Ref 7 catalytic kinetics

Catalytic Kinetics by Dmitry Murzin, Tapio Salmi • ISBN: 0444516050 • Pub Date: September 2005 • Format: Hardcover, 492pp • Publisher: Elsevier Science & Technology Books Preface 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 The performance of a majority of chemical reactors (and hence the processes) is significantly influenced by the performance of the catalysts Catalyst research has been devoted to increase the catalyst activity and selectivity to improve process economics and reduce environmental impact through better feedstock utilization Catalysis-based chemical synthesis accounts for 60% of today's chemical products and 90% of current chemical processes Catalysis development and understanding thus is essential to the majority of chemical synthesis advances Because the topic of chemical synthesis is so broad and catalysis is so crucial to chemical synthesis, catalysis should be specifically addressed 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 For instance bioprocesses have become widely used in several fields of commercial biotechnology, such as production of enzymes (used, tbr example, in tbod processing and waste management) and antibiotics As techniques and instrumentation are refined, bioprocesses may have applications in other areas where chemical processes are now used Advantages of bioprocesses over conventional chemical methods of production are lower temperature, pressure, and pH and application of renewable resources as raw materials with less energy consumption Catalyst development in industry is inseparable from understanding of catalysis on microscopic (elementary reactions) and macroscopic levels (transport phenomena) This book presents an attempt to unify the main sub disciplines forming the cornerstone of practical catalysis Catalysis according to the very definition of it deals with enhancement of reaction rates, i.e with catalytic kinetics Diversity of catalysts, e.g catalysis by acids, organometallic complexes, solid inorganic materials, enzymes resulted in the fact, that these topics are usually treated separately in textbooks, despite the fact, that there are very many analogues in the kinetic treatment of homogeneous, heterogeneous and enzymatic catalysis Catalytic engineering includes as an essential part also macroscopic considerations, more specifically transport phenomena Such an integrated approach to kinetics and transport phenomena in catalysis, still recognizing the fundamental differences between different types of catalysis, could be seldom found in the literature, where quite often artificial borders are build, preventing free exchange of useful ideas and concepts Cross-disciplinary approach can be only beneficial for the advancement of catalytic reaction engineering it should be mentioned, that it is not the aim of the authors to provide exhaustive bibliography Contrary, as we are trying to cover a variety of topics, we would like to limit ourselves to the main monographs, review articles and key references The hope of the authors is that the book could be also used as a textbook in catalytic kinetics and catalytic reaction engineering vi This book is partially based on several courses, which the authors have taught at Abo Akademi University over the recent years, namely "Heterogeneous Catalysis", "Chemical Kinetics", Chemical Reaction Engineering", "Chemical Reactors", "Chemical Technology", "Bioreaction Engineering", where topics covered in the present textbook were touched in one way or another Chapters 1-8, 9.4, 9.6-9.11, 10.1-10.2, 10.7-10.9 were written by D.Yu Murzin, material for chapters 9.1-9.3, 9.5 and 10.3-10.6 was prepared by T Salmi The authors are very grateful to many colleagues from academia and industry who shared their knowledge and expertise in kinetics and mass transfer In particular the late Professor M.I Temkin introduced one of the authors into the field of heterogeneous catalysis and chemical reaction engineering in the broader context of physical chemistry and practical industrial needs and was a role model as a scientist and a person Special thanks go to Dr Nikolai DeMartini, who carethlly read the manuscript and corrected the language, also giving several advices regarding the presentation of material Finally help ofElena Murzina in making the corrections is appreciated, as well as her patience during the many weekends and evenings when I was working on the book The authors understand that it is very difficult to cover the whole field in one book, therefore the selection of topics and examples and especially allocated space to particular topics might be considered biased We will be delighted to receive critics and comments, which will help to improve the text Dmitry Murzin June, 2005, Turku/Abo Table of Contents Ch Setting the scene Ch Catalysis 27 Ch Elementary reactions 73 Ch Complex reactions 111 Ch Homogeneous catalytic kinetics 149 Ch Enzymatic kinetics 189 Ch Heterogeneous catalytic kinetics 225 Ch Dynamic catalysis 285 Ch Mass transfer and catalytic reactions 341 Ch 10 Kinetic modelling 419 Chapter Setting the scene 1.1 History All processes