)

5.1.1 Differential Method of Rate Analysis

224

(11)

5.1.2 Integral Method

235

(4)

5.2 Method of Initial Rates

239

(3)

5.3 Method of Half-Lives

242

(1)

5.4 Differential Reactors

243

(7)

5.5 Least-Square Analysis

250

(12)

5.5.1 Linearization of the Rate Law

250

(2)

5.5.2 Nonlinear Least-Squares Analysis

252

(9)

5.5.3 Weighted Least-Squares Analysis

261

(1)

5.6 Experimental Planning (CD-ROM)

262

(1)

5.7 Evaluation of Laboratory Reactors (CD-ROM)

263

(5)

5.7.1 Integral (Fixed-Bed) Reactor

264

(1)

5.7.2 Stirred Batch Reactor

264

(1)

5.7.3 Stirred Contained Reactor (SCSR)

265

(1)

5.7.4 Continuous-Stirred Tank Reactor (CSTR)

265

(1)

5.7.5 Straight-Through Transport Reactor

266

(1)

5.7.6 Recirculating Transport Reactor

266

(1)

5.7.7 Summary of Reactor Ratings

267

(1)

Summary

268

(1)

Questions and Problems

269

(10)

Journal Critique Problems

279

(1)

CD-ROM Material

280

(1)

Supplementary Reading

280

(2)

6 MULTIPLE REACTIONS

282

(57)

6.1 Maximizing the Desired Product in Parallel Reactions

284

(7)

6.1.1 Maximizing the Rate Selectivity Parameter S for One Reactant

285

(3)

6.1.2 Maximizing the Rate Selectivity Parameter S for Two Reactants

288

(3)

6.2 Maximizing the Desired Product in Series Reactions

291

(4)

6.3 Algorithm for Solution to Complex Reactions

295

(19)

6.3.1 Mole Balances

295

(1)

6.3.2 Net Rates of Reaction

296

(1)

6.3.3 Rate Laws

297

(1)

6.3.4 Stoichiometry: Relative Rates of Reaction

297

(3)

6.3.5 Stoichiometry: Concentrations

300

(1)

6.3.6 Combining Step

301

(6)

6.3.7 Multiple Reactions in a CSTR

307

(7)

6.4 Sorting It All Out

314

(1)

6.5 The Fun Part

315

(1)

6.6 The Attainable Region CD-ROM

316

(2)

Summary

318

(2)

Questions and Problems

320

(15)

Journal Critique Problems

335

(1)

CD-ROM Material

335

(1)

Supplementary Reading

336

(3)

7 NONELEMENTARY REACTION KINETICS

339

(87)

7.1 Fundamentals

340

(4)

7.1.1 Active Intermediates

340

(2)

7.1.2 Pseudo-Steady-State Hypothesis (PSSH)

342

(2)

7.2 Searching for a Mechanism

344

(10)

7.2.1 General Considerations

344

(8)

7.2.2 Reaction Pathways

352

(2)

7.3 Polymerization

354

(29)

7.3.1 Step Polymerization

356

(4)

7.3.2 Chain Polymerizations Reactions

360

(8)

7.3.3 Modeling a Batch Polymerization Reactor

368

(2)

7.3.4 Molecular Weight Distribution

370

(5)

7.3.5 Anionic Polymerization

375

(8)

7.4 Enzymatic Reaction Fundamentals

383

(10)

7.4.1 Definitions and Mechanisms

383

(3)

7.4.2 Michaelis-Menten Equation

386

(3)

7.4.3 Batch Reactor Calculations

389

(2)

7.4.4 Inhibition of Enzyme Reactions

391

(1)

7.4.5 Multiple Enzyme and Substrate Systems

392

(1)

7.5 Bioreactors

393

(15)

7.5.1 Cell Growth

394

(2)

7.5.2 Rate Laws

396

(2)

7.5.3 Stoichiometry

398

(2)

7.5.4 Mass Balances

400

(4)

7.5.5 Chemostats

404

(1)

7.5.6 Design Equations

404

(2)

7.5.7 Wash-out

406

(1)

7.5.8 Oxygen-Limited Germentation

407

(1)

7.5.9 Scale-up

407

(1)

Summary

408

(2)

Questions and Problems

410

(13)

CD-ROM Material

423

(1)

Journal Critique Problems

424

(1)

Supplementary Reading

424

(2)

8 STEADY-STATE NONISOTHERMAL REACTOR DESIGN

426

(108)

8.1 Rationale

426

(1)

8.2 The Energy Balance

427

(13)

