Electrochemical Kinetics of

Corrosion
Electrochemical Reactions
Characteristics of EC reactions that both
oxidation(produce e
-
)

and reduction
( consume electrons) occur and electrons
transfer. eg : Zinc or iron in HCl
Electrodes
Electrodes are pieces of metal on which an
electrochemical reaction is occurring
An anode is an electrode on which an
anodic or oxidation reaction is occurring
A cathode is an electrode on which a
cathodic or reduction reaction is occurring
Single and mixed electrodes

A copper electrode in contact with its own ions (single
electrode) and with an aerated solution (mixed electrode).
CuCu2+ + 2 e
1/2O2+2H++2eH2O
Corrosion of zinc in acid
When zinc is placed in acid the metal will
start to dissolve and hydrogen will start to
be liberated according to the potential of the
metal
Consider the anodic zinc dissolution
reaction
Zn Zn
2+
+ 2e
-
8
Two reactions are necessary:
-- oxidation reaction:
-- reduction reaction:


Zn Zn
2+
+ 2e

2H
+
+2e

H
2
(gas)
Other reduction reactions:
-- in an acid solution -- in a neutral or base solution


O
2
+4H
+
+4e

2H
2
O


O
2
+2H
2
O+4e

4(OH)

Adapted from Fig. 17.1, Callister 7e.

(Fig. 17.1 is from M.G. Fontana,
Corrosion Engineering, 3rd ed.,
McGraw-Hill Book Company, 1986.)
CORROSION OF ZINC IN ACID
Zinc
Oxidation reaction
Zn
Zn
2+
2e
-
Acid
solution
reduction reaction
H
+
H
+
H
2
(gas)
H
+
H
+
H
+
H
+
H
+
flow of e
-

in the metal
Review of the Electrochemical Basis of
Corrosion

Corrosion normally occurs at a rate determined by an
equilibrium between opposing electrochemical reactions.
The first is the anodic reaction, in which a metal is
oxidized, releasing electrons into the metal. The other is
the cathodic reaction, in which a solution species (often O2
or H
+
) is reduced, removing electrons from the metal.
When these two reactions are in equilibrium, the flow of
electrons from each reaction is balanced, and no net
electron flow (electrical current) occurs.
Corrosion of zinc in acid
Zn Zn
2+
+ 2e
-
Rate of Reaction
E
l
e
c
t
r
o
c
h
e
m
i
c
a
l

P
o
t
e
n
t
i
a
l

2H
+
+ 2e
-
H
2

Corrosion Potential
Corrosion Rate
At the Corrosion
Potential, E
corr
, we have a
stable mixed equilibrium
Then the corrosion
rate may be
expressed as the
corrosion current
density, i
corr

Current density i
corr
E
corr

Graphical Representation of the Butler-Volmer Relationship between
Potential and Current in a Mixed Potential System

J. Scully & R. Kelly, ASM Handbook, Volume 13A,
2003
M + 2H
+
M
2+
+ H
2
An experiment like this is called
a Tafel Plot and is relatively
common in todays corrosion
laboratory.
Experimental result from the
corrosion measurement system.
The equilibrium potential assumed by the metal in the
absence of electrical connections to the metal is called the
Open Circuit Potential, Eoc. The terms Eoc (Open Circuit
Potential) and Ecorr (Corrosion Potential) are usually
interchangeable, but Eoc is preferred.
The value of either the anodic or cathodic current at Eoc is
called the Corrosion Current, Icorr. If we could measure
Icorr, we could use it to calculate the corrosion rate of the
metal.
Unfortunately, Icorr cannot be measured directly. However,
it can be estimated using electrochemical techniques. In any
real system, Icorr and Corrosion Rate are a function of many
system variables including type of metal, solution
composition, temperature, solution movement, metal history,
and many other
When the potential of a metal sample in solution is
forced away from Eoc, it is referred to as polarizing the
sample.







The response (current) of the metal sample is measured
as it is polarized. The response is used to develop a
model of the sample's corrosion behavior.


The polarization expresses the difference
between the potential of a mixed electrode
subjected to anodic or cathodic polarization and
its corrosion potential.

