Modern aspects of electrochemistry no 31 bockris

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MODERN ASPECTS OF ELECTROCHEMISTRY No 31 LIST OF CONTRIBUTORS JENS E T ANDERSEN Department of Chemistry The Technical University of Denmark DK-2800 Lyngby, Denmark MARIA JURKIEWICZ-HERBICH Department of Chemistry University of Warsaw 02-089 Warsaw, Poland AKIKO ARAMATA Catalysis Research Center Hokkaido University Sapporo 060, Japan SHAHED U M KHAN Department of Chemistry and Biochemistry Duquesne University GREGERS BECH-NIELSEN Department of Chemistry The Technical University of Denmark DK-2800 Lyngby, Denmark JOHN C REEVE Department of Chemistry The Technical University of Denmark DK-2800 Lyngby, Denmark ILAN BENJAMIN Department of Chemistry University of California Santa Cruz, California 95064 JERZY SOBKOWSKI Department of Chemistry University of Warsaw 02-089 Warsaw, Poland Pittsburgh, Pennsylvania 15282-1503 ANNE DORTHE BISGÅRD Department of Manufacturing Engineering The Technical University of Denmark DK-2800 Lyngby, Denmark A Continuation Order Plan is available for this series A continuation order will bring delivery of each new volume immediately upon publication Volumes are billed only upon actual shipment For further information please contact the publisher MODERN ASPECTS OF ELECTROCHEMISTRY No 31 Edited by J O’M BOCKRIS Texas A&M University College Station, Texas RALPH E WHITE University of South Carolina Columbia, South Carolina and B E CONWAY University of Ottawa Ottawa, Ontario, Canada KLUWER ACADEMIC PUBLISHERS NEW YORK, BOSTON, DORDRECHT, LONDON, MOSCOW eBook ISBN: Print ISBN: 0-306-46910-3 0-306-45650-8 ©2002 Kluwer Academic Publishers New York, Boston, Dordrecht, London, Moscow Print ©1999 Kluwer Academic / Plenum Publishers New York All rights reserved No part of this eBook may be reproduced or transmitted in any form or by any means, electronic, mechanical, recording, or otherwise, without written consent from the Publisher Created in the United States of America Visit Kluwer Online at: and Kluwer's eBookstore at: http://kluweronline.com http://ebooks.kluweronline.com Preface Prof Jerzy Sobkowski starts off this 31st volume of Modern Aspects of Electrochemistry with a far-ranging discussion of experimental results from the past 10 years of interfacial studies It forms a good background for the two succeeding chapters The second chapter is by S U M Khan on quantum mechanical treatment of electrode processes Dr Khan’s experience in this area is a good basis for this chapter, the contents of which will surprise some, but which as been well refereed Molecular dynamic simulation is now a much-used technique in physical electrochemistry and in the third chapter Ilan Benjamin has written an account that brings together information from many recent publications, sometimes confirming earlier modeling approaches and sometimes breaking new territory In Chapter 4, Akiko Aramata’s experience in researching single crystals is put to good advantage in her authoritative article on underpotential deposition Finally, in Chapter 5, the applied side of electrochemistry is served by Bech-Neilsen et al in the review of recent techniques for automated measurement of corrosion J O’M Bockris, Texas A&M University B E Conway, University of Ottawa R E White, University of South Carolina This Page Intentionally Left Blank Contents Chapter METAL/SOLUTION INTERFACE: AN EXPERIMENTAL APPROACH Jerzy Sobkowski and Maria Jurkiewicz-Herbich I Introduction II Molecular Approach to the Metal/Solution Interface Double-Layer Structure: General Considerations Solid Metal/Electrolyte Interface Methods Used to Study Properties of the Metal/Solution Interface: Role of the Solvent and the Metal 15 III The Thermodynamic Approach to the Metal/Solution Interface 35 The Standard Gibbs Energy of Adsorption, 35 Effect of Supporting Electrolyte on Electrosorption 54 References 63 Chapter QUANTUM MECHANICAL TREATMENTS IN ELECTRODE KINETICS Shahed U.M Khan I Introduction 71 II Continuum Theory of Electron Transfer Reactions 72 Born Equation and the Free Energy of Activation, (continuum) 74 vii viii Contents Reorganization Energy (Continuum) and the Free Energy of Activation 76 (Continuum) and the Inverted Region 79 III General 79 ET Reactions at Electrodes and the Inverted Region 83 IV Molecular Models of Electron Transfer Reactions at Electrodes 85 Free Energy of Activation, and the Molecular Models 86 V Molecular Models of Bond-Breaking Ion and Electron Transfer Reactions 94 Classical and Semiclassical Treatments 