8.2.1 First Law Thermodynamics

427

(2)

8.2.2 Evaluating the Work Term

429

(1)

8.2.3 Dissecting the Steady-State Molar Flow Rates to Obtain the Heat of Reaction

430

(2)

8.2.4 Dissecting the Enthalpies

432

(2)

8.2.5 Relating DeltaH(Rx)(T), DeltaH(0)(Rx), and DeltaC(p)

434

(1)

8.2.6 Constant of Mean Heat Capacities

435

(1)

8.2.7 Variable Heat Capacities

436

(2)

8.2.8 Heat Added to the Reactor, Q

438

(2)

8.3 Nonisothermal Continuous-Flow Reactors

440

(28)

8.3.1 Application to the CSTR

441

(10)

8.3.2 Adiabatic Tubular Reactor

451

(7)

8.3.3 Steady-State Tubular Reactor with Heat Exchange

458

(10)

8.4 Equilibrium Conversion

468

(10)

8.4.1 Adiabatic Temperature and Equilibrium Conversion

468

(8)

8.4.2 Optimum Feed Temperature

476

(2)

8.5 Nonadiabatic Reactor Operation: Oxidation of Sulfur Dioxide Example

478

(12)

8.5.1 Manufacture of Sulfuric Acid

478

(3)

8.5.2 Catalyst Quantities

481

(1)

8.5.3 Reactor Configuration

482

(1)

8.5.3 Operating Conditions

482

(8)

8.6 Multiple Steady States

490

(10)

8.6.1 Heat-Removed Term, R(T)

491

(1)

8.6.2 Heat of Generation, G(T)

492

(1)

8.6.3 Ignition-Extinction Curve

493

(4)

8.6.4 Runaway Reactions

497

(1)

8.6.5 Steady-State Bifurcation Analysis

498

(2)

8.7 Nonisothermal Multiple Chemical Reactions

500

(7)

8.7.1 Plug-Flow Reactors

500

(4)

8.7.2 CSTR

504

(3)

Summary

507

(4)

Questions and Problems

511

(19)

Journal Critique Problems

530

(1)

CD-ROM Material

530

(2)

Supplementary Reading

532

(2)

9 UNSTEADY-STATE NONISOTHERMAL REACTOR DESIGN

534

(47)

9.1 The General Equation

534

(1)

9.2 Unsteady Operation of CSTRs and Semibatch Reactors

535

(18)

9.2.1 Batch Reactors

537

(1)

9.2.2 Adiabatic Operation of a Batch Reactor

537

(11)

9.2.3 Transient CSTR, Batch, and Semibatch Reactors with Heat Exchanger--Ambient Temperature Not Spatially Uniform

548

(5)

9.3 Approach to the Steady State

553

(5)

9.4 Control of Chemical Reactors

558

(8)

9.4.1 Falling Off the Steady State

558

(3)

9.4.2 Adding a Controller to a CSTR

561

(5)

9.5 Nonisothermal Multiple Reactions

566

(4)

9.6 Unsteady Operation of Plug-Flow Reactors

570

(1)

Summary

571

(1)

Questions and Problems

572

(7)

CD-ROM Material

579

(1)

Supplementary Reading

579

(2)

10 CATALYSIS AND CATALYTIC REACTORS

581

(105)

10.1 Catalysts

581

(10)

10.1.1 Definitions

582

(1)

10.1.2 Catalyst Properties

583

(1)

10.2 Steps in a Catalytic Reaction

591

(12)

10.2.1 Adsorption Isotherms

594

(5)

10.2.2 Surface Reaction

599

(2)

10.2.3 Desorption

601

(1)

10.2.4 The Rate-Limiting Step

601

(2)

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

603

(16)

10.3.1 Is the Adsorption of Cumene Rate-Limiting?

606

(3)

10.3.2 Is the Surface Reaction Rate-Limiting?

609

(1)

10.3.3 Is the Desorption of Benzene Rate-Limiting?

610

(2)

10.3.4 Summary of the Cumene Decomposition

612

(4)

10.3.5 Rate Laws Derived from the Pseudo-Steady-State Hypothesis

616

(3)

10.4 Design of Reactors for Gas-Solid Reactions

619

(1)

10.4.1 Basic Guidelines

619

(1)

10.4.2 The Design Equations

619

(1)

10.5 Heterogeneous Data Analysis for Reactor Design

620

(11)

10.5.1 Deducing a Rate Law from the Experimental Data

622

(1)

10.5.2 Finding a Mechanism Consistent with Experimental Observations

623

(1)

10.5.3 Evaluation of the Rate Law Parameters

624

(3)

