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Electrochemistry Encyclopedia

Jerome Kruger The Johns Hopkins University Baltimore, MD 21218, USA (April, 2001)

Ulick R. Evans, the British scientist who is considered the "Father of Corrosion Science", has said that "Corrosion is largely an electrochemical phenomenon, [which] may be defined as destruction by electrochemical or chemical agencies...". Corrosion in an aqueous environment and in an atmospheric environment (which also involves thin aqueous layers) is an electrochemical process because corrosion involves the transfer of electrons between a metal surface and an aqueous electrolyte solution. It results from the overwhelming tendency of metals to react electrochemically with oxygen, water, and other substances in the aqueous environment. Fortunately, most useful metals react with the environment to form more or less protective films of corrosion reaction products that prevent the metals from going into solution as ions. While the term corrosion has in recent years been applied to all kinds of materials in all kinds of environments, this article will only consider the electrochemistry of corrosion of metals and alloys in aqueous solutions at ambient temperatures. Electrochemical corrosion occurring under such conditions is a major destructive process that results in such costly, unsightly, and destructive effects as the formation of rust and other corrosion products, the creation of the gaping holes or cracks in aircraft, automobiles, boats, gutters, screens, plumbing, and many other items constructed of every metal except gold. Systems such as boiling water nuclear reactors involving aqueous solutions are also examples of electrochemical corrosion but will not be covered. This article will also not cover the non-electrochemical process termed high temperature oxidation, a destructive process which is the exposure of a metal or alloy to high temperatures in a gaseous environment (usually including oxygen or gases with sulfur containing compounds)

inflammation caused by corrosion products in the tissue around implants. automobiles. hip joints. Technological effects The economic consequences of corrosion affect technology. economy was $70 billion.2% of the gross national product. This technologically important corrosion process leads to the failure of such applications as gas turbines. a difference in electrode potential between phases or heterogeneities in an alloy can lead to hot corrosion which has electrochemical features similar to that of the condensed aqueous films involved in atmospheric corrosion. and fracture of weightbearing prosthetic devices. An example of the latter is the use of metallic hip joints. health. Consequences of corrosion Corrosion has many serious economic. it must be pointed out that if the high temperature oxidation process results in the formation of salt layers that melt at the high temperatures used. The situation has improved in recent years. which can result in severe injuries or even loss of life. because they will last longer. and cultural consequences to our society. A great deal of the development of new technology is held back by corrosion problems because materials are . plates. which can alleviate some of the problems of arthritic hips. technological.S. heat exchangers. and other implants. Safety is compromised by corrosion contributing to failures of bridges. or 4. and many others that operate at high temperatures. but corrosion continues to create problems. However. gas pipelines etc. The most extensive of these studies was the one carried out in the United States in 1976 which found that the overall annual cost of metallic corrosion to the U. Economic effects Studies in a number of countries have attempted to determine the national cost of corrosion. pacemakers. – the whole complex of metal structures and devices that make up the modern world. so that hip joints which were was at first limited to persons over 60 are now being used in younger persons. we may compare it to another economic impact everyone is worried about – the importation of foreign crude oil. Safety effects An even more significant problem is corrosion of structures. aircraft. safety. To get a feeling for the seriousness of this loss.where much thicker layers of corrosion products are formed. New alloys and better techniques of implantation have been developed. Health effects Recent years have seen an increasing use of metal prosthetic devices in the body. such as pins. Examples include failures through broken connections in pacemakers. which cost $45 billion in 1977.