= E Ecor


Types of Polarization
Activation Polarization
The polarization necessary for the electrochemical
reaction to go at the given rate
Given by Tafels Law:
o
o
i
i
E E log | + =
E = potential at current i
E
o
= potential at current i
o

= Tafel slope

An electrochemical reaction under kinetic control obeys the
Tafel Equation.
I = I
0

e
(2.3(E-E)/)

In this equation,
I is the current resulting from the reaction
I
0

is a reaction dependent constant called the
Exchange Current
E is the electrode potential
E
o
is the equilibrium potential (constant for a
given reaction)
is the reaction's Tafel Constant (constant for
a given reaction).
Beta has units of volts/decade.

Hydrogen Evolution
Consider hydrogen evolution in acid:
2 H
+
+ 2 e
-
H
2
Actually occurs in two steps:
1 H
+
+ e
-
H
ads

either

2a 2 H
ads
H
2

or 2b H
ads
+ H
+
+ e
-
H
2


Anodic Dissolution of Iron
Fe Fe
2+
+ 2 e
-

Rate of reaction is proportional to [OH
-
] in acid
solutions
Reaction sequence is thought to be:
1 Fe + H
2
O FeOH + H
+
+ e
-

2 FeOH FeOH
+
+ e
-
(rds)
3 FeOH
+
+ H
+
Fe
2+
+ H
2
O
The pH dependence comes from the equilibrium
in step 1
Rate Determining Step
With a multi-step reaction, one step will
typically go more slowly, and therefore
control the rate of reaction
Known as rate determining step (rds)

Concentration Polarization
Additional polarization caused by drop in
concentration of a reactant at the electrode
surface
As concentration falls, more polarization is
needed to make the current flow
Eventually, no more current can flow because
no more reactant can reach the metal, and a
limiting current is reached
Concentration Polarization
Oxygen reduction is often affected by
concentration polarization
log |current density|
E
l
e
c
t
r
o
d
e

P
o
t
e
n
t
i
a
l

Rate of cathodic oxygen
reduction without
concentration polarization
Rate of cathodic oxygen
reduction with
concentration polarization
Limiting current density
Resistance Polarization
If there 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 Ohms Law:
V = IR
This is important for paint films and for
high resistance solutions
Resistance Polarization
log |current density|
E
l
e
c
t
r
o
d
e

P
o
t
e
n
t
i
a
l

Resistance Polarization
causes potential of anode
and cathode to differ due
to potential drop across
solution, hence corrosion
current is reduced
Experimental determination of corrosion rates
Two types of experimental tests are commonly used to determine the
corrosion rate in solution:
Immersion tests;
Electrochemical tests.
Corrosion Rate Expression
Corrosion Penetration Rate (CPR)
CPR = K W/DAT
K= constant (534 for mpy, 87.6 for mm/yr)
W= weight loss,mg
D= density, g/cm
3
A = Area,in
2
or cm
2
T = time,hr
Faradays Law
Consider the reaction
Fe Fe
2+
+ 2 e
-

For every atom of iron reacting, two electrons will
be produced.
One mole contains Avogadros number (610
23
)
atoms
The charge on each electron is 1.610
-19
C
Hence each mole produces 296500 C
Faradays constant (F) = 96500 C/mole
The atomic
weight in grams,
i.e. 55.8 g for Fe
Faradays Law
(g/mole) metal of weight atomic
(g) oxidised metal of mass
(C/mole) constant s Faraday'
atom metal each for electrons of number
(C) passed charge where
=
=
=
=
=
=
M
m
F
n
Q
M
nFm
Q
More accurately
relative atomic
mass, but still
with units g/mole
According to Faradays Law, when ni moles of a given
substance react, a proportional electric charge Q passes across
the electrode-electrolyte interface
Faradays Law Divide by time
(g/mole) metal of weight atomic
(g/s) corrosion of rate
(C/mole) constant s Faraday'
atom metal each for electrons of number
(A) current corrosion where
=
=
=
=
=
=
M
K
F
n
I
M
nFK
I
Faradays law thus states that the rate of an electrode reaction is
proportional to the magnitude of the electrical current that
crosses the electrode-electrolyte interface.

