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Elements of Chemical Reaction Engineering,9780135317082

Elements of Chemical Reaction Engineering

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Edition: 3rd
ISBN13: 9780135317082
ISBN10: 0135317088
Format: Hardcover w/CD
Pub. Date: 1999-01-01
Publisher(s): 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.

Table of Contents

PREFACE xv
1 MOLE BALANCES
1(32)
1.1 Definition of the Rate of Reaction, --r(A)
2(4)
1.2 The General Mole Balance Equation
6(2)
1.3 Batch Reactors
8(2)
1.4 Continuous-Flow Reactors
10(6)
1.4.1 Continuous-Stirred Tank Reactor
10(1)
1.4.2 Tubular Reactor
11(3)
1.4.3 Packed-Bed Reactor
14(2)
1.5 Industrial Reactors
16(9)
Summary
25(1)
Questions and Problems
25(6)
CD-ROM Material
31(1)
Supplementary Reading
31(2)
2 CONVERSION AND REACTOR SIZING
33(35)
2.1 Definition of Conversion
33(1)
2.2 Design Equations
34(6)
2.2.1 Batch Systems
34(3)
2.2.2 Flow Systems
37(3)
2.3 Applications of the Design Equations for Continuous-Flow Reactors
40(8)
2.4 Reactors in Series
48(8)
2.5 Some Further Definitions
56(3)
Summary
59(3)
Questions and Problems
62(4)
CD-ROM Material
66(1)
Supplementary Reading
67(1)
3 RATE LAWS AND STOICHIOMETRY
68(57)
3.1 Basic Definitions
68(15)
3.1.1 The Reaction Rate Constant
69(4)
3.1.2 The Reaction Order
73(2)
3.1.3 Elementary Rate Laws and Molecularity
75(2)
3.1.4 Reversible Reactions
77(4)
3.1.5 Nonelementary Rate Laws and Reactions
81(2)
3.2 Present Status of Our Approach to Reactor Sizing and Design
83(1)
3.3 Stoichiometric Table
84(21)
3.3.1 Batch Systems
84(3)
3.3.2 Constant-Volume Reaction Systems
87(3)
3.3.3 Flow Systems
90(2)
3.3.4 Volume Change with Reaction
92(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)
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