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Surfaces, Interfaces, and their Application

Introduction to corrosion

11
11.1

Introduction to corrosion mechanisms


Introduction

Rusting is probably the most familiar, but by far not the only form of corrosion. In contrast to mechanical damage, metal corrosion is a reaction of the material with its environment, starting from the surface of the metal. The actual corrosion reactions take place in a few nanometers thick metal/electrolyte interface, which does not correspond to the bulk phases on either the metallic or the electrolyte side. Furthermore, corrosion products may be present as a thin, well-adhering oxidic surface film, which protects the underlying metal from further corrosion (passive film). Studies of corrosion and passivation processes are thus closely related to surface analysis.

11.2

Basic concepts of corrosion

11.2.1. Definitions and interpretation The term corrosion stands for the reaction of a material with its environment, which leads to a measurable alteration of the material (properties, behavior), and may cause functional impairment (damage) of a component part or the whole system. In the case of metallic materials, the reaction is mostly electrochemical in nature. There are different ways of getting involved and treat questions related to corrosion. In this lecture, the focus is placed on the first point of view: 1) The corrosion specialist (scientist) things in terms of which physico-chemical reactions occur on the surface. Under corrosion problems he understands a need to investigate the type of corrosion responsible for this problem and for each type, formulate the fundamental electrochemical and chemical reactions that take places. ! For example: uniform corrosion, pitting, crevice corrosion, galvanic corrosion, stress corrosion cracking, hydrogen induced cracking. 2) The engineer is concerned by the appearance of the surface and possible damages. Under corrosion, he understands the surface modification induced by the corrosion reaction and will search for a way to avoid this (surface protection, other materials, modification of the environment). ! For example: holes due to pitting, corrosion products from uniform dissolution, cracks, oxidation, etc. 3) Usually if the corrosion is related to a large failure or a safety issue, there is an additional involvement of the insurances or the justice. Lawyers will determine the effective costs of a corrosion problem and the responsibility for these damages. ! This risk is for many companies the driving force for new development in the field of corrosion research and protection. For all the corrosion investigations, it is important to be aware that we are not dealing with a material but a system problem (Fig. 11.1), with the different parameters listed below that need to be considered as well as some interaction between them in the corrosion mechanisms description. - Choice of alloying element - Heat treatment - Microstructure 225 - Surface treatment

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Material

- Design - Mechanical bulk Stresses - Internal stresses ! Production - Surface stresses ! Tribology

Stresses

Environment

- Aggressive media - Temperature - Potential /Current - Microfluidics

Figure 11.1: The different influencing factors relevant for corrosion processes 11.2.2. Corrosion as a short-circuited galvanic element Corrosion processes on metallic materials are, apart from few exceptions, always electrochemical processes (Redox processes). The total reaction (Fig. 11.2) can be formally split up into two partial reactions: a) Oxidation reaction. This is the actual corrosion process, i.e. the metal dissolution (conversion of iron atoms from the metallic into the ionic state) the oxidation reaction takes place at the anode: Fe " Fe2+ + 2 eb) Reduction reaction. Due to the electro-neutrality principle, the electrons released during the anodic reaction must be taken up by a part of the environment adjacent to the metal, which is then reduced. This process is taking place at the cathode. If the corrosive agent is an acidic solution, protons are reduced forming hydrogen gas: 2 H+ + 2 e- " H2 (gas) In contrast, if oxygen, dissolved in (neutral or alkaline) electrolytes, interacts with the metal, oxygen is the oxidizing agent, i.e. it will be reduced: O2 + 2 H2O + 4 e- " 4 OHDue to the electro-neutrality (the electrons released from the iron atom need to be taken up by the oxidizing agent), the total corrosion process is composed of at least one oxidation and one reduction process, which must take place simultaneously (Fig. 11.2).

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Figure 11.2: Schematic of a corroding metal electrode. Formal breakdown into two half-cells of a galvanic element (oxidation reaction at the anode, reduction reaction at the cathode).

