Modern electrochemistry : an introduction to an interdisciplinary area

著者

• Bockris, J. O'M. (John O'M.)
• Reddy, Amulya K. N.

書誌事項

Modern electrochemistry : an introduction to an interdisciplinary area

John O'M. Bockris and Amulya K. N. Reddy

[Plenum Pub. Corp.], 1973, c1970

• v. 1
• v. 2

注記

"A Plenum/Rosetta edition."

Includes bibliographical references and index

内容説明・目次

巻冊次

v. 1 ISBN 9780306250019

内容説明

This book had its nucleus in some lectures given by one of us (J. O'M. B. ) in a course on electrochemistry to students of energy conversion at the University of Pennsylvania. It was there that he met a number of people trained in chemistry, physics, biology, metallurgy, and materials science, all of whom wanted to know something about electrochemistry. The concept of writing a book about electrochemistry which could be understood by people with very varied backgrounds was thereby engendered. The lectures were recorded and written up by Dr. Klaus Muller as a 293-page manuscript. At a later stage, A. K. N. R. joined the effort; it was decided to make a fresh start and to write a much more comprehensive text. Of methods for direct energy conversion, the electrochemical one is the most advanced and seems the most likely to become of considerable practical importance. Thus, conversion to electrochemically powered trans portation systems appears to be an important step by means of which the difficulties of air pollution and the effects of an increasing concentration in the atmosphere of carbon dioxide may be met. Corrosion is recognized as having an electrochemical basis. The synthesis of nylon now contains an important electrochemical stage. Some central biological mechanisms have been shown to take place by means of electrochemical reactions. A number of American organizations have recently recommended greatly increased activity in training and research in electrochemistry at universities in the United States."

