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UMIST

Corrosion and Protection Centre

Module 0 – Introduction to Corrosion

Module Notes - Aqueous Corrosion

September 2003

Module 0, Aqueous Corrosion - Page 2 © 2002 - 2003, Corrosion and Protection Centre, UMIST

2003. UMIST. All rights reserved . the Corrosion and Protection Centre.This document is © 2002 .

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yet we do not observe any change in the potential of the zinc or the platinum. and consumed at the platinum. Aqueous Corrosion .Aqueous Corrosion Learning outcomes – at the end of the course you should be able to … • Use supplied E-log i diagrams to identify Ecorr and icorr • Use supplied E-log i diagrams to derives qualitative explanations of corrosion behaviour • Explain the differences between E-log i diagrams and polarisation curves • Deduce polarisation curves from E-log i diagrams • Use a supplied Pourbaix diagram to give qualitative predictions of corrosion behaviour One of the first reactions that a child studying chemistry at school will encounter is the reaction of a metal such as zinc with an acid. electrons are flowing from the zinc to the platinum. For example zinc with hydrochloric acid gives the reaction: Zn + HCl → ZnCl2 + H2 metal in solution in solution gas However this is not always what is observed. However we still find no platinum in solution. we find that an electrical current is flowing from the platinum to the zinc. the dissolution of the zinc and the generation of hydrogen gas: Zn → Zn2+ + 2 e- metal in solution in metal 2H + + 2e − → H2 in solution in metal gas Since the hydrogen is being evolved on the platinum as a result of the current passing into it from the zinc. and hydrogen gas is liberated. Corrosion and Protection Centre. Since the current is found to flow indefinitely. This is because platinum is a very non-reactive or ‘noble’ metal. If we replace zinc by platinum. We can see this by connecting two pieces of platinum to a © 2002 . we may conclude that electrons are being generated at the piece of zinc. If we connect an ammeter in the circuit between the zinc and the platinum. i. We can get further information about the nature of the corrosion reaction if we simultaneously expose zinc and platinum to the hydrochloric acid. and does not easily form salts. This can be explained in terms of the separation of the corrosion process into two parts. In this case hydrogen is seen to evolve on the surface of the platinum. with the two metals electrically connected together.e. no hydrogen is evolved.Page 1 . with the result that the metal goes into solution as a salt. we do not see any reaction. we might expect to get the same effect by artificially applying current to a piece of platinum. and we do not find any platinum in the solution.2003. UMIST Module 0.

more accurately. Module 0.Page 2 © 2002 .2003. In a similar way the potential must fall below the equilibrium potential for the reaction 2 H + + 2 e. the reaction is hydrogen evolution. the reaction is oxygen evolution: 2 H2 O + O2 + 4 e. and remove the electrons that are produced by the reaction. to which electrons are being supplied.→ H 2 before hydrogen evolution will be observed.→ H 2 At the positive electrode. Aqueous Corrosion . or cathode. At the negative electrode. 2 H + + 2 e. so the rate of the corresponding reaction will increase. this will repel the positively charged zinc cations away from the metal.R. Consequently the rate of this reaction increases as the potential of the metal becomes more positive. or anode. Figure 1 Evans diagram for the corrosion of zinc in acid A diagram of potential as a function of current associated with the reaction (Figure 1) is known as an Evans diagram (after U. → 4 OH - gas in metal in solution Having seen that the corrosion reactions are associated with the flow of electrical current. it is reasonable to suppose that the voltage (or. UMIST . from which electrons are being removed.battery. potential) of the metal with respect to the solution will control the rate of corrosion. Corrosion and Protection Centre. In this case gas is generated at both electrodes. as before. and indeed this is found to be the case. If we consider the corrosion of zinc again: Zn → Zn2+ + 2 e- as the potential of the metal becomes more positive. As the difference in potential is increased. Evans).

Corrosion and Protection Centre.Page 3 .7 Anodic reaction -0. and it is convenient to record the rate of reaction in terms of the current per unit area. Aqueous Corrosion . an electrode that is not electrically connected to anything else) must have zero total current.1 1 Current density Figure 2 E-log I diagram for the corrosion of zinc in acid The rate of an electrochemical reaction is proportional to the area of the metal reacting.00001 0. Then an E-log i diagram is a plot of potential versus current density for the individual electrochemical reactions. a corroding electrode will adopt the potential at which the cathodic and anodic currents are equal.1 icorr -0. leading to the point shown on Figure 2 at the corrosion potential.5 -0.1 1E-08 0. 0. the sources of this polarization are discussed further in the next section. then it can be seen that a freely corroding electrode (i.001 0. It is common (though not universal) to use I to refer to current and i to refer to current density. Consequently.9 -1.The change in potential associated with the change in the rate of the reaction is known as polarization. although strictly Evans plotted the current on a linear scale). Consequently it is common to plot a diagram of potential against log current (). If there is only one anodic reaction and one cathodic reaction.000001 0.1 Potential -0.2003.3 Ecorr -0. One of the main sources of polarization has the characteristic that the change in potential is proportional to the logarithm of the current. so the current of the cathodic reaction must be equal and opposite to the current of the anodic reaction. corresponding to a corrosion rate of icorr. The are three main sources of polarization: 1. although its magnitude may vary. This type of polarization will always be observed.0001 0. known as current density. since this is independent of the size of the electrode.3 Cathodic reaction 0.01 0. UMIST Module 0. The potentials resulting from activation polarization take the mathematical form © 2002 . known as an E-log I diagram (it is also often called an Evans diagram. Activation polarization results from the chemical processes necessary to make the reaction go faster in one direction than the other.0000001 0. Ecorr.e.

