Murzin / Salmi Catalytic Kinetics

1. Auflage 2005
ISBN: 978-0-08-045546-4
Verlag: Elsevier Science & Techn.
Format: EPUB
Kopierschutz: 6 - ePub Watermark

E-Book, Englisch, 492 Seiten

Chemistry and chemical technology have been at the heart of the revolutionary developments of the 20th century. The chemical industry has a long history of combining theory (science) and practice (engineering) to create new and useful products. Worldwide, the process industry (which includes chemicals, petrochemicals, petroleum refining, and pharmaceuticals) is a huge, complex, and interconnected global business with an annual production value exceeding 4 trillion dollars. Although in industry special focus is in heterogeneous catalysis, homogeneous, enzymatic, photochemical and electrochemical catalysis should not be overlooked; as the major aim is to produce certain chemicals in the best possible way, applying those types of catalysis, which suit a particular process in the most optimal way. Catalysis according to the very definition of it deals with enhancement of reaction rates, that is, with catalytic kinetics. This book unifies the main sub disciplines forming the cornerstone of catalytic kinetics.
* Provides a broad overview catalytic kinetics
* Bridges the gaps that exist between hetero-, homo- and bio-catalysis
* Written by internationally renowned experts in this field

Dmitry Murzin is Professor of Chemical Technology at Åbo Akademi University in Turku, Finland. For the past 10 years Murzin has been Professor at the Finland University's Laboratory of Industrial Chemistry and Reaction Engineering. Before that, he headed the chemicals division of BASF in Moscow. He also spent seven years as a researcher in the Department of Catalysis at the Karpov Institute of Physical Chemistry in Moscow. He is author or co-author of more than 530 journal articles and book chapters.

Autoren/Hrsg.