occur over a time ranging from femtosecond to billions of years The same holds for chemical and biochemical transformations Kinetics (derived from the Greek word KtvrlxtZo ¢ meaning dissolution) is a science which investigates fine rates of processes Chemical kinetics is the study of reaction rates However complex a process is, it can be in principle divided into a number of elementary processes which can be studied separately Chemical kinetics emerged as a branch of physical chemistry in the 1880-s with seminal works of Harcourt and Esson demonstrating the dependence of reaction rates on the concentrations of reactants It was a German scientist K Wenzel who stated that the affinity of solid materials towards a solvent is inversely proportional to dissolution time and 100 years before Guldberg and Waage (Norway) formulated a law, which was later coined the "law of mass action," meaning that the reaction "forces" are proportional to the product of the concentrations of the reactants When the rate of a certain process is measured, especially if it is of practical importance, a curious mind is always eager to know if it is possible to accelerate its velocity Moreover, one could even imagine a situation that for a system demonstrating complete inertness introduction of a foreign substance could enhance the rate dramatically Conversion of startch to sugars in the presence of acids, combustion of hydrogen over platinum, decomposition of hydrogen peroxide in alkaline and water solutions in the presence of metals, etc were critically summarized by a Swedish scientist J J Berzelius in 1836, who proposed the existance of a certain body, which "effectiing the (chemical) changes does not take part in the reaction and remains unaltered through the reaction" He called this unknown tbrce, catalytic force, and defined catalysis as decomposition of bodies by this force J6ns Jakob Berzelius Wilhelm Ostwald and Svante Arrhenius This new concept was immediately critized by Liebig, as this notion was putting catalysis somewhat outside other chemical disciplines A catalyst was later defined by Ostwald as a compound, which increases the rate of a chemical reaction, but which is not consumed by the reaction This definition allows for the possibility that small amounts of the catalyst are lost in the reaction or that the catalytic activity is slowly lost 1.2 Catalysis Already from these definitions it is clear that there is a direct link between chemical kinetics and catalysis, as according to the very definition of catalysis it is a kinetic process There are different views, however, on the interrelation between kinetics and catalysis While some authors state that catalysis is a part of kinetics, others treat kinetics as a part of a broader phenomenon of catalysis Despite the fact that catalysis is a kinetic phenomenon, there are quite many issues in catalysis which are not related to kinetics Mechanisms of catalytic reactions, elementary reactions, surface reactivity, adsorption of reactants on the solid surfaces, synthesis and structure of solid materials, enzymes, or organometallic complexes, not to mention engineering aspects of catalysis are obviously outside the scope of chemical kinetics Some discrepancy exists whether chemical kinetics includes also the mechanisms of reactions In fact if reaction mechanisms are included in the definition of catalytic kinetics it will be an unnecessary generalization, as catalysis should cover mechanisms Catalysis is of crucial importance for the chemical industry, the number of catalysts applied in industry is very large and catalysts come in many different forms, from heterogeneous catalysts in the form of porous solids to homogeneous catalysts dissolved in the liquid reaction mixture to biological catalysts in the form of enzymes Catalysis is a multidisciplinary field requiring efforts of specialists in different fields of chemistry, physics and biology to work together to achive the goals set by the mankind Knowledge of inorganic, organometallic, organic chemistry, materials and surface science, solid state physics, spectroscopy, reaction engineering, and enzymology is required for the advancements of the discipline of catalysis Despite the fundamental differences between elementary steps in catalytic process on surfaces, with enzymes or homogeneous organometalics there are stricking similarities also in terms of chemical kinetics Although superficially it is difficult to find something in common between the reaction of nitrogen and hydrogen forming ammonia on a surface of iron, Dfructose 6-phosphate with ATP involving an enzyme phosphofructokinase, or ozone decomposition in the atmosphere in the presence of NOx, all these trasnformations require that bonds are formed with the reacting molecules Such a complex then reacts to products leaving the catalyst unaltered and ready for taking part in a next catalytic cycle iiiiiiiiiii iiiiiiii~ Figure 1.1 Catalytic cycle iiiiiiiiiiiiiiii :~iiiiiiii Figure 1.1 is an example of a catalytic reaction between two molecules A and B with the involvment of a catalyst In order to understand how a