95 Quantal Treatments 99 VI Electronic Transmission Coefficient κ 102 VII Proton Transfer Reactions 104 VIII Solvent Dynamic Effects on ET Reactions at Electrodes 107 References 110 Chapter MOLECULAR DYNAMIC SIMULATIONS IN INTERFACIAL ELECTROCHEMISTRY Ilan Benjamin I Introduction 115 II The Water/Metal Interface 116 Preliminary Notes Potential Energy Functions Structure of Water at Metal Surfaces Dynamics Effect of External Electric Field III Ionic Adsorption and Solvation at the Water/Metal Interface Overview Potential Energy Functions Single Ion Adsorption at the Water/Metal Interface Simulations of Electrolyte Solutions at the Water/Metal Interface 116 117 127 135 138 143 143 145 146 153 Contents ix IV Interfacial Electron Transfer Reactions Preliminaries Two-State Models Multistate Models V Processes at the Liquid/Liquid Interface VI Conclusions and Outlook References 154 154 156 168 170 172 173 Chapter UNDERPOTENTIAL DEPOSITION ON SINGLE-CRYSTAL METALS Akiko Aramata I Introduction 181 Scope of this Chapter 181 Preparation and Qualification of Single Crystals 183 Well-Defined Surface Structure and Reconstruction of Single-Crystal Surfaces 191 Anion Adsorption Behavior 196 II Underpotential Deposition on Single-Crystal Electrodes 200 Underpotential Deposition on Au Single Crystals 201 Underpotential Deposition on Single-Crystal Pt Group Metals 212 Underpotential Deposition on Ag Single Crystals 219 Underpotential Deposition and Anion Adsorption 224 III Mechanism of Underpotential Deposition 231 Kinetics and Dynamics 231 IV Electrocatalysis on Electrodes Modified by Underpotential Deposition 240 V Miscellaneous 241 Bimetallic Underpotential Deposition 241 Effect of Underpotential Deposition on Overpotential Deposition 241 Effect of Organic Additives on Underpotential Deposition 242 Underpotential Deposition in Nonaqueous Solvents 243 VI Conclusion 243 References 245 336 Cumulative Title Index Title The Mechanism of the Electrodeposition of Metals The Mechanism of Formation of Coarse and Disperse Electrodeposits Mechanism of the Hydrogen Electrode Reaction as Studied by Means of Deuterium as a Tracer The Mechanism of Oxidation of Organic Fuels Mechanisms of Stepwise Electrode Author Bockris, J O’M Damjanovic, A Popov, K I Krstaji,ü N V Enyo, M Number 30 11 Gileadi, E Piersma, B Losev, V V Damjanovic, A Processes on Amalgams Mechanistic Analysis of Oxygen Electrode Reactions Membrane Chlor-Alkali Process Metal Displacement Reactions The Metal–Gas Interface Metal Hydride Electrodes Metal/Solution Interface: An Experimental Approach Methods and Mechanisms in Electroorganic Burney, H S Power, G P Ritchie, I M Oriani, R A Johnson, C A Fuller, T H Newman, J Sobkowski, J 24 11 27 31 Jurkiewicz-Herbich, M Humffray, A A Microelectrode Techniques in Electrochemistry Scharifker, B R 22 Models for Molten Salts Bloom, H Snook, I K Salvarezza, R C Arvia, A J Vorotyntsev, M A Chemistry A Modern Approach to Surface Roughness Applied to Electrochemical Systems Modern State of Double Layer Study of Solide Metals Molecular Dynamic Simulations in Interfacial Benjamin, I Electrochemistry Bloom, H Molten Electrolytes Bockris, J O’M The Nickel Oxide Electrode NMR Studies of Electrolyte Solutions McBreen, J Lynn, K G von Goldammer, E 28 17 31 21 10 Cumulative Title Index Title 337 Author Number NMR Studies of the Structure of Electrolyte Solutions Covington, A K Newman, K E 12 Oscillatory Behavior in Electrochemical Systems Perspectives in Electrochemical Physics Phase Transitions in the Double Layer at Electrodes Wojtowicz, J Vijh, A K Benderskii, V A Brodskii, A N 17 26 Daikhin, L I Velichko, G I Sides, R J 18 Phenomena and Effects of Electrolytic Gas Evolution Photoelectrochemical Devices for Solar Energy Conversion Orazem, M E Newman, J 18 Photoelectrochemical Kinetics and Related Khan, S U M 14 Devices Bockris, J O’M Photoelectrolysis and Photoelectrochemical Tributsch, H Catalysis Photovoltaic and Photoelectrochemical Cells Badawy, W A Based on Schottky Barrier Heterojunctions 17 30 Physical Chemistry of Ion-Exchange Resins Kitchener, J A Physical Chemistry of Synthetic Polyelectrolytes Physical Mechanisms of Intercalation Eisenberg, H, Fuoss, R M McKinnon, W R Haering, R R Physics and Applications of Semiconductor Allongue, P 23 Gutiérrez, C 28 Perkins, R S Electrodes Covered with Metal Clusters Potential-Modulated Reflectance Spectroscopy Studies of the Electronic Transitions of Chemisorbed Carbon Monoxide Potentials of Zero Charge Electrodes Power Sources for Electric Vehicles Preparation and