Electrochemistry of Solids: An Introduction

Electrochemistry of Solids: An Introduction

by Hans Rickert

Paperback(Softcover reprint of the original 1st ed. 1982)

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Product Details

ISBN-13: 9783642683145
Publisher: Springer Berlin Heidelberg
Publication date: 12/07/2011
Series: Inorganic Chemistry Concepts , #7
Edition description: Softcover reprint of the original 1st ed. 1982
Pages: 240
Product dimensions: 6.69(w) x 9.61(h) x 0.02(d)

Table of Contents

1 Introduction.- 1.1 References.- 2 Disorder in Solids.- 2.1 General Considerations Regarding Lattice Defects and Their Significance.- 2.2 Point Defects.- 2.3 Disorder Equilibria.- 2.4 The Chemical Potentials of Defects.- 2.5 Internal Disorder Equilibria.- 2.6 Kinetic Derivation of Disorder Equilibria.- 2.7 Disorder Equilibria Involving Neighbouring Phases.- 2.8 Disorder Equilibria Involving Surfaces.- 2.9 References.- 3 Examples of Bisorder in Solids.- 3.1 Disorder in Doped Zirconium Dioxide and Thorium Dioxide.- 3.2 Disorder in ZnO, Cu2O and CuO.- 3.3 Structural Disorder.- 3.4 References.- 4 Thermodynamie Quantities of Quasi-Free Electrons and Electron Defects in Semiconductors.- 4.1 General Considerations.- 4.2 Electrochemical Potential $$\tilde\eta_{\rm e}$$ of Electrons.- 4.3 The Fermi Distribution Function f (?).- 4.4 The Density of States D(?).- 4.5 Relation Between the Concentration of Electrons or Electron Defects and Their Electrochemical Potential.- 4.6 Chemical Potential of Electrons and Standard States.- 4.7 The Activity Coefficient of Electrons and Electron Defects in the Case of Degeneracy.- 4.8 The Phase Boundary Solid/Vacuum. The Work Function W.- 4.9 The Volta Potential or Contact Potential.- 4.10 The Phase Boundary Solid I/Solid II. The Galvani Voltage.- 4.11 References.- 5 An Example of Electronic Disorder. Electrons and Electron Defects in ?-Ag2S.- 5.1 Disorder in ?-Ag2S and Coulometric Titration Curve.- 5.2 Quantitative Evaluation of Coulometric Titration Curves of ?-Ag2S.- 5.3 Entropy and Enthalpy of the Electrons in Ag2S.- 5.4 References.- 6 Mobility, Diffusion and Partial Conductivity of Ions and Electrons.- 6.1 Phenomenological Treatment of Transport Processes.- 6.1.1 Diffusion Equations.- 6.1.2 The Mechanical Mobility Bm.- 6.1.3 The Nernst-Einstein Equation.- 6.1.4 The Component Diffusion Coefficient DK.- 6.1.5 Relationship Between D and DK.- 6.1.6 Relationship Between the Component Diffusion Coefficient DK and the Tracer Diffusion Coefficient DTr.- 6.1.7 Particle Flux in an Electrical Field.- 6.1.8 Particle Flux in the Presence of a Concentration or Activity Gradient and an Electrical Field.- 6.1.9 Description of Particle Fluxes Using the General Transport Equations of Irreversible Thermodynamics.- 6.1.10 Chemical Diffusion.- 6.2 Statistical Treatment of Transport Quantities.- 6.3 Experimental Determination of Partial Conductivities.- 6.3.1 Transference Measurements.- 6.3.2 Measurements of Transference Numbers by Means of Emf Measurements Using Galvanic Cells.- 6.3.3 Determination of Partial Conductivities by Means of Stationary Polarization Measurements.- 6.4 Alternating Current Measurements. Complex Impedance Diagrams.- 6.5 References.