巻冊次

v. 2 ISBN 9780306250026

目次

• 7 The Electrified Interface.- 7.1 Electrification of an Interface.- 7.1.1 The Electrode-Electrolyte Interface: The Basis of Electrodics.- 7.1.2 New Forces at the Boundary of an Electrolyte.- 7.1.3 The Interphase Region Has New Properties and New Structures.- 7.1.4 An Electrode Is Like a Giant Central Ion.- 7.1.5 The Consequences of Compromise Arrangements: The Electrolyte Side of the Boundary Acquires a Charge.- 7.1.6 Both Sides of the Interface Become Electrified: The So-Called "Electrical Double Layer".- 7.1.7 Double Layers Are Characteristic of All Phase Boundaries.- 7.1.8 A Look into an Electrified Interface.- Further Reading.- 7.2 Some Problems in Understanding an Electrified Interface.- 7.2.1 What Knowledge Is Required before an Electrified Interface Can Be Regarded as Understood?.- 7.2.2 Predicting the Interphase Properties from the Bulk Properties of the Phases.- 7.2.3 Why Bother about Electrified Interfaces?.- 7.2.4 The Need to Clarify Some Concepts.- 7.2.5 The Potential Difference across Electrified Interfaces.- 7.2.5a What Happens when One Tries to Measure the Absolute Potential Difference across a Single Electrode-Electrolyte Interface.- 7.2.5b The Absolute Potential Difference across a Single Electrified Interface Cannot Be Measured.- 7.2.5c Can One Measure Changes in the Metal-Solution Potential Difference?.- 7.2.5d The Extreme Cases of Ideally Nonpolarizable and Polarizable Interfaces.- 7.2.5e The Development of a Scale of Relative Potential Differences.- 7.2.5f Can One Meaningfully Analyze an Electrode-Electrolyte Potential Difference?.- 7.2.5g A Thought Experiment Involving a Charged Electrode in Vacuum.- 7.2.5h The Test Charge Must Avoid Image Interactions with the Charged Electrode.- 7.2.5i The Outer Potential ? of a Material Phase in Vacuum.- 7.2.5j What is the Relevance of the Outer Potential to Double-Layer Studies?.- 7.2.5k Another Thought Experiment Involving an Uncharged, Dipole- Covered Phase.- 7.2.5l The Dipole Potential Difference M?S? across an Electrode- Electrolyte Interface.- 7.2.5m The Sum of the Potential Differences Due to Charges and Dipoles: The Absolute Electrode-Electrolyte (or Galvani) Potential Difference.- 7.2.5n The Outer, Surface, and Inner Potential Differences.- 7.2.5o An Apparent Contradiction: The Sum of the ??fis across a System of Interfaces Can and the ?? across One Interface Cannot Be Measured.- 7.2.5p What Deeper Understanding Has Been Hitherto Gained Regarding the Absolute Potential Difference Across an Electrified Interface?.- 7.2.6 The Accumulation and Depletion of Substances at an Interface.- 7.2.6a What Would Represent Complete Structural Information Regarding an Electrified Interface?.- 7.2.6b The Concept of Surface Excess.- 7.2.6c Does Knowledge of the Surface Excess Contribute to Knowledge of the Distribution of Species in the Interphase Region?.- 7.2.6d Is the Surface Excess Equivalent to the Amount Adsorbed?.- 7.2.6e Is the Surface Excess Measurable?.- 7.2.6f The Special Position of Mercury in Double-Layer Studies.- Further Reading.- 7.3 The Thermodynamics of Electrified Interfaces.- 7.3.1 The Measurement of Interfacial Tension as a Function of the Potential Difference across the Interface.- 7.3.2 Some Basic Facts about Electrocapillary Curves.- 7.3.3 A Digression on the Electrochemical Potential.- 7.3.3a Definition of Electrochemical Potential.- 7.3.3b Can the Chemical and Electrical Work Be Determined Separately?.- 7.3.3c A Criterion of Thermodynamic Equilibrium between Two Phases: Equality of Electrochemical Potentials.- 7.3.3d Nonpolarizable Interfaces and Thermodynamic Equilibrium.- 7.3.4 Some Thermodynamic Thoughts on Electrified Interfaces.