nn tj CD-ROM INCLUDED ‘Elements of Chemical Reaction Engineering _ Third Edition = S [eormayy jo syuomery = ° x oO $C) °° fe So 5 & S a, ® oO 5. Ss weElements of Chemical Reaction Engineering Third Edition H. SCOTT FOGLER ‘Ame and Catherine Vennema Professor of Chemical Engineering The University of Michigan, Ann Arbor Prentice-Hall of India Private Limiied) New Bali 110.001, 2004‘This indian Rprint—As. 425.00 (Original U'S. Eation—Rs. 3805.00) ELEMENTS OF CHEMICAL REACTION ENGINEERING, 3rd Ed. (with CD-ROM) by H. Scott Fogler (© 1900 by Prentce-Hal, Inc, (now known as Pearson Education, Inc), Upper Sade River, Naw ‘lorsey 07458, USA. AI rights resorved. No part of is book ‘ray be reproduced in any'fom, ‘by mmeogragh oF any other means, wihout permission in witing fom the publisher. 19BN-61-209.2236-7 Pubiehed by Asoka K. Ghosh, Prentice-Hall of India Private Linited, M-97, Connaught Gis, ‘Now Delhi 1000% end Printed by: Syndicato Binders, A-20, Hoslery Compior, Nola, Phase: Extension, Notda-201908 (NR. Deh.Dedicated to the memory of Professors ‘Giuseppe Parravano Joseph J. Martin Donald L. Katz of the University of Michigan ‘whose standards and lifelong achievements serve to inspire usContents PREFACE xv 1 MOLE BALANCES 1 1.1 Definition of the Rate of Reaction, —r_ 2 1.2 ‘The General Mole Balance Equation 6 13 Batch Reactors 8 1.4 Continuous-Flow Reactors 10 14.1 Continuous-Stirred Tank Reactor 10 142 Tubular Reactor 1 143 Packed-Bed Reactor 4 15 Industrial Reactors 16 Summary 25 Questions and Problems 25 CD-ROM Material 31 Supplementary Reading 31 2 CONVERSION AND REACTOR SIZING 33 2.1 Definition of Conversion 33 22 Design Equations 34 221 Batch Systems 34 222 FlowSystems 37 2.3 Applications of the Design Equations for Continuous-Flow Reactors 40 24 Reactors in Series 48 25 Some Further Definitions 56 Summary 59Contents Questions and Problems 62 CD-ROM Material 66 Supplementary Reading 67 3. RATE LAWS AND STOICHIOMETRY 8 3 32 33 34 35 Basic Definitions 68 3.1 The Reaction Rate Constant 69 3.2 The Reaction Order and the Rate Law 73 3.13 Elementary Rate Laws and Molecularity 75 3.14 — Reversible Reactions 77 3.1.5 _Nonelementary Rate Laws and Reactions 81 Present Status of Our Approach to Reactor Sizing and Design 83 Stoichiometric Table 84 331 Batch Systems 84 3.32 Constant-Volume Reaction Systems 87 333° Flow Systems 90 3.34 Volume Change with Reaction 92 Expressing Concentrations in Terms Other Than Conversion 105 Reactions with Phase Change 107 Summary 111 Questions and Problems 114 CD-ROM Material 123, Supplementary Reading 123 4 ISOTHERMAL REACTOR DESIGN 125 41 42 43 4s 46 4a Design Structure for Isothermal Reactors 125 Scale-Up of Liquid-Phase Batch Reactor Data tothe Design ofaCSTR 129 42.1 Batch Operation 129 42.2 Designof CSTRs 137 ‘Tubular Reactors 147 Pressure Drop in Reactors 183 44.1 Pressure Drop and the Rate Law 183 44.2 Flow Througha Packed Bed 154 44.3 Spherical Packed-Bed Reactors 168 444 Pressure Drop in Pipes 173 ‘Synthesizing a Chemical Plant 174 Using Cz (liquid) and F (gas) in the Mole Balances and Rate Laws 176 46.1 CSTRs, PFRs, PBRs, and Batch Reactors X77 462 — Membrane Reaciors 182 Unsteady-State Operation of Reactors 187Contents ix 48 47.1 Startup ofa CSTR 189 472 Semibaich Reactors 190 473 Reactive Distillation 197 Recycle Reactors 200 Summary 202 ODE Solver Algorithm — 204 Questions and Problems 205 Journal Critique Problems 219 Some Thoughts on Critiquing What You Read 220 CD-ROM Material 220 Supplementary Reading 222 5 COLLECTION AND ANALYSIS OF RATE DATA 23 5 32 53 55 56 Batch Reactor Data 224 SL Differential Method of Rate Analysis 224 S12 Integral Method 238 ‘Method of Initial Rates 239 Method of Half-Lives 242 Differential Reactors 243 Least-Square Analysis 250 5.5.1” Linearization of the Rate Law 280 5.5.2 Nonlinear Least-Squares Analysis 252 5.5.3 Weighted