Tutorials : Corrosion

Part 1: Theory and basics

 Outline

A. Definition and effects of corrosion

B. General thermodynamics and kinetics in electrochemistry

C. Thermodynamics and kinetics in corrosion

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 A. Corrosion : What is it ?

D.A. Jones : « Destructive result of a chemical reaction between a metal and its
environment »

M.G. Fontana : « Deterioration of a material because of reaction with its

environment »

If a degradation of a material is only physical and does not involve chemical

mechanisms it is not considered to be corrosion.

Corrosion is an unwanted spontaneous electrochemical reaction

that can lead to the structural degradation of a material.

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 A. Corrosion : Unwanted

Recent studies (2002) estimate the direct cost of corrosion in the United States
to be nearly $300 billion dollars per year or 3,1% of US GNP.

Corrosion has been the cause of many catastrophic damages.

Famous example : 1999, Sinking of the Erika, broke in two 70 kilometers from the coast
of Brittany, France, whilst carrying approximately 30 000 tons of heavy fuel oil. Some 19
800 tons were spilled.

Holes due to corrosion were found on the main deck coaming, the inert gas
system risers, the «watertight » ship's doors...

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 A. Corrosion : Electrochemical

An electrochemical reaction is the sum of two half-reactions :

. An oxidation (electrons loss) Red → Ox + ne-
. A reduction (electrons gain) Ox + ne-→ Red

In an oxidation, the oxidation number (o.n.) of the concerned element increases.

In a reduction, the o.n. of the concerned element decreases.

The oxidation number characterizes in which electronic state an element is.

o.n. = 0, the element is in its elementary state (Fe, Ni, O 2 H2...)

o.n. > 0, the element is positively charged (one or more electrons are gone) : Fe 2+, H+, Na+,
Cu2+, Al3+...

o.n. < 0, the element is negatively charged (one or more electrons are in excess) : Cl -, O2-...

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 A. Corrosion : Electrochemical

In corrosion, the oxidation reaction is ALWAYS the destructive oxidation of the metal :

M → Mz+ + ze-
Fe → Fe2+ + 2e-
Ni → Ni2+ + 2e-
Al → Al3+ + 3e-

In corrosion, the reduction reactions mostly are :

Water (proton) reduction : 2H2O + 2e- → 2OH- + H2
Dissolved oxygen reduction : O2 + 2H2O + 4e- → 4OH-

A complete corrosion reaction is written as the sum of the partial reaction

(ex : Fe in an acidic solution)
Fe + 2H+ → Fe2+ + H2
If either the oxidation or the reduction cannot occur,then the corrosion is inhibited.

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 A. Corrosion : Electrochemical

Two fundamental aspects to consider in corrosion (and

electrochemistry) :

. Thermodynamics : which reactions will occur ?

. Kinetics : how fast these reactions will occur ?

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 B. General thermodynamics

Consider the following reaction written as an equilibrium:

Mn+ + ne- ↔ M

In the case where an electrode made of the metal M is immersed in a solution

containing the cation Mz+ this electrochemical reaction reaches an equilibrium
and the electrode M takes a potential called the equilibrium potential Eeq.

The potential of an electrode is always defined vs. a reference potential.

The Nernst equation is used to calculate this equilibrium potential observed in

specific conditions.

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 B. General thermodynamics

For the general reaction :

aA + bB + ne- ↔ cC + dD

In a dilute solution, the activity is equal to the concentration, the Nernst

equation writes:
a b
0 RT [ A] [B]
E eq =E  ln c d (1)
nF [C ] [D ]
With :
E0 the equilibrium potential in the standard conditions*
R the perfect gas constant (8.315 J.K-1.mol-1)
T the temperature (K)
n the number of exchanged electrons
F the Faraday constant (96487 C.mol-1)
[x] the concentration of the species x (mol.L-1)

*standard conditions : pure solids, gases at 1 atm pressure, dissolved species at 1 mol.L -1
concentration, 0°C

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 B. General thermodynamics
From D.A. Jones

Each species has a different

equilibrium potential.

It is generally given in the

standard conditions and vs. the
standard hydrogen reference
electrode.

Such a table is used to

determine which reactions are
likely to occur.

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 B. General kinetics

Let us consider again the following electrochemical reaction at an equilibrium :

Iox
Mn+ + ne- M
Ired
An electrochemical reaction involves an electron flow i.e. an electrical current.

At the equilibrium, a current of equal magnitude flows in both directions.

Inet = Iox+ Ired = 0

Iox = |Ired| = I0

I0 is the exchange current, which is equivalent to a reversible reaction rate at the

equilibrium.

The exchange current density i0 (= I0/A) depends on the catalytic properties of the
material used for the electrode. For the proton reduction, i 0 varies over 9 orders of
magnitude1.
1. Table 3.2, J. M. West, Electrodeposition and Corrosion Processes, Van Nostrand 1965

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 B. General kinetics

What happens when the potential of the electrode moves away from the equilibrium
potential of the considered reaction ?