- 7.3.5 Interfacial Tension Varies with Applied Potential: Determination of the Charge Density on the Electrode.- 7.3.6 Electrode Charge Varies with Applied Potential: Determination of the Electrical Capacitance of the Interface.- 7.3.7 The Potential at Which an Electrode Has a Zero Charge.- 7.3.8 Surface Tension Varies with Solution Composition: Determination of the Surface Excess.- 7.3.9 Reflections on Electrocapillary Thermodynamics.- 7.3.10 Retrospect and Prospect in the Study of Electrified Interfaces.- Further Reading.- 7.4 The Structure of Electrified Interfaces.- 7.4.1 The Parallel-Plate Condenser Model: The Helmholtz-Perrin Theory.- 7.4.2 The Double Layer in Trouble: Neither Perfect Parabolas nor Constant Capacities.- 7.4.3 The Ionic Cloud: The Gouy-Chapman Diffuse-Charge Model of the Double Layer.- 7.4.4 Ions under Thermal and Electric Forces near an Electrode.- 7.4.5 A Picture of the Potential Drop in the Diffuse Layer.- 7.4.6 An Experimental Test of the Gouy-Chapman Model: Potential Dependence of the Capacitance, but at What Cost?.- 7.4.7 Some Ions Stuck to the Electrode, Others Scattered in Thermal Disarray: The Stern Model.- 7.4.8 A Consequence of the Stern Picture: Two Potential Drops across an Electrified Interface.- 7.4.9 Another Consequence of the Stern Model: An Electrified Interface Is Equivalent to Two Capacitors in Series.- 7.4.10 The Relative Contributions of the Helmholtz-Perrin and Gouy-Chapman Capacities.- 7.4.11 Some Questions Regarding the Sticking of Ions to the Electrode.- 7.4.12 An Electrode Is Largely Covered with Adsorbed Water Molecules.- 7.4.13 Metal-Water Interactions.- 7.4.14 The Orientation of Water Molecules on Charged Electrodes.- 7.4.15 How Close Can Hydrated Ions Come to a Hydrated Electrode?.- 7.4.16 Is It Only Desolvated Ions which Contact-Adsorb on the Electrode?.- 7.4.17 The Free-Energy Change for Contact Adsorption.- 7.4.18 What Determines the Degree of Contact Adsorption?.- 7.4.19 How Is Contact Adsorption Measured?.- 7.4.20 Contact Adsorption, Specific Adsorption, or Superequivalent Adsorption.- 7.4.21 Contact Adsorption: Its Influence of the Capacity of the Interface.- 7.4.22 Looking Back to Look Forward.- 7.4.23 The Complete Capacity-Potential Curve.- 7.4.24 The Constant-Capacity Region.- 7.4.24a The So-Called "Double Layer" Is a Double Layer.- 7.4.24b The Dielectric Constant of the Water between the Metal and the Outer Heimholtz Plane.- 7.4.24c The Position of the Outer Heimholtz Plane and an Interpretation of the Constant Capacity.- 7.4.25 The Capacitance Hump.- 7.4.26 How Does the Population of Contact-Adsorbed Ions Change with Electrode Charge?.- 7.4.27 The Test of the Population Law for Contact-Adsorbed Ions.- 7.4.28 The Lateral-Repulsion Model for Contact Adsorption.- 7.4.29 Flip-Flop Water on Electrodes.- 7.4.30 Calculation of the Potential Difference Due to Water Dipoles.- 7.4.31 The Excess of Flipped Water Dipoles over Flopped Water Dipoles.- 7.4.32 The Contribution of Adsorbed Water Dipoles to the Capacity of the Interface.- Further Reading.- 7.5 The Competition between Water and Organic Molecules at the Electrified Interfaces.- 7.5.1 The Relevance of Organic Adsorption.- 7.5.2 The Forces Involved in Organic Adsorption.- 7.5.3 Does Organic Adsorption Depend on Electrode Charge?.- 7.5.4 The Examination of the Water Flip-Flop Model for Simple Cases of Organic Adsorption.- 7.5.5 At What Potential Does Maximum Organic Adsorption Occur?.- Further Reading.- 7.6 Electrified Interfaces at Metals Other than Mercury.- Further Reading.- 7.7 The Structure of the Semiconductor-Electrolyte Interface.- 7.7.1 How Is the Charge Distributed inside a Solid Electrode?.- 7.7.2 The Band Theory of Crystalline Solids.- 7.7.3 Conductors, Insulators, and Semiconductors.