ELECTROCHEMICAL KINETICS OF

CORROSION

Reading Material: Chapter 3 in

“Principles and Prevention of Corrosion”, Denny Jones, Prentice-Hall, 1996.

Dr. Ramazan Kahraman

Chemical Engineering Department

King Fahd University of Petroleum & Minerals
Dhahran, Saudi Arabia

Faraday’s Law

z Charge is related to mass of material

reacted in an electrochemical reaction:
M o Mn+ + ne-

One mol of metal n mols of electrons

To produce one mol

of metal ion and

Reacts
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 Faraday’s Law (Cont.)
z Onemole of metal (MW g) contains Avogadro’s number
(6u1023) of metal atoms
z Henceeach mole of metal will produce n times that
many number of electrons
z Charge on the electron is 1.6 u 10-19 C (coulomb)
z Charge of one mol of electrons (6u1023 electrons) will
then be 96500 C
z Hence one mole of metal will produce a charge of
n u 96500 C
z 96500 C/equivalent is known as Faraday’s constant
(also in units of J/V˜equivalent)
z Conversions: 1 A (ampere) = 1 C/s, 1 J = 1 C˜V
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Faraday’s Law (Cont.)

m QM ItM
nF nF
where Q charge (coulomb, C)
I current (amperes, A) (1 A 1 C/s)
F Faraday' s constant (96500 C/equivalent ˜ mol)
n number of equivalents (mols of electrons) transferred per mol of metal
m mass of metal oxidized (g)
M molecular (atomic) weight of metal (g/mole)

corrosion rate, r m I t M / nF i M
tA tA nF
where A surface area
i current density, I/A
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 How Fast will Corrosion Occur?
z Corrosionkinetics
– Concerned with the rates of corrosion reactions
z Mixed potential theory:
– The corrosion potential will be that potential at which the
sum of all anodic (positive) and cathodic (negative)
currents on the electrode is zero
(i.e. ~anodic current~=~cathodic current~)
(mixed equilibrium) (not an electrochemical equilibrium)
z Polarization
– The change in the potential of an electrode
as current flows to or from it
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Corrosion of Zinc in Acid

z When zinc is placed in acid the metal will start to
dissolve (Zn o Zn2+ + 2e-) and hydrogen will start to
be liberated (2H+ + 2e- o H2) according to the
potential of the metal

Zn
Zn+2
c a e- H+ H2
H+

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 Corrosion of Zinc in Acid
Electrochemical Potential

Zn o Zn2+ + 2e-

At the Corrosion
Potential, Ecorr, we have a
Ecorr stable mixed equilibrium

2H+ + 2e- o H2

icorr Rate
Current
of Reaction
density
As the reaction involves transfer of
Then the corrosion rate may be charge, the rate of reaction may be
expressed as the corrosion current expressed as a current per unit area, or
density, icorr 7
current density

Corrosion of Zinc in Acid (Cont.)

Electrochemical Potential

Zn o Zn2+ + 2e-
If the potential is above the
Corrosion Potential, then it will fall
due to production of electrons

x If the potential is below the Corrosion

Potential, then it will rise, due to
consumption of electrons
2H+ + 2e- o H2

Rate
Current
of Reaction
density

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 Types of Polarization

z ActivationPolarization
z Concentration Polarization
z Resistance (IR-drop) Polarization

Activation Polarization

z Result of a slow step in an electrode reaction at the anode or

cathode

– For example, when hydrogen evolves at the cathode, the reaction

might be considered as:

Step 1: H+ + e- Æ Hads
Step 2: Hads + Hads Æ H2
Step 3: Sufficient molecules of H2 combine and nucleate
a hydrogen bubble.

Any one of these steps can control the rate of reaction and cause
activation polarization.

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 Activation Polarization (Cont.)
Example: Hydrogen reduction reaction under activation control.

[“Corrosion Engineering”, Mars Fontana, McGraw-Hill, 1986]

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Tafel’s Law for Activation Polarization

i i
E Eo  b log or K b log
io io

where E= potential at current i

Eo = potential at current io (ec for cathodic rxn and ea for anodic rxn)
b= Tafel slope ((+) for anodic rxn, (-) for cathodic rxn)
K= polarization (E-Eo at current i)

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 Tafel’s Law at icorr

Anodic Polarization
i i
Ecorr ea  ba log corr or Kaat i ba log corr
io corr io

Cathodic Polarization
i i
Ecorr ec  bc log corr or Kcat i bc log corr
io corr io

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E-log i and Evans Diagrams

z Plot E against log |i|, then activation

polarization gives a straight line
Electrode Potential

Tafel slope expressed as mV per decade of

current

mV

log |i2 | - log |i1 |

log |current|
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E-log i and Evans Diagrams (Cont.)

Eo and io for the cathodic reaction Anodic reaction, Tafel slope is

positive
Electrode Potential

Mixed equilibrium occurs when

sum of all currents is zero, i.e. at
Ecorr and icorr for the corrosion
reaction

log |current|
Eo and io for the anodic reaction Cathodic reaction, Tafel
slope is negative
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Exchange Current Density, io

When a piece of metal is sitting in a solution at its

equilibrium potential, this does not mean that the rates of
the metal dissolution and reprecipitation reactions are zero.

Instead it implies that the rates of the two reactions are

equal.

When the metal dissolution and reprecipitation reactions

are in equilibrium, we refer to the (equal and opposite) rates
(in terms of current density) of each of the two reactions as
the exchange current density, io.

