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
This document is 2002 - 2003, the Corrosion and Protection Centre, UMIST.

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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, with the result that the metal goes into
solution as a salt, and hydrogen gas is liberated. 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. If we replace zinc by platinum, we do not
see any reaction, no hydrogen is evolved, and we do not find any platinum in the
solution. This is because platinum is a very non-reactive or noble metal, and does not
easily form salts.
We can get further information about the nature of the corrosion reaction if we
simultaneously expose zinc and platinum to the hydrochloric acid, with the two metals
electrically connected together. In this case hydrogen is seen to evolve on the surface of
the platinum. However we still find no platinum in solution. If we connect an ammeter in
the circuit between the zinc and the platinum, we find that an electrical current is flowing
from the platinum to the zinc, i.e. electrons are flowing from the zinc to the platinum.
Since the current is found to flow indefinitely, yet we do not observe any change in the
potential of the zinc or the platinum, we may conclude that electrons are being generated
at the piece of zinc, and consumed at the platinum. This can be explained in terms of the
separation of the corrosion process into two parts; 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, we might expect to get the same effect by artificially applying
current to a piece of platinum. We can see this by connecting two pieces of platinum to a

2002 - 2003, Corrosion and Protection Centre, UMIST Module 0, Aqueous Corrosion - Page 1
battery. In this case gas is generated at both electrodes. At the negative electrode, or
cathode, to which electrons are being supplied, the reaction is hydrogen evolution, as
before.

2 H + + 2 e- H 2
At the positive electrode, or anode, from which electrons are being removed, the reaction
is oxygen evolution:
2 H2 O + O2 + 4 e- 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, more accurately, potential) of the metal
with respect to the solution will control the rate of corrosion, 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, this will repel the positively charged
zinc cations away from the metal, and remove the electrons that are produced by the
reaction. Consequently the rate of this reaction increases as the potential of the metal
becomes more positive.
In a similar way the potential must fall below the equilibrium potential for the reaction

2 H + + 2 e- H 2
before hydrogen evolution will be observed. As the difference in potential is increased,
so the rate of the corresponding reaction will increase.

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.R. Evans).
Module 0, Aqueous Corrosion - Page 2 2002 - 2003, Corrosion and Protection Centre, UMIST
The change in potential associated with the change in the rate of the reaction is known as
polarization; the sources of this polarization are discussed further in the next section.
One of the main sources of polarization has the characteristic that the change in potential
is proportional to the logarithm of the current. Consequently it is common to plot a
diagram of potential against log current (), known as an E-log I diagram (it is also often
called an Evans diagram, although strictly Evans plotted the current on a linear scale).

0.3

Cathodic reaction
0.1

icorr
-0.1
Potential

-0.3
Ecorr
-0.5

-0.7
Anodic reaction
-0.9

-1.1
1E-08 0.0000001 0.000001 0.00001 0.0001 0.001 0.01 0.1 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,
and it is convenient to record the rate of reaction in terms of the current per unit area,
known as current density, since this is independent of the size of the electrode. It is
common (though not universal) to use I to refer to current and i to refer to current
density. Then an E-log i diagram is a plot of potential versus current density for the
individual electrochemical reactions.
If there is only one anodic reaction and one cathodic reaction, then it can be seen that a
freely corroding electrode (i.e. an electrode that is not electrically connected to anything
else) must have zero total current, so the current of the cathodic reaction must be equal
and opposite to the current of the anodic reaction. Consequently, a corroding electrode
will adopt the potential at which the cathodic and anodic currents are equal; leading to
the point shown on Figure 2 at the corrosion potential, Ecorr, corresponding to a corrosion
rate of icorr.

The are three main sources of polarization:

1. Activation polarization results from the chemical processes necessary to make the
reaction go faster in one direction than the other. This type of polarization will always be
observed, although its magnitude may vary. The potentials resulting from activation
polarization take the mathematical form
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 E = Constant ln(current)

2. Concentration polarization occurs because the concentrations of chemical species

taking part in the reaction change at the metal surface. For example, in a reaction
involving the reduction of oxygen, the concentration of oxygen at the surface of the metal
will rapidly be depleted as the reaction proceeds, and it will not be possible for the rate of
reaction to exceed the rate at which oxygen arrives at the metal surface.

