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Elements of Chemical Reaction Engineering

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Edition:
4th
ISBN13:

9780130473943

ISBN10:
0130473944
Media:
Hardcover
Pub. Date:
8/23/2005
Publisher(s):
Prentice Hall
List Price: $160.00

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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.

Author Biography

H. Scott Fogler is the Arthur F. Thurnau Professor, Vennema Professor of Chemical Engineering at the University of Michigan. His research interests include flow and reaction in porous media, fused chemical relations, gellation kinetics, and chemical reaction engineering problems in the petroleum industry. He has graduated 37 Ph.D. students and has more than 200 refereed publications in these areas. Fogler is the AIChE 2008 President-elect. He has chaired ASEE’s Chemical Engineering Division, served as director of the American Institute of Chemical Engineers, earned the Warren K. Lewis Award from AIChE for contributions to chemical engineering education, and received the Chemical Manufacturers Association’s National Catalyst Award. He is the co-author of the bestselling textbook Strategies for Creative Problem Solving, Second Edition (Prentice Hall, 2008).

Table of Contents

Preface xix
Mole Balances
1(36)
The Rate of Reaction, --rA
4(4)
The General Mole Balance Equation
8(2)
Batch Reactors
10(2)
Continuous-Flow Reactors
12(9)
Continuous-Stirred Tank Reactor
12(2)
Tubular Reactor
14(3)
Packed-Bed Reactor
17(4)
Industrial Reactors
21(16)
Summary
25(1)
CD-ROM Material
26(3)
Questions and Problems
29(6)
Supplementary Reading
35(2)
Conversion and Reactor Sizing
37(42)
Definition of Conversion
38(1)
Batch Reactor Design Equations
38(2)
Design Equations for Flow Reactors
40(5)
CSTR (also known as a Backmix Reactor or Vat)
43(1)
Tubular Flow Reactor (PFR)
44(1)
Packed-Bed Reactor
45(1)
Applications of the Design Equations for Continuous-Flow Reactors
45(9)
Reactors in Series
54(12)
CSTRs in Series
55(3)
PFRs in Series
58(2)
Combinations of CSTRs and PFRs in Series
60(4)
Comparing the CSTR and PFR Reactor Volumes and Reactor Sequencing
64(2)
Some Further Definitions
66(13)
Space Time
66(2)
Space Velocity
68(1)
Summary
69(2)
CD-ROM Materials
71(1)
Questions and Problems
72(5)
Supplementary Reading
77(2)
Rate Laws and Stoichiometry
79(64)
Part 1 Rate Laws
80(1)
Basic Definitions
80(2)
Relative Rates of Reaction
81(1)
The Reaction Order and the Rate Law
82(9)
Power Law Models and Elementary Rate Laws
82(4)
Nonelementary Rate Laws
86(2)
Reversible Reactions
88(3)
The Reaction Rate Constant
91(7)
Present Status of Our Approach to Reactor Sizing and Design
98(1)
Part 2 Stoichiometry
99(1)
Batch Systems
100(6)
Equations for Batch Concentrations
102(1)
Constant-Volume Batch Reaction Systems
103(3)
Flow Systems
106(37)
Equations for Concentrations in Flow Systems
107(1)
Liquid-Phase Concentrations
108(1)
Change in the Total Number of Moles with Reaction in the Gas Phase
108(16)
Summary
124(2)