catalyst can accelerate a reaction a potential energy diagram should be considered x~ P÷Q R e o n ¢oerdinate Figure 1.2 Potential energy diagram Figure 1.2 represents a concept for a non-catalytic reaction of An'henius, who suggested that reactions should overcome a certain barrier before a reaction can proceed X* "1 I \ /F~', If G ~/ \ ~ (the reduction in AG~ bythe catalyst) Catalyzed A+B A+B " P+Q ~ Reactioncoordinate Figure 1.3 Potential energy diagram for catalytic reactions The change in the Gibbs free energy between the reactants and the products AG does not change in case of a catalytic reaction, however the catalyst provides an alternative path for the reaction (Figure 1.3) In general reaction rates increase with increasing temperature Kooij and van't Hoff (1893) proposed an equation for the temperature dependence of reaction rates k = AT" e -E~T (1.1) where A is pre-exponential factor and activation energy, Ea, is related to the potential energy barrier This equation, which could be derived on the basis of transition sate theory, in a slightly simplified tbrm k = ko e K G (1.2) was applied by Arrhenius and is reffered to as the Arrhenius law It is immediately clear from equation (1.2) that a decrease in activation energy will lead to an increase of the rate constant and thus the reaction rate (a discussion on the relationship between the rate and rate constant will be given below) At the same time the catalyst (heterogeneous, homogeneous or enzymatic) affects only the rate of the reaction, it changes neither the thermodynamics of the reaction (Gibbs energy) nor the equilibrium composition An important conclusion is thus that a catalyst can change kinetics but not thermodynamics of a reaction and if a process is thermodynamically unfavorable, there is no need to apply any modern and fancy methods (high throughput screening and alike) to find such a catalyst Concentration Time Figure 1.4 Concentration vs time dependences for a reversible reaction The dashed line in Figure 1.4 demonstrates the equlibrium that cannot be ovecome for a given set of parameters Furthermore the ratio of rate constants in the forward and reverse direction for catalytic and noncatalytic reactions is the same _ [Pl,,, kc,,/ [AL, = x (1.3) It also implies that if a catalyst is active in enhancing a rate of the forward reaction, it will the same with a reverse reaction Figure 1.3 is somewhat simplified as it does not take into account possible bonding of the catalyst and reactant In order for a catalyst to be effective, the energy barrier between the catalyst -substrate and activated complex must be less than between substrate and activated complex in the uncatalyzed reaction The binding of substrate to an enzyme lowers the free energy of the catalyst substrate complex relative to the substrate (Figure 1.5) This is a general feature of catalysis and is relevant for heterogeneous, homogeneous and enzymatic catalysis If the energy is lowered too much, without a greater lowering of the activation energy then catalysis would not take place, meaning that bonding between a catalyst and a reactant should not be too strong Alternatively if it is too weak, then the catalytic cycle could not proceed bmulb~g reactlott sq~aration read:ion coordinate Figure 1.5 Potential energy diagram of a heterogeneous catalytic reaction (1 Chorkendorfl, J.W Niemantsverdriet, Concepts of Modern Catalysis and Kinetics, Wiley, 2003) Chemical kinetics as a discipline adresses how the reaction rates depend on reactant concentration, temperature, nature of catalysts, pH, solvent, to name a few- reaction parameters Chemical kinetics together with other means of studying catalytic reactions, like spectroscopy of catalysts and catalyst models, quantum-chemical calculations for reactants, intermediates and products, calculation of the thermodynamics of reactants, intermediates and products from measured spectra and quantum-chemical calculations form the modern basis for understanding catalysis Kinetic investigations are one of the ways to reveal reaction mechanisms The following problems can be solved using the kinetic model: • choosing the catalyst and comparing the selectivity and activity of catalysts and their performance under optimum conditions for each catalyst; • the determination of the optimum sizes and structure of catalyst grains and the necessary amount of the catalyst to achieve the specified values of the selectivity of the process and conversion of the starting products; • the determination of the composition of all byproducts formed during the process; • the determination of the stability of steady states and parametric sensitivity; that is, the influence of deviations of all parameters on the steady-state regime and the behavior of the reactor under unsteady state conditions; • the study of the dynamics of the process and deciding if the process should be carried out under unsteady-state conditions; • the study of the influence of mass and heat transfer processes on the chemical reaction rate and the determination of the kinetic region of the process; • choosing the type of a reactor and structure