An anodic (positive) current corresponds to the iron dissolution; a cathodic (negative) current corresponds to the reduction reaction. Since metals (iron) are electrical conductors and the electrolyte is in general well electrolytically conductive, both the anodic and cathodic reaction constitutes a formally short-circuited galvanic element a current I (corrosion current) is flowing: I = !U / (Ra + Rc + Re) The intensity of the corrosion current is determined by the voltage difference !U of the galvanic element and the resistance of the anode Ra, the cathode Rc and the electrolyte Re. Thermodynamic and kinetic basic principles of the corrosion reaction allow the prediction of whether a corrosion reaction is possible or not (thermodynamics) and how fast it proceeds (kinetics). Both thermodynamic and kinetic considerations have to take both the metal as well as its environment into account.

11.2.3. Cost of corrosion The direct costs related to corrosion degradation are estimated for industrial countries to be around 3-4% of their GDP. For the USA, where a detailed analysis has been performed (NACE: National Association of Corrosion Engineers source), this represents 276 B$/ year = 3.1% of GDP.

1998 U.S. GDP B$8,790


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Figure 11.3: Overall corrosion costs and main industrial fields contributing to these costs. The measures to combat corrosion are of two natures 1) Non technical Increase awareness of the large corrosion costs and potential savings Change the misconception that nothing can be done about corrosion Change policies, regulations, standards, and management practices to increase corrosion savings Improve education and training of staff

2) Technical Advance design practices for better corrosion management Advance life prediction and performance assessment methods Advance corrosion technology through research, development, and implementation

11.2.4. Some preliminary considerations In relation with the measures to combat corrosion listed previously, it is necessary to stress two important facts: 1) Failure of a component is measurable and is usually documented correctly, but corrosion has initiated long before and the other consequences of corrosion processes are until now not enough investigated. One important example is the release of corrosion products that can be toxic in: - Medical application (implant, dentistry) - Environmental consideration (metal interaction with living organisms)

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a)

b)

c)

Figure 11.4: Corrosion of biomedical implants include the aspect of ionic leaching and accumulation in tissues: a) Cobalt-Chrome-Molybdenum hip implant, b) Co, Cr, Mo release in tissues as function of fixation, c) Histological section showing local accumulation of toxic ions. (54000 time more than the blank level) When implants are placed in-vivo (ASTM-F75-92 test, 8.5 months implantation in sheep), and if they are not completely fixed, an important amount of corrosion products will end up in the tissues or the blood and possibly generate allergies or even cancer, Fig. 11.4. On this figure, it is clearly visible that significant amount of Co, Cr, Mo are released from the implants surface (b) and that they also tend to locally accumulate (colored areas) in the tissue near the implant (c).

2) The choice of a wrong material because of an inadequate assessment of its corrosion resistance. Examples of common heard statements after damages are evidenced: I used a stainless Steel, it is corrosion resistant Aluminum does not corrode (the surface is never getting brown ?)

Most of these mistakes rely on the fact that it is not yet well understood in the industrial community that localized attack are the most critical ones and have to be analyzed seriously. Once, such an attack has started and is growing, an autocatalytic processes that is very difficult to control and identify takes place and will lead to later failure (Fig. 11.5). Another aspect that is important to mention is that these attacks do not always lead to visible corrosion products like rust. Formation of rust is in fact by far not the most dangerous corrosion process.

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Figure 11.5: Complexity of the localized corrosion phenomena, from the femtoampere current responsible from oxide breakdown and initiation to the macroscopic failure a) b)

Figure 11.6: Very local electrochemical measurements with a microcapillary cell (a) on different part of an MnS defect in 18Cr10Ni Stainless Steel (b) Corrosion prediction (lifetime and risk analysis) as well as materials development requires a detailed understanding of the corrosion susceptibility of any defects and microstructural part of a material or coating. New very local electrochemical methods with highest current resolution in the femtoampere range are necessary to assess oxide film stability and corrosion kinetics at small defects (Fig. 11.6). The example of the electrochemical polarization measurement on the interface between a MnS inclusion and the stainless steel shows where the highest corrosion susceptibility is found in this material. This specific steel system will serve as example for the discussion of localized corrosion mechanism and role of defects during the lecture. Corrosion processes and their characterization are complex mechanisms requiring interdisciplinary know-how and experimental techniques ranging from surface physics to mechanical testing. Investigation of biological interactions with metallic surfaces is a growing field of interest related to the ionic release problematic, but also to the fact that biofilm can modify significantly the passivation and corrosion mechanisms.