Faradays Law
Divide by area:
(g/mole) metal of weight atomic
) m (g/s corrosion of rate
(C/mole) constant s Faraday'
atom metal each for electrons of number
) (A/cm density current corrosion where
2
2
=
=
=
=
=
=
=
M
k
F
n
i
nF
iM
k
M
nFk
i
Calculation of Corrosion Rate from i
corr
From the engineering standpoint, it is convenient to express
Corrosion Rate in units of penetration, mpy (milli-inches per year)
or mmpy (mm per year).

Divide both sides of the equation by area and density (g/cm
3
),

Corrosion Rate (mpy) = 0.13 i
corr
(M/n)/d
Corrosion Rate (mmpy) = 0.00327 i
corr
(M/n)/d


where i
corr
is corrosion current density in A/cm
2
.

M/n = equivalent weight, for Iron = 27.92

Calculation of i
corr
from R
P

Stern-Geary Equation:
R
P
= AE/Ai =
a

c
/2.3 i
corr
(
a
+

c
)


R
P
= Slope at the origin of the Polarization Resistance Plot in
ohms
i
corr
= corrosion current, Amperes

a
,

c
= Tafel Constants from a Tafel Curve, volts/current decade.


In Short
Electrochemical kinetics of a corroding metal can be characterized
by determining at least three polarization parameters, such as
corrosion current density (icorr),corrosion potential( Ecorr) and
Tafel slopes (a and/or c).

Then the corrosion behavior can be disclosed by a polarization
curve (E vs.log i).

Evaluation of these parameters leads to the determination of the
polarization resistance Rp and the corrosion rate as icorr which is
often converted into Faradaic corrosion rate CR having units of
mm/yr.

Butler-Volmer Equation
The Butler-Volmer equation describes the relationship between the
potential and the current (kinetics) in a mixed potential system.

I= I
a
+ I
c
= I
CORR
(e
(2.3(E-Eoc)/|a)
e
(-2.3(E-Eoc)/|c)
)

Where:
I = cell current (A)
I
CORR
= corrosion current (A)
E = applied potential (V)
E
oc
= corrosion potential (V)
|
a
= anodic Tafel constant (V/decade)
|
c
= cathodic Tafel constant (V/decade)
Rate of anodic reaction Rate of cathodic reaction
E-log i and Evans Diagrams
Plot E against log |i|, then activation
polarization gives a straight line
log |current|
E
l
e
c
t
r
o
d
e

P
o
t
e
n
t
i
a
l

Cathodic reaction,
Tafel slope is
negative
Tafel slope
expressed as
mV per decade
of current
mV
log (-i
2
) - log (-i
1
)
Anodic reaction,
Tafel slope is
positive
Mixed equilibrium
occurs when sum of
all currents is zero
E
o
and i
o
for the
cathodic reaction
E
o
and i
o
for the
anodic reaction
E
corr
and i
corr
for the
corrosion reaction
LPR
( ) ( )
|
|
.
|

\
|
(

=
c
corr
a
corr
corr app
E E 3 . 2
exp
E E 3 . 2
exp i i
c a app
i i i =
! n
x
! 2
x
x 1 e
n 2
x
+ + + =
RELATIONSHIP BETWEEN APPLIED
ELECTROCHEMICAL CURRENT DENSITY AND
POTENTIAL FOR A CORRODING ELECTRODE
|
|
.
|

\
|
|
A

|
A
=
(
(

|
|
.
|

\
|
|
A
+
|
|
.
|

\
|
|
A
+ =
c a
corr
c a
corr app
E 3 . 2 E 3 . 2
i
E 3 . 2
1
E 3 . 2
1 i i
STERN-GEARY EQUATION

A potential, usually 10-20 mV is applied
to a freely corroding element and the
resulting linear current response is measured.
Ohms Law
I=E/R
Therefore
R=E/I
This R is inversely
related to the
Corrosion Rate
(CR)

( )
( )
p c a
c a
p
corr
c a corr
c a
0 E E
app
2
p
R
B
R 3 . 2
1
i
i 3 . 2 i
E
cm R
corr
=
|
|
.
|

\
|
| + |
| |
=
|
|
.
|

\
|
| + |
| |
=
A
A
= O

|
|
.
|

\
|
|
+
|
A =
c a
corr app
1 1
E 3 . 2 i i
TYPICAL LINEAR POLARIZATION RESISTANCE
CURVE

Polarization resistance, defined as the slope of the
polarization curve at the origin
The extent of linearity depends on the values of Tafel constants
selected