Modern Aspects of Electrochemistry

by Bockris, J. O'M.; White, Ralph E.; Conway, B. E.

• ISBN13: 9780306456503
• ISBN10: 0306456508
• Format: Hardcover
• Copyright: 1997-12-01
• Publisher: Springer Verlag

Summary

This is the latest volume of the series praised by JACS for its "high standards," and by Chemistry and Industry for rendering a "valuable service." Experts from academic and industrial laboratories worldwide present: -- Experimental results from the last decade of interfacial studies -- A surprising quantum mechanical treatment of electrode processes -- Recent work in molecular dynamic simulations, which confirms some earlier modelistic approaches and also breaks new ground -- An in-depth look at underpotential deposition on single crystal metals, and -- The practical matter of automated corrosion measurement.

Table of Contents

Chapter 1 METAL/SOLUTION INTERFACE: AN EXPERIMENTAL APPROACH	1	(70)
Jerzy Sobkowski
Maria Jurkiewicz-Herbich
I. Introduction	1	(2)
II. Molecular Approach to the Metal/Solution Interface	3	(32)
1. Double-Layer Structure: General Considerations	3	(5)
2. Solid Metal/Electrolyte Interface	8	(7)
3. Methods Used to Study Properties of the Metal/Solution Interface: Role of the Solvent and the Metal	15	(20)
III. The Thermodynamic Approach to the Metal/Solution Interface	35	(28)
1. The Standard Gibbs Energy of Adsorption, XXXG	35	(19)
2. Effect of Supporting Electrolyte on Electrosorption	54	(9)
References	63	(8)
Chapter 2 QUANTUM MECHANICAL TREATMENTS IN ELECTRODE KINETICS	71	(44)
Shahed U.M. Khan
I. Introduction	71	(1)
II. Continuum Theory of Electron Transfer Reactions	72	(7)
1. Born Equation and the Free Energy of Activation, XXXG(#) (continuum)	74	(2)
2. Reorganization Energy lamda(s) (Continuum) and the Free Energy of Activation XXXG(#)	76	(3)
III. XXXG(#)(Continuum) and the Inverted Region	79	(6)
1. General	79	(4)
2. ET Reactions at Electrodes and the Inverted Region	83	(2)
IV. Molecular Models of Electron Transfer Reactions at Electrodes	85	(9)
1. Free Energy of Activation, XXXG(#) and the Molecular Models	86	(8)
V. Molecular Models of Bond-Breaking Ion and Electron Transfer Reactions	94	(8)
1. Classical and Semiclassical Treatments	95	(4)
2. Quantal Treatments	99	(3)
VI. Electronic Transmission Coefficient k	102	(2)
VII. Proton Transfer Reactions	104	(3)
VIII. Solvent Dynamic Effects on ET Reactions at Electrodes	107	(3)
References	110	(5)
Chapter 3 MOLECULAR DYNAMIC SIMULATIONS IN INTERFACIAL ELECTROCHEMISTRY	115	(66)
Ilan Benjamin
I. Introduction	115	(1)
II. The Water/Metal Interface	116	(27)
1. Preliminary Notes	116	(1)
2. Potential Energy Functions	117	(10)
3. Structure of Water at Metal Surfaces	127	(8)
4. Dynamics	135	(3)
5. Effect of External Electric Field	138	(5)
III. Ionic Adsorption and Solvation at the Water/Metal Interface	143	(11)
1. Overview	143	(2)
2. Potential Energy Functions	145	(1)
3. Single Ion Adsorption at the Water/Metal Interface	146	(7)
4. Simulations of Electrolyte Solutions at the Water/Metal Interface	153	(1)
IV. Interfacial Electron Transfer Reactions	154	(16)
1. Preliminaries	154	(2)
2. Two-State Models	156	(12)
3. Multistate Models	168	(2)
V. Processes at the Liquid/Liquid Interface	170	(2)
VI. Conclusions and Outlook	172	(1)
References	173	(8)
Chapter 4 UNDERPOTENTIAL DEPOSITION ON SINGLE-CRYSTAL METALS	181	(70)
Akiko Aramata
I. Introduction	181	(19)
1. Scope of this Chapter	181	(2)
2. Preparation and Qualification of Single Crystals	183	(8)
3. Well-Defined Surface Structure and Reconstruction of Single-Crystal Surfaces	191	(5)
4. Anion Adsorption Behavior	196	(4)
II. Underpotential Deposition on Single-Crystal Electrodes	200	(31)
1. Underpotential Deposition on Au Single Crystals	201	(11)
2. Underpotential Deposition on Single-Crystal Pt Group Metals	212	(7)
3. Underpotential Deposition on Ag Single Crystals	219	(5)
4. Underpotential Deposition and Anion Adsorption	224	(7)
III. Mechanism of Underpotential Deposition	231	(9)
1. Kinetics and Dynamics	231	(9)
IV. Electrocatalysis on Electrodes Modified by Underpotential Deposition	240	(1)
V. Miscellaneous	241	(2)
1. Bimetallic Underpotential Deposition	241	(1)
2. Effect of Underpotential Deposition on Overpotential Deposition	241	(1)
3. Effect of Organic Additives on Underpotential Deposition	242	(1)
4. Underpotential Deposition in Nonaqueous Solvents	243	(1)
VI. Conclusion	243	(2)
References	245	(6)
Chapter 5 AUTOMATED METHODS OF CORROSION MEASUREMENT	251	(66)
Gregers Bech-Nielsen
Jens E.T. Andersen
John C. Reeve
Anne D. Bisgard
Lars Vendelbo Nielsen
I. Introduction	251	(1)
II. Corrosion Measurements by Titration	252	(17)
1. General	252	(1)
2. Restrictions and Limitations of CMT Measurements	253	(4)
3. CMT Measurements with a Polarized Electrode	257	(2)
4. Instrumentation and Recording of CMT Measurements	259	(4)
5. Aim and Results of CMT Measurements	263	(6)
6. Concluding Remarks	269	(1)
III. Imaging Corrosion by Scanning Probe Microscopy	269	(13)
1. General	269	(1)
2. Use of STM and AFM in Corrosion Studies	270	(11)
3. Concluding Remarks	281	(1)
IV. Critical Pitting Temperature	282	(17)
1. General	282	(4)
2. Experimental Equipment for CPT Testing	286	(4)
3. Methods for Pitting Characterization	290	(7)
4. Summary	297	(2)
5. Concluding Remarks	299	(1)
V. Applications of the Electrochemical Hydrogen Permeation Cell	299	(13)
1. General	299	(1)
2. The Principle	299	(2)
3. Diffusion of Hydrogen into Metal	301	(1)
4. Studies on the Hydrogen Evolution Reaction	302	(4)
5. Hydrogen-Related Stress Corrosion Cracking	306	(3)
6. Cell Types	309	(2)
7. Summary	311	(1)
References	312	(5)
Cumulative Author Index	317	(14)
Cumulative Title Index	331	(10)
Subject Index	341