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Figure 11.7: Interdisciplinary approach necessary in corrosion science

11.3

Thermodynamic aspects related to corrosion

11.3.1. Corrosion of iron in non-oxidizing acids Thermodynamic considerations help to understand under which conditions, a corrosion reaction is possible. Even if the corrosion rates cannot be obtained yet, it is always necessary to analyze thermodynamic stability of each specific material-electrolyte interface. This procedure is especially important for new materials development and when the use of existing classical materials is extended in more complex media. Considering first a welldocumented case of the corrosion processes of iron in acidic media, the overall reaction is: Fe + 2HCl Partial reactions: anodic (oxidation) Fe " Fe2+ + 2eFeCl2 + H2 cathodic (reduction) 2H+ + 2e- " H2

Figure 11.8 schematically shows the different steps of a corrosion reaction at an electrode:

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Figure 11.8: Schematic description of corrosion processes of an iron bar in hydrochloric acid

The anodic as well as the cathodic partial reaction take place at the same electrode. This means that both partial reactions cannot be separated, thus no external voltage can be measured. The electrochemical cell is short-circuited. Nevertheless, a (theoretical) cell potential can be defined, which is calculated from the potentials of the anodic Ea and cathodic Ec partial reactions. The equilibrium potentials of a given reaction can be calculated with the aid of the standard potentials (tabulated) and Nernsts law: Ea = E0 + 2.3 RT/nF ln (cMe z+) Letters stand for:

Ea
0

E c Me z+ n

normal potential standard potential concentration of metal ions in solution number of transmitted electrons

Using the common logarithm, the equation can be written as: Ea = E0 + 0.059/n * log (cMe z+) 11.3.2. Meaning and application of the Nernst law The Nernst equation is the starting point for assessment of the thermodynamic stability of metallic materials in contact with electrolytes. It is also an important tool for the formulation of Pourbaix Diagrams routinely used to assess corrosion susceptibility. For this reason, it is important to first briefly repeat some general concepts of how and why the interface parameters such as chemical and electrochemical energies are related to a measured potential. This section is not meant at a derivation of fundamental thermodynamic concepts but should allow discussing their application in corrosion and also limitations and danger of the use of the Nernst equation. 232

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First a chemical equilibrium between three compounds (A,B,C) is considered:

The reaction can be described by the following change in Gibbs free energy #G resulting from the transformation of substance A and B to form a new compound C.

The chemical energy of each individual component i is divided in interaction energy with similar species (i0) and an interaction term with the solution (ln X).

Thermal oxidation containing only chemical interaction terms: In relation with the field of corrosion, such chemical equilibrium can be applied to thermal oxidation processes where the electrolyte is a gas. From the thermodynamic laws one can then derive whether a reaction can take place or not. #G < 0 : #G > 0 : the reaction takes place the reaction does not take place

Obviously, in this case, additional thermal energy will be produced if the reaction is spontaneously occurring or need to be furnished to the system. Gibbs free energy variation can, for example for oxide formation, be plotted as a function of temperature in the form of Ellingham diagrams, Fig. 11.9.

Following information can be obtained directly from Fig. 11.9: All the oxidation reactions that will occur spontaneously (negative Gibbs free energy). Titanium and Aluminum oxides are then clearly seen as being the most stable ones. Which reduction of oxides can take place through oxidation of a more reactive element. For example, alumina is more stable than most of other element when oxidation of alloys is considered.

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Figure 11.9: Ellingham diagram of Gibbs free energy evolution for different oxides as function

Electrochemical potential: The difference between a chemical equilibrium and an electrochemical interface is that in the latter case, charged species are moving in the system and especially across an interface such as an electrochemical double layer. For these species, an electrical energy component has to be added to their chemical interaction potential.

Chemical energy + Energy necessary to bring a charged species (z) on the surface The electrochemical Double layer Upon contact of two phases with freely moving charges, a boundary with accumulation of opposite charges on both sides is generated and this is called the electrochemical double layer. In general for corrosion processes, we are dealing with a solid / liquid interface. The excess charges create a potential gradient through this interface (the electrode potential), Fig. 11.10.

