Basic Concepts in Corrosion and

Electrochemistry

Christofer Leygraf, Prof

Royal Institute of Technology (KTH), Stockholm, Sweden; chrisl@kth.se

The content and equations are based on Chapter 1 in Corrosion Mechanisms in

Theory and Practice, 3rd Edition, Ed. P. Marcus, CRC Press, Boca Raton (2011)

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 Corrosion cell.
4

2
1

3
1. Anode reaction: Me → Me2+ + 2e- (oxidation of Me to Me2+)
2. Cathode reaction: 2H+ + 2e- → H2 (reduction of H+ to H)
3. Electron conductor (metal)
4. Ion conductor (water solution)

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 Redox reactions.

The overall reaction in the Corrosion Cell (M + 2H+ → M2+ + H2) is an

important example of a Redox Reaction. It involves:
- A reduction process of species (2H+ to H2)
- A complementary oxidation process (Me to Me2+) and
- Transfer of electrons from oxidized to reduced species.

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 An important example of redox reaction:
The extraction of iron from its ore.

2Fe2​O3​(s)+3C(s)→4Fe(s)+3CO2​(g)

Fe is reduced from oxidation state Fe3+ to Fe0 by gaining electrons from C.

C is oxidized from oxidation state C0 to C4+ by losing electrons to Fe.

General schematics
of redox reaction.

Source: owlcation

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 Faraday´s law.
Expresses how the metal dissolution rate
can be calculated from anodic current density.

νm : metal dissolution rate or

corrosion rate (mol/cm2, s)
νm = ia,M ia,M : anodic current density for
nF metal dissolution (A/cm2)
F : Faraday´s constant (96500 C/mol)
n : number of electrons involved
in the anodic reaction,
e.g. Me Me n+ + ne-

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 Electrode potential.
A metal (M) is immersed in a water solution
containing ions of the metal (Mn+).

Exchange occurs between metal and solution

M← → Mn+ + ne-
whereby the metal assumes an electrode potential.
Noble metal (Au, Pt) Non-noble metal (Zn, Mg)

Due to low electron reactivity, Due to high electron reactivity,

the metal is unwilling to release the metal will readily release
ions. Hence, it assumes a high ions. Hence, it assumes a low
electrode potential. electrode potential.
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Electrochemical cell 0.78 V
with iron and copper - V +
as half-cells.

[Fe2+ ]=1 [Cu 2+]=1

Fe Cu

Porous membrane

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 Introduction of
0.44 V reference electrode (SHE).
- V +

[Fe2+]=1 [H+]=1

Fe Pt Standard Hydrogen-
Electrode (SHE), 0V
H2 ( PH = 1 atm)
2

Porous membrane
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 Electrode reaction Standard potential/V
Standard potentials of Au3+ + 3e- → Au +1.42
electrode reactions. ½O2 + 2H+ + 2e- → H2O +1.23
Pt2+ + 2e- → Pt +1.20
Ag+ + e- → Ag +0.80
Fe3+ + e- → Fe2+ + 0.77
Cu2+ + 2e- → Cu +0.34
2H+ + 2e- → H2 ±0.00
• Potentials vs SHE Pb2+ + 2e- → Pb -0.13
• Equilibrium is assumed Ni2+ + 2e- → Ni -0.25
Cd2+ + 2e- → Cd -0.40
• Activitiy = 1 Fe2+ + 2e- → Fe -0.44
• Temperature 25 oC Cr3+ 3e- → Cr -0.74
• All reactions written as Zn2+ 2e- → Zn -0.76
cathodic reactions. Ti2+ + 2e- → Ti -1.63
Al3+ + 3e- → Al -1.66
Mg2+ + 2e- → Mg -2.36
Na+ + e- → Na -2.71
Ca2+ 2e- → Ca -2.76

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 Metal/alloy Electrode potential,V

Gold +0.42
The galvanic series Silver +0.19
in seawater. Stainless steel (18/8), passive +0.09
Copper +0.02
Tin -0.26
Stainless steel (18/8), active -0.29
Lead -0.31
Steell -0.46
Cadmium -0.49
Aluminium -0.51
Galvanized steel -0.81
Zinc -0.86
Magnesium -1.36

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 Nernst´s equation.
Expresses how the equilibrium potential (E)
varies with activity of species involved.