Characterization of Highly Dispersed Electrocatalytic Materials The Present State of the Theory of Electrolytic Solutions Proton Solvation and Proton Transfer Processes in Solution Andersen, T N Kordesch, K V Kinoshita, K Stonehart, R Falkenhagen, H Kelbg, G Conway, B E 15 10 12 338 Cumulative Title Index Title Author Number Erdey-Grúz, T Lengyel, S 12 Quantum Chemical Treatment of Adsorbed Blyholder, G Species Quantum Mechanical Treatments in Electrode Khan, S U M Kinetics Quantum Theory of Charge-Transfer ProcChristov, S G esses in Condensed Media Proton Transfer in Solution Reaction Engineering and Digital Simulation in Electrochemical Processes Reaction Kinetics and Mechanism on Metal Single Crystal Electrode Surfaces Recent Advances in the Study of the Dynamics of Electrode Processes Recent Advances in the Theory of Charge Transfer Recent Developments in Faradaic Rectification Studies The Role of Electrochemistry in Environmental Control The Role of the Electronic Factor in the Kinetics of Charge-Transfer Reactions Scanning Tunneling Microscopy: A Natural for Electrochemistry The Semiconductor/Electrolyte Interface: A Surface Science Approach Small-Particle Effects and Structural Considerations for Electrocatalysis Solvated Electrons in Field- and Photo-Assisted Processes at Electrodes Solvent Adsorption and Double-Layer Potential Drop at Electrodes Solvent Dipoles at the Electrode-Solution Interface Some Aspects of the Thermodynamic Structure of Electrochemistry Scott, K 31 28 27 21 Fahidy, T Z Gu, Z H Kuznetsov, A M 27 Agarwal, H P 20 Kuhn, A T 20 German, E D Kuznetsov, A M 24 Sonnenfeld, R Schneir, J Hansma, P K Jaegermann, W 21 Kinoshita, K 14 Conway, B E 30 Trasatti, S 13 Habib, M A 12 Rysselberghe, P van Cumulative Title Index 339 Title Some Fundamental Aspects of Electrode Author Number Khna, S U M 15 Mizuno, T Enyo, M 30 Charle, K.-P Willig, F 19 Yeo, R S Yeager, H L Mauritz, K A Hopfinger, A J 16 Heiland, W Bewick, A 11 Processes Sorption of Hydrogen on and in Hydrogen-Absorbing Metals in Electrochemical Environments Spin-Dependent Kinetics in Dye-Sensitized Charge-Carrier Injection into Organic Crystal Electrodes Structural and Transport Properties of Perfluorinated Ion-Exchange Membranes Structural Properties of Membrane Ionomers The Structure of the Metal-Vacuum Interface The Study of Simple Consecutive Processes in Electrochemical Reactions Surface Analysis by Electron Spectroscopy Surface-Enhanced Raman Scattering (SERS) Surface Potential at Liquid Interfaces Surface States on Semiconductors 14 Thirsk, H R Baker, B G Efrima, S Llopis, J Batchelor, R A Hamnett, A Temperature Dependence of Conductance of Barthel, J Wachter, R Electrolytes in Nonaqueous Solutions Gores, H.-J The Temperature and Potential Dependence of Conway, B E Electrochemical Reaction Rates, and the Real Form of the Tafel Equation Uosaki, K Theoretical Aspects of Semiconductor Kita, H Electrochemistry Goodisman, J Theories for the Metal in the Metal-Electrolyte Interface Sacher, E Theories of Elementary Homogeneous Laidler, K J Electron-Transfer Reactions Pesco, A M Theory and Applications of Periodic Cheh, H Y Electrolysis 10 16 22 13 16 18 20 19 Popov, K I Theory of the Effect of Electrodeposition at a Maksimovic, M D Periodically Changing Rate on the Morphology of Metal Deposits Markin, V S Thermodynamics of Membrane Energy Tsong, T Y Transduction in an Oscillating Field 19 24 340 Cumulative Title Index Title Author Transport-Controlled Deposition and Dissolution of Metals Transport Models for Ion-Exchange Membranes Transport Phenomena in Electrochemical Kinetics Popov, K I Verbrugge, M W Pintauro, P N Arvia, A J Marchiano, S L Ultrahigh-Vacuum Surface Analytical Methods in Electrochemical Studies of Soriaga, M P Harrington, D A Single-Crystal Surfaces Ultrasonic Vibration Potentials Underpotential Deposition on Single-Crystal Metals Number 19 28 Stickney, J L Wieckowski, A Zana, R Yeager, E B Aramata, A 14 31 Water Electrolysis and Solar Hydrogen Dem- Sandstede, G Wurster, R onstration Projects 27 X-Rays as Probes of Electrochemical Interfaces 20 Index Acetic acid, a voltammogram, 34 Acetone, its adsorption on mercury, 52, 61 Adiabatic electron transfer, a classical Hamiltonian, 93, 166, 169 Adiabatic free energy curves, effect of the Aliphatic compounds, adsorption on mercury electrodes, 44 Aluminum, pitting, 281 Aluminum surfaces, corroding, 280 Amokrane and Badiali, double layer capacitance model, a semi-empirical approach to absorption effects, 58 Anderson-Newns, Hamiltonian, 91 Anion adsorption