Preface ....................................................... xxv
Notations .................................................... xxxi
Overview ................................................... xxxvii
PART I FUNDAMENTALS REVISITED
Objectives ................................................... 1
Introduction ................................................. 1
The essential minimum of chemical reaction engineering ....... 2
The skill development ........................................ 2
Getting started .............................................. 2
Warm-up questions ............................................ 3
Qualitative ............................................... 3
Quantitative .............................................. 3
1 Reactions and reactors: Basic concepts ....................... 5
Chapter objectives ........................................... 5
Introduction ................................................. 5
Reaction rates ............................................... 5
Different definitions of the rate ......................... 6
Basic rate equation ....................................... 8
Stoichiometry of the rate equation ........................... 9
Basic relationships ....................................... 9
Conversion-concentration relationships ................... 10
Variable-density reactions ............................... 11
Reactors ................................................. 12
Batch reactor ............................................ 13
Reactions without volume change ....................... 14
Reactions with volume change .......................... 14
Nonisothermal operation .................................. 16
Optimal operating policies ............................ 18
Plug-flow reactors ....................................... 19
Basic PFR equation .................................... 20
Design equations ...................................... 21
Nonisothermal operation ............................... 21
Perfectly mixed flow reactor (MFR) ....................... 23
Basic CSTR equation ................................... 23
Nonisothermal operation .................................. 24
Multiple steady states ...................................... 26
MSS in a CSTR ............................................ 26
Adiabatic CSTR ........................................... 27
Stability of the steady states ........................ 28
Comparison of BR, PFR, and MFR ........................... 29
Explore yourself ............................................ 30
References .................................................. 31
Bibliography ................................................ 31
2 Complex reactions and reactors .............................. 33
Chapter objectives .......................................... 33
Introduction ................................................ 33
Reduction of complex reactions .............................. 34
Stoichiometry of simple and complex reactions ............ 34
Mathematical representation of simple and complex
reactions ................................................ 35
Independent reactions .................................... 36
Rate equations .............................................. 38
The concept of extent of reaction ........................ 38
Determination of the individual rates in a complex
reaction ................................................. 39
Selectivity and yield ....................................... 39
Definitions .............................................. 40
Analytical solutions ..................................... 40
Maximizing selectivity in a complex reaction:
Important considerations .............................. 43
Multistep reactions ...................................... 46
Definitions ........................................... 46
Yield versus number of steps ................................ 47
Reactor design for complex reactions ........................ 48
Batch reactor design based on number of components ....... 48
Use of extent of reaction or reaction coordinates ........ 50
Plug-flow reactor ........................................ 52
Continuous stirred tank reactor .......................... 53
Reactor choice for maximizing yields/selectivities .......... 56
Parallel reactions (nonreacting products) ................ 56
The general case ...................................... 56
Effect of reaction order .............................. 58
One of the reactants undergoes a second reaction ...... 59
Parallel-consecutive reactions ........................... 59
Plug-flow reactor with recycle .............................. 60
The basic design equation ................................ 60
Optimal design of RFR .................................... 62
Use of RFR to resolve a selectivity dilemma .............. 64
Semibatch reactors .......................................... 64
Constant-volume reactions with constant rates of
addition and removal: Scheme 1 ........................... 64
Variable-volume reactor with constant rate of inflow:
Scheme 2 ................................................. 66
Variable-volume reactor with constant rate of outflow
of one of the products: Scheme 3 ......................... 67
General expression for an SBR for multiple reactions
with inflow of liquid and outflow of liquid and vapor:
Scheme 4 ................................................. 70
Nonisothermal operation .................................. 71
Optimum temperatures/temperature profiles for maximizing
yields/selectivities ........................................ 71
Optimum temperatures ..................................... 72
Optimum temperature and concentration profiles in a PFR .. 72
Parallel reactions .................................... 72
Consecutive reactions ................................. 73
Extension to a batch reactor .......................... 73
Explore yourself ............................................ 74
