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Characteristics of EC reactions that both

oxidation(produce e
-
)

and reduction
( consume electrons) occur and electrons
transfer. eg : Zinc or iron in HCl
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
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
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.)
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
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.
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

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


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.

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


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
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)

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
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
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
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 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
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
(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
(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.

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
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.


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.

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
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
( ) ( )
|
|
.
|

\
|
(

=
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

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

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