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Fundamentals of Chemical Reaction Engineering Fundal11entals of Chel11ical Reaction Engineering Mark E. Davis California Institute ofTechnology Robert J. Davis University ofVirginia Boston Burr Ridge, IL Dubuque, IA Madison, WI NewYork San Francisco St. Louis Bangkok Bogota Caracas Kuala Lumpur Lisbon London Madrid Mexico City Milan Montreal New Delhi Santiago Seoul Singapore Sydney Taipei Toronto 'ZZ McGraw-Hill Higher Education A Division ofThe MGraw-HillCompanies FUNDAMENTALSOFCHEMICALREACTIONENGINEERING PublishedbyMcGraw-Hili,abusinessunitofTheMcGraw-HiliCompanies,Inc., 1221Avenueofthe Americas,NewYork,NY 10020.Copyright©2003byTheMcGraw-HiliCompanies,Inc.Allrightsreserved. Nopartofthispublicationmaybereproducedordistributedinanyformorbyanymeans,orstoredina databaseorretrievalsystem,withoutthepriorwrittenconsentofTheMcGraw-HiliCompanies,Inc.,including, butnotlimitedto,inanynetworkorotherelectronicstorageortransmission,orbroadcastfordistancelearning. Someancillaries,includingelectronicandprintcomponents,maynotbeavailabletocustomersoutsidethe UnitedStates. Thisbookisprintedonacid-freepaper. International 1234567890DOCroOC098765432 Domestic 1234567890DOCroOC098765432 ISBN 0-07-245007-X ISBN 0-07-119260-3(ISE) Publisher:ElizabethA.Jones Sponsoringeditor:SuzanneJeans Developmentaleditor:MajaLorkovic Marketingmanager:SarahMartin Projectmanager:JaneMohr Productionsupervisor:SherryL.Kane Seniormediaprojectmanager:TammyJuran Coordinatoroffreelancedesign:RickD.Noel Coverdesigner: MaureenMcCutcheon Compositor: TECHBOOKS Typeface: 10/12TimesRoman Printer:R.R.Donnelley/Crawfordsville,IN Coverimage:Adaptedfrom artworkprovidedcourtesyofProfessorAhmedZewail'sgroupatCaltech. In1999,ProfessorZewailreceivedtheNobelPrizeinChemistryforstudiesonthetransitionstatesof chemicalreactionsusingfemtosecondspectroscopy. LibraryofCongressCataloging-in-PublicationData Davis,MarkE. Fundamentalsofchemicalreactionengineering/MarkE.Davis,RobertJ.Davis.- 1sted. p. em.- (McGraw-Hilichemicalengineeringseries) Includesindex. ISBN0-07-245007-X(acid-freepaper)- ISBN0-07-119260-3(acid-freepaper:ISE) I. Chemicalprocesses. I. Davis,RobertJ. II. Title. III. Series. TP155.7 .D38 2003 660'.28-dc21 2002025525 CIP INTERNATIONALEDITION ISBN0-07-119260-3 Copyright©2003.ExclusiverightsbyTheMcGraw-HillCompanies,Inc.,formanufactureandexport. Thisbookcannot bere-exportedfrom thecountrytowhichitissoldbyMcGraw-HilI.TheInternational EditionisnotavailableinNorthAmerica. www.mhhe.com McGraw.Hili Chemical Engineering Series Editorial Advisory Board Eduardo D. Glandt, Dean, SchoolofEngineeringandAppliedScience, UniversityofPennsylvania Michael T. Klein, Dean, SchoolofEngineering, Rutgers University Thomas F. Edgar, ProfessorofChemicalEngineering, UniversityofTexasatAustin BaileyandOllis Marlin BiochemicalEngineeringFundamentals ProcessControl: DesigningProcessesandControl SystemsforDynamicPerformance Bennettand Myers Momentum,HeatandMassTransfer McCabe,Smith,and Harriott UnitOperationsofChemicalEngineering Coughanowr ProcessSystemsAnalysisand Control Middlemanand Hochberg ProcessEngineeringAnalysisinSemiconductor deNevers DeviceFabrication AirPollutionControlEngineering PerryandGreen de Nevers Perry'sChemicalEngineers'Handbook FluidMechanicsfor ChemicalEngineers PetersandTimmerhaus Douglas PlantDesignandEconomicsforChemicalEngineers ConceptualDesignofChemicalProcesses Reid,Prausnitz,andPoling Edgarand Himmelblau PropertiesofGasesandLiquids