of the contact unit that provide the best approximations to the optimum conditions Very often the rates of chemical transformations are affected by the rates of other processes, such as heat and mass transfer The process should be treated as a part of kinetics The gas/liquid mass transfer in multiphase heterogeneous and homogeneous catalytic reactions could be treated in a similar way The mathematical framework for modelling diffusion inside solid catalyst particles of supported metal catalysts or immolisided enzymes does not differ that much, but proper care should be taken of the reaction kinetics The immense importance o f catalysis in chemical industry is manisfested by the tact that roughly 85-90% o f all chemical products have seen a catalyst during the course o f production 1997 Chemical 2003 Chemical olymer Polymer Refinerl Refiner Environmental Billion US$ 7.4 Environmental 9.0 * toll manufacturing fees only The Catalyst Group: The Intelligence Report: Global Shifts in the Catalyst Industt2¢ Figure 1.6 Worldwide catalyst market Figure 1.6 demonstrates applications o f catalysis in industry In the last years there is an increase o f catalytic applications also for non-chemical industries: treatment o f exhaust gases from cars and other mobile sources, as well as power plants (Figure 1.7) Figure 1.7 Catalytic treatment of NOx in a) mobile b) stationary sources A comparison between homogeneous and heterogeneous catalysts from the viewpoint o f a homogeneous catalysis expert is presented below Activity Selectivity Conditions of reaction Life time of catalyst Sensitivity to deactivation Problems due to diffusion Recycling of catalyst Steric and electronic properties Mechanism Homogeneous Heterogeneous high high mild variable low none usually difficult easily changed realistic models exist variable variable harsh long high difficult to solve can easily be done no vm'iation possible not obvious 467 The generation rates (ri) are obtained for each x-value by utilizing the concentration profiles which are solved numerically from the reaction-diffusion equation (10.117) The model equations were solved numerically by discretizing the partial differential equations (PDEs) with respect to the spatial coordinate (x) Central finite difference formulae were used to approximate the first and second derivatives (e.g dcjdx, dT/dx) Thus the PDEs were transformed to ODEs with respect to the reaction time and the finite difference method was used in the numerical solution The recently developed software of Buzzi Ferraris and Manca was used, since it turned out to be more rapid than the classical code of Hindmarsh For the sake of comparison hydrogenation experiments with large cylindrical catalyst particles were carried out The increase of the particle size diminished the velocity of catalytic hydrogenation These experimental results provide a path for the process scale-up, i.e a prediction of the hydrogenation rate on large catalyst particles starting from crushed particles The values of the kinetic constants obtained for crushed particles were utilized and the ratio of porosity to tortuosity from the reactio~diffusion model was adjusted (0.167) to fit successfully the experimental data (Figure 10.40) c (mol/kg) o 20 40 60 80 Time, rain 100 120 140 Figure 10.40 Fit of the kinetic model compared to experimental data in aldol hydrogenation for catalyst pellets The temperature gradients inside the catalyst pellet turned out to be negligible, clearly less than K for realistic approximations for AH and heat conductivity Thus, the final calculations were made by the isothermal model by simply assuming the same temperature inside the catalyst particle as in the liquid phase The concentration profiles of aldol and hydrogen during the experiment are displayed in Figures 10.41 and 10.42 07[ C(mol/kg) 01 centre o2 o3 o4 os o~ 07 oa os x Figure 10.41 The concentrationprofilesofaldol 468 0~25 0-2 g O X Figure 10.42 The concentrationprofiles of hydrogen Figures 10.41 and 10.42 indicate that the process is limited by hydrogen and aldol diffusion in the beginning of the experiment, but the concentration gradient of hydrogen diminishes very much during the experiment The diffusional limitation of aldol prevails throughout the whole experiment Taking into account the fact that the description of the pore structure of the catalyst particle is very much simplified, we can conclude that the predictions are good and that they provide an example of a satisfactory scale-up approach based on the physico-chemical properties and kinetic behaviour of the system 469 Recommended literature Chapter I Chorkendorff, J.W.Niemanstverdriet, Concepts of modern catalysis and kinetics, Wiley-VCH, Weinheim, 2003 Handbook of heterogeneous catalysis, Volume Set, Editors: G Ertl, H.Km6zinger; J Weitkamp, Wiley-VCH, Weinheim, 1997 S.R Logan, Fundamentals of chemical kinetics, Longman, Edinburgh Gate, 1996 R.I.Masel, Chemical kinetics and catalysis, Wiley-Interscience, New York, 2001 M.J Pilling, P.W.Seakins, Reaction kinetics, Oxtbrd University Press, Oxtbrd, 1995 J.M.Thomas, W.J.Thomas, Principles and practice