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Figure 11.10: Electrochemical double layer structure with charge separation inducing an electrical energy component in the measured potential The very high electronic conductivity of the metals results in very narrow charge separation on this side of the interface. In the electrolyte, the charge distribution extends far inside the liquid phase. There is a distinction between the well-defined Helmoltz plane (OHP) that is resulting from the ordering of a monolayer of charged species (water dipoles, ions) and is responsible for most of the potential variation in concentrated electrolytes. The diffuse part (Gouy-Chapman) is resulting from charged molecules ordering in the solution and is playing a more important role in very dilute electrolytes for examples. In semiconductors, a diffuse layer (space charge layer) can also develop on the solid side of the interface.

In summary: the electrical double layer induces potential differences at the solid/liquid interface determining the thermodynamic stability and kinetic evolution of an electrochemical reaction. An important fact about electrochemical equilibrium is that no energy (at constant temperature and volume) can be generated by single processes. As a consequence, this means that the Gibbs energy will not change during the process:

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Lets now consider, what this means for a simple electrochemical equilibrium. O indicates the oxidized species, R the reduced one.

L: liquid M: metal
First, it is necessary to emphasize the difference between a corrosion and a classical electrochemical process and their characterization, Fig. 11.11. In a corrosion process, thermodynamic equilibrium is initially totally undefined, because of the absence of oxidized species in solution. It is furthermore constantly varying during the process because of the modification of the concentration in solution and of the electrode. For this reason, electrochemists prefer to investigate charge transfer reactions between two species in solution on a conducting inert electrode. This difference should always be kept in mind when applying electrochemical concepts/methods on corroding interfaces. It is often not possible to perform data interpretation to the same accuracy/precision in the field of corrosion and some cyclic electrochemical methods are meaningless. a) b)

Figure 11.11: Corrosion (a) versus electrochemical processes (b) on electrodes

For this reason, the equilibrium between two species in solution will first be considered from an electrochemical point of view, like for example different iron ions.

With following Gibbs energy expression

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The expression can be developed with all the single components. For each ionic species involved, there are two chemical terms: the interaction with similar species and the logarithmic expression of the interaction with other species in solution. For the electrons e-, there is only a chemical energy term in the solid. All the species have to cross the electrochemical double layer; the electrical term is then constituted by the potential drop through this interface multiplied by the species charges.

With the X= C / C0

C0 : 1mol/L (standard conditions)

It is then straightforward to separate electrical and chemical energy terms. n is than the difference between the specific charges of the oxidized ZO and reduced ZR ionic species.

F($ M - $ L) is the work necessary to transfer one Mol of electrons (1 Farad) through the Metal-Electrolyte interface. The potential established through the solid-liquid interface E= F($ M - $ L) is often the only measurable quantity in electrochemical systems and is directly related to chemical interaction information. This relation between chemical and electrical energy is nothing else then the Nernst equation:

Some important comments: Measured potentials are directly related to chemical interaction energies, so that there is only one potential value for a given electrochemical equilibrium process. The sign inversion of the potential often found in chemistry and engineering textbooks is just a convention used to determine galvanic cell potentials between electrodes. Information about the chemical stability of compounds can be derived from potential measurements. This fact is of practical importance especially for heterogeneous electrodes (real materials) where local determination of chemical energy is much more difficult than measurement of a potential.

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Reference electrode The measured electrode potential is directly related to the chemical energy as mentioned previously but is difficult to assess in an absolute way. For this reason, the electrochemical potential scale is always measured versus a reference electrode. The universal one, is the so called Standard hydrogen electrode (SHE) and all the other reactions are related to this potential value in handbooks. This electrode has however a real disadvantage, because it involves hydrogen gas. In practice, hydrogen at a pressure of 1 bar should be bubbled near the platinum electrode to guarantee a constant potential, Fig. 11.12. This is not very convenient and is therefore seldom used. The better alternative is to use a so called Standard Calomel electrode (SCE) where a mercury-chloride stable salt is in equilibrium with its anionic species. This electrode, called of the second kind, has the advantage to be very stable because of the salt stability and the fact that it can be used with a saturated chloride solution. Currently, another alternative used to replace to toxic mercury is the silver-chloride electrode working on the same principle.

a)

b)

