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half-cell reaction
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Series: ASM Handbook
Volume: 13A
Publisher: ASM International
Published: 01 January 2003
DOI: 10.31399/asm.hb.v13a.a0003579
EISBN: 978-1-62708-182-5
... of simplicity, the concentration of metal ions is maintained at unit activity; that is, each solution contains approximately 1 mole of metal ion per liter. The reactions for copper and zinc electrodes in each half-cell are given in Eq 9 and 10 . However, at equilibrium, metal dissolution and deposition occur...
Abstract
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.
Book Chapter
Book: Corrosion: Materials
Series: ASM Handbook
Volume: 13B
Publisher: ASM International
Published: 01 January 2005
DOI: 10.31399/asm.hb.v13b.a0003799
EISBN: 978-1-62708-183-2
... on the definition that the half-cell reaction: 0.5 H 2 ( g , 1 atm ) = H + ( aq , α = 1 ) + e − where H 2 (g, 1 atm) is hydrogen gas at one atmosphere pressure, and H + (aq, α=1) is hydrogen ion in aqueous solution at unit activity, and the reaction has a zero electrode...
Abstract
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.
Book Chapter
Series: ASM Handbook
Volume: 13A
Publisher: ASM International
Published: 01 January 2003
DOI: 10.31399/asm.hb.v13a.a0003709
EISBN: 978-1-62708-182-5
... OH, CH 3 NH 2 , N 2 H 4 , OH − , Cl − , CN − , CH 3 COO − , or [Zn(H 2 O) 3 OH] + . Electrochemical Cell It is convenient to consider an electrochemical cell as consisting of two independent electrode or half-cell reactions. The anode supports an anodic reaction, and the cathode supports...
Abstract
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.
Series: ASM Handbook
Volume: 13A
Publisher: ASM International
Published: 01 January 2003
DOI: 10.31399/asm.hb.v13a.a0003601
EISBN: 978-1-62708-182-5
... as the standard half-cell potential for the oxidation reaction (− E 0 in Table 1 , where E 0 is defined as the standard reduction potential, per common convention) and assuming m is then equal to M , the atomic weight of the electrode material (the metal). (Note that this is the same as coupling...
Abstract
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.
Series: ASM Handbook
Volume: 2A
Publisher: ASM International
Published: 30 November 2018
DOI: 10.31399/asm.hb.v02a.a0006522
EISBN: 978-1-62708-207-5
... can confidently be considered the electro-active component in the corrosion reaction. The reaction presented as Eq 2 can be separated into half-cell reactions as follows: (Eq 3) Al → Al 3 + + 3 e − anodic reaction (Eq 4) 6 H + + 6 e − → 3 H 2...
Abstract
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.
Series: ASM Handbook
Volume: 13A
Publisher: ASM International
Published: 01 January 2003
DOI: 10.31399/asm.hb.v13a.a0003592
EISBN: 978-1-62708-182-5
... of unit activity of protons saturated with hydrogen gas at a fugacity of one bar (14.5 psia). The half-cell reaction is H + (aq) + e − ↔ 1 2 H 2 (g). Any non-standard reversible hydrogen electrode with well-controlled H + activity and H 2 fugacity can also be used as a reference...
Abstract
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.
Series: ASM Handbook
Volume: 13C
Publisher: ASM International
Published: 01 January 2006
DOI: 10.31399/asm.hb.v13c.a0004135
EISBN: 978-1-62708-184-9
... and acuminate powder are hot pressed to form a solid piece). The ionic current in the cell is carried by the carbonate ion (CO 2– 3 ); therefore, the half-cell reactions at the anode and cathode are different from their PAFC counterparts. In this case, the cathode reaction is the reduction of oxygen...
Abstract
Batteries and fuel cells are popular forms of portable electrical energy sources. This article discusses the operation and corrosion problems inherent in batteries and fuel cells. Batteries are classified into two groups: primary or nonrechargeable batteries and secondary or rechargeable batteries. Fuel cells are classified into five types: phosphoric acid fuel cell (PAFC), solid polymer electrolyte fuel cell, alkaline electrolyte fuel cell, molten carbonate fuel cell (MCFC), and solid oxide fuel cell. The article presents reactions that occur during charging and discharging of lead-acid batteries, PAFCs, and MCFCs.