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 Polarization

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Effect of Degree of Polarization

As degree of polarization gets higher (i.e. ~slope~ increases)

Î icorr (corrosion rate) decreases.
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 Example (Zinc in Acid)

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Example (Cont.)

Note that the reverse reactions, zinc deposition (Zn2++2e-ÆZn)

and hydrogen oxidation (H2Æ2H++2e-), do not occur since the
corrosion potential lies between 0.0 and -0.762 volt. Zinc
deposition (Zn2++2e-ÆZn) can only occur at potentials more
negative than -0.762 V, and hydrogen oxidation (H2Æ2H++2e-)
only occurs at potentials more positive than
0.0 V.

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 Concentration Polarization
z Additional polarization (i.e. slowing down of a reaction)
caused by depletion / drop in concentration of a
reactant at the electrode surface or an excess of the
unwanted species at the electrode surface (diffusion
controlled polarization)
z Concentration polarization is low / insignificant until a
limiting current density, iL, is approached (i.e. it
becomes effective at high rates approaching iL)
z Limiting current density, iL, is the measure of a
maximum reaction rate that cannot be exceeded
because of a limited diffusion rate of a reactant
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Concentration Polarization (Cont.)

[“Principles and Prevention of Corrosion”, Denny Jones, Prentice-Hall, 1996]

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 Concentration Polarization (Cont.)
Example: Concentration polarization during hydrogen reduction.

[“Corrosion Engineering”, Mars Fontana, McGraw-Hill, 1986]

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Concentration Polarization (Cont.)

Effect of Solution Conditions on Concentration Polarization

[“Principles and Prevention of Corrosion”, Denny Jones, Prentice-Hall, 1996]

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Concentration Polarization (Cont.)

2.303RT § i ·
K conc E  Eo log¨¨1  ¸¸
nF © iL ¹

Concentration polarization is usually negligible (insignificant)

on anodes and usually ignored.

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Combined Polarization

Total Cathodic Polarization

i 2.303RT § i ·
K c K act ,c  K conc ,c bc log c  log¨¨1  c ¸¸
io nF © iL ¹

Anodic Polarization
i
K a K act ,a ba log a
io

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 Combined Polarization (Cont.)

[“Principles and Prevention of Corrosion”, Denny Jones, Prentice-Hall, 1996]

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Combined Polarization (Cont.)

z Oxygen reduction is often affected by

concentration polarization
Rate of cathodic oxygen reduction
without concentration polarization
Electrode Potential

Rate of cathodic oxygen reduction

with concentration polarization
Limiting current density - rate of
reaction limited by availability of
oxygen at the metal surface
log |current density|
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Combined Polarization (Cont.)

[“Principles and Prevention of Corrosion”, Denny Jones, Prentice-Hall, 1996]

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Resistance Polarization

z Ifthere is a resistance between the anode and

the cathode in a cell, then the current flowing
through that resistance will cause a potential
drop given by Ohm’s Law:

V = IR

z This is important for paint films and for high

resistance solutions

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 Resistance Polarization
Resistance Polarization causes
potential of anode and cathode to differ
due to potential drop across solution,
hence corrosion current is reduced
Electrode Potential

log |current density|

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Sample Polarization Curves

z Iron in hydrochloric acid

Electrode Potential

Anodic iron dissolution

Cathodic hydrogen evolution

log |current density|

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Sample Polarization Curves (Cont.)

z Iron in aerated neutral NaCl solution

Electrode Potential

Anodic iron dissolution

Cathodic oxygen reduction

Cathodic hydrogen evolution

log |current density|

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Sample Polarization Curves (Cont.)

z Iron in sulphuric acid (passivity to be studied later)

Electrode Potential

Oxygen evolution on passive film (or

transpassive corrosion as metal is oxidised to
a higher oxidation state)

Anodic iron dissolution (with

active-passive transition)

Cathodic hydrogen evolution

log |current density|

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 Effect of Oxidizer
Ecorr n, icorr n, rate of hydrogen evolution p

[“Principles and Prevention of Corrosion”, Denny Jones, Prentice-Hall, 1996]

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Effect of Exchange Current Density

[“Principles and Prevention of Corrosion”, Denny Jones, Prentice-Hall, 1996]

The deriving force (difference between the half-cell reaction potentials is much larger for zinc
than iron. However, the corrosion rate of zinc, icorr,Zn, is lower than that of iron, icorr,Fe,
because of the low exchange current density for hydrogen reduction on zinc compared to
iron and the comparatively low exchange current density for zinc dissolution.
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Effect of Dissolved Ion Concentration

Drawing appropriate polarization diagrams, determine the effect of “increasing

the concentration of dissolved H+” on “Ecorr” and “icorr” of a metal M corroding to
dissolved M+ in a deaerated acid solution under activation control with all other
parameters constant.

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Example Problem

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 Home Work Problems

Prbs. 1, 6, 7 and 8 of Ch.3

in “Principles and Prevention of Corrosion”, Denny Jones, Prentice-Hall, 1996.

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References

z “Principles and Prevention of Corrosion”, Denny Jones, Prentice-Hall, 1996.

z “Corrosion Engineering”, Mars Fontana, McGraw-Hill, 1986.
z “Corrosion and Corrosion Control”, H. H. Uhlig and R. W. Revie, John Wiley &
Sons, 1985.
z Web Site of Dr. R. A. (Bob) Cottis.

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