Electrochemical Methods: Fundamentals and Applications

Citation

Bard, A. J., Faulkner, L. R., & White, H. S. (2022). Electrochemical Methods: Fundamentals and Applications (3rd ed.). Wiley.

Chapter Summary

The third edition has 21 chapters and three appendices in about 1,100 pages. Section 1.7 explains how the book is organized: Chapter 1 is the introduction; Chapters 2 to 4 are the core fundamentals; Chapters 5 to 7 are the core methods; Chapters 8 to 12 are additional methods; Chapters 13 to 16 are advanced fundamentals; and Chapters 17 to 21 are advanced systems and methods. The first seven chapters are meant to be read in sequence, and the remaining groups can largely be chosen according to interest. Most chapters end with references and problems, and many contain "Lab Notes" linking concepts to laboratory practice.

Chapter 1: Overview of Electrode Processes

An extensively revised introduction for readers arriving from different backgrounds. It covers basic ideas, faradaic processes and the factors that control electrode reaction rates, mass-transfer-controlled reactions, a semiempirical treatment of Nernstian reactions with coupled chemical reactions, cell resistance and potential measurement, and the electrode/solution interface and charging current. It ends with the book's organization, a guide to the literature of electrochemistry and a Lab Note on potentiostats.

Chapters 2–4: Potentials and Thermodynamics of Cells; Basic Kinetics of Electrode Reactions; Mass Transfer by Migration and Diffusion

Chapter 2 treats electrochemical thermodynamics, interfacial potential differences, liquid junction potentials and ion-selective electrodes. Chapter 3 reviews homogeneous kinetics and develops the Butler–Volmer model, microscopic theories of charge transfer, open-circuit potentials and multistep mechanisms. Chapter 4 sets out the mass-transfer equations, migration, diffusion and the formulation and solution of mass-transfer problems.

Chapters 5–7: Steady-State Voltammetry at Ultramicroelectrodes; Transient Methods Based on Potential Steps; Linear Sweep and Cyclic Voltammetry

Chapter 5 is new to this edition: steady-state responses at ultramicroelectrodes for reversible, quasireversible and irreversible reactions, with a Lab Note on preparing electrodes. Chapter 6 covers chronoamperometry, sampled-transient voltammetry, reversal techniques and chronocoulometry. Chapter 7 covers linear sweep and cyclic voltammetry for Nernstian, quasireversible and irreversible systems, fast cyclic voltammetry, convolution and voltammetry at liquid–liquid interfaces.

Chapters 8–12: Additional methods

Chapter 8, Polarography, Pulse Voltammetry, and Square-Wave Voltammetry; Chapter 9, Controlled-Current Techniques; Chapter 10, Methods Involving Forced Convection—Hydrodynamic Methods (rotating disk and ring-disk electrodes); Chapter 11, Electrochemical Impedance Spectroscopy and ac Voltammetry; and Chapter 12, Bulk Electrolysis (controlled-potential and controlled-current methods, flow electrolysis, thin-layer electrochemistry and stripping analysis).

Chapters 13–16: Advanced fundamentals

Chapter 13, Electrode Reactions with Coupled Homogeneous Chemical Reactions, classifies such reactions and surveys their behavior with cyclic voltammetry and other methods. Chapter 14, Double-Layer Structure and Adsorption, covers double-layer thermodynamics, models and effects on reaction rates. Chapter 15, Inner-Sphere Electrode Reactions and Electrocatalysis, is new and also treats computational analyses, electrocatalytic correlations and electrochemical phase transformations. Chapter 16, Electrochemical Instrumentation, covers operational amplifiers, potentiostats, galvanostats and the measurement of low currents.

