Modern Aspects of Electrochemistry

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

• ISBN13: 9780306459641
• ISBN10: 0306459647
• Format: Hardcover
• Copyright: 1999-06-01
• 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

Principles of Temporal and Spatial Pattern Formation in Electrochemical Systems
Katharina Krischer
Introduction	1	(5)
Principles of Temporal Pattern Formation	6	(65)
Bistability	6	(6)
Simple Periodic Oscillations of Type I: Negative Differential Resistance Oscillators	12	(13)
Simple Periodic Oscillations of Type II: Hidden Negative Differential Resistance Oscillators	25	(28)
Mixed-Mode Oscillations	53	(15)
Concluding Remarks	68	(3)
Principles of Spatial Pattern Formation	71	(64)
Models	73	(31)
Experiments	104	(30)
Concluding Remarks	134	(1)
Summary	135	(8)
Acknowledgments	137	(1)
References	138	(5)
Electrochemical Impedance Spectroscopy and Its Applications
Andrzej Lasia
Introduction	143	(13)
Response of Electrical Circuits	144	(4)
Impedance of Electrical Circuits	148	(6)
Interpretation of Complex Plane and Bode Plots	154	(2)
Impedance Measurements	156	(11)
ac Bridges	156	(1)
Lissajous Curves	157	(1)
Phase-Sensitive Detection	157	(3)
Frequency Response Analyzers	160	(2)
Fast Fourier Transform	162	(5)
Impedance of Faradaic Reactions in the Presence of Diffusion	167	(20)
The Ideally Polarizable Electrode	167	(1)
Semi-Infinite Linear Diffusion	167	(7)
Spherical Diffusion	174	(1)
Cylindrical Electrodes	175	(2)
Disk Electrodes	177	(1)
Finite-Length Diffusion	178	(4)
Analysis of Impedance Data in the Case of Semi-Infinite Diffusion: Determination of Kinetic Parameters	182	(5)
Impedance of a Faradaic Reaction Involving Absorption of Reacting Species	187	(14)
Faradaic Reaction Involving One Adsorbed Species	188	(3)
Impedance Plots in the Case of One Adsorbed Species	191	(5)
Faradaic Impedance in the Case Involving Two Adsorbed Species	196	(3)
Impedance Plots in the Case of Two Adsorbed Species	199	(1)
Faradaic Impedance for a Process Involving Three or More Adsorbed Species	199	(2)
Impedance of Solid Electrodes	201	(23)
Frequency Dispersion and Electrode Roughness	201	(1)
Constant Phase Element	202	(5)
Fractal Model	207	(3)
Porous Electrode Model	210	(13)
Generalized Warburg Element	223	(1)
Conditions for ``Good'' Impedances	224	(7)
Linearity, Casuality, Stability, Finiteness	224	(2)
Kramers-Kroing Transforms	226	(4)
Nonstationary Impedances	230	(1)
Modeling of Experimental Data	231	(8)
Selection of the Model	231	(4)
CNLS Approximations	235	(4)
Instrumental Limitations	239	(3)
Conclusion	242	(7)
References	242	(7)
Establishing the Link Between Multistep Electrochemical Reaction Mechanisms and Experimental Tafel Slopes
Mark C. Lefebvre
Introduction	249	(5)
Structure of this Chapter	253	(1)
Chemical Kinetics	254	(1)
Simple One-Step, One-Electron Elecrochemical Kinetics	255	(11)
Introduction	255	(1)
Energetics of the Electrochemical Transition State at Equilibrium	256	(3)
Electrochemical Reaction under Polarization	259	(2)
The Symmetry Factor	261	(3)
Double-Layer Considerations	264	(1)
Rate Equation	265	(1)
Sequence of Consecutive Electrochemical Reactions Involving a Single Rate-Determining Step	266	(15)
Reaction Schemes and Intermediates	266	(2)
Underlying Assumptions	268	(1)
Steady-State and Quasi-Equilibrium Treatments	269	(3)
Rate Equation for Consecutive Electrochemical Reactions	272	(2)
Adsorption of Intermediates	274	(1)
Validity of the Quasi-Equilibrium Approximation	275	(6)
Modifications to the Consecutive Electrochemical Reaction	281	(4)
General Remarks	281	(1)