Least-Squares Analysis 261 Experimental Planning (CD-ROM) 262 Evaluation of Laboratory Reactors (CD-ROM) 263 S71 Integral (Fixed-Bed) Reactor 264 S72 Stirred Batch Reactor 264 5.73 Stirred Contained Reactor (SCSR) 265 3.74 Continuous-Stirred Tank Reactor (CSTR) 268 57.5 Straight-Through Transport Reactor 266 5.7.6 Recirculating Transport Reactor 266 S77 Summary of Reactor Ratings 267 Summary 268 Questions and Problems 269 Journal Critique Problems 279 CD-ROM Material 280 Supplementary Reading 280 6 MULTIPLE REACTIONS 282 61 ‘Maximizing the Desired Product in Parallel Reactions 284 6.1.1 Maximizing the Rate Selectivity Parameter S for One Reactant 285 6.12 Maximizing the Rate Selectivity Parameter S for Two Reaciants 288x conten 6.2 Maximizing the Desired Product in Series Reactions 291 63. Algorithm for Solution to Complex Reactions 295 631 Mole Balances 295 632 NetRates of Reaction 296 633 RateLaws 297 6.34 Stoichiometry: Relative Rates of Reaction 297 63.5 Stoichiometry: Concentrations 300 63.6 Combining Step 301 63.7 Multiple Reactions ina CSTR 307 64 SoningtAIOut 314 63 TheFunPat 315 6. The Attainable Region CD-ROM 316 Summary 318 Questions and Problems 320 Journal Critique Problems 335 CD-ROM Material 335 Supplementary Reading — 336 7 NONELEMENTARY REACTION KINETICS 339 7.1 Fundamentals 340 7.11 Active Intermediates. 340 7.1.2 Pseudo-Steady-State Hypothesis (PSH) 342 7.2. Searching fora Mechanism — 44 7.2.1 General Considerations 344 7.2.2 Reaction Pathways 382 73 Polymerization 354 73.1 Step Polymerization 386 73.2 Chain Polymerizations Reactions 360 73.3 Modeling a Batch Polymerization Reactor 368 734 — Molecular Weight Distribution 370 735 Anionic Polymerization 375 74 Enzymatic Reaction Fundamentals 383 74.1 Definitions and Mechanisms 383 742 Michaelis-Menten Equation 386 74.3 Batch Reactor Calculations 389 744 — Inhibition of Enzyme Reactions 391 745 — Multiple Enzyme and Substrate Systems 392 7.8 Bioreactors 393 751 Cell Growth 394 752 RateLaws 396 753 Swichiomerry 398 734 Mass Balances 400 735 Chemosiats 404 756 Design Equations 404 73.7 Wash-our 406CContenss x 75.8 — Oxygen-Limited Fermentation 407 73.9 Scale-up 407 Summary 408 Questions and Problems 410 CD-ROM Material 423, Journal Critique Problems 424 Supplementary Reading 424 8 STEADY-STATE NONISOTHERMAL REACTOR DESIGN 426 8.1 Rationale 426 82 TheEnergy Balance 427 83 84 85 86 87 821° “FirstLaw Thermodynamics 427 822 Evaluating the Work Term 428 823 Dissecting the Steady-State Molar Flow Rates {0 Obiain the Heat of Reaction 430 824 Dissecting the Enthalpies. 432 825 Relating SHyy(T), BH "yy, and BC, 434 826 Constant of Mean Heat Capacitich 435 827 Variable Heat Capacities "436 828 Heat Added othe Reactor. 438 Nonisotermal Continuous-Fow Reaciors 440 83.1 Application tothe CSTR at 832 Adiabatic Tubular Reactor 481 833 Steady-State Tabular Reactor with Heat Exchange 458 Equilibrium Conversion 468 S41 Adiabatic Temperature and Equilibrium Conversion 468 84.2 Optimum Feed Temperature 476 Nonadiabatic Reactor Operation: Oxidation of Sulfur Dioxide Example 478 85.1 Manufacture of Sulfuric Acid 478 85.2 Catalsst Quantities 481 853 Reactor Configuration 482 454 Operating Conditions 482 Multiple Steady States 490 861° HeatRemoved Term RT) 494 862 Heat of Generation. G(T) 492 863° Igntion-Estinction Curve 993 864 — Runaway Reactions 497 865 SteadyState Bifercation Analysis 498 Nonisothermal Multiple Chemical Reactions 300 87.1 Plug-Flow Reactors 500 872 CSTR S04 Summary $07Contents Questions and Problems S11 Journal Critique Problems 530 CD-ROM Material $30 ‘Supplementary Reading $32 9 UNSTEADY-STATE NONISOTHERMAL REACTOR DESIGN 534 oa 92 93 94 95 96 ‘The General Equation 534 Unsteady Operation of CSTRs and Semibatch Reactors 535 92.1 Batch Reactors 537 922 Adiabatic Operation of a Batch Reactor $37 923 Transient CSTR, Batch, and Semibatch