of heterogeneous catalysis, VCH, Weinheim, 1997 R A van Santen, P W N M van Leeuwen, A A Moulijn, B A Averill, Catalysis: An integrated approach, Elsevier, Amsterdam, 2002 Chapter R.L Augustine, Heterogeneous catalysis for the synthetic chemist, Marcel Dekker Inc., New York, 1996 A.S.Bommarius, B.R.Riebel, Biocatalysis, Weinheim, 2004 Fundamentals and applications Wiley-VCH M Boudart, Turnover rates in heterogeneous catalysis Chemical Reviews, 95 (1995) 661 I Chorkendorfl; J.W.Niemanstverdriet, Concepts of modern catalysis and kinetics, Wiley-VCH, Weinheim, 2003 A.Clark, The theory of adsorption and catalysis, Academic Press, New- York, 1970 470 Handbook of heterogeneous catalysis, Volume Set, Editors: G Ertl, H.KnOzinger; J Weitkamp, Wiley-VCH, Weinheim, 1997 K.W.Kolasinski, Surface science Foundations of catalysis and nanoscience, Wiley, Chichester, 2002 K.J Laidler, Chemical kinetics, Harper and Row, New York, 1987 R.i.Masel, Chemical kinetics and catalysis, Wiley-lnterscience, New York, 2001 Yu S Snagovskii, G.M Ostrovskii, Modelling of kinetics of heterogeneous catalytic reactions, Chimia, Moscow, 1976 G.A Somorjai, Introduction to surface chemistry and catalysis, Wiley-Interscience, New York, 1994 M.I Temkin, The kinetics of some industrial heterogeneous catalytic reactions, Advances in Catalysis, 28 (1979) 173 P.W van Leeuwen, Homogeneous catalysis: understanding the art, Kluwer Academic, 1999 R A van Santen, P W N M van Leeuwen, A A Moulijn, B A Averill Catalysis: An integrated approach, Elsevier, Amsterdam, 2002 Chapter M.Boudart, G Djega-Mariadassou, Kinetics of heterogeneous catalytic reactions, Princeton University Press, Princeton, 1984 I ChorkendorfL J.W.Niemanstverdriet, Concepts of modern catalysis and kinetics, Wiley-VCH, Weinheim, 2003 E.T Denisov, O.M Sarkisov, G.I Likhtenshtein, Chemical kinetics Fundamentals and new developments, Elsevier, Amsterdam, 2003 J.A Dumesic, D.F.Rudd, L Aparicio, The microkinetics of heterogeneous catalysis, American Chemical Society, Washington, 1993 B Hammer, J.K Norskov, Theoretical surface science and catalysis - calculations and concepts Advances in Catalysis, 45 (2000) 71 L.P.Hammett, Physical organic chemistry, McGraw-Hill, New York, 1970 K.J Laidler, Chemical kinetics, Harper and Row, New York, 1987 471 S.J Lombardo, A.T Bell, A review of theoretical models for adsorption, diffusion, desorption and reaction of gases on metals, Surface Science Reports, 13 (1991) R.I.Masel, Chemical kinetics and catalysis, Wiley-Interscience, New York, 2001 P.Stolze, Microkinetic simulation of catalytic reactions, Progress in SulJhce Science, 65 (2000) 65 M.I Temkin, The kinetics of some industrial heterogeneous catalytic reactions, Advances in Catalysis 28 (1979) 173 Yu K Tovbin, Lattice-gas model in kinetic theory of gas-solid interface processes, Progress in Surface Science, 34 (1990) R A van Santen, P W N M van Leeuwen, A A Moulijn, B A Averill Catalysis: An integrated approach, Elsevier, Amsterdam, 2002 F Zaera, Kinetics of chemical reactions on solid surfaces Deviations from conventional theory, Accounts" of Chemistry Research, 35 (2002) 129 Chapter J Horiuti, Theory of reaction rates as based on the stoichiometric number concept Annals of the New YorkAcademy of Sciences, 213 (1973) J Horiuti, T Nakamura, Theory of heterogeneous catalysis, Advances in Catalysis, 17 (1967) S.L.Kiperman, Foundations of chemical kinetics in heterogeneous catalysis, Khimia, Moscow, 1979 E.L King, C Altman, A schematic method of deriving the rate laws for enzyme-catalyzed reactions, Journal of Physical Chemistry, 60 (1956) 1375 L.A Petrov, Application of graph theory to study of the kinetics of heterogeneous catalytic reactions, Mathematical Chemistry, (1992) Yu S Snagovskii, G.M Ostrovskii, Modelling of kinetics of heterogeneous catalytic reactions, Chimia, Moscow, 1976 M.I Temkin, The kinetics of some industrial heterogeneous catalytic reactions, Advances in Catalysis, 28 (1979) 173 472 R A van Santen, P W N M van Leeuwen, A A Moulijn, B A Averill Catalysis: An integrated approach, Elsevier, Amsterdam, 2002 Chapter D.G Blackmond, Reflections on asymmetric catalysis A kinetic view of enantioselectivity, CATTECH (1998) 17 E.T Denisov, O.M Sarkisov, G.I Lildatenshtein, Chemical kinetics Fundamentals and new developments, Elsevier, Amsterdam, 2003 F.G Helfferich, Kinetics of homogeneous multistep reactions, in Comprehensive chemical kinetics, vol 38 ed R.G Compton, G Hancock, Elsevier, Amsterdam, 2001 K.J Laidler, Chemical kinetics, Harper and Row, New York, 1987 R.I.Masel, Chemical kinetics and catalysis, Wiley-Interscience, New York, 2001 R A van Santen, P W N M van Leeuwen, A A Moulijn, B A Averill Catalysis: An integrated approach, Elsevier, Amsterdam, 2002 Chapter J.E.Bailey, D.F.Ollis, Biochemical engineering fundamentals, McGraw-Hill Book Company, NY 1986 H.Bisswanger, Enzyme kinetics, principles and methods Wiley-VCH Weinheim, 2002 A.S.Bommarius, B.R.Riebel, Biocatalysis, Fundamentals and applications Wiley-VCH Weinheim, 2004 A Cornish-Bowden, Foundamentals of enzyme kinetics (3d edition), Portland Press, London, 2004 E.T