higher pressures. Examples of these reactions are given in the Appendix. Several cathodic reactions are possible depending on what reducible species are present in the solution. which require materials to withstand highly concentrated solutions of corrosive salts at high temperatures and pressures. The anodic reaction is the dissolution of the metal to form either soluble ionic products or an insoluble compound of the metal. Another example. and geothermal systems. involves overcoming such corrosion problems as sulfide stress corrosion. and the vast array of difficulties involved in working in the highly corrosive marine environment. inside the world's museums conservators and restorers labor to protect cultural treasures against the ravages of corrosion or to remove its traces from artistically or culturally important artifacts. in many cases simultaneously. Corrosion problems that are less difficult to solve affect solar energy systems. Because these anodic and cathodic reactions occur simultaneously on a metal surface. microbiological corrosion. Corrosive processes will accelerate the deterioration of precious artifacts such as those in Venice by the highly polluted environments that now are prevalent in most of the countries of the world. Typical reactions are the reduction of dissolved oxygen gas. . they create an electrochemical cell of the type shown in Figure 1. or the reduction of the solvent (water) to produce hydrogen gas. Likewise. which require alloys to withstand hot circulating heat transfer fluids for long periods of time. corrosion is a limiting factor preventing the development of economically or even technologically workable systems. usually an oxide. Electrochemistry of corrosion The same metallic surface exposed to an aqueous electrolyte usually possesses sites for an oxidation (or anodic chemical reaction) that produces electrons in the metal. and more highly corrosive environments. In many of these instances. Cultural effects International concern was aroused by the disclosure of the serious deterioration of the artistically and culturally significant gilded bronze statues in Venice. higher temperatures. Italy.required to withstand. and a reduction (or cathodic reaction) that consumes the electrons produced by the anodic reaction. These "sites" together make up a "corrosion cell". the drilling for oil in the sea and on land.

grain boundaries. at those sites exposed to the environment containing the lower oxygen content – differential aeration corrosion. (iii) there can exist variations over the surface of oxygen Fig. such as water. for example.The sites where the anodic and cathodic reactions take place. (v) variations in the homogeneity of the metal surface. due to the presence of inclusions. are not chemical but are electrochemical. (iv) or similarly. if two metals are in contact. The process occurring at the anodic sites is the dissolution of metal as metallic ions in the electrolyte or the conversion of these ions to insoluble corrosion products such as rust. (ii) they can be adjacent or widely separated so that. This driving force is the difference in potential between the anodic and cathodic sites. corrosion tendencies A driving force is necessary for electrons to flow between the anodes and the cathodes. the anodes and the cathodes of the corrosion cell. disturbed metal. The electrochemical cell set up between concentration in the environment that anodic and cathodic sites on an iron surface result in the establishment of an anode undergoing corrosion. must be equal or a buildup of charge would occur. one metal can be the anode and the other the cathode. can lead to the establishment of anodic and cathodic sites. variations in the concentration of metal ions or other species in the environment. Driving force. The potential is a measure of this tendency. leading to galvanic corrosion of the more anodic metal. The rates of electron production and consumption. the use of chemical equilibria is of minimal use for studying aqueous corrosion. and other causes. 1. are determined by many factors: (i) they are not necessarily fixed in location. arising because of the spatial orientation of the corroding metal and gravity. or finally. The flow of electrons between the corroding anodes and the non-corroding cathodes forms the corrosion current. different phases. This is the destructive process called corrosion. A useful way to study the relation of potential to corrosion is through the use of an electrochemical equilibrium diagram – called the "Pourbaix . of course. This difference exists because each oxidation or reduction reaction has associated with it a potential determined by the tendency for the reaction to take place spontaneously. the value of which is determined by the rate of production of electrons by the anodic reaction and their consumption by the cathodic reaction. Electrochemical equilibria: oxidation and reduction Since most corrosion reactions occurring in the presence of a liquid.

but lower. Pourbaix. Because even though the tendency for corrosion may be high. in some cases. . corrosion rates While it is necessary to determine corrosion tendencies by measuring potentials. through potential and pH measurements. The potential – pH (Pourbaix ) drastically affect the rate of corrosion. or (iii) in a region where the tendency for corrosion may still exist but where there is also a tendency for a protective or passive film to exist. Thus. Equations [2] or [3]) and hydrogen evolution (Appendix. and. Lines drawn parallel to (a). Such a film can Fig. and thus corrosion may not be a problem. whether (i) a metal surface is in a region of immunity where the tendency for corrosion is nil. or corroding regime and also to estimate the influence of limited or ready access of oxygen on the corrosion process. The simplified Pourbaix diagram for iron is shown in Figure 2. it will not be sufficient to ascertain whether a given metal or alloy will suffer corrosion under a given set of environmental conditions. the rate of corrosion may be very low. Equation [4]). a parameter also of great importance to corrosion processes. The potential plotted is that of iron as measured against a standard hydrogen reference electrode. some idea can be gained about the tendency of a metal to be in an immune. Kinetics. the potential of a specimen can give some indication of the oxygen concentration in the environment.Diagram" – developed by M. Lines (a) and (b) on Figure 2 represent oxygen reduction (Appendix. The Pourbaix diagram enables the determination. practically stop it (see Passivity and breakdown). equilibrium diagram for iron. by means of potential and pH measurements. 2. passive. (ii) in a region where the tendency for corrosion is high. The differences in oxygen concentration between different sites on a metal lead to the differential aeration corrosion mentioned above. it plots potential against pH. They are a measure of the concentration of oxygen or hydrogen in solution and show the variation of potential with pH for solutions in equilibrium with one atmosphere of either oxygen or hydrogen. would give the variation of potential with pH for a solution containing less oxygen than that represented by (a). By means of the Pourbaix diagram. respectively.

