The University of Edinburgh

Division of Engineering
Session 2001-2002
Materials Science and Engineering

Corrosion of metals

Electrochemical theory of wet corrosion: fundamentals

As with dry corrosion wet corrosion reactions are only possible if the free energy
of the products of reaction is lower than the free energy of the reactants. This is
the case however for the reaction of nearly all metals with water and oxygen to
give metal hydroxides:

M
H2 Ol
MOH s

2 (1)

for example

 for Mg: ∆G  597 kJ/mol

 and for Cu: ∆G  120 kJ/mol
In addition, and unfortunately, the rate of wet corrosion may often be very high
compared with dry corrosion on the same metal at the same temperature. There
are two underlying reasons for this:

 the dipolar water molecule stabilizes the free (dissociated) metal ions in
solution;

 the metallic structure and water in contact with it can both conduct electric
current.

This enables reaction 1 above to proceed through the coupling of two primary
corrosion reactions:

A: M
M

2e

2
(2)

1
(Anode reaction: destroys metal, releases electrons, oxidation)

C : 2e

H2 O
O2
1
2

2OH
(3)

(Cathode reaction: consumes electrons; electron sink reaction: reduction).

Electrons liberated in the anode reaction A flow to the site of the cathode reaction
C through the conducting metal. The movement of dissociated ions carries an
equal ionic current in the water. The distances over which these currents flow can
vary from microns to many metres.
All wet corrosion processes can be analysed in terms of anodic and cathodic re-
actions. The anodic process is the direct cause of damage to metallic structures
but both an anodic and a cathodic process must occur for a corrosion cell to be
formed
The corrosion of metals by reaction with air and water to form metal hydroxides as
shown above is a very important wet corrosion process, especially in the construc-
tion industries. There are other corrosion reactions resulting from, for example,
other cathode reactions (electron-consuming)

2e

2H

H 2 (4)

2e

M2

M (5)

or other anode reactions (electron releasing)

M
H2 O
MO
2H
2e
(6)

When a metal M is placed in pure water, some ions will immediately pass into
solution:

M
M

2e

2
(7)

The build-up of negative charge on the metal and the build-up of metal ions in
solution makes possible a back-reaction:

M  M

2e

2
(8)

2
and ultimately an equilibrium is established:
M
M

2e

2
(9)
At this stage, a steady potential difference now exists between metal and solution.
The magnitude of this potential difference depends on the metal and composition
of the solution. It is not possible to measure this potential difference for a sin-
gle metal, but the potential difference (emf) between two metals dipping into a
solution can be measured. Under well-defined conditions, this enables a single
potential Em (relative to a common reference) to be assigned to every metal.

The Electrochemical Series

The single electrode potential Em developed by a material M acting as an electrode
depends on the constitution of the material and the composition of the solution
with which it is in contact. The Electrochemical Series lists electrodes according
to the standard single potential Em developed in contact with a 1 mol/L solution

of the ion produced by the electrode reaction, at equilibrium (that is, no current
flowing), at 25 Æ C. On this scale, the hydrogen electrode H2 2H
+ 2e
, H2
pressure 1 atm) is given the arbitrary value zero.

 
The recommended sign convention (Stockholm) is such that the more noble metals
show increasingly positive potentials (eg Cu2
Cu E 
0.34 V, not 0.34 V).


Some older texts (especially American) use the opposite sign convention.
Note that single potentials can be assigned to electrode reactions other than Mn
M,
including familar cathode reactions.


Nernst Equation
Describes how Em varies with concentration of metal ions for the electrode Mn
M.

Em  Em
log c
b
(10)
n
where b  0.059 V at 25 Æ C.

For the electrode O2 4OH

E O2  EO
b4 log cp4 O

2
2

(11)
OH

3
Practical use of reference electrodes
The hydrogen electrode is not a practical reference electrode for field use. The
copper/copper sulphate electrode is perhaps the most widely used. In sea water,
the even simpler zinc electrode is often employed.

Polarisation
In active corrosion cells, a net corrosion current flows at each electrode surface.
At the anode, the electrode reaction (see note 4 above) is no longer in equilibrium.
The rate of the forward reaction exceeds the rate of the back reaction: i f  ib .

Potential

←
i

EM

←
i
i0 logi
Current

Figure 1: Ideal polarisation curve for a metal surface in contact with water.

This net anodic current requires a shift of the electrode potential to a more positive
value. This favours the forward reaction and disfavours the back reaction.
A second surface acting as a cathode is cathodically polarised, as shown in Figure
2.