Figure 11.12: Reference electrodes: a) Universal Standard hydrogen electrode, b) Practically used Standard Calomel electrode 11.3.3. Electrochemical series of metals For an electrochemical process with multiple reactions, !G is then replaced by the cell potential U (!G = nF!U), which can be calculated from the equilibrium potentials Ea und Ec of the anodic and cathodic partial reactions, respectively: 238

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!U = Ea Ec The standard potentials E0 are tabulated for standard conditions (metal immersed in a solution of its metal ions with the concentration cMe z+ = 1 Mol/l): Partial reaction Au " Au3+ + 3eAg " Ag+ + eCu " Cu2+ + 2eH2 " 2H+ + 2ePb " Pb2+ + 2eNi " Ni2+ + 2eFe " Fe2+ + 2eZn " Zn2+ + 2eAl " Al3+ + 3eMg " Mg2+ + 2eE0Me/Me z+ (Volt) + 1.50 + 0.80 + 0.34 0.00 - 0.13 - 0.25 - 0.44 - 0.76 - 1.66 - 2.37 E'Me/Me z+ (Volt) with cMe z+ = 10-6 mol/l + 1.38 + 0.44 + 0.16 - 0.30 - 0.42 - 0.61 - 0.94 - 1.78 - 2.54

- "Precious" metals possess standard potentials E0 > 0, meaning very strong metallic bonds. The cell potential !U is positive in combination with a hydrogen electrode, i.e. no corrosion takes place in non-oxidizing (oxygen free) acids. - "Non-noble" metals possess standard potentials E0 < 0, meaning that electron can be removed easily. The cell potential !U is negative in combination with a hydrogen electrode, i.e. corrosion in non-oxidizing acids is possible. The standard conditions cj = cj 0 are usually not fulfilled in the case of corrosion processes as mentioned before, i.e. the corrosive agent contains only traces of metal ions, e.g. cMe+ = 10-6 mol/l. It is better for practical calculations to use the calculated value of the potential Ea (see column 3 in table above). 11.3.4 Electrochemical series of nonmetals

The application of Nernsts equation to cathodic partial reactions results in the normal potentials of the partial reactions. Example: Hydrogen electrode H2 + 2H2O " 2H3O+ + 2e(anodic notation)

For a hydrogen partial pressure pH2 = 1 and room temperature, the hydrogen electrode potential is only dependent on the pH-value:

Example:

Oxygen electrode 4OH- " O2 + 2H2O + 4e-

(anodic notation)

For an oxygen partial pressure pO2 = 1 bar and room temperature, the oxygen electrode potential is only dependent on the pH-value:

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The following table gives an overview of the normal potentials of some electrode reactions, which are important as cathodic partial reactions in corrosion processes " electrochemical series of nonmetals: Partial reaction 2Cl- " Cl2 + 2e2Cr3+ " Cr2O72- + 7H2O + 14H+ + 6e2Br- " Br2 + 2eNO + 2H2O " NO3- + 4H+ + 3eFe2+ " Fe3+ + e4OH- " O2 + 2H2= + 4eCu " Cu2+ + 2eH2 " 2H+ + 2eE0 (Volts) + 1.36 + 1.33 + 1.07 + 0.96 + 0.77 + 0.44 + 0.34 0.00

11.4. Potential pH diagram (Pourbaix diagram)


The thermodynamic equilibrium data can be presented in graphical form to allow easier interpretation of the corrosion susceptibility of materials. These diagrams were first introduced by Marcel Pourbaix (in 1945) Most of the metal ions react with water and as a first step with OH- to produce solid oxide / hydroxide corrosion products that can result in some cases in the formation of a very protecting surface layer (passivation). Using single Nernst equation turned out to be very non intuitive. Pourbaix Diagrams present similar information about the surface stability of an element but as a function of two very important parameters (applied potential, pH) because: It is always necessary to determine the corrosion behavior of the metal as a function of the solution composition and of a broad pH range. Applied potential is also an essential parameter because the surface can be easily polarized by the presence of a cathodic reaction

Pourbaix diagrams provide information about possible equilibria between metal, solution with dissolved metal ions, and stable oxygen compounds, as a function of the pH-value and the electrode potential.