Denisov, O.M Sarkisov, G.I Likhtenshtein, Chemical kinetics Fundamentals and new developments, Elsevier, Amsterdam, 2003 V.Leskovac, Comprehensive enzyme kinetics, Kluwer Academic/Plenum publishers, New- York, 2003 S.D.Varfolomeev, K.G Gurevich, Biokinetics, Grand, Moscow, 1999 473 Chapter I Chorkendorff; J.W.Niemanstverdriet, Concepts of modern catalysis and kinetics, Wiley-VCH, Weinheim, 2003 A Clark, The theory of adsorption and catalysis, Academic Press, New York, 1970 G Djega-Mariadassou, M Boudart, Classical kinetics of catalytic reactions, Journal of Catalysis, 216 (2003) 89 H S Fogler, Elements of chemical reaction engineering (3d ed), Prentice Hall, N J, 1998 A.N.Frumkin, V.N.Andreev, L.I.Boguslavskii, B.B.Damaskin, R.R.Dogonadze, V.E.Kazarinov, L.I.Krishtalik, A.M.Kuznetsov, O.A.Petrii, Yu.V.Pleskov, Double layer and electrode kinetics, Nauka, Moscow, 1981 Handbook of heterogeneous catalysis, Volume Set, Editors: G Ertl, H.Kn6zinger; J Weitkamp, Wiley-VCH, Weinheim, 1997 Yu S Snagovskii, G.M Ostrovskii, Modelling of kinetics of heterogeneous catalytic reactions, Chimia, Moscow, 1976 M.I Temkin, The kinetics of some industrial heterogeneous catalytic reactions, Advances in Catalysis, 28 (1979) 173 J.M.Thomas, W.J.Thomas, Principles and practice of heterogeneous catalysis, VCH, Weinheim, 1997 R A van Santen, P W N M van Leeuwen, A A Moulijn, B A Averill Catalysis: An integrated approach, Elsevier, Amsterdam, 2002 Chapter G Ertl, Dynamics of reactions at surfaces, Advances in Catalysis 45 (2000) K.J Laidler, Chemical kinetics, Harper and Row, New York, 1987 N.M.Ostrovskii, Kinetics of catalyst deactivation, Nauka, Moscow, 2001 M.J Pilling, P.W.Seakins, Reaction kinetics, Oxford University Press, Oxford, 1995 S.L Shannon, J.G Goodwin, Characterization of catalytic surfaces by isotopic-transient kinetics during steady-state reaction, Chemical Reviews, 95 (1995) 677 474 K.Tamaru, Dynamic heterogeneous catalysis, Academic Press, New York, 1978 Chapter J.E.Bailey, D.F.Ollis, Biochemical engineering fundamentals, McGraw-Hill Book Company, NY 1986 J.B Butt, Reaction kinetics and reactor design, Marcel Dekker, New York, 2000 L K Doraiswamy, M M Sharma, Heterogeneous reactions: Analysis, examples and reactor design Vol 1, Gas-solid and solid-solid reactions, Vol 2, Fluid-fluid and fluid-fluid-solid reactions, John Wiley, New York, 1984 H S Fogler, Elements of chemical reaction engineering (3d ed.), Prentice Hall, N J, 1998 G Froment, K Bischoff, Chemical reactor analysis and design, 2d ed., Wiley, New York, 1990 Handbook of heterogeneous catalysis, Volume Set, Editors: G Ertl, H.I~a6zinger; J Weitkamp, Wiley-VCH, Weinheim, 1997 I.I.Ioffe, V.A.Reshetov, A.M.Dobrotvorskii, Heterogeneous catalysis, Khimia, Leningrad, 1985 O Levenspiel, Chemical reaction engineering, 3rd Edition, Wiley, 1998 B E Poling, J M Prausnitz, J.P O'Connell, The properties of gases and liquids, McGraw-Hill, 2000 T.Salmi, J.P.Mild~ola, J.W~irngt, Bridging chemical reaction engineering and reactor technology, Abo Akademi Press, Turku/Abo, 2004 Y Sasson, R Neumann, Handbook of phase transfer catalysis, Kluwer Academic Publishers, 1997 C.N.Satterfield, Mass transfer in heterogeneous catalysis, MIT press, Cambridge, 1970 J.M.Smith, Chemical engineering kinetics, McGraw-Hill, 1981 R A van Santen, P W N M van Leeuwen, A A Moulijn, B A Averill Catalysis: An integrated approach, Elsevier, Amsterdam, 2002 475 Chapter 10 K A Brownlee Statistical theory and methodology in science and engineering Wiley, New York, 1960 D R Cox, Planning of experiments Wiley, New York, 1958 J.A Dumesic, D.F.Rudd, L Aparicio, The microkinetics of heterogeneous catalysis, American Chemical Society, Washington, 1993 G.F Froment, L.Hosten, Catalytic kinetics: modeling, in Catalysis Science and technology (ed J.A.Anderson, M.Boudart) Springer-Verlag, Berlin, 1981 C.W Gear, Numerical initial value problems in ordinary differential equations, Prentice Hall, Englewood Cliffs, N J, 1971 Handbook of heterogeneous catalysis, Volume Set, Editors: G Ertl, H.Kn6zinger; J Weitkamp, Wiley-VCH, Weinheim, 1997 P.Henrici, Discrete variable methods in ordinary differential equations, Wiley, NY, 1962 A C Hindmarsh, "ODEPACK, A Systematized Collection of ODE Solvers," in Scientific Computing, R S Stepleman et al (eds.), North-Holland, Amsterdam, 1983 (vol of IMACS Transactions on Scientific Computation), pp 55-64 J V Villadsen, W E Stewart, Solution of boundary-value problems by orthogonal collocation, Chemical Engineerin,g Science, 22 (1967) 1483 B J Winer, Statistical principles in experimental design McGraw-Hill, New York, 1962 477 Subj ect index acid-base catalysis, 28 acidity function, 153 activation energy, 23 Adams-Moulton method, 439 adsorbate-adsorbate interactions, 57 adsorption, 47 adsorption isotherms, 46 adsorption modes, 71 affinity, 22 agitation speed, 416 allosteric enzyme, 205 ammonia synthesis, 242 Anderson, 400 apparent activity, 397 apparent activation energy, 25 Aris, 378 Arrhenius, Arrhenius equation, 4, 23 Arrhenius number, 383,401 asymmetric amplification, 179 asymmetric catalysis, 179 asymmetric depletion, 179 Athena