The values of the exchange current densities for the . film formation. inherent rate of the electrode reaction). The former is called concentration polarization the latter activation polarization. they should intersect.Corrosion rates are determined by applying a current to produce a polarization curve (the degree of potential change as a function of the amount of current applied) for the metal surface whose corrosion rate is being determined. a negative direction signifies that it is cathodically polarized. Evans diagrams (produced from the part of the polarization curve and by extrapolation shown in Figure 3. polarization measurements can thereby determine the rate of the reactions that are involved in the corrosion process – the corrosion rate. ease of release of electrons. and (c) control by a density "io" (that is expressing the mixture of both. It is possible to extrapolate the anodic and cathodic linear portions of the polarization curves to the corrosion potential "Ecorr". where. The value of the current at their intersection will be the rate of corrosion "icorr" expressed in current density. The degree of polarization is a measure of how the rates of the anodic and the cathodic reactions are retarded by various environmental (concentration of metal ions. 4. The be mainly controlled: (a) control by the "intercept" is proportional to the reactions on the anode. oxygen reduction or hydrogen evolution). in solution) and/or surface process (adsorption. "Eo. under ideal conditions.) factors. The values of these characteristic constants in the Tafel equation depend on the metal and the environment under consideration. In Figure 3 the potential "E" is plotted as a function of the logarithm of the current density "i".c" are the equilibrium potentials for the reactions under consideration (anodic or cathodic). etc. On this figure. Hence. dissolved oxygen.a" and "Eo. (b) control by the logarithm of the exchange current reactions on the cathode. Figure 3 shows anodic and cathodic polarization curves that represent anodic reactions (like metal dissolution) or cathodic reactions (for example. etc. illustrating their "intercept" when extrapolated to three main ways in which the corrosion rate can the equilibrium potential. When the potential of the metal surface is polarized by the application of the current in a positive direction. The variation of potential as a function of current (a polarization curve) allows one to study the effect of concentration and activation processes on the rate at which anodic or cathodic reactions can give up or accept electrons. it is said to be anodically polarized. When the corrosion reactions are controlled by activation polarization. polarization behavior will be a straight line on this plot following the Tafel equation (see also the Appendix). The "Tafel lines" are characterized by the "slope" of the linear Fig. as is frequently observed.

because of the presence of a protective film whose nature is the source of the controversy.c" is constant): the larger the "io. determine whether the anodic. it is sufficient to characterize passivity as the conditions existing on a metal surface.c" (but assuming. Two types of breakdown processes exist: electrochemical breakdown where many studies have found that breakdown takes place at a potential above a specific "breakdown potential. Considerable controversy still exists about what process is responsible for the existence of the phenomenon of passivity. and stress corrosion (see below). Parts of the extrapolations shown in Figure 3 produce the diagrams (Evans diagrams) shown in Figure 4. Competing with the passive film breakdown process is the passive film repassivation process. This is illustrated with an example of using two values of "io. Passivity and the breakdown of passivity Since both driving force (corrosion-tendency) and kinetic (corrosion-rate) considerations are crucial in determining the extent of corrosion of a metal surface.c" – the larger the corrosion rate. To be effective. even though active corrosion would be expected from driving force (corrosion-tendency) considerations. An effective film is one that resists the breaching (called the breakdown) of the passive film. Thus. for sake of simplicity." and mechanical breakdown which occurs when the passive film is ruptured as a result of stress or abrasive wear. The relative values of the "slopes" of the anodic or cathodic polarization curves. pitting. The many mechanisms proposed for chemical breakdown are based on two models. intergranular. Breakdown processes lead to the forms of localized corrosion that are some of the major sources of corrosion failures. "icorr" (see Figure 3). cathodic. a crucial factor controlling the rate is the existence of the phenomenon of passivity for certain metals and alloys.cathodic and anodic reactions have a profound effect on the corrosion rate. a passive film must provide a protective barrier that keeps the corrosion current on a metallic surface at a low enough value so that the extent of corrosion damage is minimized. They cause the disruption of the passive film and thus expose discrete bare sites on the metal surface to an environment where the tendency for attack is very high. Evans diagrams are used extensively by corrosion scientists and engineers to evaluate the effect of various factors on corrosion rates. For the purposes of this discussion. or both reactions control the rate of the corrosion process. even though many studies were carried out to develop a better understanding of it. that markedly lower the rate of corrosion. They are (i) Adsorbed Ion Displacement Models and (ii) Ion Migration or Penetration Models. each having many variations. It should be noted that all breakdown mechanisms involve a damaging species. such as stainless steels and titanium. crevice. a damaging species abundantly available in nature. that "Eo. an effective alloy for resisting localized corrosion would be one whose surface not only forms a passive film that resists the process leading to breakdown but . one of the major species causing breakdown of passivity is the chloride ion. Unfortunately.

