It is old hat that classic kinetics (e.g. in chemistry) is inherently based on the assumption that reactions take place in small vessels under well-stirred conditions; homogeneity, rapid mixing, etc. It is also well-known, and likewise accepted, that this assumption is often not justified (biology, chemical industry and so on). There have however been arguments about how to deal with this matter: kinetics of particles in open heterogeneous systems. This monograph, available for download below, attempts to formulate a basis for a kinetics where the "mixin呂 condition” is relaxed: the condition is qualitatively deleted — not merely neutralized by use of various approximations. In the resulting theory, Dynamics of Markovian Particles (DMP), the classic notion of geometric volume is eliminated: the familiar notion of'concentration' (amount of substance)/(unit volume) appears nowhere, and substance flows are not in terms of, say (litres)/(time unit), but in terms of (number of particles)/(time unit). Elementary as this might sound (and is) it has rather broad implication.
The approach is based on the notion of stochastic process being accepted as a physical entity: the particle moves because there is a transition probability acting upon it. The resulting theory (DMP) generalizes the particle concept: not only can two oxygen molecules or two benzene molecules be considered as two 'equivalent particles*, but so can also two fish, two cells, two coins or, why not, two cars (with driver) — in spite of the "pattides” being different in classic (physical) terms. Strict and direct definitions of open and closed system can be formulated (steady state vs. equilibrium). Also is derived, for open system, an ergodic like relation between the motion of particles and the resulting steady state. The notion "state of particle” proves, of course, to be central but is nevertheless left unspecified. This is perhaps one of the more salient features of DMP in its present from 一 and it promotes the theory's generality.
The first task is thus to formulate an appropriate language. And the first thing then to do is to find a proper set of primary concepts but, as so often happens, what looks fine on paper does not function without disturbances as the practical application goes. Thus, as it turns out in this case, there are some primary concepts that look more primary than the other primary concepts, so to speak. And rather arbitrarily I shall name them fundamental concepts. Yes, they are indeed primary but needed at the very beginning for the formulation of the other concepts. The first fundamentai concept that comes into my mind is particle. Now, a basic feature of primary concepts is that they cannot be defined but should be understood on intuitive grounds and abo ut the only thing t hat can be done is to at tempt illustrations. For instance, let us assume that a small population of rats is given a certain dose of gamma irradiation.
If I am interested in how this treatment affects the calcium metabolism, calcium ions (atoms) are particles. If the concern is the effect on red cell survival, red blood cells are particles. And should my interest be the effects of the gamma dose on rat survival, rats are particles. So this particle concept is quite broad and, as will be elucidated subsequently, this is because of what here is considered as the main property of particle is not the particle is structure but its motion (dynamics). However, I shall soon introduce some constrains on the present particle concept, but yet it will remain significantly broader than the corresponding particle concepts in classic theories like Newtonian mechanics and statistical mechanics. But here comes the practical reality into the picture.
Hardly any flow of particles into a system is truly constant; for instance, frequently the particle uptake is quite irregular because it is associated with the food intake. But practical experiences teach us that the dynamic inertia of a steady state population is often so large that those variations merely show up as ripples on the surface as it were. But, naturally, this does not mean that one should disregard the matter tot ally. That is, an expression like should occasionally be regarded as a model of a sort, and the notion 'test of modeF might become a piece of reality that must be taken into account.
The book has been designed to cover the syllabus of this subject. Care has been taken to make the treatment of the subject simple and accessible to the average students.

Preface vii

1. Chemical Kinetics Factors Affecting Reaction Rate • Law of Mass Action and Heterogeneous System • Zero Order Reaction • First Order Reaction • Pseudo First Order Reaction • Arrhenius Equation • Progressive Curve Methods 1

2. Kinetics of Heterogeneous Processes Heterogeneous Atmospheric Chemistry • Heterogeneous Reactions of the Trace Gases on Atmospheric Particulate Matters • The Effect of Cellulose Components in Degradation of Cotton Fibres • Materials And Met hods • Multivariate Regression Analysis • Neural Network Modelling • Experimental Section • Neural Net work Calculations • Reduction Process Modelling 33

3. Catalysis and its Role in Indus trial Technology Trends in Catalysis R&D • Technical Goals • Industrial Catalysis • Alkane Activation and Selective Oxidation • Synthesis of Fine Chemicals • Alternative and Renewable Resources • Olefin Polymerization • Alkylation Technology • Environmental Applications 57

4. Catalysis and Catalysts Catalysts and Catalysis • Catalysis • Types of Catalytic Reactions • Heterogeneous Catalysis • Examples of Het erogeneous Cat alysis • Homogeneous Catalysis • Autocatalysis • General Principles of Catalysis • Catalysis and Reaction Energetics • Typical Catalytic Materials • Types of Catalysis • Classes of Heterogeneous Catalysts • Examples • Kinetics • Organometallic Chemistry • Electrocatalysts • Thiourea Organocatalysis 102

5. Theories of Heterogeneous CatalysisDensity Functional Theory • Density Functional Theory Calculations of Surface Chemistry • From Surface Science to Heterogeneous Catalysis • Challenges in Theoretical Surface Reactivity and Heterogeneous Catalysis • Surface Diffusion • Kinetics • Mechanisms • Cluster Diffusion • Surface Diffusion and Heterogeneous Catalysis 141

6. Chemical DiffusionDiffusion in Physics • Advances in Thermo-Chemical Diffusion Processes • Nitriding • Molecular Diffusion • Choosing an Injector or Chemical Diffuser System 168

7. Chemical AdsorptionAbsorption (Chemistry) • Reactions • Uses • Chemisorption 189

8. Chemical Reactions and CatalysisSurface St rue ture • Trunca ted Bulk, Relaxation, Reconstruction, Defects and Super-Structures • Lattice and Reciprocal Lattice• Diffi'action Pattern and their Analysis • Some Examples from LEED Structure Determination • Semiconductor Surfaces• Insulator Surfaces • Other Scattering Techniques • EXAFS• SEXAFS • Photoelectron Diffraction (PhD, PED) • Structure Determination: Experimentai Results 210

Bibliography 259

Index 263

Owen Parker is Professor of Chemistry & Biochemistry. His specialization is in Homogeneous catalysis (C-H and C-halogen bond activation,oxidation), Luminescent materials, Conducting polymers, Metal coordination chemistry, Development of highly fluorinated ligands,Bioinorganic chemistry and Metals in medicine and disinfection science. Most of his research projects are interdisciplinary in nature.

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