3. Resistance polarization results from the electrical resistance of components of the

circuit involved in the reaction, usually associated with the resistance of the solution. If
the solution has a high resistance, or more particularly if there are high resistance films
on the metal surface, the passage of current through this resistance will create a potential
drop according to Ohm's law.

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, with only a small
amount of concentration polarization, and
little resistance polarization. Fortunately the
evolution of hydrogen on zinc is very
difficult, and this reaction is strongly
polarized. Even so the rate of corrosion is
rapid because of the large difference in
equilibrium potentials.
Iron in seawater In this case, although the evolution
of hydrogen is thermodynamically possible, the
difference in the equilibrium potential for this
reaction and for the dissolution of iron is very small,
and the rate is insignificant. Consequently iron
corrodes in this case as a result of the reduction of
oxygen. Because of the low solubility of oxygen in
water this reaction is usually subject to significant
concentration polarization, which restricts the rate of
corrosion. If the solution is stirred this helps to
increase the concentration of oxygen at the surface of
the metal, and the corrosion rate may increase. A second very important phenomenon can
be seen in the shape of the curve for the dissolution of iron at high potentials, where it is
seen that the rate of reaction falls off rapidly. 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.
For pure iron this condition is very difficult to maintain, but for iron-chromium alloys the
passive film may form very easily, and stainless steels rely on this for their corrosion
resistance.

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We can also see how E-log i diagrams can be used to understand some of the more
common corrosion control methods. In essence all such methods are concerned with
reducing the anodic metal dissolution current. 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, thereby producing a large
resistance polarization of the reaction.
The coating will also act as a barrier to
the diffusion of oxygen, and produce
large concentration polarization of this
reaction.

Inhibitors
Corrosion inhibitors are chemicals that
are added to the environment to slow
down the rate of corrosion. These
usually act by interfering with either
or both of the corrosion reactions,
increasing the activation polarization
and/or the concentration polarization.

Cathodic protection
By artificially lowering the potential of
the metal the rate of the anodic, metal
dissolution reaction can be reduced,
even though this will be at the expense
of increasing the cathodic hydrogen
evolution or oxygen reduction reaction.

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Passivation
One of the most effective methods of
controlling corrosion is to use metals
that can form a film of solid corrosion
product, known as a passive film,
which protects them against corrosion.
Well-known examples of this are stain-
less steels, aluminium and its alloys and
titanium. In suitable conditions the
passive film will reform if damaged, and
thereby provide a self-healing
non-metallic coating. However if the
film fails to repair this may lead to
severe forms of localized corrosion.

A polarization curve plots the effect of an applied current on the potential of a metal
electrode1. The current that will flow in the external circuit will be the difference between
the anodic and cathodic currents, so the expected relationship between the polarization
curve and the E log i curve will be as shown in Figure 3. Note, however, that there may
be additional complications, such as changes in local pH and chemical composition at the
surface of the electrode.

0.3

Cathodic reaction
0.1

-0.1
Potential

-0.3

-0.5

Overall reaction
-0.7
Anodic reaction
-0.9

-1.1
1E-08 0.0000001 0.000001 0.00001 0.0001 0.001 0.01 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 is why it is more common to plot log i on the
x axis. Modern measurements will normally control the potential of the specimen and observe the resultant
current. Because the potential is the independent variable in this case, some workers prefer to plot the
potential on the x axis.
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When a metal is immersed in a solution of its own ions (e.g. Zn in Zn2+ solution), as well
as the anodic, metal dissolution reaction, the reverse, metal deposition, reaction is
possible:
Forward, anodic reaction Zn Zn2+ + 2 e-
Reverse, cathodic reaction Zn 2+ + 2e Zn

In the absence of any other reactions the rates of the forward and reverse reactions will be
equal, and the potential at which this occurs is known as the Equilibrium Potential. The
chemical equilibrium is conventionally written as:
Zn Zn2+ + 2e-
where the symbol implies simultaneous forward and reverse reactions.