Equation [5]). First. Since the surface area of the pit is a very small fraction of the cathodic surface area. all of the anodic corrosion current flows to the extremely small surface area of the breakdown initiation site.also is capable of repassivating at a rate sufficiently high so that. chloride or another damaging negative ions diffuse into the pit to maintain charge neutrality. and penetration of a metal structure bearing only a few pits can be rapid. contains a large concentration of damaging ions and metallic ions. This covering traps the solution in the pit and allows the buildup of positive hydrogen ions through a hydrolysis reaction (Appendix. Thereby the rate of pit growth accelerates. Then. or places where environmental variations exist. but some possibilities are at scratches. The sites where pits initiate are not completely understood. and contains a low oxygen concentration. two new conditions develop. The pit grows if the high current density – the area of breakdown initiation is exceedingly small – involved in the repassivation process does not prevent the formation of a large local concentration of metal ions produced by dissolution at the point of initiation. the anodic current density becomes very high. Crevice corrosion . and the cathode of the cell is the non-pitted surface. surface compositional heterogeneities (inclusions). Pitting corrosion The initiation of a pit occurs when electrochemical or chemical breakdown exposes a small local site on a metal surface to damaging species such as chloride ions. once breakdown has occurred. If the rate of repassivation is not sufficient to choke off the pit growth. the metal ions produced by the breakdown process are precipitated as solid corrosion products (such as the Fe(OH)2. the repassivation becomes considerably difficult because the solution in the pit is highly acidic. Consequently. Types of corrosion The breakdown and repair of passivity process just described is involved in many but not all of the various types of corrosion. The pit is the anode of an electrochemical corrosion cell. exposure to a corrosive environment is minimal. Appendix. Equation [7]) which usually cover the mouth of the pit. Thus.

Corrosion fatigue has a somewhat similar mode of failure to SCC. It mainly differs from SCC in that it involves situations where the stress is applied cyclically rather than as a static sustained tensile stress. and corrosion fatigue Stress corrosion cracking (SCC) is a form of localized corrosion which produces cracks in metals by the simultaneous action of a corrodent and tensile stress. hydrogen embrittlement. The environment that eventually forms in the crevice is similar to that formed under the precipitated corrosion product that covers a pit Fig. The electrochemical cell between the exterior and the interior environments of a crack is similar to that described above for a crevice. An idealized picture of the environment (Figure 5). Similarly. A typical example of crevice corrosion is the crevice formed at the area between two metal surfaces in close contact with a gasket or another metal surface. the breakdown of the passive layer on a metal surface in SCC is generally ascribed to mechanical causes but many suggest that electrochemistry is a significant factor because it controls the rate of repair of the passive layer ruptured by mechanical stress. an electrochemical that develops in a crevice by the corrosion cell corrosion cell is formed from the couple produced on iron by an anode in a crevice and between the unshielded surface and the crevice interior exposed to an a cathode outside of the crevice. usually chloride ions. Because of the necessity for the application of stress. adsorption of damaging species. Such surrounding environments contain damaging corrosion species. This combination of being the anode of a corrosion cell and existing in an acidic. With both corrosion fatigue and SCC. hydrogen damage. 5. high-chloride environment where repassivation is difficult makes the crevice interior subject to corrosive attack. environment with a lower oxygen concentration compared with the surrounding medium.Crevice corrosion results when a portion of a metal surface is shielded in such a way that the shielded portion has limited access to the surrounding environment. Intergranular corrosion . repassivation. Stress corrosion cracking. and electrochemical dissolution are to greater or lesser extents involved in determining susceptibility. the issues of film mechanical breakdown.