CD-ROM Material
126(5)
Questions and Problems
131(10)
Supplementary Reading
141(2)
Isothermal Reactor Design
143(110)
Part 1 Mole Balances in Terms of Conversion
144(1)
Design Structure for Isothermal Reactors
144(4)
Scale-Up of Liquid-Phase Batch Reactor Data to the Design of a CSTR
148(8)
Batch Operation
148(8)
Design of Continuous Stirred Tank Reactors (CSTRs)
156(12)
A Single CSTR
157(1)
CSTRs in Series
158(2)
CSTRs in Parallel
160(2)
A Second-Order Reaction in a CSTR
162(6)
Tubular Reactors
168(7)
Pressure Drop in Reactors
175(21)
Pressure Drop and the Rate Law
175(2)
Flow Through a Packed Bed
177(5)
Pressure Drop in Pipes
182(3)
Analytical Solution for Reaction with Pressure Drop
185(11)
Spherical Packed-Bed Reactors
196(1)
Synthesizing the Design of a Chemical Plant
196(2)
Part 2 Mole Balances Written in Terms of Concentration and Molar Flow Rate
198(2)
Mole Balances on CSTRs, PFRs, PBRs, and Batch Reactors
200(1)
Liquid Phase
200(1)
Gas Phase
200(1)
Microreactors
201(6)
Membrane Reactors
207(8)
Unsteady-State Operation of Stirred Reactors
215(11)
Startup of a CSTR
216(1)
Semibatch Reactors
217(2)
Writing the Semibatch Reactor Equations in Terms of Concentrations
219(4)
Writing the Semibatch Reactor Equations in Terms of Conversion
223(3)
The Practical Side
226(27)
Summary
227(3)
ODE Solver Algorithm
230(1)
CD-ROM Material
231(3)
Questions and Problems
234(15)
Some Thoughts on Critiquing What You read
249(1)
Journal Critique Problems
249(3)
Supplementary Reading
252(1)
Collection and Analysis of Rate Data
253(52)
The Algorithm for Data Analysis
254(2)
Batch Reactor Data
256(21)
Differential Method of Analysis
257(10)
Integral Method
267(4)
Nonlinear Regression
271(6)
Method of Initial Rates
277(3)
Method of Half-Lives
280(1)
Differential Reactors
281(8)
Experimental Planning
289(1)
Evaluation of Laboratory Reactors
289(16)
Criteria
289(1)
Types of Reactors
290(1)
Summary of Reactor Ratings
290(1)
Summary
291(2)
CD-ROM Material
293(1)
Questions and Problems
294(8)
Journal Critique Problems
302(1)
Supplementary Reading
303(2)
Multiple Reactions
305(72)
Definitions
305(5)
Types of Reactions
305(5)
Parallel Reactions
310(10)
Maximizing the Desired Product for One Reactant
311(6)
Reactor Selection and Operating Conditions
317(3)
Maximizing the Desired Product in Series Reactions
320(7)
Algorithm for Solution of Complex Reactions
327(8)
Mole Balances
327(2)
Net Rates of Reaction
329(5)
Stoichiometry: Concentrations
334(1)
Multiple Reactions in a PFR/PBR
335(8)
Multiple Reactions in a CSTR
343(4)
Membrane Reactors to Improve Selectivity in Multiple Reactions
347(4)
Complex Reactions of Ammonia Oxidation
351(5)
Sorting It All Out
356(1)
The Fun Part
356(21)
Summary
357(2)
CD-ROM Material
359(2)
Questions and Problems
361(11)
Journal Critique Problems
372(3)
Supplementary Reading
375(2)
Reaction Mechanisms, Pathways, Bioreactions, and Bioreactors
377(94)
Active Intermediates and Nonelementary Rate Laws
377(17)
Pseudo-Steady-State Hypothesis (PSSH)
379(4)
Searching for a Mechanism
383(3)
Chain Reactions