References .................................................. 75
Bibliography ................................................ 76
Interlude I
Reactive distillation ....................................... 77
Membrane reactors ........................................... 78
Inorganic membranes for organic reactions/synthesis ...... 78
Potentially exploitable features of membranes ......... 79
Equilibrium shift in membrane reactors ................ 79
Controlled addition of reactants ...................... 80
Preventing excess reactant "slip" in reactions
requiring strict stoichiometric feeds ................. 80
Mimicking trickle-bed operation with improved
performance ........................................... 80
Coupling of reactions ................................. 80
Hybridization ......................................... 80
Phase transfer catalysis ................................. 81
References ............................................... 82
3 Nonideal reactor analysis Chapter objectives ................ 85
Introduction ................................................ 85
Two limits of the ideal reactor .......................... 86
Plug-flow reactors with recycle .......................... 86
Tanks-in-series model .................................... 87
Nonidealities defined with respect to the ideal reactors .... 88
Nonidealities in tubular reactors ........................ 88
Axial dispersion model ................................ 89
Nonidealities in MFR .................................. 90
Residence time distribution ................................. 91
Theory ................................................... 91
Types of distribution .................................... 93
Concept of mixing ........................................... 95
Regions of mixing ........................................ 95
Fully segregated flow .................................... 97
Micromixing policy ....................................... 98
Models for partial mixing ................................ 99
Axial dispersion model ................................ 99
Tanks-in-series model ................................ 100
Models for partial micromixing ....................... 100
Degree of segregation defined by the age of the
fluid at a point ..................................... 101
Turbulent mixing models .................................... 101
Characteristic timescales ............................... 102
Engulfment-deformation diffusion model .................. 104
Interaction by exchange with a mean ..................... 104
Zone model .............................................. 105
Joint PDF ............................................... 105
Practical implications of mixing in chemical synthesis ..... 106
General considerations .................................. 106
Dramatic illustration of the role of addition sequence
of reagents ............................................. 108
Explore yourself ........................................... 109
References ................................................. 110
Bibliography ............................................... 110
Interlude II .................................................. 111
Limits of mean field theory ................................ 111
The predator-prey problem or surface mixing ................ 111
Mixing problem addressed ................................... 113
Short contact time reactors ............................. 113
Microfluidic reactors ................................... 114
Passive devices for mixing and pumping ............... 115
Knudsen pump ............................................ 115
Mixing ..................................................... 115
Slug flow as a mixer .................................... 115
Dean flow as a static mixer ............................. 115
Elastic turbulence ......................................... 116
References ................................................. 116
PART II BUILDING ON FUNDAMENTALS
Introduction ............................................... 117
The different tools of the trade ........................... 117
Relationship between thermodynamics and chemical
reaction engineering .................................... 118
Relationship between transport phenomena and chemical
reaction engineering .................................... 118
Relationship between chemical reaction engineering and
kinetics ................................................ 118
Chemical reaction engineering as an experimental and
theoretical science ..................................... 118
4 Rates and equilibria: The thermodynamic and
extrathermodynamic approaches .............................. 121
Chapter objectives ......................................... 121
Introduction ............................................... 121
Basic thermodynamic relationships and properties ........ 122
Basic relationships ..................................... 122
Heats of reaction, formation, and combustion ............ 122
Implications of liquid phase reactions .................. 124
Free energy change and equilibrium constant ............. 124
Standard free energy change and equilibrium
constant ............................................. 124
Equilibrium compositions in gas phase reactions ...... 126
Accounting for condensed phase(s) .................... 126
Complex equilibria ...................................... 128
Simultaneous solution of equilibrium equations ....... 128
Extension to a nonideal system ....................... 129
Minimization of free energy .......................... 130
Thermodynamics of reactions in solution .................... 131
Partial molar properties ................................ 131
Medium and substituent effects on standard free energy
change, equilibrium constant, and activity coefficient .. 132
General considerations ............................... 132
Solvent and solute operators ......................... 133
