Overpotential is the current-producing potential difference between a nonequilibrium electrode potential and its corresponding equilibrium value for an electrode reaction. This article provides information on the overpotential of an electrode reaction. It contains a table that lists the values based on the electrode reaction. Because overpotential is a kinetic parameter and depends on current density, overpotential values presented are for a specific current density.

Electrochemical, or electrode, reactions occur with charge transfer between neutral or ionic reactants and a conducting material called the electrode. This article discusses cathodic reactions that result in reduction and anodic reactions that result in oxidation. It reviews the effects of an electric field near an electrode and illustrates the solvation of ions in metal-aqueous solution.

Principles of metallic corrosion play a fundamental role in developing industrial processes that employ corrosion for constructive purposes. This article examines the changes in kinetics that occur with differentially small potential changes around the equilibrium electrode potentials of two reversible electrodes, such as copper and silver electrodes, in an electrochemical system. It provides a schematic illustration of a reversible cell with copper and silver electrodes to determine a reversible cell potential between the electrodes. An electrode becomes irreversible when the electrode reactions are displaced from equilibrium and the electrode potential is no longer at the equilibrium potential. The article describes irreversible cell potential by using galvanic cells, electrolytic cells, and corrosion cells.

The electrode potential is one of the most important parameters in the thermodynamics and kinetics of corrosion. This article discusses the fundamentals of electrode potentials and illustrates the thermodynamics of chemical equilibria by using the hydrogen potential scale and the Nernst equation. It describes galvanic cell reactions and corrosion reactions in an aqueous solution in an electrochemical cell. The article explores the most common cathodic reactions encountered in metallic corrosion in aqueous systems. The reactions included are proton reduction, water reduction, reduction of dissolved oxygen, metal ion reduction, and metal deposition. The article also presents the standard equilibrium potentials measured at 25 deg C relative to a standard hydrogen electrode for various metal-ion electrodes in a tabular form.

This article presents common conventions and definitions in corrosion, electrochemical cells, cathodic protection (CP), electricity, and oxidation. Evans diagrams for impressed current CP in neutral or basic environment and galvanic or sacrificial CP, in both neutral or basic environment and acidic environment, are illustrated.

Corrosion of metallic materials is governed by electrochemical kinetics, so that the general concepts developed for studying electrochemical reaction mechanisms may be applied to corrosion. This article presents the fundamental aspects of electrode kinetics. The processes of charge transfer taking place at the electrode interface within the double layer and of mass transport at the vicinity of the electrode surface are discussed. The article describes the corrosion processes, which involve anodic and cathodic reactions at specific electrode sites. Some experimental methods for devising a reliable reaction model are detailed. The article explains some reaction mechanisms for cathodic and anodic processes to illustrate the great variety of reaction mechanisms occurring at the electrode interface.

Electrode potential is a key parameter in the thermodynamic and kinetic processes that drive aqueous corrosion. This article discusses the complexities associated with measuring electrode potential and explains where and how to use reference electrodes to improve measurement accuracy. It describes a three-electrode approach that compensates for measurement error stemming from nonequilibrium conditions. It also examines electrode materials and behaviors and offers insights on selection and operating conditions.

Molten salts, in contrast to aqueous solutions in which an electrolyte (acid, base, salt) is dissolved in a molecular solvent, are essentially completely ionic. This article begins with an overview of the thermodynamics of cells and classification of electrodes for molten salts: reference electrodes and indicator electrodes. It explains that corrosion in molten salts can be caused by the solubility of the metal in the salt, particularly if the metal dissolves in its own chloride. The article describes the factors that affect the corrosion of titanium, namely, the titanium chloride content of the magnesium chloride melt, magnesium or sodium content, and oxygen content of the product. It concludes with a discussion on the oxygen activity in the titanium metal product.

This article describes various methods of electrochemical analysis, namely coulometry, electrogravimetry, voltammetry, electrometric titration, and nanometer electrochemistry. The discussion covers the general uses, sample requirements, application examples, advantages, and limitations of these methods. Some of the factors pertinent to electrochemical cells are also provided. In addition, the article provides information on various potentiometric membrane electrodes used to quantify numerous ionic and nonionic species.

This article contains tables that list standard reduction potentials for electrochemical reactions. The first table lists reactions alphabetically by element of interest. The second table is ranked by potential value. Potential is measured versus the Standard Hydrogen Electrode which has a value of 0.0000 V. Reactions with more than one voltage indicate that results have not been reconciled. Parenthetical materials not needed to balance reactions are catalysts.

Electropolishing is an electrochemical process that involves anodic dissolution of a metal specimen (anode electrode) in an electrolytic cell. This article reviews the two-electrode and three-electrode systems for electropolishing. It presents the equations of anodic reactions and the selection criteria of electrolyte for electropolishing. The article also describes the mechanism of electropolishing and the effect of electropolishing on properties of metals.

Voltammetry is the study of the current voltage relationships observed when electroactive species in solution are subject to oxidation or reduction at electrodes under carefully controlled conditions. This article describes the basic principle of voltammetry performed using the dropping mercury electrode (polarography). It discusses the various methods of voltammetry, namely, linear sweep voltammetry, cyclic voltammetry, and stripping voltammetry that are carried out with different electrode material. The article also explores the modern instrumentation and developments achieved in voltammetry, and provides an outline of additional data, such as values of the formation, or stability, and constants of complexes formed by shifting the half-wave potential, which can be obtained by voltammetry. Additionally, the article provides a brief account of the applications of voltammetry.

This article describes the classification of fuel cells depending on the operating temperature and type of electrolytes used. This classification includes alkaline fuel cells, phosphoric acid fuel cells, polymer electrolyte membrane fuel cells (PEMFCs), molten carbonate fuel cells (MCFCs), and solid oxide fuel cells (SOFCs). The article explains the corrosion processes in fuel cells due to solid-gas interactions, solid-liquid interactions, and solid-solid interactions. It discusses the long-term performance stability and long-term degradation processes of PEMFCs, MCFCs, and SOFCs. The article reviews the development of chemically and structurally compatible component materials in PEMFCs, MCFCs, and SOFCs.

This article is a comprehensive collection of terms related to corrosion fundamentals, testing, and protection.

Electrogravimetry is the oldest electroanalytical technique in which the element of interest is deposited electrolytically onto an electrode and weighed. This article discusses the principles involved in determining the electrolysis rate of the solution, and describes different methods for the separation of ion in the electrolyte and their corresponding instrumentation. Furthermore, it explores the various types of analysis, such as the separation and quantitative determination of metal ions and internal electrolysis, and provides a detailed account of the applications of electrogravimetry with examples.

Electrochemical refining is the purification process for producing commercially pure metals from crude metals. This article describes the principles of electrochemical reactions. It discusses the physical properties of the basic components of electrochemical refining cell. The article also explains the engineering considerations required in the refining process. Theoretical and technological principles of electrochemical refining are illustrated, with examples.

Controlled-potential coulometry is a highly precise and accurate method primarily used for major constituent analysis of analyte substances such as alloys, compounds, nonmetallic materials and organic compounds. This article illustrates the apparatus required for controlled-potential coulometry, and provides information on its techniques and applications. It contains a table that lists the metals for which accurate methods have been developed and the basic electrochemistry of the procedures. The article explains that gold and uranium are the elements that are determined frequently in various sample types.