• Chapter 3

• Electrochemical nature of
Corrosion
• The Corrosion Process and Affecting
Factors
• There are four basic requirements for
corrosion to occur.

• Among them is the anode, where dissolution

of metal occurs, generating metal ions and
electrons.
• These electrons generated at the anode
travel to the cathode via an electronic path
through the metal, and eventually they are
used up at the cathode for the reduction of
positively charged ions.

• These positively charged ions move from the

anode to the cathode by an ionic current
path.
• Thus, the current flows from the anode to the
cathode by an ionic current path and from
the cathode to the anode by an electronic
path, thereby completing the associated
electrical circuit.

• Anode and cathode reactions occur

simultaneously and at the same rate for this
electrical circuit to function.
 Shorthand Notation for Galvanic Cells
In Daniell cell:
Anode half-reaction: Zn(s) Zn2+ + 2e-
Cathode half-reaction Cu(s) + 2e- Cu
• The rate of anode and cathode reactions
(that is the corrosion rate), is defined by
American Society for Testing and Materials
as material loss per area unit and time unit.

• In addition to the four essentials for

corrosion to occur, there are secondary
factors affecting the outcome of the
corrosion reaction.
• Among them there are temperature, pH,
associated fluid dynamics, concentrations of
dissolved oxygen and dissolved salt.

• Based on pH of the media, for instance,

several different cathodic reactions are
possible.
• The most common ones are :

• Hydrogen evolution in acid solutions,

• 2H+ + 2e  H2 (2.1)

• Oxygen reduction in acid solutions,

• O2 + 4H+ + 4e  2H2O (2.2)

• Hydrogen evolution in neutral or basic

solutions,

• 2H2O + 2e  H2 + 2OH (2.3)

• Oxygen reduction in neutral or basic
solutions,

• O2 + 2H2O + 4e  4OH (2.4)

• The metal oxidation is also a complex

process and includes hydration of resulted
metal cations among other subsequent
reactions.

• M°  Mn+ + ne- (2.5)

 Among cathode reactions in neutral or basic
solutions, oxygen reduction is the primary
cathodic reaction due to the difference in
electrode potentials.

 Thus, oxygen supply to the system, in which

corrosion takes place, is of utmost
importance for the outcome of corrosion
reaction.
• When corrosion products such as
hydroxides are deposited on a metal
surface, a reduction in oxygen supply
occurs, since the oxygen has to diffuse
through deposits.

• Since the rate of metal dissolution is equal to

the rate of oxygen reduction, a limited supply
and limited reduction rate of oxygen will also
reduce the corrosion rate.
• In this case the corrosion is said to be under
cathodic control.

• In other cases corrosion products form a

dense and continuous surface film of oxide
closely related to the crystalline structure of
metal.
• Films of this type prevent primarily the
conduction of metal ions from metal-oxide
interface to the oxide-liquid interface,
resulting in a corrosion reaction that is under
anodic control.

• When this happens, passivation occurs and

metal is referred as a passivated metal.

• Passivation is typical for stainless steels and

aluminum.
 Fundamental Components
• Corrosion can be defined as the
deterioration of material by reaction to its
environment.

• Corrosion occurs because of the natural

tendency for most metals to return to their
natural state; e.g., iron in the presence of
moist air will revert to its natural state, iron
oxide.
• Four required components in an
electrochemical corrosion cell: 1) An anode;
2) A cathode; 3) A conducting environment
for ionic movement (electrolyte); 4) An
electrical connection between the anode and
cathode for the flow of electron current.

• If any of the above components is missing or

disabled, the electrochemical corrosion
process will be stopped.
 Electrochemical Corrosion
Corrosion of zinc in an acid solution
• Two reactions are necessary:
-- oxidation reaction: Zn  Zn 2  2e 
-- reduction reaction:
2H  2e  H2 (gas)
H+
Oxidation reaction
flow of e- Zn Zn2+ H+
in the metal
Zinc 2e- 
H+
H+ Acid
solution
H+
H+
H2(gas)
H+
reduction reaction

• Other reduction reactions in solutions with dissolved oxygen:

-- acidic solution -- neutral or basic solution
 
17
O 2  4H  4e  2H2O O2  2H2O  4e  4(OH)
 Standard EMF Series
• EMF series o
Emetal
• Metal with smaller
o
metal Emetal corrodes.
Au +1.420 V
more anodic more cathodic

• Ex: Cd-Ni cell

Cu +0.340 o < E o  Cd corrodes
ECd Ni
Pb - 0.126
Sn - 0.136 -
Ni - 0.250
+
o
Co - 0.277 DE =
Cd - 0.403 0.153V
Fe - 0.440
Cr - 0.744 Cd 25°C Ni
Zn - 0.763
Al - 1.662
Mg - 2.363 1.0 M 1.0 M
Na - 2.714 Cd 2+solution Ni 2+ solution
K - 2.924
18
 Driving force
• A driving force is necessary for electrons to flow
between the anodes and the cathodes.