→ →
aA + bB + … ne- → lL + mM + … Ox + ne- → Red (10)

RT [A]a [B]b 0.059 [ox]

E= E0 + log E = E0 + log
nF [L]l [M]m n [red]

E0 : standard potential (activities = 1)

R : gas constant (VAs/mol, °)
T : temperature (°K)
n : number of participating electrons
F : Faraday’s constant (96500 As/mol)
[ox] : activity of oxidized species
[red] : activity of reduced species
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 Oxidizing
conditions
1

Potential, V (SHE)
0
Potential-pH
Diagram:
Al2O3
Example -1 Al3+ AlO2-
Passivity
Corrosion Corrosion
Aluminum.
-2 Al
Reducing Immunity
conditions -2 -1 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

Solution pH

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 Inner layer of adsorbed
water molecules
Cations surrounded
by water molecules
-
←
-
←
-
←
-
The electric -
←
←
double layer -
←
Metal -
(1-10 nm) ←
-
←
-
←
-
←
-
←
-
←

Outer layer of
hydrated ions

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 Deviation from equilibrium conditions.

Example of reaction: 2H+ + 2e- ⇔ H2

Polarisation or overvoltage: η
η = E- E0

At equilibrium: i = ia = ic η=0

At deviation from equilibrium: ia ≠ ic , and η ≠ 0

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The equal forward and reverse partial reaction at equilibrium
of any electrochemical reaction: exchange current density, i0 .
Example of reaction: 2H+ + 2e- ⇔ H2
Electrode potential

Hg Fe Pt
E

10-12 10-7 10-3

Current density / A cm-2

i0 depends on catalytic properties and varies over

many orders of magnitude between the metals.
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 Anodic and cathodic Anodic polarization
polarisation,
H2
e.g., 2H+ + 2e- => H2
H+
Equilibrium
ia > ic H2 => 2H+ + 2e-
Free energy

H2 H+
Cathodic polarization
2H+ + 2e- => H2 H+
Metal surface Solution H2
ia = ic
ic > ia 2H+ + 2e- => H2

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 Butler-Volmer equation.
Describes the relationship between current density and potential
for an electrode reaction controlled by charge transfer at the surface.

i = i0 * exp αnFη – i0 * exp - (1-α)nFη

RT RT

ia ic
io = exchange current density
η = overvoltage or polarization
α = charge transfer coefficient, near 0.5
n = number of electrons involved in electrode reaction
F = Faradays constant
R = gas constant
T = absolute temperature
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 Butler-Volmer equation, cont.

At high anodic overvoltage

αnFη η
i = ia = i0 * exp = i0 * exp
RT βa

At high cathodic overvoltage

- nFη = - i*0 exp - η

i = i c = - i0 * exp (α-1)
RT βc

βa and βc are Tafel constants

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 Evans diagram displaying cathodic overvoltage.
Electrode potential

E=E0 - ηc
E0
ηc I =  ic - ia

E
i
ia ic

log current

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Evans diagram displaying anodic overvoltage

Electrode potential

E
E=E0 + ηa

ηa
E0
i =  ia - ic

ic i ia

log current

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 Evans diagrams can be used to explore
important phenomena, e.g., passivity.

Transpassive state
Potential

Passive state

Active state

log current
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 Basic Concepts in Corrosion and
Electrochemistry: Summary.

The corrosion cell Potential-pH diagram

Redox reaction Electric double layer
Faraday´s law Polarization, overvoltage
Electrode potential Exchange current density
Electrochemical half-cells Butler-Volmer equation
Standard potentials Tafel coefficient
The galvanic series Polarization (Evans) diagram
Nernst´s equation

1st training school – mcBEEs network, Delft 15-20 July 2018