Series: ASM Handbook
Volume: 13A
Publisher: ASM International
Published: 01 January 2003
DOI: 10.31399/asm.hb.v13a.a0003604
EISBN: 978-1-62708-182-5
... nitrate solution at unit activity of Ag + . The choice of these electrodes (or half-cells) avoids the complexity that arises with many electrodes of commercial interest where oxides or other stable corrosion products form on the surface. It also avoids the complexity that arises with reactions involving...
Abstract
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.
Series: ASM Handbook
Volume: 10
Publisher: ASM International
Published: 15 December 2019
DOI: 10.31399/asm.hb.v10.a0006679
EISBN: 978-1-62708-213-6
... other ( Ref 12 ) Examination of corroded materials ( Ref 13 ) Determination of uranium and plutonium assays in nuclear fuel ( Ref 14 , 15 ) Electrochemical Cells The basic process of an electrochemical reaction requires an electrochemical cell comprised of two half cells...
Abstract
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.
Series: ASM Desk Editions
Publisher: ASM International
Published: 01 December 1998
DOI: 10.31399/asm.hb.mhde2.a0003169
EISBN: 978-1-62708-199-3
... be applied to oxidized forms of minerals with limited efficiency. The separation is based on whether or not mineral surfaces are wettable. The finely ground ore in an aqueous pulp is fed to a flotation machine with an impeller that provides vigorous agitation. Air is introduced into the cell either from...
Abstract
Ores, which consist of the primary valuable mineral, predominant gangue content, valuable by-products, and detrimental impurities, are extracted and directed to mineral processing. This article describes the mineral processing facilities, such as crushers, grinders, concentrators, separators, and flotation devices that are used for particle size reduction, separation of particles according to their settling rates in fluids and dewatering of concentrate particles. It explains the basic principles, flow diagrams, ore concentrate preparation methods, and equipment of major types of metallurgical processes, including pyrometallurgical, hydrometallurgical, and electrometallurgical processes.
Series: ASM Handbook
Volume: 2A
Publisher: ASM International
Published: 30 November 2018
DOI: 10.31399/asm.hb.v02a.a0006483
EISBN: 978-1-62708-207-5
..., magnetohydrodynamic forces, and cathode lining. It reviews the electrochemical reactions and thermodynamics for aluminum electrolysis standard Gibbs. The article also describes the cell operations and cell stability, as well as the key indicators of cell performance. It schematically illustrates the typical costs...
Abstract
This article describes the Bayer process for the purification of alumina. The process includes four major stages: digestion, clarification, precipitation, and calcination. The article discusses the aluminum electrolytic process in terms of aluminum electrolysis cell design, magnetohydrodynamic forces, and cathode lining. It reviews the electrochemical reactions and thermodynamics for aluminum electrolysis standard Gibbs. The article also describes the cell operations and cell stability, as well as the key indicators of cell performance. It schematically illustrates the typical costs producing aluminum in an aluminum smelter. The article also discusses various environmental issues, such as fluoride recovery; perfluorocarbons, polycyclic aromatic hydrocarbons, and sulfur emissions; spent pot lining; and development of inert anodes and CO2 emissions.
Series: ASM Handbook
Volume: 13A
Publisher: ASM International
Published: 01 January 2003
DOI: 10.31399/asm.hb.v13a.a0003586
EISBN: 978-1-62708-182-5
... overall electrochemical reaction can be algebraically divided into half-cell oxidation and reduction reactions in which there can be no net electrical charge accumulation ( Ref 17 ). For open-circuit corrosion in the absence of an applied potential, the oxidation of the metal and the reduction of some...
Abstract
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.
Series: ASM Handbook
Volume: 13A
Publisher: ASM International
Published: 01 January 2003
DOI: 10.31399/asm.hb.v13a.a0003581
EISBN: 978-1-62708-182-5
... is of this type, and its half-cell is: (Eq 12) Ag / AgCl , NaCl ( reference melt ) × LJ | ( melt under study ) The melt under study contains the same ions as the reference melt, but its concentration is variable. If the concentrations of the two melts...
Abstract
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.