- 7 Solid Ionic Conductors, Solid Electrolytes and Solid-Solution Electrodes.- 7.1 Solid Ionic Conductors, Solid Electrolytes.- 7.1.1 Oxygen Ion Conductors.- 7.1.2 Sodium Ion Conductors.- 7.1.3 Silver Ion Conductors.- 7.1.4 Copper Ion Conductors.- 7.1.5 Lithium Ion Conductors.- 7.1.6 Fluorine Ion Conductors.- 7.2 Solid-Solution Electrodes.- 7.3 References.- 8 Galvanic Cells with Solid Electrolytes for Thermodynamic Investigations.- 8.1 Determination of Gibbs Reaction Energies.- 8.2 Determination of Chemical Potentials, Thermodynamic Activities or Partial Pressures.- 8.2.1 Galvanic Cells of the First Kind.- 8.2.2 Galvanic Cells of the Second Kind.- 8.3 Determination of ?S and ?H from the Temperature-Dependence of the Electromotive Force of Galvanic Cells.- 8.4 References.- 9 Technical Applications of Solid Electrolytes —-Solid-State Ionics.- 9.1 Sensors.- 9.2 Fuel Cells and Electrolyzers.- 9.3 Batteries with Solid Electrolytes. The Sodium-Sulfur Battery.- 9.4 Chemotronic Building Units.- 9.4.1 Coulometers and Time Switches.- 9.4.2 Analog Memories.- 9.4.3 Capacitors Containing Solid Electrolytes.- 9.5 References.- 10 Solid-State Reactions.- 10.1 Theory of the Formation of Tarnishing Layers on Metal Surfaces.- 10.1.1 Rate Laws Describing the Formation of Tarnishing Layers.- 10.1.2 Calculation of the Parabolic Rate Law Constant Using the Method of C. Wagner.- 10.2 Examples of the Formation of Tarnishing Layers on Metals and Other Solid-State Reactions.- 10.2.1 Oxidation of Copper to Cu2O at 1000°C.- 10.2.2 Oxidation of Zinc at 400°C.- 10.2.3 Reaction of Silver with Liquid Sulfur at 400°C.- 10.2.4 Formation of Double Salts and Double Oxides via Solid-State Reactions.- 10.3 References.- 11 Galvanic Cells with Solid Electrolytes for Kinetic Investigations.- 11.1 Electrochemical Measurements of Oxygen Diffusion in Metals at Higher Temperatures Using Zirconium Dioxide as Solid Electrolyte.- 11.1.1 The Principle of Electrochemical Measurements of Oxygen Diffusion in Metals.- 11.1.2 The Potentiostatic Method.- The Linear Geometry.- The Cylindrical Geometry.- 11.1.3 The Galvanostatic Method.- 11.2 Electrochemical Investigations on the Formation of Nickel Sulfide in the Solid-State at Higher Temperatures.- 11.2.1 Potentiostatic Measurements.- 11.2.2 Galvanostatic Measurements.- 11.3 Electrochemical Investigations of the Transfer of Silver, Silver Ions and Electrons Across the Phase Boundary Solid Silver/Solid Silver Sulfide.- 11.3.1 Simplified Experimental Arrangement.- 11.3.2 Extended Experimental Arrangement.- 11.3.3 Results and Discussion of Polarization Measurements at the Phase Boundary Ag(s)/Ag2S(s)..- 11.4 Electrochemical Studies of Evaporation and Condensation.- 11.5 An Electrochemical Knudsen Cell for the Investigation of the Thermodynamics of Gases.- 11.6 Electrochemical Measurements of the Chemical Diffusion Coefficient of Wüstite and Silver Sulfide.- 11.7 References.- 12 Non-Isothermal Systems. Soret Effect, Transport Processes, and Thermopowers.- 12.1 Basic Equations of Irreversible Thermodynamics.- 12.2 The Soret Effect.- 12.3 Stationary Transport Processes in Solids Subjected to a Temperature Gradient.- 12.4 Thermoelectric Powers.- 12.5 References.- Author Index.

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