Murzin, Dmitry Yu

Salmi, Tapio

Inhaltsverzeichnis

1;Cover;1
2;Preface;6
3;Setting the scene;12
3.1;History;12
3.2;Catalysis;13
3.3;Formal kinetics;19
3.4;Acquisition of kinetic data;23
3.4.1;Batch reactors;23
3.4.2;CSTR;26
3.4.3;Plug flow reactors;27
3.4.4;Gradient-free recycle reactors;30
3.5;Kinetics and thermodynamics;33
4;Catalysis;38
4.1;Homogeneous catalysis;38
4.1.1;Gas-phase catalysis;38
4.1.2;Acid-base catalysis;39
4.1.3;Catalysis by transition metals;40
4.1.4;Biocatalysis (catalysis by enzymes);8
4.1.5;Heterogeneous catalysis;51
4.1.5.1;Classification;51
4.1.5.2;Kinetics in heterogeneous catalysis;52
4.1.5.3;Elementary steps;54
4.1.5.4;Adsorption isotherms - ideal surfaces;57
4.1.5.5;Adsorption isotherms - real surfaces;60
4.1.5.5.1;Adsorption isotherms - induced nonuniformity;68
4.1.5.6;Adsorption isotherms - multicentered adsorption;76
4.1.5.7;Different adsorption modes;82
5;Elementary reactions;84
5.1;Reaction rate theory;84
5.2;Reaction mechanism;92
5.3;Quasi-equilibrium approximation;95
5.4;Relationship between thermodynamics and kinetics;99
5.5;Transition state theory of surface reactions;102
5.6;Rates of reactions on nonideal surfaces;105
5.6.1;Biographical nonuniformity;105
5.6.2;Lateral interactions;111
5.6.3;Limited mobility of adsorbed species;114
5.7;Determenistic and stochastic models;115
5.8;Micro kinetic modelling;118
5.9;Compensation effect;119
6;Complex reactions;122
6.1;Steady-state kinetics of complex reactions;122
6.2;Basic routes of complex reactions;132
6.3;Single-route steady-state reaction;134
6.4;Topological analysis of complex reactions;138
6.5;Kinetic aspects of selectivity;146
6.6;Parallel reactions : kinetic coupling;154
6.7;Reduction of complexity;159
7;Homogeneous catalytic kinetics;160
7.1;Homogeneous acid-base catalysis;160
7.2;Nucleophilic catalysis;169
7.3;Catalysis by metal ions;173
7.4;Catalysis by organometallic compexes;175
7.4.1;Single catalytic cycles;175
7.4.2;Ligand deficient catalysis and inhibition;183
7.4.3;Multiple cycles;187
8;Enzymatic kinetics;200
8.1;Enzymatic catalysis;200
8.2;Cooperative kinetics;213
8.3;Inhibition;223
8.4;Effects of pH;231
8.5;Heterogeneos systems/immobilized enzymes;233
9;Heterogeneous catalytic kinetics;236
9.1;Reactions on ideal surfaces;236
9.2;Reactions on nonideal surfaces;246
9.2.1;Intrinsic nonuniformity;246
9.2.2;Induced nonuniformity;251
9.2.3;Thermodynamic considerations of kinetics on non-ideal surfaces;252
9.2.4;Ammonia synthesis;253
9.2.5;Linear sequence on nonuniform surfaces;258
9.2.6;Kinetic considerations of optimum catalyst for two-step sequence;262
9.3;Selectivity;264
9.4;Polyatomic nature of reactants and coverage dependent adsorption mode;267
9.5;Ionic species;274
9.6;Transfer of labeled atoms in heterogeneous catalytic reactions;276
9.7;Electrocatalytic kinetics;281
9.8;Combined heterogeneous-homogeneous reactions;289
10;Dynamic catalysis;296
10.1;Transient kinetics;296
10.1.1;Relaxation to steady state;296
10.2;Relaxation methods;299
10.3;Temperature programmed desorption;315
10.4;Oscillations;9
10.4.1;Homogeneous catalysis;9
10.4.2;Enzymatic catalysis;323
10.4.3;Heterogeneous catalysis;325
10.5;Activity changes (deactivation);328
10.6;Heterogeneous catalysis;328
10.6.1;Coking;332
10.6.2;Batch reactors;341
10.6.3;Multilayer coking;343
10.6.4;Poisoning;345
10.6.5;Enhancement of activity while deactivating;347
10.7;Enzyme deactivation;348
11;Mass transfer and catalytic reactions;352
11.1;Catalytic multi-phase systems;352
11.2;Simultaneous reaction and diffusion in fluid films and in porous materials;353
11.3;Gas-liquid reactions;356
11.3.1;Slow reactions;361
11.3.2;Reactions with a finite liquid film reaction velocity;362
11.3.3;Zero-order reactions;362
11.3.4;First order reactions;365
11.3.5;Utilization factor;367
11.4;Liquid-liquid diffusion, phase transfer catalysis;369
11.5;Catalytic two-phase systems;373
11.5.1;Chemical reaction and diffusion inside a catalyst particle;373
11.5.2;First-order reaction;376
11.5.2.1;Sphere and first order kinetics;377
11.5.2.2;Slab and first order kinetics;383
11.5.3;Asymptotic effectiveness factors for arbitrary kinetics;386
11.5.4;Non-isothermal conditions;390
11.6;Mass transfer and enzymatic kinetics;396
11.7;External mass transfer;401
11.8;Internal diffusion and selectivity;403
11.9;Internal diffusion and deactivation;408
11.10;Elucidation of the impact of mass transfer;409
11.10.1;Criteria for the absence of mass and heat transfer limitations (fixed bed);409
11.10.2;Mass transfer coefficients;412
11.10.3;Calculation of diffusion coefficients;415
11.10.4;Heat conductivity;422
11.11;Three-phase systems;422
12;Kinetic modelling;430
12.1;Basic principles;430
12.2;Heuristic design of experiments;436
12.3;Parameter estimation : clasical methods;439
12.4;Parameter estimation: regression;442
12.5;Numerical strategies;446
12.5.1;Solution of algebraic equation systems;446
12.5.2;Solution of differential equations;448
12.5.2.1;Ordinary differential equations;448
12.5.2.2;Partial differential equations;451
12.5.3;Analysis of parameters;451
12.5.3.1;Statistical analysis;451
12.5.3.2;Supression of the correlation between parameters;454
12.5.3.3;Systematic deviations and normalization of experimental data;457
12.5.3.4;Physico-chemical testing;461
12.5.3.5;Significance of kinetic parameters;462
12.5.4;Model discrimination;463
12.5.5;Software;465
12.5.6;Case study;473
13;Recommended literature;480
14;Subject Index;488