Comments ................................................ 134
Extrathermodynamic approach ................................ 134
Basic principles ........................................ 134
Group contributions or additivity principle ............. 135
Extrathermodynamic relationships between rate and
equilibrium parameters ..................................... 136
Polanyi and Brønsted relations .......................... 136
Hammett relationship for dissociation constants ....... 137
Extrathermodynamic approach to selectivity .............. 138
Theoretical analysis ....................................... 138
Thermodynamics of adsorption ............................ 139
Henry's law ............................................. 141
Langmuir isotherm ....................................... 141
Inhomogeneities expressed in terms of a site-energy
distribution ............................................ 142
Two-dimensional equations of state and their
corresponding adsorption isotherms ...................... 143
Appendix ................................................... 144
Derivation of chemical equilibrium relationships for
simple reactions ........................................ 144
Reactions in gas phase ............................... 146
Reactions in liquid phase ............................ 146
Explore yourself ........................................... 147
References ................................................. 147
Bibliography ............................................... 148
Interlude III
Reactor design for thermodynamically limited reactions ..... 149
Kinetics ................................................ 149
Optimization of temperatures and pressures ............... 150
References ................................................. 152
5 Theory of chemical kinetics in bulk and on the surface ..... 153
Chapter objectives ......................................... 153
Chemical kinetics .......................................... 153
Collision theory ........................................... 154
Transition state theory .................................... 155
Proposing a kinetic model .................................. 158
Brief excursion for the classification of surface
reaction mechanisms ........................................ 159
Langmuir-Hinshelwood-Hougen-Watson models ............... 159
Langmuir isotherm .................................... 159
Rate-determining step ................................ 160
Basic procedure ...................................... 160
Eley-Rideal mechanism ................................... 165
Mars-van Krevelen mechanism ............................. 166
Michelis-Menten mechanism ............................... 168
Influence of surface nonideality ..................... 168
Paradox of heterogeneous kinetics ................. 169
Microkinetic analysis ...................................... 169
Postulate a mechanism ................................... 171
Determine the kinetic parameters ........................ 171
Simplify the mechanism .................................. 171
Compare the model predictions with the kinetic data ..... 172
Explore yourself ........................................... 174
References ................................................. 175
Bibliography ............................................... 175
6 Reactions with an interface: Mass and heat transfer
effects .................................................... 177
Chapter objectives ......................................... 177
Introduction ............................................... 177
Diffusivity ............................................. 178
Diffusivities in gases .................................. 178
Diffusivities in liquids ................................ 179
Effective diffusivity ................................... 179
Transport between phases ................................... 180
General remarks ......................................... 180
Film theory ............................................. 182
Penetration theory ...................................... 183
Surface renewal theory .................................. 184
Characteristic times for diffusion, reaction, and mass
transfer ................................................ 185
Two-film theory of mass and heat transfer for fluid-
fluid reactions in general .............................. 185
Mass transfer ........................................ 185
Heat transfer ........................................ 186
Mass transfer across interfaces: Fundamentals .............. 187
Solid catalyzed fluid reactions ............................ 189
Overall scheme .......................................... 189
Role of diffusion in pellets: Catalyst
effectiveness ........................................ 189
First-order isothermal reaction in a spherical
catalyst ............................................. 191
Weisz modulus: Practical useful quantity ................ 196
Nonisothermal effectiveness factors ..................... 197
Multicomponent diffusion ............................. 199
Miscellaneous effects ................................ 199
Extension to complex reactions .......................... 200
Noncatalytic gas-solid reactions ........................... 200
Gas-liquid reactions in a slab ............................. 204
Two-film theory ......................................... 205
Slow reactions ....................................... 205
Instantaneous reactions .............................. 206
Effect of external mass and heat transfer .................. 209
External effectiveness factor ........................... 209
Combined effects of internal and external diffusion ..... 209
Relative roles of mass and heat transfer in internal
and external diffusion .................................. 210
Gas phase reactants .................................. 210
Liquid phase reactants ............................... 211
