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.

A potential pH diagram is a graphical representation of the relations, derived from the Nernst equation, between the pH and the equilibrium potentials (E) of the most probable electrochemical reactions occurring in a solution containing a specific element. This article describes three types of reactions for calculation and construction of E-pH diagrams: electrochemical reactions of pure charge (electron) transfer; reactions involving both electron and solvated proton transfer; and acid-base reactions of pure solvated proton transfer. It illustrates the practical use of E-pH diagrams for temperature aqueous solutions and adsorbed species and in prediction of corrosion of nickel and copper.

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.

This article discusses the properties of aluminum surface and the applications of aluminum alloys. It explains the effects of trace elements on aluminum alloys. The article considers microstructural development of aluminum in terms of the surface and explains how it will impact corrosion resistance and surface treatment. It describes the thermodynamics of equilibrium oxidation processes and non-equilibrium corrosion processes. The article provides a discussion on aluminum oxidation under atmospheric and dynamic conditions. It presents the potential/pH (Pourbaix) diagram for aluminum under atmospheric and dynamic conditions. The article also explains the polarization effects during the formation of stable aluminum oxide under dynamic conditions. It concludes with information on the designation system for aluminum finishes.

This article focuses on the internal corrosion of iron and copper in potable water. It tabulates the corrosion and water-quality problems caused by materials in contact with drinking water. The article provides a theoretical description of the reduction-oxidation reactions in water to analyze the causes of corrosion of metals in contact with water. It discusses the Langelier saturation index and the Larson index for determining corrosion in potable water systems. The article describes the two major ways of mitigation against corrosion in potable water systems. The first is to line the pipe surface physically such that water and dissolved oxygen cannot reach the metal surface and the second is to add chemical inhibitors to alter water chemistry.

This article focuses on the testing and typical corrosion behavior of coating-substrate systems in aqueous solutions and humid aggressive atmospheres. It includes a short review of the fundamentals of corrosion, followed by a discussion of specific system behavior, electrochemical and laboratory accelerated tests, and simulated service tests. The article also contains examples of different types of corrosion damage and presents guidelines for improving corrosion resistance.

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.

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.

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 introduces the fundamental concepts of chemical thermodynamics and chemical kinetics in describing presolidification phenomena. For metallurgical systems, the most important thermodynamic variables are enthalpy and Gibbs free energy. A qualitative demonstration of the interrelationship between phase diagrams and thermodynamics is presented. The article discusses processes that generally limit the rates of chemical processes. These include nucleation of the product phase and interphase mass transport. The article provides a discussion on the dissolution of alloy with melting point lower than bath temperature and dissolution of alloy that is solid at bath temperatures.

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.

This article provides a general introduction to the kinetics of aqueous corrosion with an emphasis on electrochemical principles. It describes the thermodynamic basis for corrosion by determining the equilibrium potentials of electrochemical reactions from the Nernst equation. A corrosion process can be controlled by the electronic conductivity of passive films when the cathodic reaction occurs on the surface of the film and by activation control of corrosion. Passivation becomes thermodynamically possible when the corrosion potential exceeds the potential corresponding to the equilibrium between a metal and one of its oxides/hydroxides. The article schematically illustrates a current-potential or polarization curve for an anodic process.

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.

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.

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.

Metals can react chemically with oxygen when exposed to air. Essential to an understanding of the gaseous corrosion of a metal are the crystal structure and the molar volume of the metal on which the oxide builds, both of which may affect growth stresses in the oxide. This article presents crystal structures and thermal properties of pure metals and oxides in a tabular form. The free energy of reaction, which describes the oxidation process of a pure divalent metal, is presented. The article illustrates the Richardson-Jeffes diagram, which is used in the determination of the standard Gibbs energy change of formation of oxides and the corresponding dissociation pressures of the oxides as a function of temperature. It demonstrates the Kellogg diagram which shows stability range in more complicated multioxidant systems. The article explains the determination of partial pressures of gas mixtures and partial pressures of volatile oxidation products.