- 7.7.4 Some Analogies between Semiconductors and Electrolytic Solutions.- 7.7.5 The Diffuse-Charge Region inside an Intrinsic Semiconductor: The Garrett-Brattain Space Charge.- 7.7.6 The Differential Capacity Due to the Space Charge.- 7.7.7 Impurity Semiconductors, n Type and p Type.- 7.7.8 Surface States: The Semiconductor Analogue of Contact Adsorption.- 7.7.9 Semiconductor Electrochemistry: The Beginnings of the Electrochemistry of Nonmetallic Materials.- Further Reading.- 7.8 A Bird's-Eye View of the Structure of Charged Interfaces.- 7.9 Double Layers between Phases Moving Relative to Each Other.- 7.9.1 The Phenomenology of Mobile Electrified Interfaces: Electrokinetic Properties.- 7.9.2 The Relative Motion of One of the Phases Constituting an Electrified Interface Produces a Streaming Current.- 7.9.3 A Potential Difference Applied Parallel to an Electrified Interface Produces an Electro-osmotic Motion of One of the Phases Relative to the Other.- 7.9.4 Electrophoresis: Moving Solid Particles in a Stationary Electrolyte.- Further Reading.- 7.10 Colloid Chemistry.- 7.10.1 Colloids: The Thickness of the Double Layer and the Bulk Dimensions Are of the Same Order.- 7.10.2 The Interaction of Double Layers and the Stability of Colloids.- 7.10.3 Sols and Gels.- Further Reading.- Appendix 7.1 Measurement of the Electrode-Solution Volta Potential Difference.- 8 Electrodics.- 8.1 Introduction.- 8.1.1 The Situation Thus Far.- 8.1.2 Charge Transfer: Its Chemical and Electrical Implications.- 8.1.3 Can an Isolated Electrode-Solution Interface Be Used as a Device?.- 8.1.4 Electrochemical Systems Can Be Used as Devices.- 8.1.5 An Electrochemical Device: The Substance Producer.- 8.1.6 Another Electrochemical Device: The Energy Producer.- 8.1.7 The Electrochemical Undevice: The Substance Destroyer and Energy Waster.- 8.1.8 Some Basic Questions.- 8.2 The Basic Electrodic Equation: The Butler-Volmer Equation.- 8.2.1 The Instant of Immersion of a Metal in an Electrolytic Solution.- 8.2.2 The Rate of Charge-Transfer Reactions under Zero Field: The Chemical Rate Constant.- 8.2.3 Some Consequences of Electron Transfer at an Interface.- 8.2.4 What Is the Rate of an Electron-Transfer Reaction under the Influence of an Electric Field?.- 8.2.5 The Two-Way Electron Traffic across the Interface.- 8.2.6 The Interface at Equilibrium: The Equilibrium Exchange-Current Density i0.- 8.2.7 The Interface Departs from Equilibrium: The Nonequilibrium Drift- Current Density i.- 8.2.8 The Current-Producing (or Current-Produced) Potential Difference: The Overpotential ?.- 8.2.9 The Basic Electrodic (Butler-Volmer) Equation: Some General and Special Cases.- 8.2.10 The High-Field Approximation: The Exponential i versus Law.- 8.2.11 The Low-Field Approximation: The Lineariversus ? Law.- 8.2.12 Nonpolarizable and Polarizable Interfaces.- 8.2.13 Zero Net Current and the Classical Law of Nernst.- 8.2.14 The Nernst Equation.- 8.2.15 The Nernst Equation: Its Sphere of Relevance.- 8.2.16 Looking Back.- Further Reading.- 8.3 The Butler-Volmer Equation: Further Details.- 8.3.1 The Need for a Careful Look at Some Quantities in the Butler-Volmer Equation.- 8.3.2 The Relation between Structure at the Electrified Interface and the Rate of Charge-transfer Reactions.- 8.3.3 The Interfacial Concentrations May Depend on Ionic Transport in the Electrolyte.- 8.3.4 What Is the Physical Meaning of the Symmetry factor ??.- 8.3.4a The Factor ? Is at the Center of Electrode Kinetics.- 8.3.4b A Preliminary to a Second Theory of ?: Potential-Energy- Distance Relations of Particles Undergoing Charge Transfer.- 8.3.4c A Simple Picture of the Symmetry Factor.- 8.3.4d Is the ? in the Butler-Volmer Equation Independent of Over- potential?.- 8.3.5 Summing-up of Further Details on the Butler-Volmer Equation.