Regimes of control ......................................... 212
Explore yourself ........................................... 213
References ................................................. 214
7 Laboratory reactors: Collection and analysis of the data ... 217
Chapter objectives ......................................... 217
Chemical reaction tests in a laboratory .................... 217
A perspective on statistical experimental design ........... 218
Batch laboratory reactors .................................. 220
Rate parameters from batch reactor data .................... 221
From concentration data ................................. 221
From pressure data ...................................... 223
Flow reactors for testing gas-solid catalytic reactions .... 225
Differential versus integral reactors ................... 226
Eliminating or accounting for transport disguises ....... 229
Eliminating the film mass transfer resistance ........ 229
Eliminating the pore diffusion resistances ........... 230
Eliminating axial dispersion effects ................. 231
Koros-Nowak criterion ................................ 231
Catalyst dilution for temperature uniformity ......... 231
Gradientless reactors ................................... 231
Transport disguises in perspective ......................... 231
Guidelines for eliminating or accounting for transport
disguises ............................................... 234
Analyzing the data ......................................... 235
Modeling of solid catalyzed reactions ................... 235
The overall scheme ................................... 235
LHHW models .......................................... 236
Selection of the most plausible model ................ 236
Influence of surface nonideality ........................ 239
Explore yourself ........................................... 239
References ................................................. 240
PART III BEYOND THE FUNDAMENTALS
Objectives ................................................. 243
Introduction ............................................... 244
The different tools of the trade ........................... 244
Process intensification ................................. 246
Microfluidics ........................................... 247
Membrane reactors ....................................... 248
Combo reactors .......................................... 249
Homogeneous catalysis ................................... 249
Phase-transfer catalysis ................................ 249
References ................................................. 249
8 Fixed-bed reactor design for solid catalyzed fluid-phase
reactions .................................................. 251
Chapter objectives ......................................... 251
Introduction ............................................... 251
Effect of catalyst packing in a tubular reactor ......... 251
Fixed-bed reactor ....................................... 252
Nonisothermal, nonadiabatic, and adiabatic reactors ........ 254
Design methodologies for NINA-PBR ....................... 256
Quasi-continuum models ............................... 257
Cell model ........................................... 257
Models based on the pseudo-homogeneous assumption ....... 257
Homogeneous, pseudo-homogeneous, and heterogeneous
models .................................................. 257
ID pseudo-homogeneous nonisothermal, nonadiabatic
flow ................................................. 260
Reduction to isothermal operation .................... 261
Momentum balance ..................................... 261
The basic model: 2D pseudo-homogeneous
nonisothermal, nonadiabatic with no axial diffusion .. 262
Extension to nonideal models with and without
heterogeneity ........................................ 265
Adiabatic reactor .......................................... 266
The approach ............................................ 266
A unique conversion-temperature relationship ......... 266
Single-bed reactor ................................... 268
Multiple-bed reactor ................................. 270
A simple graphical procedure ............................ 273
Strategies for heat exchange ......................... 273
Choice between NINA-PBR and A-PBR .......................... 274
Some practical considerations ........................... 275
Backmixing or axial dispersion ....................... 275
Nonuniform catalyst distributions between tubes ...... 275
Scale-up considerations ................................. 276
Alternative fixed-bed designs .............................. 276
Radial-flow reactors .................................... 276
Material, momentum, and energy balances ................. 279
Material balance ..................................... 279
Mass balance ......................................... 279
Momentum balance ..................................... 279
Some important observations .......................... 279
Catalytic wire-gauze reactors ........................... 280
Explore yourself ........................................... 281
References ................................................. 282
Bibliography ............................................... 282
9 Fluidized-bed reactor design for solid catalyzed fluid-
phase reactions ............................................ 285
Chapter objectives ......................................... 285
General comments ........................................... 285
Fluidizatiom Some basics ................................... 286
Minimum fluidization velocity ........................... 286
Two-phase theory of fluidization ........................... 287
Geldart's classification ................................... 287
Classification of fluidized-bed reactors ................ 288
Velocity limits of a bubbling bed ....................... 289
Fluid mechanical models of the bubbling bed .......... 291
