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Fundamentals of ChemicalReaction EngineeringFundal11entals of Chel11icalReaction EngineeringMark E. DavisCalifornia Institute of TechnologyRobert J. DavisUniversity of VirginiaBoston Burr Ridge, IL Dubuque, IA Madison, WI New York San Francisco St. LouisBangkok Bogota Caracas Kuala Lumpur Lisbon London Madrid Mexico CityMilan Montreal New Delhi Santiago Seoul Singapore Sydney Taipei TorontoMcGraw-Hill Higher Education 'ZZA Division of The MGraw-Hill CompaniesFUNDAMENTALS OF CHEMICAL REACTION ENGINEERINGPublished by McGraw-Hili, a business unit of The McGraw-Hili Companies, Inc., 1221 Avenue of theAmericas, New York, NY 10020. Copyright 2003 by The McGraw-Hili Companies, Inc. All rights reserved.No part of this publication may be reproduced or distributed in any form or by any means, or stored in adatabase or retrieval system, without the prior written consent of The McGraw-Hili Companies, Inc., including,but not limited to, in any network or other electronic storage or transmission, or broadcast for distance learning.Some ancillaries, including electronic and print components, may not be available to customers outside theUnited States.This book is printed on acid-free paper.InternationalDomestic1234567890DOCroOC0987654321234567890DOCroOC098765432ISBN 0-07-245007-XISBN 0-07-119260-3 (ISE)Publisher: Elizabeth A. JonesSponsoring editor: Suzanne JeansDevelopmental editor: Maja LorkovicMarketing manager: Sarah MartinProject manager: Jane MohrProduction supervisor: Sherry L. KaneSenior media project manager: Tammy JuranCoordinator of freelance design: Rick D. NoelCover designer: Maureen McCutcheonCompositor: TECHBOOKSTypeface: 10/12 Times RomanPrinter: R. R. Donnelley/Crawfordsville, INCover image: Adaptedfrom artwork provided courtesy of Professor Ahmed Zewail's group at Caltech.In 1999, Professor Zewail received the Nobel Prize in Chemistry for studies on the transition states ofchemical reactions using femtosecond spectroscopy.Library of Congress Cataloging-in-Publication DataDavis, Mark E.Fundamentals of chemical reaction engineering / Mark E. Davis, Robert J. Davis. - 1st ed.p. em. - (McGraw-Hili chemical engineering series)Includes index.ISBN 0-07-245007-X (acid-free paper) - ISBN 0-07-119260-3 (acid-free paper: ISE)I. Chemical processes. I. Davis, Robert J. II. Title. III. Series.TP155.7 .D38 2003660'.28-dc21 2002025525CIPINTERNATIONAL EDITION ISBN 0-07-119260-3Copyright 2003. Exclusive rights by The McGraw-Hill Companies, Inc., for manufacture and export.This book cannot be re-exported from the country to which it is sold by McGraw-HilI. The InternationalEdition is not available in North America.www.mhhe.comMcGraw.Hili Chemical Engineering SeriesEditorial Advisory BoardEduardo D. Glandt, Dean, School of Engineering and Applied Science, University of PennsylvaniaMichael T. Klein, Dean, School of Engineering, Rutgers UniversityThomas F. Edgar, Professor of Chemical Engineering, University of Texas at AustinBailey and OllisBiochemical Engineering FundamentalsBennett and MyersMomentum, Heat and Mass TransferCoughanowrProcess Systems Analysis and Controlde NeversAir Pollution Control Engineeringde NeversFluid Mechanics for Chemical EngineersDouglasConceptual Design of Chemical ProcessesEdgar and HimmelblauOptimization of Chemical ProcessesGates, Katzer, and SchuitChemistry of Catalytic ProcessesKingSeparation ProcessesLuybenProcess Modeling, Simulation, and Control forChemical EngineersMarlinProcess Control: Designing Processes and ControlSystems for Dynamic PerformanceMcCabe, Smith, and HarriottUnit Operations of Chemical EngineeringMiddleman and HochbergProcess Engineering Analysis in SemiconductorDevice FabricationPerry and GreenPerry's Chemical Engineers' HandbookPeters and TimmerhausPlant Design and Economics for Chemical EngineersReid, Prausnitz, and PolingProperties of Gases and LiquidsSmith, Van Ness, and AbbottIntroduction to Chemical Engineering ThermodynamicsTreybalMass Transfer OperationsTo Mary, Kathleen, and our parents Ruth and Ted._________________C.Ott:rEHl:SPreface xiNomenclature xiiChapter 1The Basics of Reaction Kineticsfor Chemical ReactionEngineering 11.1 The Scope of Chemical ReactionEngineering I1.2 The Extent of Reaction 81.3 The Rate of Reaction 161.4 General Properties of the Rate Function for aSingle Reaction 191.5 Examples of Reaction Rates 24Chapter 2Rate Constants of ElementaryReactions 532.1 Elementary Reactions 532.2 Arrhenius Temperature Dependence of theRate Constant 542.3 Transition-State Theory 56Chapter 3Reactors for Measuring ReactionRates 643.1 Ideal Reactors 643.2 Batch and Semibatch Reactors 653.3 Stirred-Flow Reactors 703.4 Ideal Tubular Reactors 763.5 Measurement of Reaction