Surface and Defect Properties of Solids, Volume 1 PDF
Preview Surface and Defect Properties of Solids, Volume 1
A Specialist Periodical Report Surface and Defect Properties of Solids Volume 1 A Review of the Literature Published between January 1970 and April 1971 Senior Reporters M. W. Roberts, School of Chemistry, University of Bradford J. M. Thomas, Edward Davies Chemical Laboratories, University College of Wales, A beryst wyth Reporters J. S. Anderson, F.R.S., University of Oxford C. H. Bamfard, F.R.S., University of Liverpool L. L. Ban, Cities Service Co., Cranbury, New Jersey, U.S.A C. R. Brundle, University of Bradford G. C. Eastmond, University of Liverpool R. P. H. Gasser, University of Oxford J. Pritchard, Queen Mary College, University of London P. B. Wells, University of Hull J. 0. Williams, University College of Wales, Aberystwyfh ISBN: 0 85186 250 0 @ Copyright 1972 The Chemical Society Burlington House, London, W1V OBN Printed in Great Britain by Billing & Sons Limited Guildford and London Preface A few aspects of this Report merit elaboration. The first involves editorial policy, and is concerned with the question of what one should expect from a volume devoted to current trends in a given area of scientific enquiry. Rather than call for one or other of the two extreme types of report, that is, a factual account of recent experiments, or, alternatively, a general interpretative essay setting out to review recent progress, we have deliberately adopted an ambi- valent approach. Some of the articles in this first volume are distinctly phenomenological and seek to be comprehensive; others are of a more general nature. Through the sections dealing with defective solids runs one noticeable thread of coherence, namely the necessity to invoke extended defects in order to rationalize the properties of these solids. It is now absolutely clear that point defects alone fail to account for a wide range of solid-state phenomena and properties, and that both line defects (dislocations) and planar defects are demonstrably real. Surface Chemistry and Catalysis are considered on a broad front, keeping very much in mind that catalysis is concerned with molecular events involving a solid surface whose nature changes during reaction. In this volume, emphasis is laid on the identity and reactions of chemisorbed species on metal surfaces, as studied by ex- change and infrared techniques, catalytic selectivity, and the nature of surfaces as deduced from stimulated electron emission. M. W. R. J. M. T. Cont ents Chapter 1 Shear Structures and Non-stoicheiometry By J. S. Anderson 1 Crystallographic Shear 5 2 The Mechanism and Kinetics of Crystallographic Shear 10 3 The Characterization of Compounds with Planar Defects or Superstructures 12 4 Crystallographic Stiear in Specific Systems 13 Derivatives of the ReO, Structure 13 Tungsten (and Molybdenum) Oxides 13 Niobium Oxyfluoride 18 Derivatives of the MOO, Structure 18 Derivatives of the Rutile Structure 21 5 Thermodynamics of Rutile CS Phases 26 6 Ternary Defect Rutile Oxides 32 7 Double Shear and Block Structures 36 Symbolism 37 Ordered Block Structures 39 8 Stoicheiometric Faults, Intergrowths, and Non-stoicheio- metric Faults 44 9 Related Types of Non-stoicheiometry 51 Chapter 2 Direct Study of Structural Imperfections by High- resolution Electron Microscopy By L. L. Ban 1 Introduction 54 2 Electron Optical Considerations 57 3 Instrumentation 65 vi Contents 4 Materials Studied 66 Carbons 66 Carbon Blacks 67 Distribution of graphitic layer spacings 71 Different types of images in heat-treated carbon blacks 76 Carbon Films 80 Pyroly~edP olymers - Glassy Carbon 84 Coal and Char Samples 86 Po I y mers 89 Amorphous Polymers 89 Macromolecules - DNA 90 5 Summary and Conclusions 94 Chapter 3 The Role of Defects in Solid-phase Polymerization By C.H . Bamford and G. C. Eastmond 1 Introduction 95 2 Some General Considerations 96 3 Vinyl Polymerization 97 Reaction Kinetics 99 Nature of Reaction Sites 100 Molecular Mobility 102 U.V.I nitiation 105 E,S.R. Studies 106 Polymerization at Low Temperatures 112 Topotactic Polymerization 114 The Influence of Additives 117 Effects of Pressure 119 4 Polymerization of Cyclic Monomers 120 5 Co-polymerization 127 6 Concluding Remarks 127 Chapter 4 Structural Imperfections in Organic Molecular Crystals By J. M. Thomas and J. 0. Williams 1 Point Defects 130 2 Dislocations 132 Contents 3 Stacking Faults 4 Long-range Disorder and Short-range Order Chapter 5 Surface Studies by Photoemission By M.W . Roberts 1 Introduction Formal Description of the Photoemission Process Photoemission near the Threshold Escape Depth of Photoelectrons 2 Experimental Approaches in Photoemission 3 Information from Photoemission Studies Alloy Surfaces Studies of Silicon Nickel + Oxygen and Copper + Oxygen Systems Yield Energy Distribution The Aluminium-Oxygen and Aluminium-Water Interfaces Density of States Chapter 6 The Application of Electron Spectroscopy to Suf Studies By C. R. Brundle 1 Introduction 2 Principles of Electron Spectroscopy Summary of the Techniques Involved Chemical Information from Electron Spectroscopy Photoelectron Spectroscopy Energy Loss Electron Spectroscopy Electron Impact Auger Spectroscopy Ion Neutralization (I.N.) Spectroscopy 3 Application to Surface Studies Mean Free Path Lengths of Electrons Electron Impact Auger Spectroscopy Ion Neutralization Spectroscopy Photoelectron Spectroscopy Molecular Photoelectron Spectroscopy: P hotoemissior Studies X-Ray Photoelectron Spectroscopy, ESCA Energy Loss Spectroscopy ... Vlll Contents Chapter 7 Exchange and Equilibration Reactions on Metal Surfaces By R. P. H. Gasser 1 The Hydrogen-Deuterium Reaction 205 2 Nitrogen Isotope Reactions 21 1 3 Carbon Monoxide Isotope Reactions 21 5 4 Oxygen Isotope Reactions 217 5 Exchange of Hydrogen Isotopes in Organic Molecules 218 Chapter 8 Infrared Spectra of Adsorbed Species on Metals By J. Pritchard 1 Carbon Monoxide 223 2 Reflection Spectroscopy of Chemisorbed Carbon Monoxide 228 3 Other Reflection Spectra 230 4 Hydrogen, Nitrogen, and Nitric Oxide 23 1 5 Hydrocarbons and other Compounds 233 Chapter 9 Some Aspects of the Selective Action of Metal Catalysts By P. B. Wells 1 Introduction 236 2 Selectivity and Catalyst Structure 237 3 Selectivity and Reaction Mechanism 244 Consecutive Reactions 245 The Thermodynamic Factor 245 The Kinetic Factor 246 A Selectivity Pattern and its Interpretation 246 The Role of Occluded Hydrogen 249 Unresolved Problems 250 Parallel React ions 25 1 Substituent Effects in Selectivity 254 Isomerization of Product before Desorption 254 Reduction of Selectivity by Polymerization 255 4 Selective Poisoning and Shape-selective Catalysts 255 5 Summary 258 Author Index 259
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