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.

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.

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.

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.

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.

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.

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 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.

This article provides a discussion on the fundamentals of corrosion thermodynamics. The discussion focuses on electrochemical reactions, molten salt corrosion thermodynamics, and geochemical modeling.

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.

Potentiometric membrane electrodes are electrochemical devices that can be used to quantify numerous ionic and nonionic species. This class of electrochemical sensors can be divided into ion-selective and gas-sensing membrane electrodes. The first half of this article mainly focuses on the subclasses, the membrane potential, electrode selectivity limitations and the methods of analysis of the ion-selective membrane electrodes. These methods of analysis include the use of calibration curves, addition techniques, subtraction techniques, and titration. The second half outlines gas sensing membrane electrodes, and discusses important elements that must be considered in addition to the potentiometric membrane electrode to ensure proper electrode response. These elements are reference electrodes, temperature controls, recording of the potential with respect to time, electrode storages, and sample pretreatment. The article also explains the applications of the potentiometric membrane electrodes with the aid of an example.

Electrogravimetry is a method used to separate and quantify ions of a substance, usually a metal. Quantification of these ions primarily depends on the rate of movement of charged species (ions) in an electric field. This article details the various types of electrometric titrations, namely, conductometric titration, oscillometric (high frequency) titration, potentiometric titration, amperometric titration, biamperometric titration, bipotentiometric titration, and coulometric titration. It also provides a brief outline of the applications of electrometric titrations.

The interaction of an implant with the human body environment may result in degradation of the implant, called corrosion. This article discusses the corrosion testing of metallic implants and implant materials. The corrosion environments for medical implants are the extracellular human body fluids, very complex solutions containing electrolytes and nonelectrolytes, inorganic and organic constituents, and gases. The article describes the fundamentals of electrochemical corrosion testing and provides a brief discussion on various types of corrosion tests. It illustrates corrosion current density determination by Tafel extrapolation, potentiodynamic measurement of the polarization resistance, electrochemical impedance measurement, and potentiostatic deaeration. Tests combining corrosion and mechanical forces, such as fretting corrosion tests, environment-assisted cracking tests, and ion-leaching tests are also discussed.

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.

This article discusses a tool for the conversion of measurements made against various reference electrodes at different temperatures. It reviews different electrode potential temperature coefficients, namely, isothermal temperature coefficient and thermal temperature coefficient. The article contains a table that lists the electrode potentials and conversion factors for various reference electrodes.

This article describes the characteristics of continuous cathodic arc sources and filtering process for removing macroparticles from a cathodic arc. It provides information on the types of arc sources and the properties of deposited materials. The advantages, limitations, and applications of arc deposition are also discussed.

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