- Further Reading.- 8.4 The Current-Potential Laws at Other Types of Charged Interfaces.- 8.4.1 Semiconductor n-p Junctions.- 8.4.2 The Current across Biological Membranes.- 8.4.3 The Hot Emission of Electrons from a Metal into Vacuum.- 8.4.4 The Cold Emission of Electrons from a Metal into Vacuum.- Further Reading.- 8.5 The Quantum Aspects of Charge-Transfer Reactions at Electrode-Solution Interfaces.- 8.5.1 A Few Words on the Mechanics of Electrons.- 8.5.2 The Penetration of Electrons into Classically Forbidden Regions.- 8.5.3 The Probability of Electron Tunneling through Barriers.- 8.5.4 The Distribution of Electrons among the Energy Levels in a Metal.- 8.5.5 Under What Conditions Do Electrons Tunnel between the Electrode and Ions in Solution?.- 8.5.6 The Tunneling Condition and the Proton-Transfer Curve.- 8.5.7 Electron Tunneling and the De-electronation Reaction.- 8.5.8 A Perspective View of Charge-Transfer Reactions at an Electrode.- 8.5.9 The Symmetry Factor ?: A Better View.- 8.5.10 Quantifying the Charge-Transfer Picture.- 8.5.11 Some Desirable Refinements and Generalizations.- 8.5.12 Surveying the Progress.- Further Reading.- 8.6 Electrodic Reactions and Chemical Reactions.- Further Reading.- Appendix 8.1 The Number of Electrons Having Energy EF Striking the Surface of a Metal from the Inside.- 9 Electrodics: More Fundamentals.- 9.1 Multistep Reactions.- 9.1.1 The Question of Multistep Reactions.- 9.1.2 Some Ideas on Queues, or Waiting Lines.- 9.1.3 The Overpotential ? Is Related to the Electron Queue at an Interface.- 9.1.4 A Near-Equilibrium Relation between the Current Density and Over- potential for a Multistep Reaction.- 9.1.5 The Concept of a Rate-Determining Step.- 9.1.6 Rate-Determining Steps and Energy Barriers for Multistep Reactions.- 9.1.7 How Many Times Must the Rate-Determining Step Take Place for the Overall Reaction to Occur Once? The Stoichiometric Number v.- 9.1.8 The Order of an Electrodic Reaction.- 9.1.9 Blockage of the Electrode Surface during Charge Transfer: The Surface-Coverage Factor.- Further Reading.- 9.2 The Transient Behavior of Interfaces.- 9.2.1 The Interface under Equilibrium, Transient, and Steady-State Conditions.- 9.2.2 How an Interface Is Stimulated to Show Time Variations.- 9.2.3 Some Ideas on the Understanding of Transients.- 9.2.4 Intermediates in Electrodic Reactions and Their Effects on Potential- Time Transients.- 9.2.5 Experimental Methods for the Determination of Partial Coverage, with Adsorbed Entities, of the Surface of Electrocatalysts.- 9.2.5a Radiotracer Method.- 9.2.5b Galvanostatic Transient Method.- 9.2.5c Potentiostatic Transients.- 9.2.5d The Potential-Sweep, or Potentiodynamic, Method.- Further Reading.- 9.3 Transport in the Electrolyte Effects Charge Transfer at the Interface.- 9.3.1 Ionics Looks after the Material Needs of the Interface.- 9.3.2 How the Transport Flux Is Linked to the Charge-Transfer Flux: The Flux-Equality Condition.- 9.3.3 Appropriations from the Theory of Heat Transfer.- 9.3.4 A Qualitative Study of How Diffusion Affects the Response of an Interface to a Constant Current.- 9.3.5 A Quantitative Treatment of How Diffusion to an Electrode Affects the Response with Time of an Interface to a Constant Current.- 9.3.6 The Concept of Transition Time.- 9.3.7 Convection Can Maintain Steady Interfacial Concentrations.- 9.3.8 The Origin of Concentration Overpotential.- 9.3.9 The Diffusion Layer.- 9.3.10 The Limiting Current Density and Its Practical Importance.- 9.3.10a Polarography: The Dropping-Mercury Electrode.- 9.3.10b The Rotating-Disc Electrode.- 9.3.11 The Steady-State Current-Potential Relation under Conditions of Transport Control.- 9.3.12 Transport-Controlled De-electronation Reactions.