Introduction to Electrochemical Science and Engineering

Content: Acknowledgments    Introduction    Author    Electrolyte Solutions    Objectives    Formation of Electrolyte Solutions    Electrolyte Concentration and Concentration Scales    Conversion Equations for the Concentration of Solutions    Chemical Potential    Standard Chemical Potential and Activity Coefficient on Different Concentration Scales    Chemical Potential of Solvent and Solute in Electrolyte Solution    Activity and Activity Coefficient    Activity Coefficient of Electrolyte and an Ion    Chemical Potential and Gibbs Energy of Formation    Debye-Huckel Theory of Dilute Electrolyte Solutions    Calculation of Activity Coefficient Using Debye-Huckel Theory    Calculated and Observed Activity Coefficients    Mean Activity Coefficient in Concentrated Aqueous Solutions    Speciation in Weak Electrolytes    pH of Aqueous Solutions    pH of Buffer Solutions    Suggested pH of Standard Solutions    Summary    References    Electrochemical Cells    Objectives    Basic and Derived SI Units    Electrochemical Cell (System)    Electrolytic and Galvanic Cells    Electrochemical Diagrams (Traditional)    New Electrochemical Diagrams    Faraday's Law of Electrolysis    Fundamental Constants    Water Electrolysis    Ohm's Law    Kirchhoff's Law    Electrochemical Cells with Transfer    Daniell Cell in Galvanic Mode    Daniell Cell in Electrolytic Mode    Cell Potential-Current Dependence    Summary    References    Electric Conductivity    Objectives    Types of Electric Conductivity    Significance of Ion Conductive Materials for Electrochemical Engineering    Origin of Ionic Conductivity    Conductance and Conductivity of an Electrolyte    Electric Conductivity of Pure Water    Conductance by Direct and Alternating Currents    Electrode/Electrolyte Interface    Extracting the Electrolyte Resistance    Conductivity Measurements    Molar and Equivalent Conductivity    Kohlrausch's Law and Limiting Conductivity    Additivity of Electrolyte Limiting Conductivity    Transport Numbers    Diffusion and Hydration of Ions in Infinitely Diluted Solution    Proton Conductivity    Walden's Rule    Summary    References    Equilibrium Electrochemistry    Objectives    Equilibrium Thermodynamics and Electrochemistry    Equilibrium between Phases in Electrochemical Cell    Galvani Potential of the Hydrogen Electrode    Gibbs Energy of Reaction and Equilibrium Electrode Potential    Nernst Equation    Standard Hydrogen Electrode    Ag/AgCl Reference Electrode    Harned Cell    Electrochemical Series    Calculation of Equilibrium Potential of Daniell Cell    Nernst Equation for Typical Electrodes    Another Example of Estimating of E0 and E    Calculation of E0 at Elevated Temperature    Temperature Dependence of the Standard Electrode Potential    Temperature Dependence of Open Circuit and Decomposition Potentials    Potential-pH (Pourbaix) Diagram    Summary    References    Electrochemical Techniques I    Objectives    Potentiometric Measurements    Commercial Ag/AgCl Reference Electrode    Commercial Calomel Reference Electrode    pH Glass Electrode    Liquid Junction (Diffusion) Potential    Henderson Equation    Calculation of the Diffusion Potential    Minimization of the Diffusion Potential in a Cell    Kinds of Potentiometry    Measurement of the Standard Electrode Potential    Measurement of pH    Combined pH/Reference Electrode Sensor and pH Meter    Summary    References    Electrochemical Kinetics    Objectives    Concept of Electrochemical Cell Overpotential    Overpotential of a Single Electrode    Polarization Curve of a Single Electrode    Mechanism of Electrochemical Reaction    Charge Transfer Overpotential: Butler-Volmer Equation    Symmetry Coefficient, ss    Exchange Current Density, jo    Experimental Data on the Exchange Current Density and Symmetry Coefficient    Simplifications of Butler-Volmer Equation    Tafel Equation    Volcano Plot    Concentration Overpotential    Mass Transfer Overpotential    Generalized Butler-Volmer Equation    Summary    References    Electrochemical Techniques II    Objectives    Transport Processes in Electrochemical Systems    Current-Time Dependence at Constant Potential (Potentiostatic Regime)    Concentration-Time Dependence at Constant Current (Galvanostatic Regime)    Effect of Hydrodynamics (Fluid Mechanics) on Electrochemical Reaction    Rotating Disk Electrode and Limiting Current    Rotating Disk Electrode Electrochemical Cell    Cyclic Voltammetry Background    Cyclic Voltammetry of Fe(CN)3-6 /Fe(CN)4-6 Couple    Summary    References    Electrochemical Energy Conversion    Objectives    Main Types of Electrochemical Energy Conversion Systems    Principle Design of a Fuel Cell    Main Kinds of Fuel Cells    Electrochemistry of Full Cells    Three-Phase Boundary Issue    New Electrochemical Diagrams for Fuel Cells    Polarization Curves of PEMFC and SOFC    Efficiency of Fuel Cell vs. Heat Engine    Total Efficiency of Fuel and Electrolytic Cells    Heat Balance in Fuel and Electrolytic Cells    Summary    References    Electrochemical Corrosion    Objectives    Origin of Electrochemical Corrosion    Pourbaix Diagram in Corrosion Science    Polarization Curve of Metal Corrosion    Corrosion Potential and Current Density    Rate of Electrochemical Corrosion    Corrosion Protection    Kinds of Corrosion    Summary    References    Data Section    Codata Values of the Fundamental Physical Constants    Physical Constants of Inorganic Compounds    Standard Thermodynamic Properties of Chemical Substances    Thermodynamic Properties as a Function of Temperature    Thermodynamic Properties of Aqueous Ions    Ionization Constant of Water as a Function of Temperature and Pressure    Electrical Conductivity of Water    Electrical Conductivity of Aqueous Solutions    Standard KCl Solutions for Calibrating Conductivity Cells    Molar Conductivity of Aqueous HCl    Equivalent Conductivity of Electrolytes    Ionic Conductivity and Diffusion at Infinite Dilution    Electrochemical Series    Dissociation Constants of Inorganic Acids and Bases    Dissociation Constants of Organic Acids and Bases    Activity Coefficients of Acids, Bases, and Salts    Mean Activity Coefficients of Electrolytes    Concentrative Properties of Aqueous Solutions    Aqueous Solubility of Inorganic Compounds at Various Temperatures    Solubility Product Constants    Solubility of Common Salts at Ambient Temperatures    Thermophysical Properties of Water and Steam at Temperatures up to 100 C    Vapor Pressure and Other Saturation Properties of Water at Temperatures up to 100 C    van der Waals Constants for Gases    Vapor Pressure of Saturated Salt Solutions    Electrical Resistivity of Pure Metals    Composition of Seawater and Ionic Strength on Molality Scale at Various Salinities S in Parts per Thousand    Error Function    Periodic Table of Elements    Appendix A: Quizzes    Appendix B: Video-Based Assignments    Index