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Figure 11.13: Pourbaix Diagram of iron in water with different types of reaction and oxide formed as function of the potential. Different reaction types and equilibrium are included in the diagrams. In the following section, the three main types corresponding to the different domains (lines I III on the diagram) will be discussed. Establishing a Pourbaix Diagram requires some assumptions about the reactions taking place at the solid- liquid interface, and this is the reason why even for simple systems, there are not unique! In our case, presence of following species has been assumed: Solids: Ions in solution: Fe, Fe3O4 Fe2O3 Fe2+,Fe3+, HFeO2-, H2O, H+, OH(cj=10-6 mol/l)

The first type of equilibrium is corresponding to a straight dissolution-redeposition process without interaction with water.

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Oxidation - reduction equilibriums with participation of water will induce a pH dependence.

Pure chemical equilibriums also induce precipitation effects and are displayed in the Pourbaix Diagrams.

In addition to all the equilibriums related to metal interaction with water, there are also cathodic reactions that are displayed in the Pourbaix Diagrams. They are also very important to consider, because the higher their potential, the more influence they will have on triggering a corrosion reaction. We previously mentioned that a spontaneous reaction will be possible, if E cathodic > E anodic . Considering the figure 11.14, it can be said that much more metals will be susceptible to corrosion problems in presence of oxygen (high equilibrium potential) than of hydrogen. Furthermore, low pHs (acidic domain) are more dangerous, from a driving force point of view than high pHs (alkaline domain).

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Figure 11.14: Pourbaix diagram and cathodic reactions. Stability domain of water and driven force for corrosion Following the comment regarding the cathodic reactions; figure 11.15 shows an example of material that is not influenced by the hydrogen reduction. In the case of copper, the electrochemical equilibrium potential for copper dissolution- redeposition is above the hydrogen line and will be influenced mainly by oxygen reduction.

Figure 11.15: Pourbaix diagram of copper: example of element stable above the reversible potential of hydrogen resulting in different corrosion mechanisms.

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Figure 11.16: Pourbaix diagrams for different metals. Example: Aluminum corrodes in the acidic and alkaline range; it is passive in the neutral range (pH 4-8). Figure 11.16 display a number of Pourbaix Diagrams for common materials. For engineers, three domains of pH-Potential are very important to be assessed correctly: Where is the material immune (can stay in the metallic state) Where can stable oxide / hydroxides be formed (passivation) In which condition can corrosion attack proceed

Pourbaix Diagrams have obviously limitations: They tell us what can happen, not necessarily what will happen No information on rate of reaction can be obtained Mostly plotted for pure metals and simple electrolytes, the database for more complex electrolytes and still incomplete and prediction even for homogeneous alloys is quite difficult.

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Knowing the different thermodynamic equilibriums that can take place and having established the Pourbaix Diagrams, it is also easier to understand the difference observed between the theory and the potential values measured in practice, Fig. 11.17. As already mentioned, thermodynamics can show which reactions are in principle possible. When comparing the electrochemical and the practical series of elements (experimental potential values) in 1% NaCl, one can observe considerable differences in many cases. By definition, thermodynamics does not allow us to draw conclusions for the reaction rate. Even if the reaction is possible according to thermodynamics, it can proceed so slowly that there is no practical corrosion risk; this is the case for the formation of protective oxide layers that dissolve only very slowly (passivity). These lead to much more positive potentials than predicted for the metal itself. Cr, Ni, Al, Mg show this important potential increase in neutral NaCl solution. From the Pourbaix diagram, it can be seen that some oxidized species can be formed on these materials and that they are protected from straight active dissolution. Some very noble elements like Au and Pt show the opposite trend with a potential decrease. Here, a statement made before about the undefined equilibrium at the beginning of the corrosion processes needs to be repeated. When no dissolved ions for a given metal are found in a solution, then the electrochemical potential is perfectly undefined. On Au and Pt, it is likely the case that another reaction is dominating. It also needs to be stated that Au and Pt are in general not adequate as reference electrodes because even if their surface is stable, reactions taking place on their surfaces are undefined and contamination can for example be the dominant factor.

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Figure 11.17: Comparison between electrochemical and practical series of elements. In particular, note the metals Al, Cr and Ni; their behavior is more noble in practice than expected in theory.

Thermodynamic calculations show whether and in which direction a reaction can proceed. However, they do not allow conclusions to be drawn about reaction rates.

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