Physical Electrochemistry: Fundamentals, Techniques, and Applications, Second Edition

A Quantitative Foundation for Electrochemical Research

Physical Electrochemistry: Fundamentals, Techniques, and Applications, Second Edition is written for readers who want to understand not only what happens at an electrode surface, but why it happens. Noam Eliaz and Eliezer Gileadi guide the reader from the thermodynamic and kinetic principles that govern charged interfaces into the experimental methods used to measure them. The result is a demanding but coherent treatment that keeps theory and laboratory practice in close conversation.

The second edition organizes its material around the questions that arise when electrochemistry moves from textbook equations to real cells: How is potential distributed? Where does resistance distort a measurement? Which electrode geometry suits a given experiment? How can mechanism be inferred from current–potential behavior?

From Phase Potentials to the Three-Electrode Cell

Early chapters establish the electrochemical potential, equilibrium between phases, and the meaning of the standard hydrogen electrode scale. From there, the book examines fundamental measurements, including current and potential control, reference electrode selection and placement, uncompensated solution resistance, cell geometry, and edge effects. These sections are especially useful for anyone who has struggled to separate a genuine electrochemical response from an experimental artifact.

Electrode Kinetics and Reaction Mechanisms

The kinetic core of the book covers overpotential, the Tafel equation, transition-state theory, the symmetry factor, and the Marcus theory of charge transfer. It distinguishes outer-sphere and inner-sphere processes and shows how mechanistic criteria, transfer coefficients, reaction orders, and pH effects are used to interpret multistep electrode reactions. Case studies include the hydrogen evolution reaction, possible paths for oxygen evolution, and the stability and catalytic role of adsorbed intermediates.

Interfacial Structure and Electrocapillary Phenomena

Interfacial structure receives detailed attention through models of the electrical double layer, including the Helmholtz parallel-plate picture, the Gouy–Chapman diffuse model, and the Stern model. The text also treats the role of the solvent at the interphase, electrocapillary thermodynamics, adsorption and surface excess, the Gibbs adsorption isotherm, the electrocapillary equation, and the measurement of electrocapillary behavior.

Techniques That Connect Theory to Data

Readers encounter the experimental tools that make physical electrochemistry a working science: polarography and the dropping mercury electrode, rotating disk, rotating cone, and rotating ring-disk electrodes, fast transient measurements, auxiliary reference electrodes, and methods for calculating uncompensated solution resistance in planar, cylindrical, and spherical geometries. The emphasis throughout is on understanding what each technique reveals and where its limitations lie.

Who Will Benefit

This second edition is aimed at advanced undergraduates, graduate students, and researchers who need a rigorous treatment of electrochemical principles rather than a purely descriptive overview. It will be particularly relevant to readers working in physical chemistry, materials science, analytical chemistry, and interdisciplinary areas where electrode processes and interfacial phenomena are central. The book rewards careful study and is suited to course use, self-directed learning, and reference work.

Why This Edition Is Worth Owning

By joining fundamentals, measurement, and mechanistic interpretation in one volume, this edition helps readers build a durable framework for electrochemical thinking. It does not shy away from equations or experimental detail, but it keeps the physical meaning of those details in view. Digital Delights is pleased to offer this technical reference as a digital edition for readers who want authoritative coverage of physical electrochemistry in a portable, accessible form.