1. If the potential is above Eeq (anodic potential), there is OXIDATION

2. If the potential is below Eeq (cathodic potential) there is REDUCTION.

Depending on how far the potential is from E eq, the oxidation or reduction current will
change.
log |i|

M z+
+ z -
ze
e -→ +
M z+
M
i0 →
M

Eeq E
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 B. General kinetics

Moving away from the equilibrium potential of an electrode = POLARIZING

η the overpotential is defined as E-Eeq

We assume that the current only depends on the rate of electron transfer across
the charged interface.

Charge transfer at the metal/electrolyte interface does not follow the Ohm's law due to
the very high electric field present there (on the order of 10 7 V/cm).

It is given by a law called the Butler-Volmer relationship.

o nF −r nF
I=I 0 exp E −E eq −exp  E −E eq  (2)
RT RT

where αo is the oxidation symmetry factor and αr is the reduction symmetry factor (αo +
αr = 1)

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 B. General kinetics

 o nF −r nF
I=I 0 exp  E−E eq −I 0 exp E −E eq 
RT RT

Anodic term Cathodic term

log |i| Cathodic branch
Considering the absolute Anodic branch
values : M z+
At Eeq the anodic term is + ze - ze
-

→ +
equal to the cathodic M z+
M
term. i0 →
At E>Eeq, the anodic term M
is larger than the cathodic
term
At E<Eeq, the cathodic
term is larger than the Eeq E
anodic term.
BV relationship is valid only if the current is not limited by mass transport.

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 C. Thermodynamics and kinetics
applied to corrosion

The relations derived before were valid for only one redox couple M n+/M.

The oxidation and the reduction half reactions involve the same species.

In corrosion, as seen above, two different redox couples are involved in the
oxidation and reduction half reaction, as most of the time, the electrolyte
does not contain the metallic cation corresponding to the electrode metal.

The electrolyte most of the time contains dissolved O 2 or H+ (H2O)

Oxidation of the metal M : M → Mn+ + ne-

Water (proton) reduction : 2H2O + 2e- → 2OH- + H2

Dissolved oxygen reduction : O2 + 2H2O + 4e- → 4OH-

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 C. Thermodynamics and kinetics
applied to corrosion : Mixed potential theory

When a metallic electrode immersed in an aqueous media in which the oxidized

species is not the metallic cation, its potential is called Ecorr, the corrosion potential.

At this potential, the oxidation rate of the metal is given by Icorr, the corrosion
current.

Ecorr and Icorr can be determined by plotting the I vs. E characteristics of each
involved redox couple and using the relation dictated by the principle of charge
conservation :
ΣIoxid = ΣIred

The sum of the oxidation currents is equal to the sum of the reduction currents.

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 C. Thermodynamics and kinetics
applied to corrosion : Mixed potential theory
Example: Zn in acidic solution

From D.A. Jones

Ecorr and Icorr are the coordinates of the intersection point of the I vs. E
characteristics of each concerned redox couple.
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 C. Thermodynamics and kinetics
applied to corrosion : Stern* relationship
Example: Zn in acidic solution
Let us write the Butler-Volmer relations for the two redox couples involved :
 o1 n1 F − r1 n1 F
I H /H =I 0 H /H exp 
+ + E −E eq H /H −exp 
+ E −E eqH / H 
+
(3)
2 2
RT 2
RT 2

 o2 n2 F −r2 n2 F
I Zn 2+ =I 0 Zn 2+ exp  E −E eq Zn 2+
/ Zn
−exp E −E eq Zn 2+  (4)
/Zn /Zn 2
RT RT /Zn

1. At Ecorr the anodic term of the relation (3) and

the cathodic term of relation (4) are negligible.

2. Furthermore, the current Icorr at the Zn

electrode is the sum of (3) and (4).

* also known as the Wagner-Traud relationship

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 C. Thermodynamics and kinetics
applied to corrosion : Stern* relationship
Example: Zn in acidic solution

Following 1 and 2, I the net current at the Zn electrode is expressed as :

 o2 nF −r1 n1 F
I =I corr exp  E −E corr −exp  E −E corr  (5)
RT RT
This is called the Stern* relationship.
It can be also written :

 o2 n2 F −r1 n1 F
I=I corr exp  E −E corr −I corr exp E −E corr  (6)
RT RT

With F
f=
RT

I =I corr exp  o2 n2 f E −E corr −I corr exp − r1 n1 f E −E corr  (7)

* also known as the Wagner-Traud relationship

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 C. Thermodynamics and kinetics
applied to corrosion : Stern* relation
Example: Zn in acidic solution

Described by Butler-Volmer relationship

Described by Stern relationship

* also known as the Wagner-Traud relationship

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 C. Thermodynamics and kinetics
applied to corrosion : Summary

Fundamental Corrosion

1 redox couple 2 redox couples

Equilibrium potential Eeq Corrosion potential Ecorr

Exchange current I0 Corrosion current Icorr

Butler-Volmer Stern (Wagner-Traud)

αo, αr (αo+ αr = 1) αo2, αr1 (αo2+ αr1 not always = 1)

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