Modern Aspects of Electrochemistry

by Brian E. Conway (Editor), John O'M. Bockris (Editor), Ralph E. White (Editor)

Overview

Recognized experts present incisive analysis of both fundamental and applied problems in this continuation of a highly acclaimed series.
Topics discussed include:

• A thorough and mathematical treatment of periodic phenomena, with consideration of new theories about the transition between ‘order' and ‘chaos';
• Impedance spectroscopy as applied to the study of kinetics and mechanisms of electrode processes;
• The use of stoichiometric numbers in mechanism analysis;
• The electro-osmotic dewatering of clays with important implications for the processing of industrial waste and geotechnical; stabilization;
• Magnetic effects in electrolytic processes and the electrolytic Hall effect; and
• The computer analysis and modeling of mass transfer and fluid flow.
These authoritative studies will be invaluable for researchers in engineering, electrochemistry, analytical chemistry, materials science, physical chemistry, and corrosion science.

Product Details

ISBN-13:	9780306459641
Publisher:	Springer US
Publication date:	08/31/1999
Series:	Modern Aspects of Electrochemistry , #32
Edition description:	1999
Pages:	420
Product dimensions:	5.51(w) x 8.50(h) x (d)

Table of Contents

Chapter 1	Nanoparticle Surfaces Studied by Electrochemical NMR
I.	Introduction	1
II.	Experimental	4
III.	Results and Discussion	5
1.	Selected Topics in [superscript 195]Pt-NMR	5
2.	Other Pt Nanoparticles (Unsupported and Supported)	7
3.	Correlation Between the [superscript 195]Pt NMR Shift and Adsorbates Electronegativity	9
4.	Spatially-Resolved Oscillation of the E[subscript f]-LDOS in a Pt Catalyst	14
IV.	[superscript 13]C NMR at the Electrochemical Interface	17
1.	[superscript 13]C NMR Knight Shift	17
2.	EC-NMR Under Potential Control	18
3.	Correlation of NMR to FTIR Data	20
4.	Correlation Between Clean Surface E[subscript f]-LDOS of Metals and the Adsorbate Knight Shift	22
5.	NMR Comparison of CO Adsorbed on Pt-Black from Different Sources	25
6.	Effect of Surface Charge on the Chemisorption Bond: CO Chemisorption on Pd	27
7.	Pt Electrodes Modified by Ruthenium: A Study in Tolerance	29
8.	EC-NMR of Pt/Ru Alloy Nanoparticles	37
V.	Summary and Conclusions	40
	Appendix	42
	References	48
Chapter 2	Ab Initio Quantum-Chemical Calculations in Electrochemistry
I.	Introduction	51
II.	Ab Initio Quantum Chemistry	54
1.	General Aspects of Quantum Chemistry and Electronic Structure Calculations	54
2.	Wave-Function-Based Methods	56
3.	Density Functional Theory Methods	57
4.	Basis Sets and Effective Potentials	60
5.	Structure, Energetics, and Vibrational Frequencies	61
6.	Methods of Analysis	61
7.	Ab Initio Molecular Dynamics	63
III.	Selected Applications	64
1.	Clusters and Slabs	64
2.	How to Model the Electrode Potential	65
3.	Chemisorption of Halogens and Halides	67
4.	Chemisorption of Carbon Monoxide on Metals and Alloys	78
5.	Field Dependent Chemisorption and the Interfacial Stark Effect: General Relationships	88
6.	Field-Dependent Chemisorption of Carbon Monoxide	98
7.	Chemisorption of Water and Water Dissociation Products	106
8.	Ab Initio Approaches to Modeling Electrode Reactions	115
IV.	Outlook	125
	References	127
Chapter 3	Macroscopic and Molecular Models of Adsorption Phenomena on Electrode Surfaces
I.	Introduction	131
II.	Features of Electrosorption and Factors Affecting Them	132
III.	Macroscopic Models	136
1.	PC Approach	136
2.	STE Approach	138
IV.	Molecular Models	140
1.	Guidealli's Approach	140
2.	Models Based on the LBS Approach	145
V.	Complicated Adsorption Phenomena	153
1.	Co-Adsorption and Reorientation	153
2.	Polylayer Formation	161
3.	Surface Segregation	164
4.	Phase Transitions	166
VI.	Polarization Catastrophe and Other Artifacts	171
VII.	The Role of the Metal Electrode--The Case of Solid Electrodes	177
VIII.	Computer Simulation	182