- 9.3.13 What Is the Effect of Electrical Migration on the Limiting Diffusion- Current Density?.- 9.3.14 Some Summarizing Remarks on the Transport Aspects of Electrodics.- Further Reading.- 9.4 Determining the Stepwise Mechanism of an Electrodic Reaction.- 9.4.1 How One Tries to Determine the Reaction Mechanism.- 9.4.2 Which Is the Rate-Determining Step in the Iron Deposition and Dissolution Reaction?.- 9.4.3 The Transfer Coefficient a and Reaction Mechanisms.- 9.4.4 Summarizing Remarks Concerning Mechanistic Studies.- Further Reading.- 9.5 More on Mechanism Determination.- 9.5.1 Why Review Mechanism Determination?.- 9.5.2 What Is Mechanism Determination?.- 9.5.3 Stages in the Elucidation of a Reaction Mechanism.- 9.5.4 The Etucidation of the Overall Reaction, the Entities in Solution, and the Surface Coverage.- 9.5.5 Some Techniques for Mechanism Determination.- 9.5.5a The Determination of Reaction Order.- 9.5.5b The Determination of the Transfer Coefficients.- 9.5.5c The Determination of the Stoichiometric Number.- 9.5.5d Auxiliary Methods.- 9.5.6 Mechanism Determination for Saturated Hydrocarbons.- Further Reading.- 9.6 Current-Potential Laws for Electrochemical Systems.- 9.6.1 The Potential Difference across an Electrochemical System.- 9.6.2 The Equilibrium Potential Difference across an Electrochemical Cell.- 9.6.3 The Problem with Tables of Standard Electrode Potentials.- 9.6.4 The pH-Potential Diagrams: A General Representation of Equilibrium Potential Differences across Cells.- 9.6.5 Are Equilibrium Cell Potential Differences Useful?.- 9.6.6 Electrochemical Cells: A Qualitative Discussion of the Variation of Cell Potential with Current.- 9.6.7 Electrochemical Cells in Action: Some Quantitative Relations between Cell Current and Cell Potential.- Further Reading.- 9.7 The Grand Divide.- 10 Electrodic Reactions of Special Interest.- 10.1 Electrocatalysis.- 10.1.1 A Chemical Catalyst and an Electrocatalyst.- 10.1.2 At What Potential Should Electrocatalysis Be Compared?.- 10.1.3 Electrocatalysis in Simple Redox Reactions.- 10.1.3a How Does the Electrocatalytic Rate Depend upon the Substrate Work Function at the Reversible Potential?.- 10.1.3b Can the Exchange-Current Density Depend upon the Work Function?.- 10.1.4 Electrocatalysis in Reactions Involving Adsorbed Species.- 10.1.4a Electrocatalysis in the Hydrogen-Evolution and -Dissolution Reaction.- 10.1.4b The Electrocatalytic De-electronation of Hydrocarbons.- 10.1.4c The Dependence of the Rate upon Substrate for the Oxidation of Ethylene.- 10.1.4d The Special Position of Platinum as an Electrocatalyst.- 10.1.5 Special Features of Electrocatalysis.- 10.1.5a The Effect of the Electric Field.- 10.1.5b Reactivity at Low Temperatures.- 10.1.5c The Activation of an Electrocatalyst.- 10.1.5d Increasing the Power Output by Changing the Reaction Path.- 10.1.5e The Use of Porous Electrodes.- Further Reading.- 10.2 The Electrogrowth of Metals on Electrodes.- 10.2.1 The Two Aspects of Electrogrowth.- 10.2.2 The Reaction Pathway for Electrodeposition.- 10.2.3 Stepwise Dehydration of an Ion
• the Surface Diffusion of Adions.- 10.2.4 Mechanism Determination on Surfaces Which Change with Time.- 10.2.5 The Time Variation of the Average Adion Concentration in Response to the Switching on of a Constant Current.- 10.2.6 The Contributions of Double-Layer Charging and Faradaic Reaction to the Total Deposition-Current Density.- 10.2.7 The Time Variation of the Overpotentiai and the Rate-Determining Step in Electrodeposition.- 10.2.8 The Contribution of Charge Transfer and Surface Diffusion to the Total Overpotentiai for Electrodeposition at Steady State.- 10.2.9 From Deposition to Crystallization.- 10.2.10 Some Devices for Building Lattices from Adions: Screw Dislocations and Spiral Growths.