• The driving force is the difference in potential

between the anodic and cathodic sites.

• This difference exists because each oxidation or

reduction reaction has associated with it a potential
determined by the tendency for the reaction to take
place spontaneously. The potential is a measure of
this tendency.
If Ecell > 0, the cell reaction is •
spontaneous

If Ecell < 0, the cell reaction is non- •

spontaneous

If Ecell = 0, the cell reaction is at •

equilibrium
 Galvanic Series
• Ranking the reactivity of metals/alloys in seawater
more cathodic

Platinum
Gold
Graphite
(inert)

Titanium
Silver
316 Stainless Steel (passive)
Nickel (passive)
Copper
Nickel (active)
Tin
more anodic

Lead
(active)

316 Stainless Steel (active)

Iron/Steel
Aluminum Alloys
Cadmium
Zinc
Magnesium
22
 Solution Concentration and Temperature

• Ex: Cd-Ni cell with • Ex: Cd-Ni cell with

standard 1 M solutions non-standard solutions
RT X
o
ENi  ECd
o
 0.153 V E Ni  ECd  ( E Ni  ECd ) 
o o
ln
nF Y
- + - +

n = #e-
per unit
Cd 25°C Ni Cd T Ni oxid/red
reaction
(= 2 here)
1.0 M 1.0 M XM YM F=
Cd 2+ solution Ni 2+ solution 2+ 2+
Cd solution Ni solution Faraday's
constant
= 96,500
C/mol.
24
 Kinetics, Polarization, Corrosion Rates

• While it is necessary to determine corrosion

tendencies by measuring potentials, it will
not be sufficient to determine whether a
given metal or alloy will suffer corrosion
under a given set of environmental
conditions.
• Even though the tendency for corrosion may
be high, the rate of corrosion may be very
low, so corrosion may not be a problem.

• Corrosion rates are determined by applying

a current to produce a polarization curve
(the degree of potential change as a
function of the amount of current applied) for
the metal surface whose corrosion rate is
being determined.
• The variation of potential as a function of
current (a polarization curve) enables the
study of concentration and activation
processes on the rate at which anodic or
cathodic reactions can transfer electrons.

• Polarization measurements can thereby

determine the rate of the reactions that are
involved in the corrosion process (the
corrosion rate).
Anodic Polarization Curve -1
• This curve is usually
scanned from 20 mV
below the Eoc (open
Types of Tests circuit potential)
upward.
ANODIC POLARIZATION CURVE •The curve can be
•this curve is usually scanned from 20mVused
below theto identify the
Eoc upwards
•by scanning at a slow rate (.2mV/s) thisfollowing corrosion
curve can be used to identify
several corrosion mechanisms shown below regions:

ip - passive current density

Epp - primary passivation potential

icrit - critical current density

Etrans - transpassive potential

 The degree of polarization is a measure of
how the rates for anodic and cathodic
reactions are slowed by various
environmental factors (concentration of metal
ions, dissolved oxygen in solution, diffusion
limitations; referred to as concentration
polarization) and/or surface process
(activation polarization).
 All electrochemical reactions consist of a
sequence of steps that occur in series at the
interface between the metal electrode and
the solution.

 Activation polarization is where the reaction

is limited (controlled) by the slowest rate
reaction of the steps (adsorption H+, film
formation, ease of release of electrons,
called the activation polarization).
 The Rusting Mechanism (Peel)
 4Fe + 6H2O + 3O2  4Fe(OH)3
 gives ferric hydroxide
 2Fe(OH)3  Fe2O3  3H2O
 gives iron oxide (rust) and water
 Basic “rusting” or corrosion requirements
 1. The metal is oxidized at the anode of an electrolytic cell
 2. Some ions are reduced at the cathode
 3. There is a potential or voltage difference between the
anode and cathode
 4. An electrolyte (fluid) must be present
 5. The electrical path must be completed
 CORROSION IN A GRAPEFRUIT
Cathode Anode
Cu +
-
H+ Zn
H+ Zn2+

reduction 2e - oxidation
2H  2e  H2 (gas )
H+
O2  4H  4e   2H2 O H+
Acid H+
H+ H+