OptimizationofChemicalProcesses Smith,Van Ness,andAbbott Gates,Katzer,and Schuit Introductionto ChemicalEngineeringThermodynamics ChemistryofCatalyticProcesses Treybal King MassTransferOperations SeparationProcesses Luyben ProcessModeling,Simulation,andControlfor ChemicalEngineers To Mary, Kathleen, and our parents Ruth and Ted. _________________C.Ott:rEHl:S Preface xi Chapter 4 Nomenclature xii The Steady-State Approximation: Catalysis 100 Chapter 1 4.1 Single Reactions 100 The Basics of Reaction Kinetics 4.2 The Steady-StateApproximation 105 for Chemical Reaction 4.3 Relaxation Methods 124 Engineering 1 1.1 The Scope ofChemical Reaction Chapter 5 Engineering I Heterogeneous Catalysis 133 1.2 The Extent ofReaction 8 1.3 The Rate ofReaction 16 5.1 Introduction 133 1.4 General Properties ofthe Rate Function for a 5.2 Kinetics ofElementary Steps: Adsorption, Single Reaction 19 Desorption, and Surface Reaction 140 1.5 Examples ofReaction Rates 24 5.3 Kinetics ofOverall Reactions 157 5.4 Evaluation ofKinetic Parameters 171 Chapter 2 Rate Constants of Elementary Chapter 6 Reactions 53 Effects of Transport Limitations on Rates of Solid-Catalyzed 2.1 Elementary Reactions 53 Reactions 184 2.2 Arrhenius Temperature Dependence ofthe Rate Constant 54 6.1 Introduction 184 2.3 Transition-State Theory 56 6.2 External Transport Effects 185 6.3 Internal Transport Effects 190 Chapter 3 6.4 Combined Internal and External Transport Effects 218 Reactors for Measuring Reaction Rates 64 6.5 Analysis ofRate Data 228 3.1 Ideal Reactors 64 Chapter 7 3.2 Batch and Semibatch Reactors 65 Microkinetic Analysis of Catalytic 3.3 Stirred-Flow Reactors 70 Reactions 240 3.4 Ideal Tubular Reactors 76 3.5 Measurement ofReaction Rates 82 7.1 Introduction 240 3.5.1 Batch Reactors 84 7.2 Asymmetric Hydrogenation ofProchiral Olefins 240 3.5.2FlowReactors 87 ix x Contents 7.3 Ammonia Synthesis on Transition Metal 10.2 One-Dimensional Models for Fixed-Bed Catalysts 246 Reactors 317 7.4 Ethylene Hydrogenation on Transition 10.3 Two-Dimensional Models for Fixed-Bed Metals 252 Reactors 325 7.5 Concluding Remarks 257 lOA Reactor Configurations 328 10.5 FluidizedBedswithRecirculatingSolids 331 Chapter 8 Nonideal Flow in Reactors 260 Appendix A Review of Chemical Equilibria 339 8.1 Introduction 260 8.2 Residence Time Distribution (RTD) 262 A.1 Basic Criteria for Chemical Equilibrium of 8.3 Application ofRTD Functions to the Reacting Systems 339 Prediction ofReactor Conversion 269 A.2 Determination ofEquilibrium 804 Dispersion Models for Nonideal Compositions 341 Reactors 272 8.5 Prediction ofConversion with an Axially Appendix B Dispersed PFR 277 Regression Analysis 343 8.6 Radial Dispersion 282 B.1 Method ofLeast Squares 343 8.7 Dispersion Models for Nonideal Flow B.2 Linear Correlation Coefficient 344 in Reactors 282 B.3 Correlation Probability with a Zero Y-Intercept 345 Chapter 9 BA NonlinearRegression 347 Nonisothermal Reactors 286 9.1 The Nature ofthe Problem 286 Appendix C 9.2 Energy Balances 286 Transport in Porous Media 349 9.3 Nonisothermal Batch Reactor 288 C.1 Derivation ofFlux Relationships in 9.4 Nonisothermal Plug Flow Reactor 297 One-Dimension 349 9.5 Temperature Effects in a CSTR 303 C.2 Flux Relationships in Porous Media 351 9.6 Stability and Sensitivity ofReactors Accomplishing Exothermic Reactions 305 Index 355 Chapter 10 Reactors Accomplishing Heterogeneous Reactions 315 10.1 Homogeneous Versus Heterogeneous Reactions in TubularReactors 315