Reactors with Heat Exchanger—Ambient Temperature Not Spatially Uniform S48 Approach to the Steady State $53 Control of Chemical Reactors 558 94.1 Falling Off the Steady State $58 942 Adding a Comroller toa CSTR S61 Nonisothermal Muliple Reactions 566 Unsteady Operation of Plug-Flow Reactors $70 Summary S71 ‘Questions and Problems S72 CD-ROM Material 579 Supplementary Reading $79 10. CATALYSIS AND CATALYTIC REACTORS 581 101 102 103 104 Catalysts S81 10.1.1 Definitions S82 10.12 Catalyst Properties $83 Steps in aCatalytic Reaction 591 10.2.1 Adsorption Isotherms | 594 10.2.2 Surface Reaction 599 102.3 Desorption 601 10.2.4 The Rate-Limiting Step 601 ‘Synthesizing a Rate Law, Mechanism, and Rate-Limiting Step | 603 10.3.1 Is the Adsorption of Cumene Rate-Limiting? || 606 10.3.2 Is the Surface Reaction Rate-Limiting? 609 10.3.3 Is the Desorption of Benzene Rate-Limiting? 610 10.34 Summary of the Cumene Decomposition 612 10.3.5 Rate Laws Derived from the Pseudo-Steady-State Hypothesis. 616 Design of Reactors for Gas-Solid Reactions 619 104.1 Basic Guidelines 619 1042 The Design Equations 619Contents xi 10s 106 107 os. Heterogeneous Data Analysis for Reactor Design 620 10.5.1 Deducing a Rate Law from the Experimental Data 622 10.5.2 “Finding a Mechanism Consistent with Experimental Observations 623 10.5.3 Evaluation of the Rate Law Parameters 624 1054 Reactor Design 627 Chemical Vapor Deposition. 631 Catalyst Deactivation 634 107.1 Types of Catalyst Deactivation 636 10.7.2 Temperature-Time Trajectories 647 10.7.3 Moving-Bed Reactors 649 10.74 Straight-Through Transport Reactors 688 10.7.5 Determining the Order of Deactivation 660 Reaction Engineering in Microelectronic Device Fabrication 662 108.1 Etching — 664 Summary 665 Questions and Problems 668 Journal Critique Problems 682 CD-ROM Material 683 Supplementary Reading 684 11 EXTERNAL DIFFUSION EFFECTS ON HETEROGENEOUS REACTIONS 686 ud 12 4 1s Mass Transfer Fundamentals 687 ALLL Definitions 687 W12 Molar Flux 687 ILL3 _ Fick's First Law 688 Binary Diffusion 689 112.1 Evaluating the Molar Flux 689 11.2.2 Boundary Conditions 692 11.2.3 Modeling Diffusion Without Reaction 692 24 Temperature and Pressure Dependence fDax 697 12.5 Modeling Diffusion with Chemical Reaction 698 Extemal Resistance to Mass Transfer 699 13.1 Mass Transfer Coefficient 699 1132 Mass Transfer to a Single Particle 702 13.3 Mass Transfer Limited Reactions in Packed Beds 706 11.3.4 Mass Transfer-Limited Reaction ‘on Metallic Surfaces 714 ‘What If..? (Parameter Sensitivity) 71S ‘The Shrinking Core Model 719xiv 15.1 Catalyst Regeneration 720 Contents 1152 Dissolution of Monodispersed Solid Particles 724 15.3 Flow and Dissolution in Porous Media 726 Summary 728 Questions and Problems 729 Journal Article Problem 735 Journal Critique Problems 738 CD-ROM Material 735 Supplementary Reading 736 12 DIFFUSION AND REACTION IN POROUS CATALYSTS 12.1 Diffusion and Reaction in Spherical Catalyst Pellets 12.11 Effective Difusivity 739 738 9 12.1.2 Derivation ofthe Differential Equation Describing Diffusion and Reaction 741 12.1.3 Writing the Equation in Dimensionless Form 743, 12.14 Solution tothe Differential Equation for a First-Order Reaction 746 12.2 Internal Effectiveness Factor 747 123 Falsified Kinetics 753 124 Overall Effectiveness Factor 755 12.5 Estimation of Diffusion- and Reaction-Limited Regimes 758 12.5.1 Weise-Prater Criterion for Internal Diffusion 758 12.5.2 Mears’ Criterion for External Diffusion 126 Mass Transfer and Reaction in a Packed Bed 127 Determination of Limiting Situations from Reaction Data 767 128 Multiphase Reactors 768 1281 Slurry Reactors 769 1282 Trickle Bed Reactors 783 12.9 Fluidized-Bed Reactorsep roy 786 12:10 The Overall View 787 12.11 Chemical Vapor Deposition Reactors 789 Summary 793 Questions and Problems 795 Joumal Article Problems 804 Journal Critique Problems 