Introduction to Electrochemical Science and Engineering 2nd Edition by Serguei Lvov ISBN 1138196789 9781138196780

Chapter 1 Electrolyte Solutions

1.1 Objectives

1.2 Formation of Electrolyte Solutions

1.3 Electrolyte Concentration and Concentration Scales

1.4 Conversion Equations for the Concentration of Solutions

1.5 Chemical Potential

1.6 Standard Chemical Potential and Activity Coefficient on Different Concentration Scales

1.7 Chemical Potential of Solvent and Solute in Electrolyte Solution

1.8 Activity, Ionic Strength, and Activity Coefficient

1.9 Activity Coefficient of an Electrolyte and an Ion

1.10 Chemical Potential and Gibbs Energy of Formation

1.11 The Debye–Hückel Theory of Dilute Electrolyte Solutions

1.12 Calculation of Activity Coefficient Using the Debye–Hückel Theory

1.13 Calculated and Observed Activity Coefficients

1.14 Mean Activity Coefficient in Concentrated Aqueous Solutions

1.15 Speciation in Weak Electrolytes

1.16 pH of Aqueous Solutions

1.17 pH of Buffer Solutions

1.18 Suggested pH of Standard Solutions

1.19 Summary

1.20 Exercises

References

Chapter 2 Electrochemical Cells

2.1 Objectives

2.2 Basic and Derived SI Units

2.3 Electrochemical Cell (System)

2.4 Electrolytic and Galvanic Cells

2.5 Electrochemical Diagrams (Traditional)

2.6 New Electrochemical Diagrams

2.7 Faraday’s Law of Electrolysis

2.8 Fundamental Constants

2.9 Water Electrolysis

2.10 Ohm’s Law

2.11 Kirchhoff’s Law

2.12 Electrochemical Cells with Transfer

2.13 Daniell Cell in Galvanic Mode

2.14 Daniell Cell in Electrolytic Mode

2.15 Cell Potential-Current Dependence

2.16 Summary

2.17 Exercises

References

Chapter 3 Electric Conductivity

3.1 Objectives

3.2 Types of Electric Conductivity

3.3 Significance of Ion Conductive Materials for Electrochemical Engineering

3.4 Origin of Ionic Conductivity

3.5 Conductance and Conductivity of an Electrolyte

3.6 Electric Conductivity of Pure Water

3.7 Conductance by Direct and Alternating Currents

3.8 Electrode/Electrolyte Interface

3.9 Extracting the Electrolyte Resistance

3.10 Conductivity Measurements

3.11 Molar and Equivalent Conductivity

3.12 Kohlrausch’s Law and Limiting Conductivity

3.13 Additivity of Electrolyte Limiting Conductivity

3.14 Transport Numbers

3.15 Diffusion and Hydration of Ions in Infinitely Diluted Solution

3.16 Proton Conductivity

3.17 Walden’s Rule

3.18 Summary

3.19 Exercises

References

Chapter 4 Equilibrium Electrochemistry

4.1 Objectives

4.2 Equilibrium Thermodynamics and Electrochemistry

4.3 Equilibrium between Phases in an Electrochemical Cell

4.4 Galvani Potential of the Hydrogen Electrode

4.5 Gibbs Energy of Reaction and Equilibrium Electrode Potential

4.6 Nernst Equation

4.7 Standard Hydrogen Electrode (SHE)

4.8 Ag/AgCl Reference Electrode

4.9 Harned Cell

4.10 Electrochemical Series

4.11 Calculation of Equilibrium Potential of the Daniell Cell

4.12 Nernst Equations for Typical Electrodes

4.13 Another Example of Estimating of E0 and E

4.14 Calculation of E0 at Elevated Temperature

4.15 Temperature Dependence of the Standard Electrode Potential

4.16 Temperature Dependence of Open Circuit and Decomposition Potentials

4.17 Potential–pH (Pourbaix) Diagram

4.18 Summary

4.19 Exercises

References

Chapter 5 Electrochemical Techniques I

5.1 Objectives

5.2 Potentiometric Measurements

5.3 Commercial Ag/AgCl Reference Electrode

5.4 Commercial Calomel Reference Electrode

5.5 pH Glass Electrode

5.6 Liquid Junction (Diffusion) Potential

5.7 Henderson Equation

5.8 Calculation of the Diffusion Potential

5.9 Minimization of the Diffusion Potential in a Cell

5.10 Kinds of Potentiometry

5.11 Measurement of the Standard Electrode Potential

5.12 Measurement of pH

5.13 Combined pH/Reference Electrode Sensor and pH Meter

5.14 Summary

5.15 Exercises

References

Chapter 6 Electrochemical Kinetics

6.1 Objectives

6.2 Concept of Electrochemical Cell Overpotential

6.3 Overpotential of a Single Electrode