Galvanic (and thermogalvanic) corrosion Two metals having different potentials in a conducting electrolyte result in the more anodic metal usually being attacked by galvanic corrosion. This results in an increase in the concentration of the remaining components and selective leaching occurs. This kind of corrosion can be encountered in heat exchanger systems where temperature differences are common. is usually manifested in the progressive thinning of a metal part until it virtually dissolves away or becomes a delicate lace-like structure. after the most common example. dezincification. galvanic corrosion differs from the other forms of corrosion described previously in that the anodic and cathodic sites of the corrosion cell reside separately on the two coupled different metals comprising the corrosion cell. . while for the other forms of corrosion. Such a situation leads to thermogalvanic corrosion. that are distributed over a metal surface where the anodic and cathodic reactions take place. Such boundaries or the small regions adjacent to these boundaries can under certain conditions be considerably more reactive (by being more anodic) than the interior of the grains. while in practice metals invariably have films on their surfaces and are exposed to nonstandard environments. Uniform corrosion damage. the selective leaching out of zinc from brass. these potentials are not always reliable guides to the corrosion tendencies of the anodic member of a corrosion cell produced by two coupled dissimilar metals. the cathodes and anodes exist on the surface of the same metal. Another factor besides the coupling of two different metals that can lead to galvanic corrosion is a difference in temperature at separated sites on the same metal surface. activity).With the exception of metallic glasses. The resulting corrosion is called intergranular corrosion. not necessarily fixed in location. Equation [1]). since the standard potentials assume bare metal surfaces in a standard solution containing their ions at unit concentration (strictly speaking. This type of corrosion is also called parting and. The value for the differences in potential between two dissimilar metals is usually obtained from a listing of the standard equilibrium potentials for the various metals (for reactions of the type given in Appendix. Uniform corrosion Uniform corrosion results from the sites. However. It can result in a loss of strength of metal part or the production of debris (grains that have fallen out). sometimes called wastage. Selective leaching When one component of an alloy is removed selectively by corrosion because there exist differences in potential between different constituents of an alloy – a situation analogous to that of the galvanic corrosion of coupled dissimilar metals. Because of electrical contact between two different metals. the metals used in practical devices are made up of small crystals (grains) whose surfaces join the surfaces of other grains to form grain boundaries.

Zinc coatings. ceramic coatings such as porcelain enamels and glasses . Finally. The most widely used organic coatings are paints. Corrosion prevention The types of electrochemical corrosion just described can be prevented or controlled by utilizing the current understanding of the principles underlying corrosion processes. Pourbaix diagram for iron showing how and an applied current brings the corrosion protection can be achieved by using structure's potential into the passivity measures that bring a corroding system into region of the Pourbaix diagram. however. Some metallic coatings such as chrome plate provide a protective barrier because they are more corrosion resistant than the metals they protect. which produce more effective protective films that resist breakdown and repassivate rapidly. Three corrosion control measures are based on electrochemical driving force as shown in the Pourbaix diagram given in Figure 6: (i) Cathodic protection – proposed to the British Admiralty for corrosion protection of copper-sheathed ships by Sir Humphry Davy in 1824 – provides corrosion control by making the structure to be protected the cathode of a corrosion cell by bringing the potential of the structure into or near the immunity region of the Pourbaix diagram. because it has a greater tendency to corrode than the metal to which it is applied. (ii) Coatings are an artificial barrier to the corrosive environment on a metal surface as contrasted to the naturally formed barrier that a corrosion resistant alloy provides. cathodically protects it. and greases. the electrochemical processes for the types of corrosion described above take place. 6. Environment modification by changing the pH to bring the structure to be protected into either the immunity or passivation regions. act in the opposite manner. (ii) Anodic protection makes the structure to be protected an anode Fig. This coating.Erosion corrosion Erosion corrosion result from the disruption of protective passive films by erosive or abrasive processes. This understanding has been the basis for the development of a number of corrosion prevention measures. and (iii) either the immunity or the passivity region. waxes. Once the protective or passive film is removed in an aqueous electrolyte. Other measures used to control electrochemical corrosion processes are the following: (i) Corrosion resistant alloys are developed to be corrosion resistant and contain constituents such as chromium. Other organic coatings include lacquers.

