Preface
1 Equilibrium Electrochemistry and the Nernst Equation
1.1 Chemical Equilibrium
1.2 Electrochemical Equilibrium: Introduction
1.3 Electrochemical Equilibrium: Electron Transfer at the
Solution-Electrode Interface
1.4 Electrochemical Equilibrium: The Nernst Equation
1.5 Walther Hermann Nernst
1.6 Reference Electrodes and the Measurement of Electrode Potentials
1.7 The Hydrogen Electrode as a Reference Electrode
1.8 Standard Electrode Potentials and Formal Potentials
1.9 Formal Potentials and Experimental Voltammetry
1.10 Electrode Processes: Kinetics vs. Thermodynamics
2 Electrode Kinetics
2.1 Currents and Reaction Fluxes
2.2 Studying Electrode Kinetics Requires Three Electrodes
2.3 Butler-Volmer Kinetics
2.4 Standard Electrochemical Rate Constants and Formal Potentials
2.5 The Need for Supporting Electrolyte
2.6 The Tafel Law
2.7 Julius Tafel
2.8 Multistep Electron Transfer Processes
2.9 Tafel Analysis and the Hydrogen Evolution Reaction
2.10 B. StanleyPons
2.11 Cold Fusion -- The Musical!
2.12 Why Are Some Standard Electrochemical Rate Constants Large
but Others Slow? The Marcus Theory of Electron Transfer: An
Introduction
2.13 Marcus Theory: Taking it Further. Inner and Outer Sphere
Electron Transfer
2.14 Marcus Theory: Taking it Further. Adiabatic and Non-Adiabatic
Reactions
2.15 Marcus Theory: Taking it Further. Calculating the Gibbs Energy
of Activation
2.16 Relationship between Marcus Theory and Butler-Volmer Kinetics
2.17 Marcus Theory and Experiment. Success!
3 Diffusion
3.1 Fick's 1st Law of Diffusion
3.2 Fick's 2nd Law of Diffusion
3.3 The Molecular Basis of Fick's Laws
3.4 How Did Fick Discover His Laws?
3.5 The Cottrell Equation: Solving Fick's 2nd Law
3.6 The Cottrell Problem: The Case of Unequal Diffusion Coefficients
3.7 The Nernst Diffusion Layer
3.8 Mass Transfer vs. Electrode Kinetics: Steady-State
Current-Voltage Waveshapes
3.9 Mass Transport Corrected Tafel Relationships
4 Cyclic Voltammetry at Macroelectrodes
4.1 Cyclic Voltammetry: The Experiment
4.2 Cyclic Voltammetry: Solving the Transport Equations
4.3 Cyclic Voltammetry: Reversible and Irreversible Kinetics
4.4 What Dictates 'Reversible' and'Irreversible' Behaviour?
4.5 Reversible and Irreversible Behaviour: The Effect of Voltage Scan
Rate
4.6 Reversible versus Irreversible Voltammetry: A Summary
4.7 The Measurement of Cyclic Voltammograms: Three Practical
Considerations
4.8 The Effect of Unequal Diffusion Coefficients, DA ~- D8
4.9 Multiple Electron Transfer: Reversible Electrode Kinetics
4.10 Multiple Electron Transfer: Irreversible Electrode Kinetics
4.11 The Influence of pH on Cyclic Voltammetry
4.12 The Scheme of Squares
4.13 Simultaneous Two-Electron Transfer in Electrode Kinetics? . . .
5 Voltammetry at Microelectrodes
5.1 The Cottrell Equation for a Spherical or Hemispherical Electrode
5.2 Potential Step Transients at Microdisc Electrodes
5.3 Microelectrodes Have Large Current Densities and Fast Response
Times
5.4 Applications of Potential Step Chronoamperometry Using
Microdisc Electrodes
5.5 Double Potential Step Microdisc Chronoamperometry Exploring
the Diffusion Coefficient of Electrogenerated Species