6.4 Polarization Curve of a Single Electrode

6.5 Mechanism of Electrochemical Reaction

6.6 Charge Transfer Overpotential: Butler–Volmer Equation

6.7 Symmetry Factor, β

6.8 Exchange Current Density, jo

6.9 Experimental Data on the Exchange Current Density and Symmetry Coefficient

6.10 Simplifications of the Butler–Volmer Equation

6.11 Tafel Equation

6.12 Volcano Plot

6.13 Concentration Overpotential

6.14 Mass Transfer Overpotential

6.15 Generalized Butler–Volmer Equation

6.16 Summary

6.17 Exercises

References

Chapter 7 Electrochemical Techniques II

7.1 Objectives

7.2 Transport Processes in Electrochemical Systems

7.3 Current–Time Dependence at Constant Potential (Potentiostatic Regime)

7.4 Concentration–Time Dependence at Constant Current (Galvanostatic Regime)

7.5 Effect of Hydrodynamics (Fluid Mechanics) on Electrochemical Reaction

7.6 Rotating Disk Electrode and Limiting Current

7.7 Rotating Disk Electrode Electrochemical Cell

7.8 Cyclic Voltammetry Background

7.9 Cyclic Voltammetry of Fe(CN)63−/Fe(CN)64− Couple

7.10 Electrochemical Impedance Spectroscopy

7.10.1 Complex Variables

7.10.2 Response of Current to Applied Oscillating Potential

7.10.3 Impedance of Circuit Components

7.10.4 Impedance of the Randles Circuit

7.10.5 Nyquist Plot

7.10.6 Bode Plot

7.10.7 Warburg Impedance

7.11 Summary

7.12 Exercises

References

Chapter 8 Electrochemical Energy Conversion

8.1 Objectives

8.2 Main Types of Electrochemical Energy Conversion Systems

8.3 Principal Design of a Fuel Cell

8.4 Main Kinds of Fuel Cells

8.5 Electrochemistry of Fuel Cells

8.6 Three-Phase Boundary Issue

8.7 New Electrochemical Diagrams for Fuel Cells

8.8 Polarization Curves of PEMFC and SOFC

8.9 Efficiency of Fuel Cell versus Heat Engine

8.10 Total Efficiency of Fuel and Electrolytic Cells

8.11 Heat Balance in Fuel and Electrolytic Cells

8.12 Summary

8.13 Exercises

References

Chapter 9 Electrochemical Corrosion

9.1 Objectives

9.2 Origin of Electrochemical Corrosion

9.3 Pourbaix Diagram in Corrosion Science

9.4 Polarization Curve of Metal Corrosion

9.5 Corrosion Potential and Current Density

9.6 Rate of Electrochemical Corrosion

9.7 Corrosion Protection

9.8 Kinds of Corrosion

9.9 Summary

9.10 Exercises

References

Chapter 10 Data Section

10.1 CODATA Values of the Fundamental Physical Constants

10.2 Physical Constants of Inorganic Compounds

10.3 Standard Thermodynamic Properties of Chemical Substances

10.4 Thermodynamic Properties as a Function of Temperature

10.5 Thermodynamic Properties of Aqueous Ions

10.6 Ionization Constant of Water as a Function of Temperature and Pressure

10.7 Electric Conductivity of Water

10.8 Electric Conductivity of Aqueous Solutions

10.9 Standard KCl Solutions for Calibrating Conductivity Cells

10.10 Molar Conductivity of Aqueous HCl

10.11 Molar Conductivity of Electrolytes

10.12 Ionic Conductivity and Diffusion Coefficient at Infinite Dilution

10.13 Electrochemical Series

10.14 Dissociation Constants of Inorganic Acids and Bases

10.15 Dissociation Constants of Organic Acids and Bases

10.16 Activity Coefficients of Aqueous Acids, Bases, and Salts

10.17 Mean Activity Coefficients of Aqueous Electrolytes

10.18 Concentrative Properties of Aqueous Solutions

10.19 Aqueous Solubility of Inorganic Compounds at Various Temperatures

10.20 Solubility Product Constants

10.21 Solubility of Common Salts at Ambient Temperatures

10.22 Thermophysical Properties of Water and Steam at Temperatures up to 100°C

10.23 Vapor Pressure and Other Saturation Properties of Water at Temperatures up to 100°C (373.15 K)

10.24 van der Waals Constants for Gases

10.25 Vapor Pressure of Saturated Salt Solutions

10.26 Electric Resistivity of Pure Metals

10.27 Composition of Seawater and Ionic Strength on Molality Scale at Various Salinities S in Parts per Thousand

10.28 Error Function

10.29 Periodic Table of Elements

Appendix A: Quizzes

Appendix B: Video-Based Assignments

Appendix C: Laboratory Instructions

Index