805 CD-ROM Material 805 Supplementary Reading 806 13 DISTRIBUTIONS OF RESIDENCE TIMES FOR CHEMICAL REACTORS 13.1 General Characteristics 809 13.1.1 Residence-Time Distribution Function 161 161 sicontents ~ 132 133 134 135 136 137 138 Measurement of the RTD 812 13.2.1 Pulse Input 813 1322 Step Tracer Experiment 818 Characteristics of the RTD 819 133.1 Integral Relationships 819 133.2 Mean Residence Time 821 133.3 Other Moments of the RTD 823 1334 Normalized RTD Function, E(8) 825 13.3.5 Internal-Age Distribution l(a) 826 RTDin Ideal Reactors 829 134.1 RTDs in Batch and Plug-Flow Reactors. 829 134.2 Single-CSTRRTD 829 1343 Laminar Flow Reactor 831 1344 PER/CSTR Series RTD 833 Reactor Modeling with the RTD 836 Zero-Parameter Models. 838 136.1 Segregation Model 838 13.6.2 Maximum Mixedness 844 1363 Heat Effects 851 Using Software Packages 851 RTD and Multiple Reactions 854 1381 Segregation Model 854 1382 Maximum Mixedness 855 Summary 860 Questions and Problems 861 CD-ROM Material 868 Supplementary Reading 869 14 MODELS FOR NONIDEAL REACTORS 871 Ia 142 143 Some Guidelines 871 One-Parameter Models. 872 142.1 Tanks-in-Series Model 873 142.2 Dispersion Model 877 ‘Two-Parameter Models—Modeling Real Reactors with Comt nations of Ideal Reactors 893 143.1 Real CSTR Modeled Using Bypassing ‘and Dead Space 893 143.1. Solving the Model System for CyandX 894 14.3.1B Using a Tracer to Determine the Model Parameters in CSTR-with-Dead-Space-and-Bypass Model 895 4143.2 Real CSTR Modeled with an Exchange Volume 899 4143.2A Solving the Model System for CyandX 900Appendix A Appendix B Appendix C Appendix D Appendix E Appendix F Appendix G Appendix H avi Ma 4s 146 143.2B Using a Tracer to Determine the Model Parameters ina CSTR with an Exchange Volume 900 Use of Software Packages to Determine the Model Parameters 901 Other Models of Nonideal Reactors Using CSTRs and PERs 904 Using the RTD Versus Needing a Model 904 Summary 907 Questions and Problems 909 CD-ROM Material 916 Supplementary Reading 917 NUMERICAL TECHNIQUES 921 AL Useful Integrals in Reactor Design 921 ‘2 Equal-Area Graphical Differentiation 922 3. Solutions to Differential Equations 924 ‘A4 Numerical Evaluation of Integrals 924 AS Software Packages 926 IDEAL GAS CONSTANT AND CONVERSION FACTORS 927 THERMODYNAMIC RELATIONSHIPS INVOLVING THE EQUILIBRIUM CONSTANT 929 MEASUREMENT OF SLOPES ON SEMILOG PAPER 935 SOFTWARE PACKAGES 936 NOMENCLATURE 938 MOLECULAR DYNAMICS OF CHEMICAL REACTIONS — 941. Gi G2 G3 Collision Theory 941 ‘Transition State Theory 944 Molecular Dynamics 948 OPEN-ENDED PROBLEMS 983 HL H2 #3 Design of Reaction Engineering Experiment 983 Effective Lubricant Design 953 Peach Bottom Nuclear Reactor 953Conon, i Hd Underground Wet Oxidation 984 HS Hydrosulfurization Reactor Design 954 H.6 Continuous Bioprocessing 954 1.7 Methanol Synthesis 954 H8 Cajun Seafood Gumbo 984 Appendix I HOW TO USE THE CD-ROM 956 CDI_ Components ofthe CD-ROM CD2 Interactive Lecture Notes sess QV sas I ei en, D3 Frequently Asked Questions CD4_ Living Example Problems CDS Professional Reference Shelf €D6 Additional Home Problems D7 Navigation CD8 Interactive Computer Problems (ICM's) TE.g.,ICM Simulation, Heat Effects shown below) Heat Effects 1 Appendix J USE OF COMPUTATIONAL CHEMISTRY SOFTWARE PACKAGES 988 INDEX oe ABOUT THE CD 976Preface “The man who has ceased to learn ought not to be allowed to wander around loose in these danger- cous days." ‘M.M. Coady (ca. 1870) ‘A. The Audience This book is intended for use as both an undergraduate- and graduate-level textin chemical reaction engineering, The level of difficulty will depend on the choice ‘of chapters to be covered and the type and degree of difficulty of problems assigned, Most problems requiring significant numerical computations can be solved witha personal computer using either POLYMATH or MATLAB. B. The Goals B.1, To