If the potential is above (more positive than) the equilibrium potential, then the forward
reaction will predominate and the metal will corrode, while if the potential is below
(more negative than) the equilibrium potential, then the metal will be deposited from the
solution, and it will to be possible for the metal to corrode. In the latter situation, the
metal is said to be immune, as it is thermodynamically impossible for it to corrode.

As well as being influenced by the applied potential, the corrosion of metals is also
influenced by the solution pH, because the nature of the corrosion product depends on the
pH. For example, Zn2+ ions will react with hydroxyl ions to form solid zinc hydroxide:

Zn2+ + 2 OH- Zn(OH)2

This will happen more easily when the concentrations of Zn2+ are higher, so the zinc
hydroxide is stable at higher pH (higher OH- concentration) while the Zn2+ cation is
stable at lower pH. This has important implications for corrosion; the zinc cations will
dissolve in the solution and they will not therefore interfere with the corrosion process.
However, the zinc hydroxide will form a passive film on the metal surface that will act as
a barrier to further corrosion.

As the pH is raised further, the zinc hydroxide will eventually redissolve as zincate
anions (ZnO22-):
Zn(OH)2 + 2 OH- ZnO22- + 2H2O

Like the zinc cations, zincate is soluble, and will not therefore protect the metal against
corrosion.

The regions where the various species are stable can be plotted on a map of potential
against pH, know as an E-pH or Pourbaix diagram.

There are three types of region on the Pourbaix diagram:

1. When the metal is the thermodynamically stable state, the metal is immune
from corrosion.

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 2. When the stable species is a soluble corrosion product, the metal is said to be
active, and will corrode relatively rapidly.

3. When the stable species is an insoluble corrosion product, then the metal is
said to be passive, and will corrode relatively slowly.

The equilibria for the metal and the ions of the metal describe the anodic behaviour of a
corroding system, but in order to fully understand what is likely to happen, we need to
know about the thermodynamics of the cathodic reactions as well. We can describe the
two main cathodic reactions as being concerned with the stability of water:

O2 + 4 H+ + 4 e- 2H2O H2 + 2 OH- - 2e-

(the right-hand reaction has been written in a slightly unconventional way to emphasize
the equilibria with water). The equilibrium between oxygen and water occurs at rather
positive potentials, and it is able to act as a cathodic reactant for all but the most noble
metals. The equilibrium between water and hydrogen occurs at quite low potentials, and
only the more active metals are able to displace hydrogen from water and thereby suffer
from corrosion in oxygen-free solution. On the Pourbaix diagram both of these equilibria
produce a sloping line, because the equilibrium potential is affected by the hydrogen ion
concentration and is hence a function of pH.

Example Pourbaix Diagrams

Gold
The region of thermodynamic
immunity extends to above the line
for oxygen evolution at all pH
values, and consequently gold cannot
corrode either with the reduction of
oxygen in solution or the evolution
of hydrogen. This is the reason why
gold is such a corrosion-resistant
metal, and why it is often found in
the form of the metal in nature,
rather than combined with oxygen as
an oxide.

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Copper
Cannot corrode with hydrogen
evolution at any pH, but can corrode
with dissolved oxygen reacting to
form hydroxyl ions. The corrosion
product is soluble in acids and strong
alkalis, where significant corrosion
may be expected. Protected by a
passive film of oxide in neutral
solutions.

Iron
Corrodes both with oxygen reduction
and hydrogen evolution in acid and
near neutral solutions, although it
may be passivated at high potentials
in weak acids. It is protected from
corrosion in alkaline solutions by a
passive oxide film, except possibly
in very strongly alkaline conditions.

Aluminium
Corrodes with oxygen reduction or
hydrogen evolution in strongly acid or
alkaline solutions. Protected by a
passive film of aluminium oxide in
near-neutral solutions.

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