behavior, on single crystal surfaces, 196 effect on underpotential deposition, 226, 228 Anodic polarization curve, at fixed temperature, 283 Arnbig and Bisgaard, effect of temperature on pitting corrosion, 285 Aromatic compounds, adsorption on metals, 51 Arvia, method of crystal orientation, Atomic hydrogen, its permeation through steel, 300 quantum properties of water, 170 Adiabatic free energy curves, for complexes, in electron transfer, 98 Adiabatic limit, 164 Adsorption of acetone on mercury, characterizing parameters, 61 of chlorate ions, 30 of diethyl ether from aqueous solutions of sodium chloride, tabulated, 49 effects of dissociation, 56 energy, 35 free energy, charge transfer processes, 172 at the metal–solution interface, 143 in the presence of organics, work of Parsons and Zobel, 55 of thiourea, from nonaqueous solvents, 51 of water, on platinum electrodes from nonaqueous solution, 32 Berkowitz interaction of lithium and iodine with water in the interface, 148 the theory of the potential of mean force at electrodes, 152 Bewick and Kunimatsu, the water structure at the platinum–solution interface, 24 Biological environments, corrosion, 309 AFM in corrosion studies, 270 images of aluminum surfaces, 280 images, on gold, 208 on silver, 209 341 342 Index Bockris, the linear relationship between permeation rate and the square root of current, 304 Bockris and Argade, on the relation of work function to the potential of zero charge, 17 Bockris and Blomgren, relation between Gibbs energy of adsorption; structure of organic compounds, 47 Bockris and Carbajal, study of thiourea on active and passive ion electrodes by FTIR, 49 Bockris and Habib Fourier Transform Infrared Spectroscopy, 142 Galvani potential difference at the pzc, orientation of water molecules at the surface of electrodes, confirmed by computer simulation, 29 studied by FTIR, 25 Bockris and Jeng adsorption of aliphatic and aromatic compounds, on polycrystalline platinum, 51 adsorption of 19 organic compounds on platinum, 15 Bockris and Matthews, 1966 calculation of proton transfer with special reference to isotopic effects, 104 Bockris and Wass, studies of transfer coefficients as a function of temperature, 107 Bockris–Swinkles isotherm, application to standard states, 36 Born equation free energy of activation, 74 as self energy, 74 its validity, 74 Born–Marcus theory of electrode processes, failure to explain Tafel linearity, 75 Born–Oppenheimer conditions at interfaces, 157 Breakdown of water, at the interface, 24 Brigham and Tozer, relation between temperature and pitting corrosion, 284 Butler, his seminal 1936 paper, introducing bond forming by product in the theory of charge transfer reactions, 94 Calhoun and Voth, molecular dynamic simulation, 94 Capacitance effect of ionic adsorption thereon, 58 hump, a comparison of models, 57 plots, maxima, 59 Capacitance of the double layer, and the contribution due to the metal, Capacity maxima, surface tension on mercury electrodes in various solvents, 56 Cathodic potentials, dissolution thereat, explained, 258 Cell types, for corrosion testing, 309 Charge or potential, in double layer studies, 46 Charge transfer processes adsorption of free energy, 172 Chemisorption, effect on the transmission coefficient, 103 Clavilier method of electrode preparation applied to cyclic voltammograms, 183 quenching technique, 181 voltammetric plots on platinum, 13 well defined conditions for electrode process results, 182 Compression, of water in the inner layer, 28 Computer simulation based on isotropic water-metal potential energy, 131 charge transfer calculations, 173 Index 343 Computer simulation (cont.) confirming the concepts of Bockris and Habib about orientation, 29 Contamination, effect on the work function, 17 Continuum theory, for electron transfer, 72 Conway, study of solvent displacement, 36 Conway and Bockris, 1957 paper for electron transfer, involving bond breaking, 94 Conway and Dhar, study of standard states at interface, 36 Copper underpotential deposition, 227 Corrosion, of zinc and zinc alloys, 265 Corrosion measurements effect of temperature, 296 rotating disc electrode, 260 titration, 253 instrumentation, 259 results, 263 Corrosion methods, summarized, 298 Corrosion testing, necessary apparatus, 287 Cracking of metals, by hydrogen, 307 Crevice corrosion studies, 288 Crystal platinum metals, underpotential deposition, 212 Density of water, as a function of the distance from the platinum surface, calculated, 141 Determination of roughness, of electrode, 10 Devanathan and