Modern Aspects of Electrochemistry 34

Modern Aspects of Electrochemistry 34

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Recognized experts present incisive analysis of both fundamental and applied problems in this continuation of a highly-acclaimed series. Topics discussed include: the way in which electrochemical systems may function as on a single electrode; the foundational area of voltaic measurements at liquid interfaces; direct methanol fuel cells, which would avoid the unpleasant necessity faced by the current general of fuel cells - namely, using hydrogen; dynamic processes in molten salts; electrochemical techniques and Microbial Induced Corrosion (MIC).

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Published 01 January 2001
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Chapter I
Contents
A CRITIQUE OF THE ADDITIVITY PRINCIPLE FOR MIXED COUPLES
Michael Spiro
I. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 II. The Additivity Principle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 III. Earlier Tests . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3 IV. Selected Corrosion and Electroless Plating Studies . . . . . . . . . . . . . . 4 V. Heterogeneous Catalysis of Redox Reactions . . . . . . . . . . . . . . . . . . 6 VI. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
Chapter 2
VOLTAIC CELLS IN ELECTROCHEMISTRY AND SURFACE CHEMISTRY OF LIQUIDS
Zbigniew Koczorowski
I. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13 II. Electrified Interfaces and Their Electrical Potentials . . . . . . . . . . . . 14 III. Volta Potential and Voltaic Cells . . . . . . . . . . . . . . . . . . . . . . . . . . . 16 IV. Experimental Methods for Investigating Voltaic Cells . . . . . . . . . . . 20 V. Volta Potential of the Metal/Solution Interface. . . . . . . . . . . . . . . . . 23 VI. Real Potentials of Ions in Electrolyte Solutions . . . . . . . . . . . . . . . . 24 VII. Real Ion Activity. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26 VIII. Real Potentials of Ions in Solid Electrolytes . . . . . . . . . . . . . . . . . . . 27
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IX. Voltaic Cells and Absolute Electrode Potentials . . . . . . . . . . . . X. Volta Potentials ofEx SituandNon-SituElectrodes . . . . . . . . . XI. Voltaic Cells with Interfaces of Immiscible Electrolyte Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . XII.Adsorption Potentials of Dipolar Compounds . . . . . . . . . . . . . XIII.Adsorption Potentials of Surface-. . . . . . .Active Electrolytes XIV.Adsorption Potentials of Inorganic Ions . . . . . . . . . . . . . . . . . . XV.Surface Potentials of Water and Organic Solvents . . . . . . . . . . XVI.Final Remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Chapter 3
DIRECT METHANOL FUEL CELLS: FROM A TWENTIETH CENTURY ELECTROCHEMIST’S DREAM TO A TWENTY-FIRST CENTURY EMERGING TECHNOLOGY
29 31
33 36 41 42 43 48 48
Claude Lamy, Jean-Michel Léger, and Supramaniam Srinivasan -I. A Synopsis of Fuel Cell Technologies Background . . . . . . . 53 The Incentive for Fuel Cell Development . . . . . . . . . .-. . . . 53 1.Energy Conservation and Environmental Friendliness 2.54. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Types of Fuel Cells -3.Its Important Role as a Primary Fuel forNatural Gas All Types of Fuel Cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55 4.Status of Fuel Cell Technologies . . . . . . . . . . . . . . . . . . . . . . . . . . 57 5.Electrochemical vs.EnergyOther Methods of Conversion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62 II. Direct Methanol Fuel Cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65 1.Historical Development of DMFCs . . . . . . . . . . . . . . . . . . . 65 2.67. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Principles of DMFCs 3.73. . . . . . . . . . . . . . Challenges in Developing DMFCs . . . . . . III.Electrode Kinetics and Electrocatalysis of Methanol -Oxidation Electrochemical and Spectroscopic Investigations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73 1.73Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Contents
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2. Identification of the Reaction Products and the Adsorbed Intermediates. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .75 3.How to Increase the Kinetics of the Electrooxidation of Methanol. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .82 4.Structure and Composition of the Electrode in Relation to its Electroactivity. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .83 5.Concluding Remarks on Mechanisms. . . . . . . . . . . . . . . . . . . .92 IV.Oxygen Electroreduction and Proton Exchange Membrane. . . . . . .93 1.The Oxygen Electroreduction Reaction. . . . . . . . . . . . . . . . . . .93 2.Concepts for New Oxygen Reduction Electrocatalysts. . . . . . . .96 3.Development of New Proton Exchange Membranes.. . . . . . . . . 99 V.Progress in Technology. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .100 1.Single-cell Investigations to Attain High Performance Levels. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .100 2.Cell Stack Development and Demonstration. . . . . . . . . . . . . . .111 VI.Prognosis—DMFCs for the 21st Century. . . . . . . . . . . . . . . . . . .113 References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .115
Chapter 4
TRANSPORT PROPERTIES OF MOLTENSALTS
Isao Okada
I.Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119 II.121. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Database . III.Electrical Conductance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124 1.Electrolytic Conductivity .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .124 2.Methods of Measuring Transport Numbers in Mixtures. . . . . . . .125 3.Pattern of the Isotherms in Binary Monovalent Cation Systems. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .127 4.The Chemla Effect. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .129 5.Empirical Equation for Internal Mobility. . . . . . . . . . . . . . . . . .131 6.Electrically Conducting Species. .. . . . . . . . . . . . . . . . . . . . . . 146 7.Molecular Dynamics Simulation. . . . . . . . . . . . . . . . . . . . . .. .149 IV.Diffusion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .154 1.Macroscopic Description. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .154 2.Measurement Methods. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .157
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3.Molecular Dynamics Simulation . . . . . . . . . . . . . . . . . . . V.Viscosity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1. Measurement Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . 2. Bulk Viscosity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3. Recommended Values . . . . . . . . . . . . . . . . . . . . . . . . . . . 4. Factors Determining Viscosity . . . . . . . . . . . . . . . . . . . . . 5. Molecular Dynamics Simulation . . . . . . . . . . . . . . . . . . . VI. Thermal Conductivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1. Measurement Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . 2. Evaluation of Experimental Data . . . . . . . . . . . . . . . . . . . 3. Molecular Dynamics Simulation . . . . . . . . . . . . . . . . . . . VII. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Chapter 5
165 167 168 174 176 177 180 182 184 192 195 196 197
APPLICATION OF ELECTROCHEM ICAL TECHNIQUES TO THE STUDY OF M ICROBIOLOGICALLY INFLUENCED CORROSION
Brenda J.Little and Patricia A.Wagner
I. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 205 1.Biofilm Formation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 205 2. MIC Mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 207 II. Techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 208 1. Redox Potential . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 208 2. Polarization Resistance . . . . . . . . . . . . . . . . . . . . . . . . . . 209 3. Open Circuit Potential . . . . . . . . . . . . . . . . . . . . . . . . . . . 213 4. Capacitance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 216 5. Microsensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 223 6. Dual-226Cell Technique . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7. Electrochemical Noise Analysis. . . . . . . . . . . . . . . . . . . . 227 8.Electrochemical Impedance Spectroscopy. . . . . . . . . . . .233 9.Scanning Vibrating Electrode Techniques. . . . . . . . . . . .240 10. Large Signal Polarization Techniques . . . . . . . . . . . . . . . 240 III. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 244 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 245
Contents
Cumulative Author Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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Cumulative Title Index. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .261
Subject Index. . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . 273