5.6 Cyclic and Linear Sweep Voltammetry Using Microdisc Electrode~
5.7 Steady-State Voltammetry at the Microdisc Electrode
5.8 Microelectrodes versus Macroelectrodes
5.9 Ultrafast Cyclic Voltammetry: Megavolts per Second Scan Rates .
5.10 Ultrasmall Electrodes: Working at the Nanoscale
6 Voltammetry at Heterogeneous Surfaces
6.1 Partially Blocked Electrodes
6.2 Microelectrode Arrays
6.3 Voltammetry at Highly Ordered Pyrolytic Graphite Electrodes..
6.4 Electrochemically Heterogeneous Electrodes
6.5 Electrodes Covered with Porous Films
616 Voltammetric Particle Sizing
6.7 Scanning ElectrochemicaIMicroscopy (SECM)
7 Cyclic Voltammetry: Coupled Homogeneous Kinetics and Adsorption
7.1 Homogeneous Coupled Reactions: Notation and Examples . . .
7.2 Modifying Fick's Second Law to Mlow for Chemical Reaction . .
7.3 Cyclic Voltammetry and the EC Reaction
7.4 How Do the Parameters KI and A Emerge?
7.5 Cyclic Voltammetry and the EC2 Reaction
7.6 Examples of EC and EC2 Processes
7.7 ECE Processes
7.8 ECEversus DISP
7.9 The CE Mechanism
7.10 The ECI (Catalytic) Mechanism
7.11 Adsorption
7.12 Voltammetric Studies of Droplets and Solid Particles
8 Hydrodynamic Electrodes
8.1 Convection
8.2 Modifying Fick's Laws to Allow for Convection
8.3 The Rotating Disc Electrode: An Introduction
8.4 The Rotating Disc Electrode-- Theory
8.5 Osborne Reynolds (1842-1912)
8.6 The Rotating Disc Electrode-- Further Theory
8.7 Chronoamperometry at the Rotating Disc Electrode: An
Illustration of the Value of Simulation
8.8 The Rotating Disc and Coupled Homogeneous Kinetics
8.9 The Channel Electrode: An Introduction
8.10 The Channel Electrode: The Levich Equation Derived
8.11 Channel Flow Cells and Coupled Homogeneous Kinetics
8.12 Chronoamperometry at the Channel Electrode
8.13 The Channel Electrode is not 'Uniformly Accessible' .
8.14 Channel Microelectrodes
8.15 Channel Microband Electrode Arrays for Mechanistic
Electrochemistry
8.16 The High Speed Channel Electrode
8.17 Hydrodynamic Electrodes Based on Impinging iets
8.18 Sonovoltammetry
9 Voltammetry for Electroanalysis
9.1 Potential Step Voltammetric Techniques
9.2 Differential Pulse Voltammetry .
9.3 Square Wave Voltammetry
9.4 Stripping Voltammetry
9.5 Sono-electroanalysis
10 Voltammetry in Weakly Supported Media: Migration and Other Effects
10.1 Potentials and Fields in Fully Supported Voltammetry
10.2 The Distribution of Ions Around a Charged Electrode
10.3 The Electrode-Solution Interface: Beyond the Gouy-Chapman
Theory
10.4 Double Layer Effect on Electrode Kinetics: Frumkin Effects . . .
10.5 A.N. Frumkin ,
10.6 Transport by Diffusion and by Migration
10.7 Measurement of Ion Mobilities
10.8 Liquid Junction Potentials
10.9 Chronoamperometry and Cyclic Voltammetry in Weakly
Supported Media
11 Voltammetry at the Nanoscale
11.1 Transport to Particles Supported on an Electrode
11.2 Nanoparticle Voltammetry: The Transport Changes as the
Electrode Shrinks in Size
11.3 Altered Chemistry at the Nanoscale
Appendix: Simulation of Electrode Processes
A.1 Fick's First and Second Laws
A.2 Boundary Conditions
A.3 Finite Difference Equations
A.4 Backward Implicit Method
A.5 Conclusion
Index
