Reactions at the Liquid-Solid InterfaceEdited By
- R.G. Compton, University of Oxford, Oxford, UK
Volume 28 of Comprehensive Chemical Kinetics is concerned with reactions occurring at the solid-liquid interface. Volumes 26 and 27 have dealt with electrochemical reactions. The present volume therefore covers those interfacial processes which involve no net passage of current. The first chapter covers the structure of the interfacial region and its experimental investigation. The second chapter reviews the mechanisms by which heterogeneous catalysis of solution reactions can take place. The third is concerned with the mechanism and kinetics of crystal growth from solution. The final chapter deals with corrosion processes at the metal-solution interface.
Comprehensive Chemical Kinetics
Published: July 1989
- 1. Structure of the Solid-Liquid Interface (A.T. Hubbard). 1. Introduction. Investigation of solid-liquid interfaces. Preparation of solid surfaces. Immersion of solid surfaces. Low-energy electron diffraction (LEED). Auger electron spectroscopy. Electron energy-loss spectroscopy. 2. Structure of layers formed from ionic solutions. Halides. Cyanide and thiocyanate. 3. Structure of electrodeposited layers. Electrodeposition and LEED. Influence of substrate structure. Influence of adsorbed layers. Influence of deposited element. Influence of the substrate element. 4. Structure of oxide films on single-crystal stainless steel. 5. Structure of adsorbed monolayers. Adsorption at polycrystalline platinum thin-layer electrodes. Adsorption of well-defined Pt(111) surfaces. References. 2. Heterogeneous Catalysis of Solution Reactions (M. Spiro). 1. General features. Introduction. catalytic rate. Rate-determining steps in the catalysis. Adsorption and competitive adsorption. Surface kinetics. Diffusion-controlled catalyses. Linear free energy relationships. Genuine and illusory heterogeneous catalysis. Inadvertent heterogeneous catalysis. 2. Substitution reactions. Solvolysis of tertiary organic halides. Hydrolysis of tertiary butyl acetate. Ester solvolysis and formation. Hydrolysis and formation of cobalt(III) complexes. Joint homogeneous and heterogeneous catalyses. 3. Isomerisation reactions. Racemisation of 1,1'-binaphthyls. Mutarotation of glucose. Racemisation of cobalt(III) complexes. 4. Oxidation-reduction reactions. Principles of electron transfer catalysis. Electron exchange reactions. Photographic development. The ferricyanide + iodide reaction. The iron(III) + iodide reaction. 5. Concluding comments. References. 3. Kinetics of Crystallisation of Solids from Aqueous Solution (W.A. House). 1. Introduction. 2. Fundamental concepts. Surface structure. Solubility product. Driving form for crystallisation. Rate of crystallisation. 3. Nucleation. Homogeneous nucleation. Heterogeneous nucleation. 4. Experimental methods. Direct mixing. Seeded growth methods. 5. Models of crystal growth. Growth theory of Burton, Cabrera and Frank. Chemical mechanistic models. The parabolic rate law. Polynuclear layer mechanism. Volume diffusion equations. 6. The effects of inhibitors. Surface adsorption. Glossary of main symbols. References. 4. An Introduction to Corrosion and its Prevention (P. Hammonds). 1. What is corrosion? Definition. Why study corrosion? 2. Electrochemical nature of corrosion. Thermodynamic considerations. Kinetic considerations. 3. Environmental effects on corrosion. Macro environments. Micro environments and corrosion types. 4. Properties of metals. Structure of metals. Composition of metals. 5. Testing methods. Field tests. Laboratory techniques. 6. Methods of protection. Improved design. Protective coatings. Cathodic protection. Inhibitors. 7. Future needs. References. Index.