visual studio, 454 autocatalysis, 161 Avetisov, 248 Avralni-Erofeev kinetics, 431 backward difference method, 296, 439 Bailey, 385 Bangham equation, 98 basic routes, 121 batch reactors, 12 Bayes, 453 bell-shape, 220 Belousov, 307 Belousov-Zhabotinsky reaction, 307, 311 Berty reactor, 21 Berzelius, Bessel, 366 Biloen, 302 biographical nonuniformity, 94 Blot, 370 Biot number, 370 bisubstrate reactions, 196 Bodenstein, 81, 83 Bodenstein conditions, 116 Boltzmann, 75 Boltzmann distribution, 73 Bond, 109 Bonhoeffer, 297 Bosanquet approximation, 405 Boudart, 95,418 Box-Hill method, 453 Bragg-Williams approximation, 58 Briggs, 190 Brusselator, 310 Brfindstr6m, 358 Bronsted, 88 Burk, 192 Buss loop reactor, 20 butadiene hydrogenation, 116 Butler-Volmer equation, 276 Buzzi-Ferraris, 467 Campbell, 451 carbonylation, 169, 175 catalyst market, catalytic cycle, chain polymerization, 183 Changeux, 205 Chapman, 406 Chapman-Enskog equation, 406, 408 chemisorption, 45 Chilton-Colburn analogy, 403 chiral, 30 Chorkendorff, 246 Christiansen, 172 Christiansen matrix, 172 cinnamaldehyde hydrogenation, 138, 414 citral hydrogenation, 231 cofactor, 201 collision integral, 408 collocation method, 440 compensation effect, 109, 445 competitive inhibition, 212 complex reactions, 111 478 concerted hypothesis, 205 conservation equation, 112 contour plot, 442 cooperative kinetics, 202 Cornish-Bowden, 215 correlation between parameters, 443 covalent catalysis, 38 coverage, 47 CSTR, 15 cyclic voltammetry, 272 Dalziel, 197 Damk6hler, 367 Damk6hler number, 391 deactivation, 317, 397 decomposition of N20, 293 de Donder equation, 22 degree of rate control, 451 deNOx removal, 278 design equation, 421 deterministic models, 104 dialkylbenzene hydrogenation, 129 diffusion, 342 diffusion coefficient, 345,404, 409 direct hydrogenation mechanism, 165 discrimination of models, 452 dissociative adsorption, 48 Dixon plot, 214 double logarithmic plots, 431 double reciprocal plot, 193, 198, 200, 214, 217, 219 Dumesic, 451 Eadie, 193 Eadie-Hofstee plot, 193,430 effective diffusion coefficient, 362 effectiveness factor, 356, 364, 375,384 Eigen, 289 Einstein, 410 electrocatalytic kinetics, 270 elementary reactions, 10 Eley-Rideal mechanism, 86 Elovich equation, 97 empirical deactivation functions, 326 enantioimpure catalysts, 179 enantiomers, 30 enantioselective hydrogenation, 258 energy balance, 379 energy dissipation, 404, 416 enhancement factor, 353 Enskog, 406 enzymatic catalysis 8, 35 enzyme deactivation, 337 enzymes, 35 epoxidation, 167 equilibrium, equilibrium constant, 47 Erofeev, 431 Ertl, 315 Esson, 1, esterification, 153 experimental design, 415 exponential nonuniformity, 55 extent of reaction, external heat transfer criterion, 399 external mass transfer criterion, 399 extraction mechanism, 359 Eyring, 73, 91 factorial design, 426 Farkas, 297 femtosecond spectroscopy, 80 Fick, 344 Fick law, 345,405 Field, 309 film theory, 346 Fihner, 211 Flory, 184 Fogler, 425 formal kinetics, Fourier, 379 Fowler-Guggenheim isotherm, 58 Freundlich isotherm, 56 fuel cell, 271 Fuller-Schettlet-Giddins equation, 408 gas-phase catalysis, 27 gas-phase reactions, 345 Gauss, 435 Gepasi, 456 Gibbs free energy, Glasstone, 91 479 Gleaves, 303 Goodwin, 302 graphical methods, 429 graphs of catalytic mechanisms, 127 Guldberg, Haldane, 190 Hammett, 88, 152 Hammett equation, 88 Hanes-Woolfplot, 194, 430 Happel, 302 Harcourt, 1, Hatta number, 356 Hayduk-Laudie method, 410 heat conductivity, 411 heat of adsorption, 54 heat transfer coefficient, 382 heat transfer correlations, 402 heat transfer factor, 402 Henry constant, 349 Henry law, 52 heterogeneous catalysis, 6, heterogeneous catalysts, 40 heterogeneous-homogeneous reactions, 278 Heyrovsk3), 270 Higgins, 313 Hill equation, 203 Hindmarsh, 439 Hinshelwood, 86 Hofstee, 193 homogeneous catalysis, 6, 7, 149 Horiuti, 107, 111,113,270 Hougen, 107 hydroamination, 166 hydroformylation, 170, 177 hydrogenolysis kinetics, 256 hyperbolic functions, 368 H2/O2 exchange, 297 ideal surfaces, 225 immobilized enzymes, 222, 385 increments, 409 indirect hydrogenation mechanism, 165 induced fit, 211 induced nonuniformity, 57, 240 inhibition, 39, 41,212 interfacial mechanism, 360 internal diffusion, 362, 392 internal heat transport criterion, 400 internal mass transfer criterion, 400 intrinsic nonuniformity, 235 Ioffe, 392 ionic species, 263 isotope exchange, 265 Jacobian matrix, 433 Kagan, 180 kinetic coupling, 143 kinetic modeling, 419 kinetic resolution, 177 King, 65 Kiperman, 109 Knowles, 30 Knudsen diffusion, 405 Kobayashi, 298 Kolmogorov, 403 Kooij, Koros, 418 Koshland, 211 K6r6s, 309 labelled atoms, 265 Laidler, 91 Langmuir, 44 Langmuir- Hinshelwood-Hougen-Watson method, 107 Langmuir-Hinshelwood mechanism, 86 Langmuir isotherm, 52 lateral interactions, 58 lattice gas, 57 law of mass action, Lennard-Jones parameter, 406 Levenberg, 434 Levenberg-Marquart method, 263 Levenspiel, 318 Liebig, ligand-defficient catalysis, 172 linear free energy relationship, 88 Lineweaver, 192 Lineweaver-Burk plot, 192,430 Liotta, 361 480 liquid film, 350 lock-and-key concept, 37 logarithmic isotherm, 54 logarithmic