- 10.2.11 Microsteps and Macrosteps.- 10.2.12 How Steps from a Pair of Screw Dislocations Interact.- 10.2.13 Crystal Facets Form.- 10.2.14 Deposition on Single-Crystal and Polycrystal Substrates.- 10.2.15 How the Diffusion of Ions in Solution May Affect Electrogrowth.- 10.2.16 Organic Additives and Electrodeposits.- 10.2.17 The Simultaneous Deposition of More Than One Metal: Alloy Deposition.- 10.2.18 The Sometimes Unavoidable Complication: Hydrogen Codeposition.- Further Reading.- 10.3 The Hydrogen-Evolution Reaction.- 10.3.1 A Reaction with a Special History.- 10.3.2 What Are the Possible Paths for the Hydrogen-Evolution Reaction?.- 10.3.3 What Mechanisms Are Possible in Hydrogen Evolution?.- 10.3.4 How One Determines the Path and Rate-Determining Step of the Hydrogen-Evolution Reaction.- 10.3.4a The Determination of the Exchange-Current Density.- 10.3.4b The Determination of the Transfer Coefficient.- 10.3.4c The Determination of Reaction Order with Respect to Hydrogen Ions in Solution.- 10.3.4d The Stoichiometric Number v.- 10.3.4e The Determination of Hydrogen Coverage.- 10.3.4f The Heat of Adsorption of Atomic Hydrogen on the Electrode.- 10.3.4g Isotopic Separation Factors.- 10.3.4h What Are the Probable Mechanisms for Hydrogen Evolution?.- Further Reading.- 10.4 The Electronation of Oxygen.- 10.4.1 The Importance of the Oxygen-Electronation Reaction.- 10.4.2 The Evaluation of One of the Mechanisms of Oxygen Electronation.- 10.4.3 Catalysis and the Oxygen Reaction.- 10.4.4 Some Special Difficulties with Electrodic Reactions Having Small Exchange-Current Densities.- 10.4.5 An Electrodic Method of Purifying Solutions.- 10.4.6 Observing Very Slow Reactions near Equilibrium.- Further Reading.- 11 Some Electrochemical Systems of Technological Interest.- 11.1 Technological Aspects of Electrochemistry.- 11.2 Corrosion and the Stability of Metals.- 11.2.1 Civilization and Surfaces.- 11.2.2 Charge-Transfer Reactions Are the Origin of the Instability of a Surface.- 11.2.3 A Corroding Metal is Analogous to a Short-Circuited Energy-Producing Cell.- 11.2.4 The Mechanism of the Corrosion of Ultrapure Metals.- 11.2.5 What Is the Electronation Reaction in Corrosion?.- 11.2.6 Thermodynamics and the Stability of Metals.- 11.2.7 Potential-pH (or Pourbaix) Diagrams: Uses and Abuses.- 11.2.8 The Corrosion Current and the Corrosion Potential.- 11.2.9 The Basic Electrodics of Corrosion in the Absence of Oxide Films.- 11.2.10 An Understanding of Corrosion in Terms of Evans Diagrams.- 11.2.11 Which Step in the Corrosion Process Controls the Corrosion Current?.- 11.2.12 Metals, pH, and Air.- 11.2.13 Some Common Examples of Corrosion.- 11.2.14 Electrodic Approaches to Increasing the Stability of Metals.- 11.2.14a Corrosion Inhibition by the Addition of Substances to the Electrolytic Environment of a Corroding Metal.- 11.2.14b Corrosion Prevention by Charging the Corroding Metal with Electrons from an External Source.- 11.2.15 Passivation: The Transformation from a Corroding and Unstable Surface to a Passive and Stable Surface.- 11.2.16 The Mechanism of Passivation.- 11.2.17 The Dissolution-Precipitation Model for Film Formation.- 11.2.18 Spontaneous Passivation: Nature's Method of Stabilizing Surfaces.- 11.2.19 A Competition in Models for Passivation?.- 11.2.20 The Thermodynamics of Passivation.- 11.2.21 Hydrogen Diffusion into a Metal.- 11.2.22 The Preferential Diffusion of Absorbed Hydrogen to Regions of Stress in a Metal.- 11.2.23 Interstitial Hydrogen Can Crack Open a Metal Surface.- 11.2.24 Surface Instability and the Internal Decay of Metals: Stress-Corrosion Cracking.- 11.2.25 Surface Instability and Internal Decay of Metals: Hydrogen Embrittle- ment.