Xn

X
ne
(12)

Here for example X may stand for 2H2 O + O2 , with n  4, and Xn
 4OH
.
4
 Potential ←
iX

EX ←
iX
Ecorr ←
iM
EM ←
iM

i0 logi
Current

Figure 2: Electrochemical cell working at a mixed corrosion potential Ecorr .

Potential–current (E–log i) diagrams are known as polarisation diagrams or Tafel

plots.

Simple calculations of corrosion rates

The measured current and the corrosion rate are simply and directly related be-
cause
1 mol electrons has a total charge of 96500 C (coulombs). But 1 A s = 1 C (A
current in amperes).
Therefore, for example in the case of ferrous metals for which

Fe
Fe

2e

2
(13)

The corrosion of 1 mol Fe = 56 g = 0.056 kg Fe releases 2 mol electrons = 2 


96500 C electric charge; therefore a current of 1 A corresponds to a corrosion rate
of 0.056/(2 96500) kg/s iron.
More useful units are g/year; or if density and surface area are know mm/y depth
of penetration.
Assumptions in the treatment: (1) The corrosion is uniform; (2) the entire current
of the corrosion cell passes through the measuring instrument.

5
Pourbaix diagram of iron
These widely used diagrams show how corrosion behaviour depends on electrical
potential E and pH. A simplified Pourbaix diagram for iron is shown here.

EFe/ V

pH

Passivity

EFe/ V

Active
corrosion

pH
Immunity

Figure 3: Pourbaix diagram for iron, showing regions of active corrosion, passivity and immunity.

6
Types of corrosion cell

 Dissimilar metals
 Differential aeration

Cathodic protection
Widely used in the protection of marine structures, ships, underground structures
(especially pipelines) and water filled structures. Under some circumstances used
to protect reinforcing steel in concrete structures.


Types of CP: impressed current; sacrificial anode.
Potentials (V) for cathodic protection relative to Cu CuSO4 reference electrode:

0 85 to 0 95
0 6
Iron and steel

0 5 to 0 66
Lead

0 95 to 1 2
Copper and alloys

Aluminium

Passivity
Figs 1 and 2 showed the ideal anodic polarisation curve for metal dissolution

M
M

2e

2
(14)

In the presence of oxygen and other oxidising agents this curve for some met-
als extends only a certain distance before showing a sharp drop to lower current
densities. When the anodic current density exceeds a critical value ic the metal

7
becomes passive or passivates. Passivity is caused by a chnage in the anodic re-
action. The formation of free metal ions (reaction above) gives way to a reaction
which forms an insoluble film on the metal surface:

M
H2 O
MOH
2e

2H

2 (15)

This anodic reaction proceeds more slowly because of the relatively high resis-
tance of the film. Note however that the current density does not drop to zero
in the passive region – a small residual anodic current flows and this repairs any
damage to the passivation film. The shape of the polarisation curve differs from
one metal to another. The phenomenon of passivity is especially important for
the corrosion behaviour of titanium (Ti), chromium (Cr) and stainless steels, alu-
minium (Al) and iron (Fe) and ferrous metals. The presence of aggressive anions,
notably chloride, may cause severe pitting corrosion by attacking or preventing
formation of a passive film.

Corrosion of reinforcing steel in concrete

The pH of the pore water in concrete is normally in the range 12-13 and thus
steel is passive (see Pourbaix diagram for iron). Passivity may be destroyed by
carbonation or by the presence of chloride ions. Carbonation is confined to the
surface layer of concrete and steel is protected by providing adequate depth of
cover.
Methods of protection of steel in conditions where passivity is not achieved in-
clude cathodic protection, coating of steel and choking of oxygen. There is much
current interest in the cathodic protection of marine structures.

Corrosion in the soil: microbial corrosion.

Electrochemical corrosion can be assisted by bacteria. For example, corrosion
of steel pipelines in waterlogged neutral ground containing little oxygen is often
much more severe than might be expected. Cast iron pipes of 6 mm wall may per-
forate in less than five years. Sulphate-reducing bacteria such as Desulphovibrio

which flourish in oxygen-free conditions assist the corrosion of iron apparently
by consuming hydrogen produced in the cathodic reaction e

H
H, thus

8
enhancing the rate of the cathodic reaction. The bacteria make use of the H
to
reduce sulphate (SO 
4 to sulphide (S ).
The overall corrosion cell reaction is

8H

8e

8H (16)

SO
4
8H
S
4H O 2 (17)

producing iron sulphide as the corrosion product.

Fe2

S
FeS (18)

References.
See Callister Ch 18.
Supplementary reading. Fontana: Corrosion Engineering.

Revised 25 Apr 2002