Complete modeling of the fluidized-bed reactor ....... 291
Bubbling bed model of fluidized-bed reactors ............... 292
Bubbling bed ............................................ 292
Bubble rise velocity .................................... 293
Main features ........................................... 293
Mass transfer between bubble and emulsion ............ 294
Solids distribution ........................................ 294
Estimation of bed properties ............................ 295
Heat transfer ........................................... 295
Calculation of conversion .................................. 297
End region models ....................................... 297
Dilute bed region .................................... 297
Grid or jet region ................................... 298
Practical considerations ................................ 299
Recommended scale-up procedure .......................... 300
Strategies to improve fluid-bed reactor performance ........ 302
Packed fluidized-bed reactors ........................... 303
Reactor model for packed fluidized beds .............. 303
Staging of catalyst ..................................... 305
Extension to other regimes of fluidization types of
reactors ................................................... 306
Turbulent bed reactor ................................... 307
Fast fluidized-bed reactor .............................. 307
Transport (or pneumatic) reactor ........................ 308
Circulation systems ..................................... 309
Deactivation control ....................................... 310
Heat transfer controlled ................................ 312
Reactor choice for a deactivating catalyst .............. 312
Basic equation ....................................... 313
Fixed-bed reactor .................................... 314
Fluidized-bed reactor ................................ 315
Moving bed reactor ................................... 315
Some practical considerations .............................. 318
Slugging ................................................ 318
Defluidization of bed: Sudden death ..................... 318
Gulf streaming .......................................... 318
Effects of fines ........................................ 318
Start-up ................................................ 319
Fluidized-bed versus fixed-bed reactors .................... 319
Explore yourself ........................................... 320
References ................................................. 321
10 Gas-solid noncatalytic reactions and reactors .............. 325
Chapter objectives ......................................... 325
Introduction ............................................... 325
Modeling of gas-solid reactions ............................ 326
Shrinking core model .................................... 327
Volume reaction model ................................... 329
Zone models ............................................. 331
77?e particle-pellet or grain models .................... 332
Other models ............................................... 334
Extensions to the basic models ............................. 334
Bulk-flow or volume-change effects ...................... 334
Fffect f of temperature change .......................... 335
Models that account for structural variations .............. 336
Effect of reaction ...................................... 336
Effect of sintering ..................................... 338
A general model that can be reduced to specific ones ....... 338
Gas-solid noncatalytic reactors ............................ 339
Fixed-bed reactors ...................................... 340
Moving-bed reactors ..................................... 343
Fluidized-bed reactors .................................. 345
References ................................................. 345
11 Gas-liquid and liquid-liquid reactions and reactors ........ 347
Chapter objectives ......................................... 347
Introduction ............................................... 347
Diffusion accompanied by an irreversible reaction of
general order ........................................... 350
Diffusion and reaction in series with no reaction
in film: Regimes 1 and 2 (very slow and slow
reactions), and regimes between 1 and 2 .............. 350
Regimes 1 and 2: Very slow and slow reactions ........ 350
Regimes between 1 and 2 .............................. 352
Diffusion and reaction in film, followed by negligible
or finite reaction in the bulk: Regime 3 (fast
reaction), and regime covering 1, 2, and 3 ........... 352
Reaction entirely in film ............................ 352
Reactions both in film and bulk (regimes 1-2-3) ...... 353
Measurement of mass transfer coefficients .................. 354
Microfluidic devices .................................... 354
Reactor design ............................................. 355
A generalized form of equation for all regimes ............. 356
Regime 1: Very slow reaction ............................ 356
Regime 2 and regime between 1 and 2: Diffusion in film
without and with reaction in the bulk ................... 356
Regime 3: Fast reaction ................................. 357
Regime between 2 and 3 .................................. 357
Regime 4: Instantaneous reaction ........................ 357
Classification of gas-liquid contactors .................... 358
Classification-1 (based on manner of phase contact) ..... 358
Classification-2 (based on the manner of energy
delivery) ............................................... 359
Mass transfer coefficients and interfacial areas of
some common contactors .................................. 359
Role of backmixing in different contactors .............. 359
Reactor design for gas-liquid reactions .................... 361
The overall strategy .................................... 361
Calculation of reactor volume ........................... 361