Chemical Steps	282	(1)
Multielectron Transfers	282	(1)
Combination or Dissociation as a Rate-Limiting Step	283	(2)
Tafel Slopes Greater than 118 mV dec-1	285	(9)
Introduction	285	(1)
Stoichiometric Number	285	(2)
Reaction Mechanicsms Involving a Stoichiometric Number Greater than 1	287	(2)
Prior Dissociation, Forward Reaction Direction	289	(2)
Prior Dissociation, Reverse Reaction Direction	291	(1)
Following Combination Step	292	(1)
Electron Number Coefficients	293	(1)
Application to the Processes of Aluminum Deposition and Dissolution	294	(3)
Conclusions	297	(4)
Acknowledgments	299	(1)
References	299	(2)
Electro-Osmotic Dewatering of Clays, Soils, and Suspensions
Ashok K. Vijh
Introduction	301	(2)
An Outline of Electro-Osmotic Dewatering	303	(3)
Phenomenological Equations	306	(5)
Components of Current and Flux During Electro-Osmotic Dewatering with or without Pressure	308	(2)
Connection of Electro-Osmosis to Other Electrokinetic Effects	310	(1)
The Electrochemical Approach to Electro-Osmotic Dewatering: Helmholtz-Smoluchowski Relation	311	(4)
Electro-Osmotic Dewatering: Some Experimental Aspects	315	(13)
Electro-Osmotic Dewatering under Interrupted Direct Current Conditions	321	(2)
Electro-Osmotic Dewatering under Galvanic Conditions	323	(1)
Dewatering Efficiency in Terms of Liters per Ampere-Hour (or Liters per Watt-Hour at Constant Voltage)	324	(1)
High Voltages Needed for Dewatering Al-Kaolinite and the Aluminum Electrode Effect	325	(1)
Electro-Osmotic Dewatering at Low Applied Voltages	326	(1)
Components of Voltage in an Electro-Osmotic Cell	327	(1)
Applications of Electro-Osmotic Dewatering	328	(1)
Appendix	329	(4)
Acknowledgments	330	(1)
References	331	(2)
The Effect of Magnetic Fields on Electrochemical Processes
Thomas Z. Fahidy
Introduction	333	(3)
Magnetic Field Effects on Electrolyte Behavior	336	(3)
The Hall Effect in Electrolytes	336	(1)
Diffusivity	336	(1)
Viscosity	337	(1)
Properties of Chemical Equilibrium	337	(1)
Magnetic Properties	338	(1)
Magnetic Field Effects on Surface Morphology	339	(1)
Cathode Deposits	339	(1)
Deposits Formed in Anodic Dissolution	340	(1)
The Magnetic Field Effect on Electrode Reaction Kinetics	340	(1)
The Magnetic Field Effect on Ionic Mass Transport	341	(2)
Magnetic Field Effects in Environmental Electrochemistry	343	(1)
Areas of Importance	343	(1)
Magnetic Field Effects on Corrosion Rates	343	(1)
Miscellaneous Aspects	344	(1)
Microscale Behavior: Application of Boltzmann Equation-Based Transport Models	344	(2)
Application of the Model of Slightly Ionized Plasmas	346	(1)
Macroscale Behavior: Application of MHD Theory	346	(5)
Basic Notions	346	(1)
The Application of MHD Theory to Mass Transport	347	(2)
Magnetoelectrolytic Mass Transport in a Magnetic Field Gradient	349	(1)
Profitability of Magnetoelectrolytic Processes: The MHD View	350	(1)
Final Remarks	351	(4)
Acknowledgments	351	(1)
References	351	(4)
Analysis of Mass Transfer and Fluid Flow for Electrochemical Processes
J. Deliang Yang
Vijay Modi
Alan C. West
Introduction	355	(4)
Literature Review	359	(3)
Computational Fluid Dynamics	362	(7)
CFD Algorithms	363	(3)
Grid Generation	366	(3)
Mass Transfer	369	(6)
Finite-Volume Methods	370	(2)
Two-Dimensional Formulation on an Orthogonal Grid	372	(3)
Validation of Simulations	375	(1)
Examples of Applications	375	(9)
Copper Deposition	376	(4)
Mass Transfer during Unstable Flows Generated by a Blocking Cylinder	380	(4)
Summary	384	(7)
Acknowledgments	385	(1)
Notation	385	(1)
References	386	(5)
Cumulative Author Index	391	(14)
Cumulative Title Index	405	(10)
Subject Index	415