IX.	Conclusions	184
	References	185
Chapter 4	Electrochemical Promotion of Catalysis
I.	Introduction	191
II.	The Phenomenon of Electrochemical Promotion	193
1.	Description of a Typical Electrochemical Promotion Experiment	194
2.	The Mechanism of Electrochemical Promotion	197
3.	Promotional Transients	203
III.	Fundamental Studies of Electrochemical Promotion	207
1.	Catalytic Model Systems	207
2.	Experimental Aspects	209
3.	Electrochemical Characterization of the Single-Pellet Cell	212
4.	Cyclic Voltammetry	216
5.	Fast-Galvanostatic Transients	219
6.	Permanent Electrochemical Promotion	224
7.	Electrochemical Activation of a Catalyst	228
8.	Electrochemical Promotion and Catalyst-Support Interactions	230
9.	Work Function Measurements	233
IV.	Cell Development for Electrochemical Promotion	236
1.	Bipolar Con guration for Electrochemical Promotion	236
2.	Ring-Shaped Electrochemical Cell	241
3.	Multiple-Channel Electrochemical Cell	244
4.	Perspectives	248
V.	Conclusions	250
	References	252
Chapter 5	Mechanisms of Lithium Transport Through Transition Metal Oxides and Carbonaceous Materials
I.	Introduction	255
II.	Bird's Eye View of the Models for Current Transients in Lithium Intercalation Systems: Diffusion Controlled Lithium Transport	257
1.	The Geometry of the Electrode Surface	259
2.	The Growth of a New Phase in the Electrode	260
3.	The Electric Field in the Electrode	261
III.	General Perspective on Current Transients from Transition Metal Oxides and Graphite	261
1.	Non-Cottrell behavior throughout the Lithium Intercalation/Deintercalation	264
2.	Intersection of Anodic and Cathodic Current Transients	267
3.	(Quasi-)Current Plateau	268
4.	Depression of the Initial Current Value	273
IV.	Physical Origin of the Current Transients	273
1.	Linear Relation Between Current and Electrode Potential	273
2.	Comparison of Cell Resistances Determined by the Current Transient Technique and by Electrochemical Impedance Spectroscopy	278
V.	Theoretical Description of Cell-Impedance Controlled Lithium Transport	283
1.	Governing Equation and Boundary Condition	283
2.	Calculation Procedure of the Cell-Impedance Controlled Current Transients	284
3.	Theoretical Current Transients and their Comparison with Experimental Current Transients	286
4.	Some Model Parameters Affecting the Shape and Magnitude of the Cell-Impedance Controlled Current Transients	294
VI.	Concluding Remarks	297
	References	298
	Index	303

Editorial Reviews

A collection of international studies that describe progress in both fundamental and applied aspects of electrochemical science. The five chapters address ultrahigh-vacuum surface analytical methods in electrochemical studies of single-crystal surfaces; potential- modulated reflectance spectroscopy studies of the electronic transitions of chemisorbed carbon monoxide; low-temperature electrochemistry at high-Tc superconductor/ionic conductor interfaces; quantum theory of charge-transfer processes in condensed media; and a modern approach to surface roughness applied to electrochemical systems. Annotation c. Book News, Inc., Portland, OR (booknews.com)

Booknews

The new volume of the Modern Aspects of Electrochemistry series proceeds as in the past with five chapters covering both the electrolyte solution and the interfacial electrode process sides of the field. Applications of the electrode processes involving hydrogen are, especially the behavior of underpotential-deposited H, sorption of H into metals, and the kinetics and mechanisms of cathodic evolution of H2. Electroless metal deposition is reviewed. The development of computational electrochemistry and its applications to problems in electrochemical kinetics is examined. The properties of electrolyte solutions at high concentrations are studied. Finally, applications of the Born theory to solvent polarization by ions are critically reexamined. Annotation c. Book News, Inc., Portland, OR (booknews.com)