Stachurski, hydrogen permeation cell, 299 Dielectric constant, in the double layer, Diffuse layer, its effect on the capacitancepotential curve, Diffusion of hydrogen, into metals, 301 Dissolution, at cathodic potentials, 258 Donicity, metal-water interactions, 21 Donor and acceptor numbers, Volta potential at the metalsolution interface, 22 Double layer thickness, Double layer structure, general considerations, Dynamics, of water in the interface, 135 Electric field effect upon water at the interface, 138 its influence on the free energy adsorption, 43 Current-time lines for cyclic voltammograms in copper-underpotential deposition, 238 Electrocatalysis, on electrodes modified Cyclic voltammograms Electrode roughness, 10 Electrode reactions, effect of the second coordination shell, 79 Electron overlap potential, work of Bockris and Habib, Electron structure, of the metal, 123 Electron transfer approach of Weiss, its priority, 72 classical and semiclassical treatment, 95 computed free energy curves, 158 number, 224 rate for the reduction of ferric, in the nonadiabatic limit, 165 for copper onto gold, 237 on gold, 204 on platinum, as a function of pH, 199 of polycrystalline platinum, in acetic acid, 34 showing underpotential deposition, 229 in underpotential depositions, 216 Damaskin, model for standard states, 41 Debye length, application to the ionic distribution at interfaces, Density profiles at the interface, 149 for water at metal surfaces, 128 by underpotential deposition, 240 344 Index Electron transfer (cont.) reaction of other electrodes, inverted region, 83 solvent dynamic effect, relaxation times, 109 Electrosorption in supporting electrolyte, 54 Ethylene glycol, its adsorption on mercury, 62 Ewald sum, 127 EXAFS, 210 Exchange, of protons, during studies at the interface, 34 Experimental equipment, for corrosion testing, 286 Experimental approach, to the metal-solution interface, Fleischmann, surface enhanced Raman spectra (SERS), 26 Flory–Huggins isotherm, effect upon standard state determinations, 36 Flow cell, for corrosion measurements, 262 Force constants, for ion-ligand bonds, 88 Forces, attractive, between butanol and anions, within the double layer, 62 Foresti, hydrophilicity of different metals, 49 Franck–Condon barrier, its meaning in electrode kinetic theory, 72 Free energy of activation, 78 Born equation, 74 in continuum theory, and the inverted region, 79 the George–Griffith expression, its agreement with experimental values, 86 calculated from Born–Marcus theory, compared with experiment, 75,76 in redox reactions reorganization energy, 76 Free energy-reaction coordinate relations for exothermic and endothermic reactions, 82 Free energy curves, for electron transfer, 158 Freezing of water, by means of an external field, 130 Frumkin isotherm, standard states, 37 FTIR application, to examining underpotential deposition with copper, 218 orientation of water at the interface, work of Bockris and Habib, 25 study of adsorption of thiourea on iron electrodes, 49 Gallium–solution interface, high value of the dielectric constant, George–Griffith expression for energy of activation, its priority, 86 free energy curves for ferrous-ferric, 90 Gibbs energy, adsorption of thiourea on some metallic electrodes, 42 Gibbs energy of adsorption, 35 dependence on the metal–solvent interaction, 48 Glosli and Philpot, potential energy changes as a function of charge on the metal, 132 Gold single crystals, voltammograms, 189 Gold electrodes, underpotential deposition, 201 Gouy–Chapman theory, its part in electrode kinetics, 155 Gurney 1931 theory of the density of electronic state in metals, 85 seminal approach to quantum electrochemistry, 72, 154 Gurney–Butler theory, for electron transfer at interfaces, 85 Index 345 Halley and Haatman, Molecular dynamic simulations for free energy curves, in ferrous-ferric, 89 Hamiltonian, for nonadiabatic electron transfer, 166 Heinzinger and Spohr, models of water, 129 Hydrogen bonding, in water structure at the interface, 134 Hydrogen concentration, stress corrosion cracking, 307 Hydrogen evolution reaction, Tafel mechanism, 304 Hydrogen in metals, cracking thereof, 307 Hydrogen permeation cell, use in corrosion, 299 Interfacial interactions, with water, work of Berkowitz, 148 Interfacial parameters, the work of Trasatti 18 Inverted region free energy of activation, 79 unsuccessful search for, 80 Ion adsorption, single, at the metal-water interface, 146 Ion–ligand bonds, force constants, 88 Ionic adsorption at the interface, 143 Ions, specific effect