Develop a Fundamental Understanding of Reaction Engineering The first goal of this book is to enable the reader to develop a clear understanding of the fundamentals of chemical reaction engineering. This goa! will be achieved by presenting a structure that allows the reader to solve reac tion engineering problems through reasoning rather than through memorization ‘and recall of numerous equations and the restrictions and conditions under which each equation applies. To accomplish this, we use (1) conventional problems that reinforce the studemt’s understanding of the basic concepts and Principles (included at the end of each chapter); (2) problems whose solution require’ reading the literature, handbooks, or other textbooks on chemical ‘engineering kinetics; and (3) problems that give students practice in problemSimply put, good thinkers are good questiones and vice x Protace definition and alternative pathways to solutions. The algorithms presented in the text for reactor design provide a framework through which one can develop confidence through reasoning rather than memorization. "To give a reference point as to the level of understanding required in the profes- sion, a numberof reaction engineering problems from the California Board of Regis- tration for Civil and Professional Engineers—Chemical Engineering Examinations (PECEE) are included. Typically each problem should require approximately one-half hour to solve. Hints on how to work the California exam problems can be found in the ‘Summary Notes and in the Thoughts on Problem Solving on the CD-ROM. ‘The second and third goals ofthis book are to increase the student's critical thinking skills and creative thinking skills by presenting heuristics and problems that encourage the student to practice these skills. B.2. To Develop Critical Thinking Skils ‘Due tothe mpi addition of new information and the advancement of science and technology that occur almost daly, an engineer must constantly expand his or her horizons ‘beyond simply gathering information and relying on the basic engineering principles. "A number of homework problems have been included that are designed to enhance critical thinking skills Critical thinking is the process we use to reflect fon, access and justify our own assumptions as well as others’ ideas, work and actions. Socratic questioning is atthe heart of critical thinking and a number of, homework problems draw from R. W. Paul's six types of Socratic questions: (Q) Questions for clarification: Why do you say that? How does this relate to our discussion’ 2) Questions that probe assumptions: What could we assume instead? ‘How can you verify or disprove that assumption?” (3) Questions that probe reasons and evidence: What would be an example? (8) Questions about viewpoints and perspectives: What would be an alternative? (5) Questions that probe implications and consequences: What generali- zations can you make? What are the consequences of that assumption? (© Questions about the question: What was the point of this question?” Why do you think I asked this question? Good thinkers are always asking What does this mean?, What is the nature of is? Is there another way to look at it?, Why is this happening?, What i the evi- dence for tis?, and How can I be sure? Practice in critical thinking can be achieved by assigning additional parts the problems atthe end of each chapter that utilize R. W. Paul's approach. Most of these problems have more than one part to them. The instructor may wish to assign all or some of the parts. In addition, the instructor could add the following parts to any of the problems: ‘+ Describe how you went about solving this problem. ‘+ How reasonable is each assumption you made in solving this problem? Paul, RW, Critical Thinking (Published by the Foundation for Critical Thinking, Santa Rosa, CA, 1992)