Case 1: Plug gas, plug liquid, and countercurrent
steady state ................................. 363
Case 2: Same as case 1 but with cocurrent flow ....... 363
Case 3: Plug gas, mixed liquid, and steady state ..... 364
Case 4: Mixed gas, mixed liquid, and steady state .... 364
Case 5: Mixed gas, batch liquid, and unsteady state .. 364
Comments ............................................. 365
Reactor choice ............................................. 369
The criteria ............................................ 369
Volume minimization criterion ........................... 369
General discussion ................................... 369
Limitations of volume minimization ................... 371
Steps in volume minimization ......................... 371
Energy minimization criteria ............................ 372
Criterion 2(a): Homogeneous regime (regime 1) ........ 372
Criterion 2(b): Heterogeneous regime (regimes 2-4) ... 374
Comparison of criteria ............................... 374
Liquid-liquid contactors ................................ 375
Classification of liquid-liquid reactors ............. 375
Values of mass transfer coefficients and
interfacial areas for different contactors ........... 376
Calculation of reactor volume/reaction time .......... 377
Stirred tank reactor. Some practical considerations ........ 379
References ................................................. 380
12 Multiphase reactions and reactors .......................... 383
Chapter objectives ......................................... 383
Introduction ............................................... 383
Design of three-phase catalytic reactors ................... 383
The approach ............................................ 383
Semibatch reactors: Design equations for (1,0)- and
(1,1)-order reactions ................................... 384
Continuous reactors ..................................... 385
Types of three-phase reactors .............................. 387
Mechanically agitated slurry reactors ................... 389
Mass transfer ........................................ 389
Minimum speed for complete suspension ................ 390
Gas holdup ........................................... 390
Controlling regimes in an MASR ....................... 390
Bubble column slurry reactors ........................... 390
Regimes of flow ...................................... 391
Mass transfer ........................................ 391
Minimum velocity for complete solids suspension ...... 392
Gas holdup ........................................... 392
Loop slurry reactors ....................................... 396
Types of loop reactors .................................. 396
Mass transfer ........................................ 397
Trickle bed reactors (TBRs) ................................ 397
Regimes of flow ......................................... 397
Mass transfer ........................................... 398
Controlling regimes in TBRs ............................. 398
Collection and interpretation of laboratory data for
three-phase catalytic reactions ............................ 398
Experimental methods .................................... 398
Effect of temperature ................................... 398
Interpretation of data .................................. 399
Three-phase noncatalytic reactions ......................... 401
Solid slightly soluble .................................. 402
Negligible dissolution of solid in the gas-liquid
film ................................................. 402
Significant dissolution of solid in the gas-liquid
film ................................................. 403
Solid insoluble ...................................... 403
References ................................................. 408
Bibliography ............................................... 409
13 Membrane-assisted reactor engineering ...................... 411
Introduction ............................................... 411
General considerations .................................. 411
Major types of membrane reactors ........................... 411
Modeling of membrane reactors .............................. 414
Packed-bed inert selective membrane reactor with
packed catalyst (IMR-P) ................................. 414
Model equations ...................................... 415
Extension to consecutive reactions ................... 420
Fluidized-bed inert selective membrane reactor (IMR-F) .. 420
Catalytic selective membrane reactor (CMR-E) ............ 421
Model equations ...................................... 422
Main features of the CMR-E ........................... 422
Packed-bed catalytic selective membrane reactor
(CMR-P) ................................................. 423
Catalytic nonselective membrane reactor (CNMR-E) ........ 424
Catalytic nonselective hollow membrane reactor for
multiphase reactions (CNHMR-MR) ......................... 424
Immobilized enzyme membrane reactor ..................... 425
Operational features ....................................... 425
Combining exothermic and endothermic reactions .......... 425
Controlled addition of one of the reactants in
a bimolecular reaction using an IMR-P ................ 426
Effect of tube and shell side flow conditions ............... 428
Comparison of reactors ...................................... 428
Effect (1) .............................................. 429
Effect (2) .............................................. 429
Combined effect ......................................... 429
Examples of the use of membrane reactors in organic
technology/synthesis ....................................... 429
Small- and medium-volume chemicals ...................... 430
Vitamin К ............................................ 430
Linalool (a fragrance) ............................... 431
Membrane reactors for economic processes (including