386(5)
Reaction Pathways
391(3)
Enzymatic Reaction Fundamentals
394(15)
Enzyme--Substrate Complex
395(2)
Mechanisms
397(2)
Michaelis-Menten Equation
399(5)
Batch Reactor Calculations for Enzyme Reactions
404(5)
Inhibition of Enzyme Reactions
409(9)
Competitive Inhibition
410(2)
Uncompetitive Inhibition
412(2)
Noncompetitive Inhibition (Mixed Inhibition)
414(2)
Substrate Inhibition
416(1)
Multiple Enzyme and Substrate Systems
417(1)
Bioreactors
418(21)
Cell Growth
422(1)
Rate Laws
423(3)
Stoichiometry
426(5)
Mass Balances
431(3)
Chemostats
434(1)
Design Equations
435(1)
Wash-out
436(2)
Oxygen-Limited Growth
438(1)
Scale-up
439(1)
Physiologically Based Pharmacokinetic (PBPK) Models
439(32)
Summary
447(2)
CD-ROM Material
449(5)
Questions and Problems
454(14)
Journal Critique Problems
468(1)
Supplementary Reading
469(2)
Steady-State Nonisothermal Reactor Design
471(120)
Rationale
472(1)
The Energy Balance
473(13)
First Law of Thermodynamics
473(1)
Evaluating the Work Term
474(2)
Overview of Energy Balances
476(3)
Dissecting the Steady-State Molar Flow Rates to Obtain the Heat of Reaction
479(2)
Dissecting the Enthalpies
481(2)
Relating ΔHRX(T), ΔH®RX (TR), and ΔCP
483(3)
Adiabatic Operation
486(9)
Adiabatic Energy Balance
486(1)
Adiabatic Tubular Reactor
487(8)
Steady-State Tubular Reactor with Heat Exchange
495(16)
Deriving the Energy Balance for a PFR
495(4)
Balance on the Coolant Heat Transfer Fluid
499(12)
Equilibrium Conversion
511(11)
Adiabatic Temperature and Equilibrium Conversion
512(8)
Optimum Feed Temperature
520(2)
CSTR with Heat Effects
522(11)
Heat Added to the Reactor, Q
522(11)
Multiple Steady States
533(10)
Heat-Removed Term, R(T)
534(1)
Heat of Generation, G(T)
534(2)
Ignition-Extinction Curve
536(4)
Runaway Reactions in a CSTR
540(3)
Nonisothermal Multiple Chemical Reactions
543(8)
Energy Balance for Multiple Reactions in Plug-Flow Reactors
544(4)
Energy Balance for Multiple Reactions in CSTR
548(3)
Radial and Axial Variations in a Tubular Reactor
551(10)
The Practical Side
561(30)
Summary
563(3)
CD-ROM Material
566(2)
Questions and Problems
568(21)
Journal Critique Problems
589(1)
Supplementary Reading
589(2)
Unsteady-State Nonisothermal Reactor Design
591(54)
The Unsteady-State Energy Balance
591(3)
Energy Balance on Batch Reactors
594(20)
Adiabatic Operation of a Batch Reactor
594(5)
Batch Reactor with Interrupted Isothermal Operation
599(6)
Reactor Safety: The Use of the ARSST to Find ΔHRx, E and to Size Pressure Relief Valves
605(9)
Semibatch Reactors with a Heat Exchanger
614(5)
Unsteady Operation of a CSTR
619(6)
Startup
619(4)
Falling Off the Steady State
623(2)
Nonisothermal Multiple Reactions
625(3)
Unsteady Operation of Plug-Flow Reactors
628(17)
Summary
629(1)
CD-ROM Material
630(3)
Questions and Problems
633(11)
Supplementary Reading
644(1)
Catalysis and Catalytic Reactors
645(112)
Catalysts
645(10)
Definitions
646(2)
Catalyst Properties
648(4)
Classification of Catalysts
652(3)
Steps in a Catalytic Reaction
655(16)
Step 1 Overview: Diffusion from the Bulk to the External Transport