If the solution has a high resistance. and it will not be possible for the rate of reaction to exceed the rate at which oxygen arrives at the metal surface. and the rate is insignificant. the concentration of oxygen at the surface of the metal will rapidly be depleted as the reaction proceeds. Consequently iron corrodes in this case as a result of the reduction of oxygen. Resistance polarization results from the electrical resistance of components of the circuit involved in the reaction. although the evolution of hydrogen is thermodynamically possible. Concentration polarization occurs because the concentrations of chemical species taking part in the reaction change at the metal surface. and stainless steels rely on this for their corrosion resistance. We can see the effects of the various forms of polarization by considering some real corrosion processes: Zinc in acid In this case we see the reactions for both the dissolution of zinc and the evolution of hydrogen being controlled by activation polarization. Fortunately the evolution of hydrogen on zinc is very difficult. usually associated with the resistance of the solution. but for iron-chromium alloys the passive film may form very easily. For pure iron this condition is very difficult to maintain. or more particularly if there are high resistance films on the metal surface. the difference in the equilibrium potential for this reaction and for the dissolution of iron is very small.2003. in a reaction involving the reduction of oxygen. E = Constant × ln(current) 2. which restricts the rate of corrosion. UMIST . and little resistance polarization. and the corrosion rate may increase. 3. If the solution is stirred this helps to increase the concentration of oxygen at the surface of the metal. Iron in seawater In this case. where it is seen that the rate of reaction falls off rapidly. Module 0. and this reaction is strongly polarized.Page 4 © 2002 . Even so the rate of corrosion is rapid because of the large difference in equilibrium potentials. A second very important phenomenon can be seen in the shape of the curve for the dissolution of iron at high potentials. This is due to the formation of a film of oxide on the iron as the conditions move into the passive region of the Pourbaix diagram. the passage of current through this resistance will create a potential drop according to Ohm's law. Corrosion and Protection Centre. Because of the low solubility of oxygen in water this reaction is usually subject to significant concentration polarization. Aqueous Corrosion . For example. with only a small amount of concentration polarization.

Inhibitors Corrosion inhibitors are chemicals that are added to the environment to slow down the rate of corrosion.2003. thereby producing a large resistance polarization of the reaction. UMIST Module 0. There are several ways in which this can be achieved: Non-metallic Coatings By coating the surface of the metal with an insulating coating a large resistance can be inserted into the electrical circuit of the corrosion reaction. Cathodic protection By artificially lowering the potential of the metal the rate of the anodic. even though this will be at the expense of increasing the cathodic hydrogen evolution or oxygen reduction reaction. These usually act by interfering with either or both of the corrosion reactions. In essence all such methods are concerned with reducing the anodic metal dissolution current.We can also see how E-log i diagrams can be used to understand some of the more common corrosion control methods. Aqueous Corrosion . © 2002 . The coating will also act as a barrier to the diffusion of oxygen. Corrosion and Protection Centre. metal dissolution reaction can be reduced.Page 5 . and produce large concentration polarization of this reaction. increasing the activation polarization and/or the concentration polarization.

however. some workers prefer to plot the potential on the x axis. and thereby provide a self-healing non-metallic coating.Passivation One of the most effective methods of controlling corrosion is to use metals that can form a film of solid corrosion product. that there may be additional complications.5 Overall reaction -0. known as a ‘passive film’.1 Potential -0.01 0. Well-known examples of this are stain- less steels.0001 0. which is why it is more common to plot log i on the x axis. However if the film fails to repair this may lead to severe forms of localized corrosion. aluminium and its alloys and titanium. Note. Corrosion and Protection Centre. UMIST .Page 6 © 2002 . Modern measurements will normally control the potential of the specimen and observe the resultant current.2003. Module 0.3 Cathodic reaction 0.3 -0.7 Anodic reaction -0.001 0. Because the potential is the independent variable in this case. Aqueous Corrosion . so the expected relationship between the polarization curve and the E log i curve will be as shown in Figure 3.00001 0.1 1 Current density Figure 3 Relationship between E-log i diagram and polarization curve 1 This was how the measurement was made originally. which protects them against corrosion.000001 0.9 -1.1 1E-08 0. A polarization curve plots the effect of an applied current on the potential of a metal electrode1. such as changes in local pH and chemical composition at the surface of the electrode. In suitable conditions the passive film will reform if damaged. 0.0000001 0. The current that will flow in the external circuit will be the difference between the anodic and cathodic currents.1 -0.