energy integration) ..................................... 431
References ................................................. 432
14 Combo reactors: Distillation column reactors ............... 435
Distillation column reactor ................................ 436
Enhancing role of distillation: Basic principle ............ 436
Batch reactor with continuous removal of product ........ 436
Case 1: Accumulation of S ............................ 437
Case 2: S is not completely vaporized ................ 438
Packed DCR ........................................... 439
Overall effectiveness factor in a packed DCR ............... 441
Residue curve map (RCM) ................................. 442
Design methodology ................................... 443
Generating residual curve maps ....................... 445
Distillation-reaction ...................................... 447
Dissociation-extractive distillation .................... 448
Basic principle ...................................... 448
Theory ............................................... 448
References ................................................. 451
15 Homogeneous catalysis ..................................... 453
Introduction ............................................... 453
General ................................................. 453
Formalisms in transition metal catalysis ................... 453
Uniqueness of transition metals ......................... 453
Oxidation state of a metal .............................. 455
Coordinative unsaturation, coordination number, and
coordination geometry ................................... 457
Ligands and their role in transition metal catalysis .... 457
Electron rules ("electron bookkeeping") ................. 459
18-electron rule ..................................... 459
16-18-electron rule .................................. 460
Operational scheme of homogeneous catalysis ................ 460
Basic reactions of homogeneous catalysis ................... 461
Reactions of ligands (mainly replacement) ............... 461
Elementary reactions (or activation steps) .............. 462
Coordination reactions ............................... 462
Addition reactions ................................... 462
Main reactions .......................................... 463
Insertion ............................................ 463
Elimination .......................................... 464
Main features of transition metal catalysis in organic
synthesis: A summary ....................................... 464
A typical class of industrial reactions: Hydrogenation ..... 465
Hydrogenation by Wilkinson's catalyst ................... 465
Wilkinson's catalyst .................................... 465
The catalytic cycle .................................. 466
Kinetics and modeling ................................ 466
A general hydrogenation model ........................... 467
General kinetic analysis ................................... 468
Intrinsic kinetics ...................................... 468
Multistep control .................................... 468
Role of diffusion ....................................... 469
Complex kinetics—Main issue ............................. 469
Reactions involving one gas and one liquid .............. 470
Regimes 1 and 2 ...................................... 470
Regime between 1 and 2 (reaction in bulk) ............ 470
Regime 3 (reaction in film) .......................... 472
Two gases and a liquid .................................. 473
References ................................................. 473
16 Phase-transfer catalysis ................................... 475
Introduction ............................................... 475
What is PTC? ............................................ 475
Fundamentals of PTC ........................................ 476
Classification of PTC systems ........................... 476
Phase-transfer catalysts ................................ 477
Mechanism of PTC ........................................... 478
Liquid-liquid PTC ....................................... 478
Solid-Liquid PTC ........................................ 478
Solid-supported PTC or triphase catalysis (TPC) ......... 481
Modeling of PTC reactions .................................. 482
LLPTC models ............................................ 483
SLPTC models ............................................ 484
Interpretation of the role of diffusion:
A cautionary note .................................... 486
Supported PTC (TPC) ..................................... 487
Kinetic mechanism of TPC systems ........................ 488
Methodology for modeling solid-supported PTC reactions .. 489
Supported PTC with LHHW kinetics ........................ 490
"Cascade engineered" PTC process ........................... 494
References ................................................. 495
17 Forefront of the chemical reaction engineering field ....... 497
Objective .................................................. 497
Introduction ............................................... 497
Resource economy ........................................... 497
Carbon and hydrogen ..................................... 498
Bio-renewables .......................................... 498
Energy economy ............................................. 499
Heat integration in microreactors ....................... 500
Sonochemical reaction triggering ........................ 500
Photochemical or photocatalytic systems ................. 500
Electrochemical techniques .............................. 500
Microwaves .............................................. 501
Chemical reaction engineer in the twenty-first century ..... 501
In Closing ................................................. 502
Subject Index ................................................. 503
Author Index .................................................. 515
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