on the adsorption capacitance, 58 Isotherms, used in underpotential deposition, 231 Hydrogen permeation measurements, in pipelines, 311 Hydrogen related stress corrosion cracking, 306 Hydrogen sensors, 310 Hydrophilicity sequence in mercury, silver and gold, 49 Image charges, 124 Imaging corrosion, scanning probe microscopy, 269 In situ, STM, and AFM, 203 Infrared spectroscopy, double layer, 24 Inner layer capacitance, determined by Valetti 19 Instrumentation, for corrosion measurements, by means of titration, 259 Interaction potential between a single water molecule and the 100 face of platinum, 121 Interaction energy, single water molecules, and the Pt (100) surface, 122 Interface approaches to, breakdown of water, 24 Interfacial electron transfer, calculated, 154 Jellium model, use in the double layer theory, Kazarinov, use of radiometric methods at interfaces, 31 Khan, Wright, and Bockris, the first quantum mechanical calculation of transmission coefficients, 103 Kinetics of underpotential deposition, 236 Kornyshev, use of the Jellium model in double layer theory, Kubo and Toyozawa, priority in the continuum approach to electrode kinetic theory, 72 Kuzuetsov, thermal adsorption data, quantum mechanically examined, 24 Lead, underpotential deposition, 202 Linear response theory, 73 Lipkowski, Gibbs energy of the adsorption of diethyl ether on single crystals, 48 Liquid–liquid interfaces, Monte Carlo studies, 171 Long range forces, 125 346 Index Matsui and Jorgensen, the Monte Carlo simulation of ion–ion and wallwall image interactions, 149 Maxima, of capacitance plots, 59 Mechanism, of underpotential deposition, 231 Mercury, adsorption of acetone thereon, 52 Metal dissolution and inhibition, 274 Metal–electrolyte interface, diagrammatic, 144 Metal water interactions, work of Thiel and Madey, 24 Metals effect upon the standard free energy of adsorption, 46 contribution to capacitance in the double layer, Metal interface and ionic adsorption, 143 Metal–solution interface experimental, methods for its study, 15 molecular approach, for solids, thermodynamic approach, 35 Metal–solvent interactions, donicity, 20 Metals, diffusion of hydrogen therein, 301 Methods, for study of the metal solution interface, 15 Molecules, at the interface, orientation thereof, 18 Molecular approach, to the metal-solution interface, Molecular dynamic calculations, for electrode transfer at interfaces, 159 Molecular dynamic simulation for electrode reactions, 88 made by Strauss and Voth, 92 Molecular models electron transfer at interfaces, 85 for bond breaking ion in electron trans- fer reactions, 94 Monocrystalline electrodes, roughness therefrom, 13 Monte Carlo studies for liquid–liquid interfaces, 171 Multi state models, for electron transfer, 168 Nagy and Halley effect of external field on the dynamics of water structure, calculated, 142 potential energy changes due to charge on the metal, 132 Newton, quantum mechanical computation of transmission coeffi- cient, 103 Nickel, its corrosion, 267 Nikitas and Sotiropoulos, calculations for standard free energy as a function of different standard states, 40 Nomura and Iijima, determination of the mass change in electrode on adsorption, 29 Non-adiabatic limit, 162 Non-adiabatics, work of Warshel, 163 Nonaqueous solutions the study of water on the double layer, 32 at underpotential deposition, 243 Nonaqueous solvents, adsorption of thiourea from them, 51 Nucleation growth, as a controlling process, 234 Organic additives, underpotential deposition, 242 Organic compounds adsorption, on platinum, 16 effect of their structure, on the stand- ard free energy of adsorption, 47 Orientation of water molecules at the interface change with potential, 25 computer simulation studies, 29 Index 347 Oxides Pitting (cont.) semiconductivity, 271 Oxygen distribution, near silver, in the double layer, 28 Pair correlation coefficients, 132 Palladium windows, for hydrogen measurements, 310 Parameters, for organic adsorption, thermodynamic, 60 Parsons, work upon potential or charge, as determinative in double layer studies, 46 Parsons and Bockris, 1951 quantitative model for electron transfer reactions, including bond breaking, 94 Parsons–Zobel plot, determination of roughness, 11 diagrammated, 277 function of chloride ions, 292 photographs, 278 effect of temperature, 285 Pitting characteristics, 290 Pitting corrosion, 276 the work of Brigham and Tozer, 284 Pitting measurements, 289 Platinum, interaction with water, 121 Platinum surfaces, interaction of propylene carbonate, 32 Polarization