However. © 2002 . cathodic reaction Zn 2+ + 2e − → Zn In the absence of any other reactions the rates of the forward and reverse reactions will be equal. while if the potential is below (more negative than) the equilibrium potential.concentration) while the Zn2+ cation is stable at lower pH. This has important implications for corrosion. metal deposition. Zn2+ ions will react with hydroxyl ions to form solid zinc hydroxide: Zn2+ + 2 OH. the metal is immune from corrosion. anodic reaction Zn → Zn2+ + 2 e- Reverse. Aqueous Corrosion . If the potential is above (more positive than) the equilibrium potential.2003. and it will to be possible for the metal to corrode.When a metal is immersed in a solution of its own ions (e. as it is thermodynamically impossible for it to corrode. then the metal will be deposited from the solution. so the zinc hydroxide is stable at higher pH (higher OH. as well as the anodic. the zinc hydroxide will form a passive film on the metal surface that will act as a barrier to further corrosion. In the latter situation. the corrosion of metals is also influenced by the solution pH. reaction is possible: Forward. UMIST Module 0. the reverse. There are three types of region on the Pourbaix diagram: 1. For example. the metal is said to be ‘immune’. As the pH is raised further. because the nature of the corrosion product depends on the pH. then the forward reaction will predominate and the metal will corrode. zincate is soluble. and will not therefore protect the metal against corrosion.→ ZnO22. the zinc hydroxide will eventually redissolve as zincate anions (ZnO22-): Zn(OH)2 + 2 OH. know as an E-pH or Pourbaix diagram.+ 2H2O Like the zinc cations. The chemical equilibrium is conventionally written as: Zn ⇌ Zn2+ + 2e- where the symbol ‘⇌’ implies simultaneous forward and reverse reactions.Page 7 . The regions where the various species are stable can be plotted on a map of potential against pH. Zn in Zn2+ solution). When the metal is the thermodynamically stable state. the zinc cations will dissolve in the solution and they will not therefore interfere with the corrosion process.→ Zn(OH)2 This will happen more easily when the concentrations of Zn2+ are higher. As well as being influenced by the applied potential. metal dissolution reaction.g. and the potential at which this occurs is known as the Equilibrium Potential. Corrosion and Protection Centre.

2. Example Pourbaix Diagrams Gold The region of thermodynamic immunity extends to above the line for oxygen evolution at all pH values. When the stable species is a soluble corrosion product. the metal is said to be active. UMIST .2e- (the right-hand reaction has been written in a slightly unconventional way to emphasize the equilibria with water).⇌ 2H2O ⇌ H2 + 2 OH. and consequently gold cannot corrode either with the reduction of oxygen in solution or the evolution of hydrogen. When the stable species is an insoluble corrosion product. and it is able to act as a cathodic reactant for all but the most noble metals. and will corrode relatively rapidly. On the Pourbaix diagram both of these equilibria produce a sloping line. Aqueous Corrosion . and will corrode relatively slowly. rather than combined with oxygen as an oxide. The equilibrium between water and hydrogen occurs at quite low potentials. This is the reason why gold is such a corrosion-resistant metal. We can describe the two main cathodic reactions as being concerned with the stability of water: O2 + 4 H+ + 4 e. Module 0. but in order to fully understand what is likely to happen. because the equilibrium potential is affected by the hydrogen ion concentration and is hence a function of pH. and only the more active metals are able to displace hydrogen from water and thereby suffer from corrosion in oxygen-free solution. Corrosion and Protection Centre. The equilibrium between oxygen and water occurs at rather positive potentials. The equilibria for the metal and the ions of the metal describe the anodic behaviour of a corroding system.2003. and why it is often found in the form of the metal in nature.Page 8 © 2002 . then the metal is said to be passive. we need to know about the thermodynamics of the cathodic reactions as well.. 3.

Aqueous Corrosion . It is protected from corrosion in alkaline solutions by a passive oxide film. Corrosion and Protection Centre. but can corrode with dissolved oxygen reacting to form hydroxyl ions. although it may be passivated at high potentials in weak acids. where significant corrosion may be expected. except possibly in very strongly alkaline conditions. Protected by a passive film of oxide in neutral solutions.Copper Cannot corrode with hydrogen evolution at any pH. UMIST Module 0.Page 9 . The corrosion product is soluble in acids and strong alkalis. © 2002 .2003. Aluminium Corrodes with oxygen reduction or hydrogen evolution in strongly acid or alkaline solutions. Iron Corrodes both with oxygen reduction and hydrogen evolution in acid and near neutral solutions. Protected by a passive film of aluminium oxide in near-neutral solutions.

Aqueous Corrosion .Module 0. UMIST .Page 10 © 2002 . Corrosion and Protection Centre.2003.