Understanding voltammetry 3rd Edition by Richard Guy Compton, Craig Banks ISBN 9781786345288 1786345285

The power of electrochemical measurements in respect of thermodynamics, kinetics and analysis is widely recognised but the subject can be unpredictable to the novice even if they have a strong physical and chemical background, especially if they wish to pursue quantitative measurements. Accordingly, some significant experiments are perhaps wisely never attempted while the literature is sadly replete with flawed attempts at rigorous voltammetry.This textbook considers how to implement designing, explaining and interpreting experiments centered on various forms of voltammetry (cyclic, microelectrode, hydrodynamic, etc.). The reader is assumed to have knowledge of physical chemistry equivalent to Master’s level but no exposure to electrochemistry in general, or voltammetry in particular. While the book is designed to stand alone, references to important research papers are given to provide an introductory entry into the literature.The third edition contains new material relating to electron transfer theory, experimental requirements, scanning electrochemical microscopy, adsorption, electroanalysis and nanoelectrochemistry.

Understanding voltammetry 3rd Edition Table of contents:

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

References

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. Stanley Pons

2.11 Cold Fusion —The Musical!

2.12 Why Are Some Standard Electrochemical Rate Constants Large but Others Slow? The Marcus Theory o

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!

2.18 Extending Marcus–Hush Theory: The Fermi–Dirac Distribution of Electrons. Symmetric vs. Asym

References

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

References

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 vs. Irreversible Voltammetry: A Summary

4.7 The Measurement of Cyclic Voltammograms: Five Practical Considerations

4.8 The Effect of Unequal Diffusion Coefficients, DA ≠ DB

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?

References

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 Electro

5.6 Cyclic and Linear Sweep Voltammetry Using Microdisc Electrodes

5.7 Steady-State Voltammetry at the Microdisc Electrode

5.8 Microelectrodes vs. Macroelectrodes

5.9 Ultrafast Cyclic Voltammetry: Megavolts per Second Scan Rates

5.10 Ultrasmall Electrodes: Working at the Nanoscale

References

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

6.6 Voltammetric Particle Sizing

6.7 Scanning Electrochemical Microscopy (SECM)

References

7 Cyclic Voltammetry: Coupled Homogeneous Kinetics and Adsorption

7.1 Homogeneous Coupled Reactions: Notation and Examples

7.2 Modifying Fick’s Second Law to Allow for Chemical Reaction

7.3 Cyclic Voltammetry and the EC Reaction

7.4 How Do the Parameters K1 and � Emerge?

7.5 Cyclic Voltammetry and the EC2 Reaction

7.6 Examples of EC and EC2 Processes

7.7 ECE Processes

7.8 ECE vs. DISP

7.9 The CE Mechanism

7.10 The EC’ (Catalytic) Mechanism

7.11 Adsorption

7.12 Voltammetric Studies of Droplets and Solid Particles

References

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 Jets

8.18 Sonovoltammetry

References

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

References

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

References

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

11.4 The Electrochemical Study of Nanoparticles in Solution: “Nano-impacts”

References

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

References

Index

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