Elements of Chemical Reaction Engineering

by Fogler, H. Scott

• ISBN13: 9780135317082
• ISBN10: 0135317088
• Edition: 3rd
• Format: Hardcover w/CD
• Copyright: 1999-01-01
• Publisher: Prentice Hall PTR

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)
ABOUT THE CD	976