Surface Reactions

1. Introduction.- References.- 2. The Problem of Heterogeneously Catalyzed Partial Oxidation: Model Studies on Single Crystal Surfaces.- 2.1 Modes of Oxygen Chemisorption on Metal Surfaces.- 2.2 Reactions of Molecularly Chemisorbed Oxygen.- 2.3 Reactions of Atomically Chemisorbed Oxygen.- 2.3.1 Atomic Oxygen as a Nucleophile on Silver.- 2.3.2 Atomic Oxygen as a Bronsted Base on Silver.- 2.3.3 Addition of Atomic Oxygen to Carbon-Carbon Double Bonds on Silver.- 2.3.4 Generalization to Other Metals.- 2.4 Conclusion.- References.- 3. Desulfurization Reactions Induced by Transition Metal Surfaces.- 3.1 Background.- 3.2 The Reactions of Thiols on Transition-Metal Surfaces.- 3.2.1 Spectroscopic Identification and Characterization.- 3.2.2 Structural Studies of Adsorbed Intermediates.- 3.2.3 Chemical Probes of the Mechanism.- 3.2.4 Coverage Dependence of Reactivity.- 3.3 Desulfurization of Cyclic Sulfur-Containing Molecules.- 3.4 Conclusions.- References and Notes.- 4. Tricyclisation and Heterocyclisation Reactions of Ethyne over Well-Defined Palladium Surfaces.- 4.1 Background.- 4.2 Mechanistic Studies of Ethyne Tricyclisation.- 4.2.1 Molecular Beam Results, Temperature-Programmed Reaction and Isotope Labelling: Molecular Formula of the Reaction Intermediate.- 4.2.2 Characterisation of the C4H4 Intermediate.- 4.2.3 The Reactively Formed Benzene is Tilted: Effect of Surface Packing Density on the Conformation, Yield and Desorption Kinetics of Benzene Formation.- 4.3 Studies at High Pressures.- 4.4 The Effects of Promoters, Poisons and Other Coadsorbed Species.- 4.5 The Structure and Bonding of Ethyne Chemisorbed on Transition Metal Surfaces.- 4.6 Why is Tricyclisation so Specific to Palladium and Why is the (111) Plane so Strongly Favoured?.- 4.7 Other Cyclisation Reactions.- 4.8 Conclusions.- References.- 5. Model Organic Rearrangements on Aluminum Surfaces.- 5.1 Background.- 5.2 Carbon-Halogen Bond Cleavage.- 5.2.1 Reactive Sticking Probability.- 5.2.2 High-Resolution EELS and TPRS Observations of C-X Bond Cleavage.- 5.3 Integrated Desorption Mass Spectrometry.- 5.4 Alkyl Surface Chemistry.- 5.4.1 Iodoalkanes with ?-Hydrogens.- 5.4.2 Dihaloalkanes.- 5.4.3 Radical Participation in Aluminum Alkyl Chemistry.- 5.5 Etching of Aluminum Surfaces with Alkyl Halides.- 5.6 Model and Real Systems: A Comparison.- 5.7 Aluminum Surfaces vs. Aluminum Compounds: A Summary.- 5.8 Conclusion.- References and Notes.- 6. The Adsorption of Hydrogen at Copper Surfaces: A Model System for the Study of Activated Adsorption.- 6.1 Introductory Remarks.- 6.2 A One-Dimensional Description: The Translational Degree of Freedom.- 6.2.1 The Activation Barrier.- 6.2.2 Early Adsorption Measurements with Molecular Beams.- 6.2.3 Early Desorption Measurements and Detailed Balance.- 6.3 A Two-Dimensional Description: The Translational and Vibrational Degrees of Freedom.- 6.3.1 The 2-D Potential Energy Surface.- 6.3.2 Recent Adsorption Measurements with Molecular Beams.- 6.3.3 Quantitative Treatment of Adsorption and Desorption Data.- a) Sticking Probability Models.- b) Quantitative Comparison of Adsorption Data.- c) Desorption and the Role of Surface Motion.- 6.3.4 State-Resolved Scattering Measurements.- a) Reflection Probability Measurements.- b) Inelastic Scattering Measurements: Vibrational Excitation.- 6.3.5 State-Resolved Desorption Measurements: S0(v,Ei) via Detailed Balance.- 6.4 A Multidimensional Description: The Degrees of Freedom Including Translation, Vibration, Rotation, Molecular Orientation, and Impact Parameter.- 6.4.1 Theoretical Descriptions for More than Two Dimensions.- 6.4.2 Activation Energy Measurements: The Effect of Rotation on Adsorption Rate.- 6.4.3 State-Resolved Desorption Measurements: The Role of Rotation in Adsorption and Desorption.- 6.4.4 Inelastic Scattering Measurements: The Influence of Rotation on Vibrational Excitation.- 6.5 Summary.- References.- 7. Kinetics and Dynamics of Alkane Activation on Transition Metal Surfaces.- 7.1 Background.- 7.2 Trapping-Mediated Dissociative Chemisorption.- 7.2.1 Trapping Dynamics.- 7.2.2 Kinetics.- 7.2.3 Microscopic Reaction Mechanism.- 7.3 Direct Dissociative Chemisorption.- 7.3.1 Activation via Translational Energy.- 7.3.2 Activation via Vibrational Energy.- 7.3.3 Collision-Induced Activation.- References.