658(2)
Step 2 Overview: Internal Diffusion
660(1)
Adsorption Isotherms
661(5)
Surface Reaction
666(2)
Desorption
668(1)
The Rate-Limiting Step
669(2)
Synthesizing a Rate Law, Mechanism, and Rate-Limiting Step
671(17)
Is the Adsorption of Cumene Rate-Limiting?
674(3)
Is the Surface Reaction Rate-Limiting?
677(1)
Is the Desorption of Benzene Rate-Limiting?
678(2)
Summary of the Cumene Decomposition
680(1)
Reforming Catalysts
681(3)
Rate Laws Derived from the Pseudo-Steady-State Hypothesis
684(3)
Temperature Dependence of the Rate Law
687(1)
Heterogeneous Data Analysis for Reactor Design
688(10)
Deducing a Rate Law from the Experimental Data
689(2)
Finding a Mechanism Consistent with Experimental Observations
691(1)
Evaluation of the Rate Law Parameters
692(2)
Reactor Design
694(4)
Reaction Engineering in Microelectronic Fabrication
698(6)
Overview
698(2)
Etching
700(1)
Chemical Vapor Deposition
701(3)
Model Discrimination
704(3)
Catalyst Deactivation
707(50)
Types of Catalyst Deactivation
709(12)
Temperature-Time Trajectories
721(1)
Moving-Bed Reactors
722(6)
Straight-Through Transport Reactors (STTR)
728(5)
Summary
733(3)
ODE Solver Algorithm
736(1)
CD-ROM Material
736(2)
Questions and Problems
738(15)
Journal Critique Problems
753(2)
Supplementary Reading
755(2)
External Diffusion Effects on Heterogeneous Reactions
757(56)
Diffusion Fundamentals
758(3)
Definitions
758(1)
Molar Flux
759(1)
Fick's First Law
760(1)
Binary Diffusion
761(10)
Evaluating the Molar Flux
761(4)
Boundary Conditions
765(1)
Modeling Diffusion Without Reaction
766(4)
Temperature and Pressure Dependence of DAB
770(1)
Modeling Diffusion with Chemical Reaction
771(1)
External Resistance to Mass Transfer
771(17)
The Mass Transfer Coefficient
771(2)
Mass Transfer Coefficient
773(1)
Correlations for the Mass Transfer Coefficient
774(2)
Mass Transfer to a Single Particle
776(4)
Mass Transfer--Limited Reactions in Packed Beds
780(3)
Robert the Worrier
783(5)
What If. . .? (Parameter Sensitivity)
788(4)
The Shrinking Core Model
792(21)
Catalyst Regeneration
793(5)
Pharmacokinetics--Dissolution of Monodispersed Solid Particles
798(2)
Summary
800(1)
CD-ROM Material
801(1)
Questions and Problems
802(8)
Supplementary Reading
810(3)
Diffusion and Reaction
813(54)
Diffusion and Reaction in Spherical Catalyst Pellets
814(13)
Effective Diffusivity
814(2)
Derivation of the Differential Equation Describing Diffusion and Reaction
816(3)
Writing the Equation in Dimensionless Form
819(3)
Solution to the Differential Equation for a First-Order Reaction
822(5)
Internal Effectiveness Factor
827(6)
Falsified Kinetics
833(2)
Overall Effectiveness Factor
835(3)
Estimation of Diffusion- and Reaction-Limited Regimes
838(4)
Weisz--Prater Criterion for Internal Diffusion
839(2)
Mears' Criterion for External Diffusion
841(1)
Mass Transfer and Reaction in a Packed Bed
842(6)
Determination of Limiting Situations from Reaction Data
848(1)
Multiphase Reactors
849(2)
Slurry Reactors
850(1)
Trickle Bed Reactors
850(1)
Fluidized Bed Reactors
