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