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.

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.

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.

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.

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 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.

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 addresses electrochemical methods for instantaneous rate determination and threshold determination as well as nonelectrochemical methods that can determine incremental or cumulative rates of corrosion. Electrochemical methods for the study of galvanic corrosion rates and localized corrosion and evaluation of corrosion rates under paints are also discussed. The article describes nonelectrochemical methods that can determine incremental or cumulative rates of corrosion. Methods presented include polarization methods, polarization resistance methods, electrochemical impedance methods, frequency modulation methods, electrochemical noise resistance, potential probe methods, cyclic potentiodynamic polarization methods, potentiostatic and galvanostatic methods, electrochemical noise (EN) methods, scratch-repassivation method, and electrochemical impedance spectroscopy (EIS) techniques. Gravimetric determination of mass loss, electrical-resistance methods, magnetic methods, quartz crystal microbalance method, solution analysis methods, and metrological methods are nonelectrochemical methods. The article presents an electrochemical test that examines the susceptibility of stainless steel alloys to intergranular corrosion.

This article examines constructive corrosion that occurs in power-generating devices, specifically batteries. It discusses the kinetic aspects of constructive corrosion in batteries and provides examples to illustrate how the kinetics of a corrosion process varies among different battery systems. The article illustrates the constructive roles played by corrosion at anodes in batteries through the use of a zinc anode in a mercury battery and a lithium metal anode in a rechargeable lithium battery. It also outlines the destructive role played by corrosion by illustrating shelf reactions in zinc-carbon batteries and lead grid corrosion in lead-acid batteries.

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 discusses four subsystems of the electrochemical machining (ECM) system: power source, electrolyte cleaning and supply system, tool and tool-feed system, and workpiece and workpiece-holding system. It describes the theory of ECM and provides information on the electrolytes used in ECM. The article reviews the methods associated with workpiece shape prediction. The procedures and integrated approach for the tool design in ECM are discussed. The article also explains the process control, capabilities, and the limitations of ECM. It concludes with information on the applications of ECM.

Chemical-mechanical planarization (CMP) of metals is described as mechanically accelerated corrosion, erosion corrosion, or metallic corrosion enhanced by wear. This article reviews the history, process, chemistry, electrochemistry, and defect issues for CMP. It provides an overview of CMP through a schematic illustration of CMP process equipment. The applications of CMP to tungsten and copper alloys are of prime interest in the semiconductor industry. The article discusses copper CMP and tungsten CMP in detail and analyzes polishing mechanism during CMP by application of direct current potentiodynamic polarization and alternating current impedance measurements. It concludes with information on chemically induced defects such as pitting corrosion, galvanic corrosion, and chemical etching.