- 11.2.26 Charge Transfer and the Stability of Metals.- 11.2.27 The Cost of Corrosion.- 11.2.28 A Bird's-Eye View of Corrosion.- Further Reading.- 11.3 Electrochemical Energy Conversion.- 11.3.1 The Present Situation in Energy Consumption.- 11.3.2 How Are the Hydrocarbon Fuels Used at Present?.- 11.3.3 The Pollution of the Atmosphere with Products from Internal-Combustion Reactions and Its Possible Effect on World Temperature and Sea Levels.- 11.3.3a Products of Combustion Other than Carbon Dioxide.- 11.3.3b Carbon Dioxide.- 11.3.3c Uncertainties in Predicting the Future Pollution of the Atmosphere.- 11.3.4 Thermal-Combustion Engines Waste the Chemical Energy Available from Burning Hydrocarbons in Air.- 11.3.5 Direct Energy Conversion.- 11.3.6 Direct Energy Conversion by Electrochemical Means.- 11.3.7 The Maximum Intrinsic Efficiency in Electrochemical Conversion of the Energy of a Chemical Reaction to Electric Energy.- 11.3.8 The Actual Efficiency of an Electrochemical Energy Converter.- 11.3.9 The Physical Interpretation of the Absence of the Carnot Efficiency Factor in Electrochemical Energy Conversion.- 11.3.10 Cold Combustion.- 11.3.11 Making V near Ve Is the Central Problem of Electrochemical Energy Conversion.- 11.3.12 The Electrochemical Quantities Which Must Be Optimized for Good Energy Conversion.- 11.3.13 The Power Output of an Electrochemical Energy Converter.- 11.3.14 The Electrochemical Engine.- 11.3.15 Was the Wrong Path Taken in the Development of Power Sources at the End of the Nineteenth Century?.- 11.3.16 Electrodes Burning Oxygen from Air.- 11.3.17 The Special Configurations of Electrodes in Electrochemical Reactors.- 11.3.18 Electrochemical Electricity Producers: The Two Basic Types.- 11.3.19 Examples of Electrochemical Generators.- 11.3.19a The Hydrogen-Oxygen Cell.- 11.3.19b Reformer-Supplied Hydrogen-Air Cells.- 11.3.19c Hydrocarbon-Air Cells.- 11.3.19d Dissolved-Fuel Fuel Cells.- 11.3.19e Natural Gas and CO-Air Cells.- 11.3.20 The Relations between Electrochemical Energy Conversion and the Future Dominance of Atomic Energy as the Source of Power.- 11.3.20a Will Atomic Power Sources Compete for Any of the Uses Foreseen for Electrochemical Power Sources?.- 11.3.20b Will Electrochemical Means Be Used to Convert Nuclear Power to Electricity?.- 11.3.20c What Is the Relation between Electricity Storage and Atomic Energy?.- 11.3.21 A Summary of the Direct Conversion of Chemical Energy to Electricity.- Further Reading.- 11.4 Electricity Storage.- 11.4.1 Conventional and Descriptive Terminology in Energy Conversion and Storage.- 11.4.2 The Important Quantities in Electricity Storage.- 11.4.2a Electricity Storage Density.- 11.4.2b Energy Density.- 11.4.2c Power.- 11.4.2d Desirable Trends.- 11.4.3 Classical Electricity Storers.- 11.4.3a The Lead-Acid Storage Battery.- 11.4.3b A Dry Cell.- 11.4.3c Two Relatively New Electricity Storers.- 11.4.4 The Large Gap between the Maximum Feasible and the Present Actual Energy Densities of Electricity Storers.- 11.4.5 Outlines of Some Possible Future Electricity Storers.- 11.4.5a Electricity Storage in Hydrogen.- 11.4.5b Storage by Using Alkali Metals.- 11.4.5c Storers Involving Nonaqueous Solutions.- 11.4.5d Storers with Zinc in Combination with an Air Electrode.- 11.4.6 The Respective Realms of Applicability of Electrochemical Energy Converters and Electricity Storers.- 11.4.7 Electrochemical Electricity Storage in a Nutshell.- Further Reading.

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詳細情報

• NII書誌ID(NCID): BA07489842
• ISBN:
  • 0306250012
  • 0306250020
• LCCN: 73013712
• 出版国コード: us
• タイトル言語コード: eng
• 本文言語コード: eng
• 出版地: [New York]
• ページ数/冊数: 2 v.
• 大きさ: 23 cm
• 分類:
  • LCC : QD553
  • DC : 541/.37
• 件名:
  • LCSH : Electrochemistry