*Dr.

M Pourbaix
(1966)
E
l
e
c
t
r
o
d
e

p
o
t
e
n
t
i
a
l
,
V

pH
eE-pH Diagram: Represent states of lowest free
energy
E.g: Fe-H
2
O system:
predicting
environment changes
that will prevent or
reduce corrosive
attacks
large region
labelled Fe in the
potential-pH
diagram for Fe-
H
2
O system
indicates that iron
is inert under
these conditions.
Use of the Pourbaix
Diagrams:
Predicting the
spontaneous direction of
reactions
Estimating the
composition of corrosion
products
Predicting
environment changes
that will prevent or
reduce corrosive attacks
Limitation :
1. Tell us what can
happen, not
necessarily what
will happen
2. Cannot predict
corrosion rates.
3. Can only be
plotted for pure
metals and
simple solutions,
NOT for alloys.
The diagramme shows conditions of solution oxidizing
power (potential) and acidity of alkalinity (pH) for the
various possible phases that are stable in aqueous
electrochemical system
The most common reduction reactions are the
reduction reactions of dissolved oxygen and the
reduction of water ( H2 evolution)
Hydrogen-Water
2H
+
+ 2e
-
= H
2
(acidic)
2H
2
O + 2e
-
= H
2
+ 2OH
-
( neutral/alkaline)
The Nernst equation gives




For 1 atm. hydrogen gas
E = -0.059 pH vs SHE
| |
| |
| | ( ) pH 059 . 0
H
log
2
059 . 0
H
H
log
2
303 . 2
2
2
2
+
=
|
|
.
|

\
|
+

E

F
RT

E
= E
0
0
Oxygen-Water
Aerated Acid O
2
+ 4 H
+
+ 4 e
-
= 2 H
2
O Acid
O
2
+ 2 H
2
O + 4 e
-
= 4 OH
-
Neutral /Alkaline

| |
V 23 . 1
SHE vs pH 059 . 0 O log
4
059 . 0
0
2
0
=
+ =
E
E E
E = 1.23 - 0.059pH
Neutral/Basic O
2
+ 2 H
2
O + 4 e
-
= 4 OH
-

| || |
| |
| || |
| |
|
|
.
|

\
|
+ =
|
|
.
|

\
|
+ =

4
2
2 2
0
4
2
2 2
0
OH
O H O
log
4
303 . 2
OH
O H O
ln
4
F
RT
E
F
RT
E E
But [H
2
O]=1, and log([OH
-
])=-14+pH
| | ( ) ( ) 56 pH 4 O log
4
303 . 2
therefore
2
0
+ + =
F
RT
E E
P
o
t
e
n
t
i
a
l

(
V

v
s
.

S
H
E
)

pH
Upper: water can be oxidized
and form O
2:
O2 can be reduced below line b

Lower: water can be
reduced to form H
2

Intermediate: water
is
thermodynamically
stable
0
_
a
b
0
2
+4H
+
+4e=2H
2
O
2H
+
+2e=H
2

0H
-
+H
+
=H
2
O
O
2

H
2

1.23
_
0
1
6
*(a) and (b) are commonly being superimposed on Pourbaix
diagrams.
How to predict corrosion from Pourbaix
When metal surface is at a potential where one or both
of reduction reactions can occur, the possibility of
corrosion exists provided the metal disssolution
reaction is thermodynamically favourable.
Reaction of pure charge transfer.
Only electrons involved & NO hydrogen ion
e.g: Ni * Ni
2+
+ 2e
] log[ 03 . 0 25 . 0
ln
2
2
/
2
+
+
+
+ =
(

=
Ni
Ni
Ni
nF
RT
E ENi
o
Ni
So potential depends on the activity
of [Ni2+] not pH.
Select 4 activities: 1, 10
-2
, 10
-4
, 10
-6
M:
then

E=(-0.25V), (-0.23+0.03log(10
-2
)=-
0.31V,
E=(-0.37V), (-0.43V)
-
0.25 -
0.31 -
0.37
-
0.43
V
pH
Reaction involving both electrons & hydrogen ion
e.g: NiO + 2H
+
+2e *Ni + H
2
O; E
o
=0.11V
pH 0.059 0.11 E then
] log[H pH since
] log[ 0295 . 0
] ][ [
] ][ [
log
2
059 . 0
2
2
2
=
=
+ =
(

=
+
+
+
H E E
H NiO
O H Ni
E E
o
o
0.11
NiO
0.05
V
pH
Ni
0
A rod of Ni is immersed in an aqueous deaerated acid solution with a pH of 1 that
contains 10
-4
g-ion/L of Ni
2+
ions. The system is under 1 atm pressure. Will the nickel
corrode? What will happen at pH more than 8? Refer to the Pourbaix Diagram for nickel.
-At the metallic Ni/water interface:
Ni
2+
+2e * Ni
E
Ni
= -0.25 + 0.026log[Ni
2+
]= - 0.37V
-Deaerated acid solution:
2H
+
+2e=H
2

E
H
= -0.059 pHEE
H
= -0.06V at pH 1
-Since E
Ni
more active than E
H
, so
the electron flow from Ni (-ve) to H
2

(+ve). Nickel not stable at low pH in
water, so the corrosion occurs.
8
0_
-
0.4_
1
Ni
2+

N
i
NiO
2

Ni(OH)
2

pH
E, V
+At pH 6 and 8:
+Hydrogen more active than Ni
+region of immunity of Ni
+No corrosion
Pourbaix diagram for Copper
P
o
t
e
n
t
i
a
l

7 14
2.0
1.6
0.8
1.2
-0.4
0.4
0.0
-1.6
-0.8
-1.2
0
Cu metal stable
Cu
2+
stable
in solution
Cu oxides
stable
C
u
O
2
2
-

s
t
a
b
l
e

i
n

s
o
l
n
.

Will copper
corrode in
acid?
No - hydrogen
evolution only
occurs below the
potential for copper
corrosion
Will copper
corrode in
neutral waters?
Usually it will just
passivate, but
corrosion can occur
in slightly acid
solutions
Reversible potential for copper metal oxidation
reaction is above line a for all pH. Thus in the
absence of O2, metallic copper is thermodymanically
stable in pure water.
Pourbaix Diagram for Iron
P
o
t
e
n
t
i
a
l

7 14
2.0
1.6
0.8
1.2
-0.4
0.4
0.0
-1.6
-0.8
-1.2
0
Fe metal stable
Fe
3+

Fe oxides
stable
Will iron
corrode in
acid?
Fe
2+
stable
Yes - there is a
reasonably wide
range of potentials
where hydrogen
can be evolved and
iron dissolved
Will iron
corrode in
neutral waters?
Yes - although iron can
form an oxide in neutral
solution, it tends not to
form directly on the
metal, as the potential
is too low.
Will iron corrode
in alkaline
solution?
No - iron forms a solid
oxide at all potentials,
and will passivate
Corrosion Control Strategies
E = -0.2 V-SHE ,pH =4
Increase pH : Water
Treatment
Change potential:
Cathodic Protection
Anodic Protection
Extending passive
region: Alloying : SS
Passivating inhibitor
such as chromate ions
Pourbaix Diagram for Gold
P
o
t
e
n
t
i
a
l

7 14
2.0
1.6
0.8
1.2
-0.4
0.4
0.0
-1.6
-0.8
-1.2
0
Gold metal stable
Immunity
C
C
Passivity
Gold cant corrode
with oxygen reduction
or hydrogen evolution