Chapters 17–21: Advanced systems and methods

Chapter 17, Electroactive Layers and Modified Electrodes; Chapter 18, Scanning Electrochemical Microscopy; Chapter 19, Single-Particle Electrochemistry (new), covering particle collision experiments, single atoms and clusters, and single molecules; Chapter 20, Photoelectrochemistry and Electrogenerated Chemiluminescence; and Chapter 21, In situ Characterization of Electrochemical Systems (microscopy, quartz crystal microbalance, UV–visible, vibrational and X-ray methods, mass spectrometry and magnetic resonance).

Appendices A–C

Appendix A: Mathematical Methods (Laplace transforms, Taylor expansions, the error function, among others); Appendix B: Basic Concepts of Simulation; Appendix C: Reference Tables.

Key Concepts

Chapters 1–4: Fundamentals

• Faradaic processes and mass-transfer control: the factors that set the current at an electrode.
• Butler–Volmer kinetics and microscopic charge-transfer theories: models of electrode reaction rates.
• Migration and diffusion: transport equations and their solution.

Chapters 5–12: Methods

• Voltammetry: steady-state, sweep, step and pulse techniques.
• Hydrodynamic and impedance methods: forced convection, rotating electrodes and impedance spectroscopy.

Chapters 13–21: Advanced topics

• Coupled chemical reactions and the double layer: complications that modify electrode responses.
• Electrocatalysis and single-particle electrochemistry: topics added in the third edition.
• Modified electrodes, scanning probes and in situ characterization: applications to surfaces and layers.

Critical Analysis

Strengths

• Clear route through the book. The authors present a map of "core" and "selectable" chapters, so readers can see which chapters depend on earlier ones and which can be taken in any order.
• A self-contained development. The publisher says it is designed to be accessible to readers with a basic university foundation in chemistry, physics and mathematics and develops key ideas from fundamental principles.
• Substantial update. Wiley lists a revised introductory chapter, new chapters on ultramicroelectrode voltammetry, inner-sphere reactions and electrocatalysis, and single-particle electrochemistry, extensive treatment of Marcus kinetics, more on migration and expanded impedance spectroscopy.
• Practical bridges. Lab Notes in many chapters help readers move from concept to practice, and Appendix B introduces digital simulation, which is used from Chapter 5 onward.

Limitations

• Size and mathematical load. At roughly 1,100 pages, with a mathematics appendix that is used extensively in Chapters 5 to 13, the book rewards a reader who works through the derivations.
• No literature survey. The authors say the extensive literature summary of the second edition has been dropped and replaced by a short list of reference sources, laboratory-technique books and review series.
• Selection is required. Because the groups of chapters are largely independent, a one-semester course must choose among the additional and advanced chapters.

Where It Fits in the Course

In the analytical chemistry course this is the most specialized title. Harvey's Analytical Chemistry 2.1 is an open text for a first analytical course that includes electrochemistry among its topics, Harris's Quantitative Chemical Analysis and the shorter Exploring Chemical Analysis cover classical and instrumental methods in introductory courses, Rouessac and Rouessac's Chemical Analysis explains the principles and instrumentation of major methods, and Skoog, Holler and Crouch's Principles of Instrumental Analysis is a standard upper-level text on instrumental methods.

Bard, Faulkner and White take electrochemistry much further than any of these, deriving the thermodynamics, kinetics and mass transport that determine the responses of voltammetric and related techniques. It is the book to move to after an instrumental analysis course, or for research that uses electrochemical methods.

How to Use This Book

The book is aimed at senior undergraduate and graduate students taking electrochemistry, physical or analytical chemistry, and at researchers in electrochemical engineering, energy conversion and storage, and sensors.

A practical plan:

• Core: Chapters 1 to 7 in order. Review Appendix A before Chapter 5.
• Methods by need: Chapters 8 to 12 individually; for example Chapter 8 for pulse techniques and Chapter 11 for impedance.
• Advanced: Chapters 13 to 16 before Chapters 17 to 21, since the latter generally build on the advanced fundamentals.
• Simulation and reference: Appendix B for digital simulation and Appendix C for tables used in the problems.

Do the end-of-chapter problems and read the Lab Notes alongside any laboratory work.