Rates 823.5.1 Batch Reactors 843.5.2 Flow Reactors 87Chapter 4The Steady-State Approximation:Catalysis 1004.1 Single Reactions 1004.2 The Steady-State Approximation 1054.3 Relaxation Methods 124Chapter 5Heterogeneous Catalysis 1335.1 Introduction 1335.2 Kinetics of Elementary Steps: Adsorption,Desorption, and Surface Reaction 1405.3 Kinetics of Overall Reactions 1575.4 Evaluation of Kinetic Parameters 171Chapter 6Effects of Transport Limitationson Rates of Solid-CatalyzedReactions 1846.1 Introduction 1846.2 External Transport Effects 1856.3 Internal Transport Effects 1906.4 Combined Internal and External TransportEffects 2186.5 Analysis of Rate Data 228Chapter 7Microkinetic Analysis of CatalyticReactions 2407.1 Introduction 2407.2 Asymmetric Hydrogenation of ProchiralOlefins 240ixx Contents7.3 Ammonia Synthesis on Transition MetalCatalysts 2467.4 Ethylene Hydrogenation on TransitionMetals 2527.5 Concluding Remarks 257Chapter 8Nonideal Flow in Reactors 2608.1 Introduction 2608.2 Residence Time Distribution (RTD) 2628.3 Application of RTD Functions to thePrediction of Reactor Conversion 269804 Dispersion Models for NonidealReactors 2728.5 Prediction of Conversion with an Axially-Dispersed PFR 2778.6 Radial Dispersion 2828.7 Dispersion Models for Nonideal Flowin Reactors 282Chapter 9Nonisothermal Reactors 2869.1 The Nature of the Problem 2869.2 Energy Balances 2869.3 Nonisothermal Batch Reactor 2889.4 Nonisothermal Plug Flow Reactor 2979.5 Temperature Effects in a CSTR 3039.6 Stability and Sensitivity of ReactorsAccomplishing Exothermic Reactions 305Chapter 10Reactors AccomplishingHeterogeneous Reactions 31510.1 Homogeneous Versus HeterogeneousReactions in Tubular Reactors 31510.2 One-Dimensional Models for Fixed-BedReactors 31710.3 Two-Dimensional Models for Fixed-BedReactors 325lOA Reactor Configurations 32810.5 Fluidized Beds with Recirculating Solids 331Appendix AReview of Chemical Equilibria 339A.1 Basic Criteria for Chemical Equilibrium ofReacting Systems 339A.2 Determination of EquilibriumCompositions 341Appendix BRegression Analysis 343B.1 Method of Least Squares 343B.2 Linear Correlation Coefficient 344B.3 Correlation Probability with a ZeroY-Intercept 345BA Nonlinear Regression 347Appendix CTransport in Porous Media 349C.1 Derivation of Flux Relationships inOne-Dimension 349C.2 Flux Relationships in Porous Media 351Index 355This book is an introduction to the quantitative treatment of chemical reaction en-gineering. The level of the presentation is what we consider appropriate for aone-semester course. The text provides a balanced approach to the understandingof: (1) both homogeneous and heterogeneous reacting systems and (2) both chemicalreaction engineering and chemical reactor engineering. We have emulated the teach-ings of Prof. Michel Boudart in numerous sections of this text. For example, much ofChapters 1 and 4 are modeled after his superb text that is now out of print (Kineticsa/Chemical Processes), but they have been expanded and updated. Each chapter con-tains numerous worked problems and vignettes. We use the vignettes to provide thereader with discussions on real, commercial processes and/or uses of the moleculesand/or analyses described in the text. Thus, the vignettes relate the material presentedto what happens in the world around us so that the reader gains appreciation for howchemical reaction engineering and its principles affect everyday life. Many problemsin this text require numerical solution. The reader should seek appropriate softwarefor proper solution of these problems. Since this software is abundant and continuallyimproving, the reader should be able to easily find the necessary software. This exer-cise is useful for students since they will need to do this upon leaving their academicinstitutions. Completion of the entire text will give the reader a good introduction tothe fundamentals of chemical reaction engineering and provide a basis for extensionsinto other nontraditional uses of these analyses, for example, behavior of biologicalsystems, processing of electronic materials, and prediction of global atmospheric phe-nomena. We believe that the emphasis on chemical reaction engineering as opposedto chemical reactor engineering is the appropriate context for training future chemi-cal engineers who will confront issues in diverse sectors of employment.We gratefully acknowledge Prof. Michel Boudart who encouraged us to write thistext and who has provided intellectual guidance to both of us. MED also thanks MarthaHepworth for her efforts in converting a pile of handwritten notes into a final prod-uct. In addition, Stacey Siporin, John Murphy, and Kyle Bishop are acknowledged fortheir excellent assistance in compiling the solutions manual.