curves, as a function of temperature, 293 Polarized electrode and corrosion measurements, 257 Polycrystalline electrodes, double layer theory thereat, Parsons and Zobel, work on adsorption of Pope, and underpotential deposition, a review, 181 organics in the presence of adsorbed ions, 55 Passivation, involving certain regions of the electrode, 272 Potential or charge, in double layer studies, 46 Potential dependence of sulphate adsorption, on platinum, 198 Passivation of surfaces, 275 Potential energy functions, molecular dynamics, 117 Potential energy surface for the iodide-iodine system, 101 Potential independent, character of temperature effects, on corrosion measurements, 296 Potential of mean force behind adsorption, calculated by Berkowitz, 152 Peak potentials, for copper underpotential deposition on gold, 227 Penov, work on nickel corrosion, 268 Perez and Benjamin, maintenance of solvation shells in the interface, 148 Perez, Monte Carlo simulation of free energy curves for electron transfer, 97 Permeation, work of Bockris and Potential of zero charge, work function, 17 McBreen, 304 pH effects, on corrosion measurements, 256 Potentiostatic determination of corrosion, 291 Preparation, of a voltammogram, 186 Philpot Propylene carbonate work on water at interfaces, 153 review of ionic adsorption, 145 Philpot and Blosli, the calculation of contact adsorption, 150 Pitting of aluminum, 281 adsorption on platinum, by means of radiotracers, 33 interaction of platinum surfaces, 32 Proton transfer reactions some difficulties in the theory, 104, 105 work of Schmickler, 104 348 Index Quantal treatments, of electron transfer, 99 Quantum electrochemistry, beginning by Gurney, 72, 94 Quantum mechanics, in electrode kinetics, 71 Quartz crystal microbalance, 211 study of surfaces, 29 Quenching described in detail, 184 effect on voltammograms, 185 Quenching technique, work of Clavilier, 181 Radiometric methods used by Kazarinov to study the double layer, 31 work of Wieckowski, 30 Reconstruction, of well defined surface structures, 191 Rotating disc electrode, corrosion measurements, 260, 261 Rotational dynamics of water at the interface, 137 Roughness determination according to methods developed by Trasatti and Petrii, 10 moncrystalline electrodes, 13 Salting out of substances, near electrodes, 55 Saveant, contribution to the theory of bond breaking at electrodes, 96 Scanning tunneling microscopy, structure of the double layer, 29 Schmickler formulation of the potential energy curves in ion-transfer, 100 Reconstruction and voltammograms, 191 Reduction of testing time, in corrosion, 294 nonlinear Tafel lines, 84 proton transfer reactions, 104 unified model for electron and ion Relaxation time, solvent dynamic effect in electron transfer, 109 Reorganization energy free energy of activation, 76 harmonic movement of the ion-solvent vibrations (compared with nonharmonic approach), 78 transfer, 94 Second coordination shell, effect upon electrode reactions, 79 SERS, for adsorbed water on silver, 26 SERS spectra, the effect of adsorbed fluoride, 26 Side reactions, in corrosion measurements, 255 Siepmann and Sprik, three bodied interaction equation, 123 Simulation, for the electrode-solution nonisotopic reactions, with harmonic free energy profile, 80 Reorientation, of organic molecules, 44 Restructuring of water, as a functional applied field, work of Bockris interface, 153 and Habib, 142 Robinson and Kilgallon, assessing hydro gen concentration in a test specimen, 308 Single crystals, 184 preparation, 183 Single crystals and polycrystals, surprisingly different voltam- Rose and Benjamin, molecular dynamic mogram, 14 Single crystal silver, 19 Single crystal surfaces, anion adsorption approach to electrode kinetics, 71, 151 Ross, voltammetric plots on platinum, surprising differences in single crystals and polycrystals, 14 behavior, 196 Smith and Hynes, introduction of electron friction, 108 Index 349 Solids, and the metal-solution interface, Solvation of ions, 143 Solvent effect upon the interface, 15 effect on the standard free energy of adsorption, 51 effect on metal, 15 Solvent dipoles, potential difference at the interface, Solvent dynamic effects on electron transfer, 108 Solvent free energy calculations for the electron transfer reaction, in ferrous-ferric, 161 Spectroscopy, thermal desorption, double layer, 23 Spohr, water pair correlation functions, 133 Spohr and Heinzinger, water-platinum potential, 120 Stability, of crystalline surface, 273 Standard states, virial isotherm, 37 Standard state