plots, 11 Lucenz III, 456 Madon, 418 Makosza, 358, 360, 361 Manca, 467 Marquart, 434 Mars-van Krevelen mechanism, 227 mass balance, 13 mass transfer, 341 mass transfer correlations, 402 mass transfer factor, 402 Maxwell, 75, 344 Maxwell-Boltzmann distribution, 74 Mears, 399 Menten, 189 metal ions, 162 metallocene, 30, 182 metathesis, 169 Metropolis, 104 Michaelis, 189 Michaelis constant, 192 Michaelis-Menten equation, 192, 195, 421 microkinetics, 107 minimum energy path, 73 ModEst 6.0, 456 molecular diffusion, 405 Monod, 205 Monte-Carlo methods, 104 most abundant surface intermediate, 148 Moulijn, 398 multi-centred adsorption, 65 multicomponent adsorption, 49 multilayer coking, 332 multiple cycles, 176 multiplicity, 384 nanokinetics, 100 Nemethy, 211 Nernst equation, 276 Newton, 435 Newton method, 262 Newton-Raphson method, 432, 434, 435 Niemantsverdriet, 246 noncompetitive inhibition, 212, 215 non-ideal surfaces, 235 non-isothermal reactors, 427 nonlinear effects, 179 nonlinear regression, 432 nonuniform surfaces, 50 normalization of data, 446 Nowak, 418 Noyes, 309 Noyori, 30 nucleophillic catalysis, 158 Nusselt, 401 Nusselt number, 401 objective function, 432 observable Thiele modulus, 388 Ollis, 385 optimum catalyst, 251 ordinary differential equations (ODE), 262, 296,423,437 Oregonator, 308 organometallic catalysts, 32, 164 oscillations, 106, 307 Ostrovskii, 332 Ostwald, oxidation, heterolytic, 164 parallel adsorption, 72 parallel-consecutive reactions, 138, 177 parameter estimation, 428 partition functions, 75 partial differential equations (PDE), 296, 440 pattern formation, 314 Peclet, 300 Peclet number, 300, 301 phase transfer catalysis, 358 physico-chemical testing, 450 physisorption, 45 pinene isomerization, 232 ping-pong mechanism, 196, 198 plug flow reactor, 12 poisoning, 334 Polanyi, 73 Polanyi parameter, 51, 88,275 481 polymer electrolite membrane, 271 polymerization, 34, 183 porosity, 362 potential energy diagram, 3, 5, 44 power law, 238,429 Prandtl, 401 Prandtl number, 402 Prater, 400 Prater number, 383,401 pre-exponential factor, 80 Prigogine, 310 promoter, 40 proximity mechanism, 38 quasi-chemical approximation, 65 quasi-equilibrium, 83 radicals, 280 rate-determining step, 83 rate equation, 10 rate law, 10 reaction orders, 10 reaction route, 112 reactors, 12, 421 recirculation reactor, 20 reconstruction of surfaces, 315 regression, 431 relaxation, 285 relaxation methods, 288 Reynolds, 401 Reynolds number, 401 Rideal, 86, 297 Roginskii, 50 Rosenbrock-Wanner method, 438 Runge, 435 Runge-Kutta methods, 437 Satterfield, 407 saturation parameter, 388 Schmidt, 401 Schmidt number, 402 Schneider, 378 screening parameter, 68 selectivity, 42, 135,253,392 -differential, 43,395 -integral, 43 Sernenov, 83 semi-competitive adsorption, 66 sensitivity plots, 442 separable kinetics, 319 sequential hypothesis, 211 shape selectivity, 135 Sharpless, 30 Sherwood, 357 Sherwood number, 357,401,403 shielding, 69 sitosterol hydrogenation, 335 Snagovskii, 67, 248 Starks, 358, 359 steady-state approximation, 81 steady state isotope transient kinetic analysis (SSITKA), 292, 302 steepest descent, 434 Stefan, 344 Stefan-Maxwell theory, 405 stiff differential equations, 439 stirred taN(, 12 stochastic models, 104 stoichiometric coefficient, stoichiometric number, 111 Stokes, 410 Stokes-Einstein equation, 410 stopped flow, 289 structure insensitive reactions, 42 structure sensitive reactions, 42 support, 40 surface electronic gas, 60, 102 systematic deviations, 446 Tafel, 270 Tafel equation, 276 Tafel plot, 276 Taft equation, 90 Tamaru, 290 Taylor, 44 Temkin, 50, 91,113,235,240, 403 Temkin-Horiuti rule, 128 Temkin isotherm, 54, 56 Temkin-Pyzhev equation, 242 temperature jump, 289 temperature programmed desorption (TPD), 304 482 temporal analysis of products (TAP), 303 Th6nard, Thiele, 367 Thiele modulus, 356, 367, 387 three-phase systems, 411 tilted adsorption, 72, 258 tortuosity, 362 tracer, 301 transient kinetics, 286 transient techniques, 291 transition metals, 29 transition state theory, 73 transmission coefficient, 79 tubular reactor, 16 turnover number, 42 two-step sequence, 227, 237 uncompetitive inhibition, 212, 218 utilization factor, 356 van't Hoff, Villadsen, 440 virtual pressure, 95 Volmer, 270 Waage, Weisz, 400 Weisz-Hicks criterion, 400 Weisz modulus, 400 Wenzel, Whyman, 205 Wilhelmy, Wilke, 407 Wilke-Chang equation, 410 Zeldovich, 50, 367 Zeldovich-Roginskii equation, 97 Zewail, 80 Zhabotinsky, 307 Ziff-Gullari-Barshad model, 105 Zucker-Hammett equation, 152 ... reactions 73 Ch Complex reactions 111 Ch Homogeneous catalytic kinetics 149 Ch Enzymatic kinetics 189 Ch Heterogeneous catalytic kinetics 225 Ch Dynamic catalysis 285 Ch Mass transfer and catalytic... chemical kinetics Some discrepancy exists whether chemical kinetics includes also the mechanisms of reactions In fact if reaction mechanisms are included in the definition of catalytic kinetics. .. between chemical kinetics and catalysis, as according to the very definition of catalysis it is a kinetic process There are different views, however, on the interrelation between kinetics and catalysis