CORROSION RATES

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Polarization phenomena
 Driving force for corrosion:

POTENTIAL DIFFERENCE BETWEEN ANODIC
AND CATHODIC REACTIONS
 If Zn is place alone in a non-aqueous
electrolyte:

The oxidation reaction: Zn  Zn++ + 2e-

and reduction : Zn2+ +2e-  Zn
 Proceed at equal rates:

No net corrosion at equilibrium

But electrons are freed and combined.

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Open circuit potentials
 When current is not drawn from a
corroding cell, the local potentials
are:
 OPEN CIRCUIT POTENTIALS
 At equilibrium the number of
electrons can be calculated = # of
amperes / cm2
 known as the Exchange current

density io
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 At
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equilibrium: io = ia =ic [equal
MN 3112 CORROSION RATES 3
 Electrochemical potential
of an Anodic half cell
(schematic)
• Common way to
monitor
Electrochemical Potential (E)

corrosion
behaviour is to
measure and
plot E vs
resulting
corrosion rate.
• This is linear if
Corrosion Rate (Log
corrosion rate is
Scale) on a logarithmic
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08:59 PM scale
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 Electrochemical potential
of a corrosion cell
(schematic)
• Intersection of
the individual
Ca cathodic and
Electrochemical Potential (E)

th o
d ic
rea anodic half-cell
ctio
n reactions gives
Ec
the Corrosion
potential Ec
n
cti o
a
re
dic
o
An

Corrosion Rate (Log Scale)

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Current flow in cells
 On flow of current certain
irreversible effects occur adjacent
to the electrode:
 These tend to oppose direction of
current flow.
 Known as POLARIZATION of the
electrodes.

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Effect of Electrode
Polarization
 Potential of anode becomes more
cathodic and
 Potential of the cathode becomes
more anodic as a result;
 p.d. between electrodes diminishes
and
 amount of current in the closed circuit
decreases (see next slide).
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Mechanism of polarization

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 Polarization explained
 E0(c) and E0(a) open
circuit potentials of
the electrodes:
 represent local
cathodic and anodic
areas on the metal
surface or
 the two potentials of
two different metals
e.g. in a galvanic
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 Polarization defined
 Departure of the
electrode potentials from
their equilibrium values,
which are the open circuit
potentials.
 During flow of I, local
anodes and cathodes
undergo polarization 
potentials changes until
steady state (when mixed
potentials
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08:59 PM MN 3112 CORROSION RATES 10
(corrosion potential))
Overpotential or
Overvoltage
 Difference between observed
potential (E) and a reversible or
open circuit potential (E0).
 η = E – E0
 At the Corrosion potential:
 Sum of all rates of reduction(cathodic)
and oxidation (anodic) are equal.
 Current flowing is the corrosion

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current icorrMN 3112 CORROSION RATES
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11
 Corrosion current icorr
 Depends on:
 Exchange current densities at the
electrodes
 Potential difference and
 Polarization characteristics
 The greater the polarization of the
electrodes (anodic or cathodic or
both),
 The smaller the corrosion current
although open circuit p.d. may be high.
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Mechanism of polarization

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 Anodic polarization control
 If only anode undergoes
polarization, the degree

Anodic Overvoltage
to which the anode can
be polarized controls the
rate of corrosion;
 System under ANODIC
CONTROL
 With increased anodic
polarization, curve
becomes much steeper
and icorr greatly
decreases.
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Mechanism of polarization
(Anodic polarization)

Anodic Overvoltage
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 Cathodic polarization
control
 If only cathode
undergoes
polarization system
is under cathodic
control

Cathodic Overvoltage
 Polarization curve
becomes steeper
towards more anodic
values and icorr
greatly reduces
 See01/30/2025
next
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Mechanism of polarization
(Cathodic polarization)

Cathodic Overvoltage
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 Mixed polarization control
 If both anode and cathode
undergo polarization
system is under mixed
control.
 Icorr cannot be completely
extinguished by
polarization:
 Some current must remain
in the circuit for self
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polarization.
Polarization Phenomena
 Can be analyzed in terms of
components as:
 Activation polarization
 Concentration polarization
 Resistance or ohmic polarization.

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Activation Polarization
 Occurs when some step in the half
cell reaction controls the rate of
charge (electron) flow.
 Reaction said to be under
activation or charge-transfer
control.