studies, Frumkin isotherm, 37 Standard states at the interface, studied by Conway Straus and Voth, study of sodium reduction at a water-platinum interface, 160 Stress corrosion cracking, and the critical hydrogen concentration, 307 Summary, of methods of measuring corrosion, 297 Supporting electrolyte its effect on differential capacity, 56 electrosorption, 54 Surfaces, examined by means of X-ray scattering, 27 Surface area, real, underpotential deposition of metals, 12 Surface corrugation, 120 Surface and enhanced Raman spectroscopy, at the interface, 25 Surface molfraction, for adsorption of acetate, compared with that of the solvent, on mercury, 53 Tafel linearity, current density at the metal solution interface, 75 Tafel recombination, transfer of hydrogen through steel, 305 the selection thereof, 41 study of Torrent, 39 Ternkin approach, to underpotential deposition, 232 Test specimen, hydrogen concentration therein, 308 work of Nikitas, 40 Testing time, reduced, 294 and Dhar, 36 STM, applied to underpotential depositions, 215 use in electrode processes, 182 corrosion studies, 270 STM images, 193 on gold, 194, 195, 205, 207 single crystals, with various crystal orientation, 206 of lead on silver, 220, 221, 223 showing reconstruction, 192 of thallium, on silver, 222 STM on platinum of copper sulphate, 217 Theory, of underpotential, deposition, 200 Thermal desorption spectroscopy, 23 Thermodynamic approach, to the metalsolution interface, 35 Thiel and Madey, metal–water interactions, 24 Thiourea, adsorption on mercury, 60 Titration method for corrosion measurements, with a polarized electrode, 257 Titrations, corrosion measurements, 252 Torrent, study of standard states, 39 350 Transfer coefficients, plotted as a function of temperature, work of Schmickler, 106 Translational diffusion of water at the interface, 136 Index Voltammograms (cont.) of platinum electrode in sulfuric acid, preparation of the electrode, 186 Transmission coefficient, calculated, 102, 167 showing reconstruction, 191 Voth, on quantum nature of water structure, adiabatic free energy curves, 170 Transpassive corrosion, 284 Trasatti and Petrii, determination of roughness, 10 Trasatti, interfacial parameter, 18 Warshel, an approximate method for nonadiabatic electron transfer, 163 Water affected by electric fields, 138 Underpotential deposition, 181, 214 anion adsorption, 226 of copper, 235 on gold, 201 on lead, 202 its mechanism, 231 from nonaqueous solutions, 243 as a function of overpotential, 241 on single crystals, 200 single crystal platinum metals, 212 on silver single crystals, 219 thallium on platinum, 230 connected to work function, 239 on zinc, 213 Valetti, work on single crystal silver on the double layer, 19 Virial isotherm, standard state, 37 Vitanov and Popov, the hydrophilicity sequence in adsorption on gold and silver, 49 Volta potential difference, 20 in terms of donor and acceptor numbers, 22 Voltammograms effect of quenching, 185 density in the inner layer, 28 diffusion at the interface, 138 at an interface, 140 rotational dynamics, 138 structure at metal surfaces, 127 Water models, 118 Water molecules at the interface, orientation, 18 Water–metal interaction potential, 119 Water–metal interface, dynamic simulation, 116 Weiss 1951 theory of electron transfer, 94 priority in the continuum approach to electron transfer theory, 72 Well defined surface structures, reconstruction, upon solution contact, 191 Wieckowski, use of radiometric methods in adsorption at interfaces, 30 Work function effect of contamination, 17 Trasatti’s contribution, underpotential deposition, 239 X-ray scattering at surfaces, 27 XANES, 210 on gold single crystals, 190 knowledge of various platinum single crystal surfaces, 187 for irridum and platinum low index single crystals, 188 Zho and Philpot, water-metal interaction equation, 121 Zinc, underpotential deposition, 212 Zinc–iron alloys, corrosion, 264, 266 .. .MODERN ASPECTS OF ELECTROCHEMISTRY No 31 LIST OF CONTRIBUTORS JENS E T ANDERSEN Department of Chemistry The Technical University of Denmark DK-2800 Lyngby, Denmark... please contact the publisher MODERN ASPECTS OF ELECTROCHEMISTRY No 31 Edited by J O’M BOCKRIS Texas A&M University College Station, Texas RALPH E WHITE University of South Carolina Columbia, South... States of America Visit Kluwer Online at: and Kluwer's eBookstore at: http://kluweronline.com http://ebooks.kluweronline.com Preface Prof Jerzy Sobkowski starts off this 31st volume of Modern Aspects
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