Series: ASM Handbook
Volume: 13A
Publisher: ASM International
Published: 01 January 2003
DOI: 10.31399/asm.hb.v13a.a0003583
EISBN: 978-1-62708-182-5
... reduction: (Eq 4) 2 H + + 2 e − → H 2 The sum of two electrochemical half-reactions, one anodic (such as Eq 1 ) and one cathodic (such as Eq 2 ), is the overall corrosion reaction: (Eq 5) M + Ox → M n + + Red An example is the dissolution of iron...
Abstract
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.
Series: ASM Handbook
Volume: 13A
Publisher: ASM International
Published: 01 January 2003
DOI: 10.31399/asm.hb.v13a.a0003584
EISBN: 978-1-62708-182-5
... and C in Eq 32 Mechanisms of Cathodic Processes Cathodic processes are half-cell reactions necessary to allow corrosion reactions to take place. Indeed, the metal-dissolving anodic reaction is forcibly coupled to a cathodic counterpart that consumes the electrons produced by the anodic...
Abstract
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.
Series: ASM Handbook Archive
Volume: 10
Publisher: ASM International
Published: 01 January 1986
DOI: 10.31399/asm.hb.v10.a0001741
EISBN: 978-1-62708-178-8
... 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...
Abstract
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.
Series: ASM Handbook
Volume: 23
Publisher: ASM International
Published: 01 June 2012
DOI: 10.31399/asm.hb.v23.a0005666
EISBN: 978-1-62708-198-6
...). After particles are “eaten” by macrophages and other phagocytic-capable cells around implants, proinflammatory reactions occur, such as the possible activation of metal-reactive T-cells ( Ref 45 ), release of proinflammatory mediators ( Ref 36 , 52 , 53 , 54 , 55 ), cytotoxicity ( Ref 46 ), DNA...
Abstract
Implant debris is known to cause local inflammation, local osteolysis, and, in some cases, local and systemic hypersensitivity. The debris can be stainless steel, cobalt alloy, and titanium alloy, and soluble debris obtained due to wear from all orthopedic implants. This article addresses the biologic aspects of implant debris, both locally and systemically. It describes debris-induced local effects, particle-induced proinflammatory responses, and debris-induced systemic effects. The article concludes with a discussion on the four systemic effects of implant debris, namely, neuropathic effects, hypersensitivity effects, carcinogenicity, and general toxicity.
Series: ASM Handbook
Volume: 13A
Publisher: ASM International
Published: 01 January 2003
DOI: 10.31399/asm.hb.v13a.9781627081825
EISBN: 978-1-62708-182-5
Series: ASM Handbook
Volume: 13C
Publisher: ASM International
Published: 01 January 2006
DOI: 10.31399/asm.hb.v13c.a0004101
EISBN: 978-1-62708-184-9
.... Theoretical Considerations Electrochemical reactions are almost always the cause of corrosion of metals in contact with water. Metals in their elemental state are unstable in the presence of water and dissolved oxygen. For corrosion to occur, all the components of an electrochemical cell are needed...
Abstract
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.
Series: ASM Handbook
Volume: 20
Publisher: ASM International
Published: 01 January 1997
DOI: 10.31399/asm.hb.v20.a0002471
EISBN: 978-1-62708-194-8
....” When computing the metal/solution potential associated with the various half-cell reactions (e.g., Eq 1 , 2 , 3 , 4 , 5(a) , 5(b) , 6 , 7 ), it is conventional to formulate the reactions as reduction processes, for example: (Eq 12) Ni 2 + + 2 e − → Ni The “reduction...
Abstract
This article discusses the principles of corrosion and the basis of the various prevention measures that can be taken for different corrosion modes. It describes aqueous corrosion phenomena in terms of the electrochemical reactions that occur at the metal-environment interface. The article explains the specific forms of corrosion, including general corrosion, localized attack, and environmentally assisted cracking. It provides a discussion on the engineering aspects of design that can, without due care and attention, precipitate unexpected premature failure. The article reviews ways to improve corrosion awareness and prevent corrosion/degradation. It describes a life prediction method with an example of environmental degradation in light-water nuclear reactors. The article concludes with a discussion on the validation of life-prediction algorithms and their applications.