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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)
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