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 Examination of the H2
evolution at a metal
surface
 2H+ + 2e- H2
 Occurs in three steps:
 Step 1: H+ reacts with an electron from the
metal  H+ + e-  Hads

Step 2 : Hads + Hads  H2

Step 3: requires sufficient H2 molecules to
combine and create a hydrogen bubble on
the surface.
 Any of these can control the rate of
reaction and cause activation
polarization.
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 Activation Polarization
 Potential changes of
electrode can be
related to current
density i by the Tafel
i

relationship:
b slope of E vs log i   log
 io =exchange current io
density of the
electrode
 Related to nature of
electrode and the
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corrosive
08:59 PM environment.
MN 3112 CORROSION RATES 22
Corrosion current
 For a corroding metal the corrosion
current is the polarizing current
 i = icorr
 If β and io are known, the Tafel
relationship can be used to
estimate the magnitude of icorr

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 Ecorr and Tafel relationship
 At equilibrium Ecorr = Ea = Ec
 In relation to the overpotential
 η = E – E
0
 Ecorr = E0(c) + ηc
Substituting the Tafel equation leads
to: icorr icorr
E E   log
corr o(c) E   log
c o(a) a
io ( c ) io ( a )
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 icorr icorr
Ecorr Eo ( c )   c log Eo ( a )   a log
io ( c ) io ( a )

 Equation permits to estimate

magnitude of icorr and thus amount
of corrosion;
 The Ecorr and the polarization
characteristics can be determined
from electrochemical measurements.
 Can be done by impressed external
current on corroding sample using:

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Galvanostatic or potentiostatic methods
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Icorr Measuring Methods
 Involves measuring corrosion
potential as function of applied
current density
 POTENTIOSTATIC method :
 Measurement of current density for
each fixed value of the applied
potential.
 Anodic and cathodic polarization
curves can be obtained by using
anodic
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or cathodic external
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Impressed external current
 Simple relation ia =ic =icorr no
longer applicable. Because of non
equilibrium new relationship:
 ia +ix = ic where ix is applied
current density
 If ix is cathodic  ix = ic – ia

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 Increasing cathodic ix
 With cathodic ix slope of
polarization curve [dE/d(log ix)]
and approaches true Tafel slope.
 At same ix -->> total ic
 since ia becomes negligible.
 Tafel equation becomes:
ix
  log
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icorr
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Estimation of icorr by anodic and cathodic
polarization using external current ix.

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Estimation of icorr by anodic and cathodic
polarization using external current ix.

Intersection of the Tafel

line with the horizontal line
corresponding to the
corrosion potential Ecorr,
gives the corrosion current
icorr

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 Estimation of icorr by anodic and cathodic
polarization using external current ix.
io H2/H+
Extrapolation of the Tafel
line to the reversible
EH+/H2 hydrogen potential give
the io for H2 evolution

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Concentration Polarization
 As reactions in corrosion cell
proceed,
 Ionic concentration in the vicinity of
the electrodes becomes different from
the main body of the electrolyte.
 Conc.  slowness in diffusion of ions
in the regions adjacent to the
electrodes.

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Factors controlling
Concentration Polarization
 Concentration polarization affected
by:
 Velocity adjacent to electrode surface
 Concentration of the diffusing species
in the environment.
 As V, diffusion rate of ions
increases and shift concentration
polarization curve to higher
currents.
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Concentration Polarization
and Electrode
 At anode:
 Conc. of metal ions gradually
increases, making anode more
positive.
 At cathode:
 Conc. of positive ions will decrease
making the cathode more negative.

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 Estimation of
Concentration Polarization
The interfacial
concentration of
 Can be estimated from:
metallic ions
 based on Nernst Eqn.
RT Cs
 2.303 log
nF Cb
Overpotential caused by
Bulk
concentration
concentration
polarization
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 Plot of Conc. Polarization
relationship
 η is low until a limiting current
density iL is reached.

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 Limiting Diffusion Current
 Conc. Polarization occurs at
very high current densities;
 Diffusion limits rate of

transfer of reacting species

from and to the electrode.
 At this limit further increase

in potential causes no
further increase in current
density;see plot

This is the LIMITING
DIFFUSION CURRENT
DENSITY (id).
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Estimation of icorr by anodic and cathodic
polarization using external current ix.

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 Concentratio
n at surface
Limiting Current Density (assumed
zero at
limitation)

nFDCb  C s 
 Can be calculated
from:
id 
Limiting
Current

density Bulk
# of concentrati
electron on
s in the Faraday Diffusion Thickness
reaction constant Coefficie of diffusion
=96,400o nt layer(Nernst
C layer)
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 LIMITING CORROSION
CURRENT DENSITY
 iL is increased by:
 higher solution
concentrations CB
 higher Temps, which
increase D
 higher solution agitation,
which decreases δ
 Conc. Polarization for
anode can be ignored.
 Unlimited supply of metal
ions available.
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