10.5.4 Reactor Design

627

(4)

10.6 Chemical Vapor Deposition

631

(3)

10.7 Catalyst Deactivation

634

(28)

10.7.1 Types of Catalyst Deactivation

636

(11)

10.7.2 Temperature-Time Trajectories

647

(2)

10.7.3 Moving-Bed Reactors

649

(6)

10.7.4 Straight-Through Transport Reactors

655

(5)

10.7.5 Determining the Order of Deactivation

660

(2)

10.8 Reaction Engineering in Microelectronic Device Fabrication

662

(3)

10.8.1 Etching

664

(1)

Summary

665

(3)

Questions and Problems

668

(14)

Journal Critique Problems

682

(1)

CD-ROM Material

683

(1)

Supplementary Reading

684

(2)

11 EXTERNAL DIFFUSION EFFECTS ON HETEROGENEOUS REACTIONS

686

(52)

11.1 Mass Transfer Fundamentals

687

(2)

11.1.1 Definitions

687

(1)

11.1.2 Molar Flux

687

(1)

11.1.3 Fick's First Law

688

(1)

11.2 Binary Diffusion

689

(10)

11.2.1 Evaluating the Molar Flux

689

(3)

11.2.2 Boundary Conditions

692

(1)

11.2.3 Modeling Diffusion Without Reaction

692

(5)

11.2.4 Temperature and Pressure Dependence of D(AB)

697

(1)

11.2.5 Modeling Diffusion with Chemical Reaction

698

(1)

11.3 External Resistance to Mass Transfer

699

(16)

11.3.1 Mass Transfer Coefficient

699

(3)

11.3.2 Mass Transfer to a Single Particle

702

(4)

11.3.3 Mass Transfer-Limited Reactions in Packed Beds

706

(8)

11.3.4 Mass Transfer-Limited Reaction on Metallic Surfaces

714

(1)

11.4 What If...? (Parameter Sensitivity)

715

(4)

11.5 The Shrinking Core Model

719

(9)

11.5.1 Catalyst Regeneration

720

(4)

11.5.2 Dissolution of Monodispersed Solid Particles

724

(2)

11.5.3 Flow and Dissolution in Porous Media

726

(2)

Summary

728

(1)

Questions and Problems

729

(6)

Journal Article Problem

735

(1)

Journal Critique Problems

735

(1)

CD-ROM Material

735

(1)

Supplementary Reading

736

(2)

12 DIFFUSION AND REACTION IN POROUS CATALYSTS

738

(71)

12.1 Diffusion and Reaction in Spherical Catalyst Pellets

739

(8)

12.1.1 Effective Diffusivity

739

(2)

12.1.2 Derivation of the Differential Equation Describing Diffusion and Reaction

741

(2)

12.1.3 Writing the Equation in Dimensionless Form

743

(3)

12.1.4 Solution to the Differential Equation for a First-Order Reaction

746

(1)

12.2 Internal Effectiveness Factor

747

(6)

12.3 Falsified Kinetics

753

(2)

12.4 Overall Effectiveness Factor

755

(3)

12.5 Estimation of Diffusion- and Reaction-Limited Regimes

758

(3)

12.5.1 Weisz-Prater Criterion for Internal Diffusion

758

(3)

12.6 Mass Transfer and Reaction in a Packed Bed

761

(6)

12.7 Determination of Limiting Situations from Reaction Data

767

(1)

12.8 Multiphase Reactors

768

(18)

12.8.1 Slurry Reactors

769

(14)

12.8.2 Trickle Bed Reactors

783

(3)

12.9 Fluidized-Bed Reactors(CD-ROM)

786

(1)

12.10 The Overall View

787

(2)

12.11 Chemical Vapor Deposition Reactors

789

(4)

Summary

793

(2)

Questions and Problems

795

(9)

Journal Article Problems

804

(1)

Journal Critique Problems

805

(1)

CD-ROM Material

805

(1)

Supplementary Reading

806

(3)

13 DISTRIBUTIONS OF RESIDENCE TIMES FOR CHEMICAL REACTORS

809

(62)

13.1 General Characteristics

809

(3)

13.1.1 Residence-Time Distribution Function

811

(1)

13.2 Measurement of the RTD

812

(7)

13.2.1 Pulse Input

813

(5)

13.2.2 Step Tracer Experiment

818

(1)

13.3 Characteristics of the RTD

819

(10)

13.3.1 Integral Relationships

819

(2)

13.3.2 Mean Residence Time

821

(2)

13.3.3 Other Moments of the RTD

823

(2)