851(1)
Chemical Vapor Deposition (CVD)
851(16)
Summary
851(1)
CD-ROM Material
852(3)
Questions and Problems
855(8)
Journal Article Problems
863(1)
Journal Critique Problems
863(2)
Supplementary Reading
865(2)
Distributions of Residence Times for Chemical Reactors
867(78)
General Characteristics
868(1)
Part 1 Characteristics and Diagnostics
868(3)
Residence-Time Distribution (RTD) Function
870(1)
Measurement of the RTD
871(7)
Pulse Input Experiment
871(5)
Step Tracer Experiment
876(2)
Characteristics of the RTD
878(7)
Integral Relationships
878(1)
Mean Residence Time
879(2)
Other Moments of the RTD
881(3)
Normalized RTD Function, E(Θ)
884(1)
Internal-Age Distribution, I(α)
885(1)
RTD in Ideal Reactors
885(6)
RTDs in Batch and Plug-Flow Reactors
885(2)
Single-CSTR RTD
887(1)
Laminar Flow Reactor (LFR)
888(3)
Diagnostics and Troubleshooting
891(11)
General Comments
891(1)
Simple Diagnostics and Troubleshooting Using the RTD for Ideal Reactors
892(5)
PFR/CSTR Series RTD
897(5)
Part 2 Predicting Conversion and Exit Concentration
902(1)
Reactor Modeling Using the RTD
902(2)
Zero-Parameter Models
904(19)
Segregation Model
904(11)
Maximum Mixedness Model
915(7)
Comparing Segregation and Maximum Mixedness Predictions
922(1)
Using Software Packages
923(4)
Heat Effects
927(1)
RTD and Multiple Reactions
927(18)
Segregation Model
927(1)
Maximum Mixedness
928(5)
Summary
933(1)
CD-ROM Material
934(2)
Questions and Problems
936(8)
Supplementary Reading
944(1)
Models for Nonideal Reactors
945(64)
Some Guidelines
946(2)
One-Parameter Models
947(1)
Two-Parameter Models
948(1)
Tanks-in-Series (T-I-S) Model
948(7)
Dispersion Model
955(2)
Flow, Reaction, and Dispersion
957(17)
Balance Equations
957(1)
Boundary Conditions
958(4)
Finding Da and the Peclet Number
962(1)
Dispersion in a Tubular Reactor with Laminar Flow
962(2)
Correlations for Da
964(2)
Experimental Determination of Da
966(4)
Sloppy Tracer Inputs
970(4)
Tanks-in-Series Model Versus Dispersion Model
974(1)
Numerical Solutions to Flows with Dispersion and Reaction
975(4)
Two-Parameter Models---Modeling Real Reactors with Combinations of Ideal Reactors
979(9)
Real CSTR Modeled Using Bypassing and Dead Space
979(6)
Real CSTR Modeled as Two CSTRs with Interchange
985(3)
Use of Software Packages to Determine the Model Parameters
988(2)
Other Models of Nonideal Reactors Using CSTRs and PFRs
990(1)
Applications to Pharmacokinetic Modeling
991(18)
Summary
993(1)
CD-ROM Material
994(2)
Questions and Problems
996(9)
Supplementary Reading
1005(4)
Appendix A Numerical Techniques 1009(8)
Appendix B Ideal Gas Constant and Conversion Factors 1017(4)
Appendix C Thermodynamic Relationships Involving the Equilibrium Constant 1021(6)
Appendix D Measurement of Slopes on Semilog Paper 1027(2)
Appendix E Software Packages 1029(4)
Appendix F Nomenclature 1033(4)
Appendix G Rate Law Data 1037(2)
Appendix H Open-Ended Problems 1039(4)
Appendix I How to Use the CD-Rom 1043(6)
Appendix J Use of Computational Chemistry Software Packages 1049(2)
Index 1051(37)
About the CD-Rom 1088