the concentration of which can. (iii) Corrosion inhibitors are added to the environment in which a given metal must be used to make the environment less corrosive. for example for iron metal is: [1] Fe ==> Fe2+ + 2eExamples of cathodic reductions involved in corrosion process are: [2] O2 + 2H2O + 4e.are used to protect metal surfaces by providing chemically resistant barriers. For example.==> H2 The cathodic reaction represented by Equation [2] exemplifies corrosion in natural environments where corrosion occurs at nearly neutral pH values. which are more stable than metals. The inhibitors act either by adsorbing on metal surfaces by providing barriers to the environment or by keeping the environment from becoming more corrosive by providing a buffering action. usually oxides. Equations [3] and [4] represent corrosion processes taking place in the acidic environments encountered in industrial processes or for the confined volumes (pits.==> 4OH[3] O2 + 4H+ + 4e. of course. Appendix Corrosion rections Some examples of the anodic and cathodic reactions that occur simultaneously on a metal surface in a "corrosion cell" are as follows. for a reaction producing insoluble hydroxide (sum of reactions [1] and [2]): [7] 2Fe + O2 + 2H2O ==> 2Fe(OH)2 .==> 2H2O [4] 2H+ + 2e. the sum of the cathodic and anodic partial reactions. The overall corrosion reaction is. become large if the H+ ions cannot readily move out from a confined volume. A typical anodic oxidation that produces dissolved ionic product. for a reaction producing dissolved ions (sum of reactions [1] and [4]): [6] Fe + 2H+ ==> Fe2+ + H2 or. uder certain conditions. crevices) where the pH can reach acidic values because of hydrolysis reactions such as: [5] Fe2+ + 2H2O ==> Fe(OH)2 + 2H+ This reaction produces H+ ions.

M. (http://electrochem. Smialowska (editors). T. Bertocci. Upper Saddle River NJ. Burstein (editors). 1974. "b" is the "Tafel slope" that provides information about the mechanism of the reaction. Corrosion (two volumes). 1988. Oxford. Pourbaix. Kruger. and "a" the intercept. Related articles Anodizing Archaeological use of electrochemistry Corrosion inhibition Bibliography • • • • • • • • • Principles and Prevention of Corrosion (2nd edition). A. Kruger (editors). A. Frankenthal and J. McGraw-Hill. Chichester . H. P. Passivity of Metals – a Materials Science Perspective. 1978. M. D. "International Materials Reviews" Vol. Corrosion and Corrosion Control: An Introduction to Corrosion Science and Engineering (3rd edition). West. A plot of electrode potential against the logarithm of the current density is called the "Tafel plot" and the resulting straight line the "Tafel line". The Electrochemical Society. and full text of some historical publications are also available in the Electrochemistry Science and Technology Information Resource (ESTIR). Atlas of Electrochemical Equilibria in Aqueous Solutions (2nd edition). 33. M. 1990. Ellis Horwood. proceedings volumes. New York. Wiley. W.cwru. 1980. Advances in Localized Corrosion: NACE-9. Isaacs.Tafel equation The Tafel equation is an early (1905) empirical relation between the overpotential of the electrode and the current density passing through the electrode: "a" and "b" are characteristic constants of the electrode system. Jones. Listings of electrochemistry books. Uhlig and R. Kruger. L. Boston. Pennington NJ. L. Basic Corrosion and Oxidation. 1985. and G. Revie. R. H. pp 113-129. H. Houston TX. 1994. Passivity of Metals. Prentice Hall. Houston TX. National Association of Corrosion Engineers. Corrosion Engineering (2nd edition). J. G. R. Jarman. and S. 1996. National Association of Corrosion Engineers. 1986. Fontana. U. S. New York. J. J. provides information about the rate constant (and the exchange current density) of the reaction. Butterworth-Heinemann. review chapters. Shreir.

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