13.3.4 Normalized RTD Function, E(Tan)

825

(1)

13.3.5 Internal-Age Distribution 1Alpha

826

(3)

13.4 RTD in Ideal Reactors

829

(7)

13.4.1 RTDs in Batch and Plug-Flow Reactors

829

(1)

13.4.2 Single-CSTR RTD

829

(2)

13.4.3 Laminar Flow Reactor

831

(2)

13.4.4 PFR/CSTR Series RTD

833

(3)

13.5 Reactor Modeling with the RTD

836

(2)

13.6 Zero-Parameter Models

838

(13)

13.6.1 Segregation Model

838

(6)

13.6.2 Maximum Mixedness

844

(7)

13.6.3 Heat Effects

851

(1)

13.7 Using Software Packages

851

(3)

13.8 RTD and Multiple Reactions

854

(6)

13.8.1 Segregation Model

854

(1)

13.8.2 Maximum Mixedness

855

(5)

Summary

860

(1)

Questions and Problems

861

(7)

CD-ROM Material

868

(1)

Supplementary Reading

869

(2)

14 MODELS FOR NONIDEAL REACTORS

871

(50)

14.1 Some Guidelines

871

(1)

14.2 One-Parameter Models

872

(21)

14.2.1 Tanks-in-Series Model

873

(4)

14.2.2 Dispersion Model

877

(16)

14.3 Two-Parameter Models--Modeling Real Reactors with Combinations of Ideal Reactors

893

(8)

14.3.1 Real CSTR Modeled Using Bypassing and Dead Space

893

(1)

14.3.1A Solving the Model System for C(A) and X

894

(1)

14.3.1B Using a Tracer to Determine the Model Parameters in CSTR-with-Dead-Space-and-Bypass Model

895

(4)

14.3.2 Real CSTR Modeled with an Exchange Volume

899

(1)

14.3.2A Solving the Model System for C(A) and X

900

(1)

14.3.2B Using a Tracer to Determine the Model Parameters in a CSTR with an Exchange Volume

900

(1)

14.4 Use of Software Packages to Determine the Model Parameters

901

(3)

14.5 Other Models of Nonideal Reactors Using CSTRs and PFRs

904

(1)

14.6 Using the RTD Versus Needing a Model

904

(3)

Summary

907

(2)

Questions and Problems

909

(7)

CD-ROM Material

916

(1)

Supplementary Reading

917

(4)

Appendix A NUMERICAL TECHNIQUES

921

(6)

A.1 Useful Integrals in Reactor Design

921

(1)

A.2 Equal-Area Graphical Differentiation

922

(2)

A.3 Solutions to Differential Equations

924

(1)

A.4 Numerical Evaluation of Integrals

924

(2)

A.5 Software Packages

926

(1)

Appendix B IDEAL GAS CONSTANT AND CONVERSION FACTORS

927

(2)

Appendix C THERMODYNAMIC RELATIONSHIPS INVOLVING THE EQUILIBRIUM CONSTANT

929

(6)

Appendix D MEASUREMENT OF SLOPES ON SEMILOG PAPER

935

(1)

Appendix E SOFTWARE PACKAGES

936

(2)

Appendix F NOMENCLATURE

938

(3)

Appendix G MOLECULAR DYNAMICS OF CHEMICAL REACTIONS

941

(12)

G.1 Collision Theory

941

(3)

G.2 Transition State Theory

944

(4)

G.3 Molecular Dynamics

948

(5)

Appendix H OPEN-ENDED PROBLEMS

953

(3)

H.1 Design of Reaction Engineering Experiment

953

(1)

H.2 Effective Lubricant Design

953

(1)

H.3 Peach Bottom Nuclear Reactor

953

(1)

H.4 Underground Wet Oxidation

954

(1)

H.5 Hydrosulfurization Reactor Design

954

(1)

H.6 Continuous Bioprocessing

954

(1)

H.7 Methanol Synthesis

954

(1)

H.8 Cajun Seafood Gumbo

954

(2)

Appendix I HOW TO USE THE CD-ROM

956

(2)

Appendix J USE OF COMPUTATIONAL CHEMISTRY SOFTWARE PACKAGES

958

(3)

INDEX

961

(15)

ABOUT THE CD

976

Elements of Chemical Reaction Engineering

Elements of Chemical Reaction Engineering

9780135317082

0135317088

Summary

Table of Contents

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Elements of Chemical Reaction Engineering

Elements of Chemical Reaction Engineering

9780135317082

0135317088

Summary

Table of Contents

Supplemental Materials

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