Excerpts

The man who has ceased to learn ought not to be allowed to wander around loose in these dangerous days. M. M. Coady A. The Audience This book and interactive CD-ROM is intended for use as both an undergraduate-level and a graduate-level text in chemical reaction engineering. The level will depend on the choice of chapters and CD-ROM Professional Reference Shelf(PRS) material to be covered and the type and degree of difficulty of problems assigned. 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 (CRE). This goal will be achieved by presenting a structure that allows the reader to solve reaction engineering problems through reasoningrather than through memorization and recall of numerous equations and the restrictions and conditions under which each equation applies. The algorithms presented in the text for reactor design provide this framework, and the homework problems will give practice at using the algorithms. The conventional home problems at the end of each chapter are designed to reinforce the principles in the chapter. These problems are about equally divided between those that can be solved with a calculator and those that require a personal computer and a numerical software package such as Polymath, MATLAB, or FEMLAB. To give a reference point as to the level of understanding of CRE required in the profession, a number of reaction engineering problems from the California Board of Registration for Civil and Professional EngineersChemical Engineering Examinations (PECEE) are included in the text.1Typically, these problems should each require approximately 30 minutes to solve. Finally, the CD-ROM should greatly facilitate learning the fundamentals of CRE because it includes summary notes of the chapters, added examples, expanded derivations, and self tests. A complete description of these learning resources is given in the "The Integration of the Text and the CD-ROM" section in this Preface. B.2. To Develop Critical Thinking Skills A second goal is to enhance critical thinking skills. A number of home problems have been included that are designed for this purpose. Socratic questioning is at the heart of critical thinking, and a number of homework problems draw from R. W. Paul's six types of Socratic questions2shown in Table P-1. TABLE P-1. SIX TYPES OF SOCRATIC QUESTIONS Questions for clarification:Why do you say that? How does this relate to our discussion? "Are you going to include diffusion in your mole balance equations?" Questions that probe assumptions:What could we assume instead? How can you verify or disprove that assumption? "Why are you neglecting radial diffusion and including only axial diffusion?" Questions that probe reasons and evidence:What would be an example? "Do you think that diffusion is responsible for the lower conversion?" Questions about viewpoints and perspectives:What would be an alternative? "With all the bends in the pipe, from an industrial/practical standpoint, do you think diffusion and dispersion will be large enough to affect the conversion?" Questions that probe implications and consequences:What generalizations can you make? What are the consequences of that assumption? "How would our results be affected if we neglected diffusion?" Questions about the question:What was the point of this question? Why do you think I asked this question? "Why do you think diffusion is important?" Scheffer and Rubenfeld3,4expand on the practice of critical thinking skills discussed by R. W. Paul by using the activities, statements, and questions shown in Table P-2. TABLE P-2. CRITICAL THINKING SKILLS2,3 Analyzing:separating or breaking a whole into parts to discover their nature, function, and relationships "I studied it piece by piece." "I sorted things out." Applying Standards:judging according to established personal, professional, or social rules or criteria "I judged it according to...." Discriminating:recognizing differences and similarities among things or situations and distinguishing carefully as to category or rank "I rank ordered the various...." "I grouped things together." Information Seeking:searching for evidence, facts, or knowledge by identifying relevant sources and gathering objective, subjective, historical, and current data from those sources "I knew I needed to look up/study...." "I kept searching for data." Logical Reasoning:drawing inferences or conclusions that are supported in or justified by evidence "I deduced from the information that...." "My rationale for the conclusion was...." Predicting:envisioning a plan and its consequences "I envisioned the outcome would be...." "I was prepared for...." Transforming Knowledge:changing or converting the condition, nature, form, or function of concepts among contexts "I improved on the basics by...." "I wondered if that would fit the situation of ...." I have found the best way to develop and practice critical thinking skills is to use Tables P-1 and P-2 to help students write a question on any assigned homework problem and then to explain why the question involves critical thinking. More information on critical thinking can be found on the CD-ROM in the section on Problem Solving. B.3. To Develop Creative Thinking Skills The third goal of this book is to help develop creative thinking skills. This goal will be achieved by using a number of problems that are open-ended to various degrees. Here the students can practice their creative skills by exploring the example problems as outlined at the beginning of the home problems of each chapter and by making up and solving an original problem. Problem P4-1 gives some guidelines for developing original problems. A number of techniques that can aid the students in practicing and enhancing their creativity can be found in Fogler and LeBlanc5and in the Thoughts on Problem Solvingsection on the CD-ROM and on the web sitewww.engin.umich.edu/~cre. We will use these techniques, such as Osborn's checklist and de Bono's lateral thinking (which involves considering other people's views and responding to random stimulation) to answer add-on questions such as those in Table P-3. TABLE P-3. PRACTICING CREATIVE THINKING Brainstorm ideas to ask another question or suggest another calculation that can be made for this homework problem. Brainstorm ways you could work this homework problem incorrectly. Brainstorm ways to make this problem easier or more difficult or more exciting. Brainstorm a list of things you learned from working this homework problem and what you think the point of the problem is. Brainstorm the reasons why your calculations overpredicted the conversion that was measured when the reactor was put on stream. Assume you made no numerical errors on your calculations. "What if..." questions: The "What if..." questions are particularly effective when used with the Living Example Problemswhere one varies the parameters to explore t


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