MODERN ASPECTS OF ELECTROCHEMISTRY. No. 31

Transcription

1 MODERN ASPECTS OF ELECTROCHEMISTRY No. 31

2 LIST OF CONTRIBUTORS JENS E. T. ANDERSEN The Technical University of Denmark DK-2800 Lyngby, Denmark AKIKO ARAMATA Catalysis Research Center Hokkaido University Sapporo 060, Japan GREGERS BECH-NIELSEN The Technical University of Denmark DK-2800 Lyngby, Denmark ILAN BENJAMIN University of California Santa Cruz, California MARIA JURKIEWICZ-HERBICH University of Warsaw Warsaw, Poland SHAHED U. M. KHAN and Biochemistry Duquesne University Pittsburgh, Pennsylvania JOHN C. REEVE The Technical University of Denmark DK-2800 Lyngby, Denmark JERZY SOBKOWSKI University of Warsaw Warsaw, Poland 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.

3 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

4 Kluwer Academic / Plenum Publishers New York

5 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

6 Contents Chapter 1 I. II. METAL/SOLUTION INTERFACE: AN EXPERIMENTAL APPROACH Jerzy Sobkowski and Maria Jurkiewicz-Herbich Introduction... 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 III. The Thermodynamic Approach to the Metal/Solution Interface The Standard Gibbs Energy of Adsorption, Effect of Supporting Electrolyte on Electrosorption References Chapter 2 QUANTUM MECHANICAL TREATMENTS IN ELECTRODE KINETICS I. II. Shahed U.M. Khan Introduction... Continuum Theory of Electron Transfer Reactions Born Equation and the Free Energy of Activation, (continuum) vii

7 viii Contents 2. Reorganization Energy (Continuum) and the Free Energy of Activation III. (Continuum) and the Inverted Region General ET Reactions at Electrodes and the Inverted Region IV. Molecular Models of Electron Transfer Reactions at Electrodes Free Energy of Activation, and the Molecular Models 86 V. Molecular Models of Bond-Breaking Ion and Electron Transfer Reactions Classical and Semiclassical Treatments Quantal Treatments VI. Electronic Transmission Coefficient κ VII. Proton Transfer Reactions VIII. Solvent Dynamic Effects on ET Reactions at Electrodes References Chapter 3 MOLECULAR DYNAMIC SIMULATIONS IN INTERFACIAL ELECTROCHEMISTRY I. II. III. Ilan Benjamin Introduction... The Water/Metal Interface Preliminary Notes Potential Energy Functions Structure of Water at Metal Surfaces Dynamics Effect of External Electric Field... Ionic Adsorption and Solvation at the Water/Metal Interface Overview... Potential Energy Functions... Single Ion Adsorption at the Water/Metal Interface... Simulations ofelectrolyte Solutions at the Water/Metal Interface

8 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 Chapter 4 I. UNDERPOTENTIAL DEPOSITION ON SINGLE-CRYSTAL METALS III. Akiko Aramata Introduction Scope of this Chapter Preparation and Qualification of Single Crystals Well-Defined Surface Structure and Reconstruction of Single-Crystal Surfaces Anion Adsorption Behavior... II. Underpotential Deposition on Single-Crystal Electrodes Underpotential Deposition on Au Single Crystals... Underpotential Deposition on Single-Crystal Pt Group Metals... Underpotential Deposition on Ag Single Crystals... Underpotential Deposition and Anion Adsorption... Mechanism of Underpotential Deposition Kinetics and Dynamics... IV. Electrocatalysis on Electrodes Modified by Underpotential Deposition... V. Miscellaneous Bimetallic Underpotential Deposition Effect of Underpotential Deposition on Overpotential Deposition Effect of Organic Additives on Underpotential Deposition 4. Underpotential Deposition in Nonaqueous Solvents.... VI. Conclusion... References

9 x Contents Chapter 5 AUTOMATED METHODS OF CORROSION MEASUREMENT Gregers Bech-Nielsen, Jens E.T. Andersen, John C. Reeve, Anne D. Bisgård and Lars Vendelbo Nielsen I. II. III. IV. V. Introduction... Corrosion Measurements by Titration General Restrictions and Limitations of CMT Measurements CMT Measurements with a Polarized Electrode Instrumentation and Recording of CMT Measurements.. 5. Aim and Results of CMT Measurements Concluding Remarks... Imaging Corrosion by Scanning Probe Microscopy General Use of STM and AFM in Corrosion Studies Concluding Remarks... Critical Pitting Temperature General Experimental Equipment for CPT Testing Methods for Pitting Characterization Summary Concluding Remarks... Applications of the Electrochemical Hydrogen Permeation Cell General The Principle Diffusion of Hydrogen into Metal Studies on the Hydrogen Evolution Reaction Hydrogen-Related Stress Corrosion Cracking Cell Types Summary... References

10 Contents Cumulative Author Index... xi 317 Cumulative Title Index Subject Index