Thermodynamics-Pourbaix

To be a partner of choice in corrosion research

Corrosion Electrochemistry :
Thermodynamics

11/2/2012

Electrode potential,V

*Dr.M Pourbaix (1966)

pH

E-pH Diagram: Represent states of lowest free energy

E.g: Fe-H2O system:

predicting

environment
changes that will
prevent or reduce
corrosive attacks
large region
labelled Fe in the
potential-pH diagram
for Fe-H2O 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

oxidizing power (potential) and acidity of
(pH) for the various possible phases
stable in aqueous electrochemical

solution
alkalinity
that are
system.

The most common reduction reactions are the

reduction reactions of dissolved oxygen and the
reduction of water ( H2 evolution)

2H+ + 2e- = H2 (acidic)

2H2O + 2e- = H2 + 2OH- ( neutral/alkaline)
The Nernst equation gives
+ 2

2.303RT
H

E = E0
log
H
2F
2

0.059
E0
log H 2 0.059pH
2

For 1 atm. hydrogen gas

E = -0.059 pH vs SHE

Aerated Acid O2 + 4 H+ + 4 e- = 2 H2O

Acid
O2 + 2 H2O + 4 e- = 4 OH- Neutral
/Alkaline

0.059
EE
logO 2 0.059pH vs SHE
4
0
E 1.23 V
0

E = 1.23 - 0.059pH

Neutral/Basic O2 + 2 H2O + 4 e- = 4 OH2

RT O 2 H 2 O
0
EE
ln
4
4 F
OH

2.303RT
O
H
O
0
2
2
E
log
4

4F
OH

But [H2O]=1, and log([OH-])=-14+pH

2.303RT
log O 2 4pH 56
therefore E E
4F
0

02+4H++4e=2H2O

Potential (V vs. SHE)

1.23
_

Upper: water can be oxidized

and form O2:

O2

O2 can be reduced below line b

0H-+H+=H2O
0
_

Intermediate: water
is
thermodynamically
stable

a
2H++2e=H2
H2

pH

1
6

Lower: water can be

reduced to form H2

*(a) and (b) are commonly being superimposed on Pourbaix

diagrams.

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 Ni2+ + 2e
So potential depends on the activity

RT Ni
of [Ni2+] not pH.
ENi / Ni E
ln 2
nF Ni
0.25 0.03 log[ Ni 2 ]
Select 4 activities: 1, 10-2, 10-4, 10-6 M:
V
then
2

E=(-0.25V), (-0.23+0.03log(10-2)=0.31V,
E=(-0.37V), (-0.43V)

-0.25
0.31
-0.37
0.43

pH

 Reaction involving both electrons & hydrogen ion

e.g: NiO + 2H++2e Ni + H2O; Eo=0.11V

[ Ni ][ H 2O]
0.059
E E
log
2
2
[
NiO
][
H
]

V
0.11

E E 0.0295 log[ H ]
o

since
then

pH log[H ]
E 0.11 0.059 pH

NiO

Ni
0.05
0

pH

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 Ni2+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.

E, V

NiO2
Ni2+

0_

Ni(OH)2

0.4_

N
i

pH

At the metallic Ni/water interface:

Ni2++2e Ni
ENi = -0.25 + 0.026log[Ni2+]= - 0.37V
Deaerated acid solution:
2H++2e=H2
EH = -0.059 pHEH = -0.06V at pH 1
Since ENi more active than EH , so
the electron flow from Ni (-ve) to H2
(+ve). Nickel not stable at low pH in
water, so the corrosion occurs.
At pH 6 and 8:
Hydrogen more active than Ni
region of immunity of Ni
No corrosion

Will copper
corrode in
acid?

Potential

Will copper
corrode in
neutral waters?

CuO22- stable in soln.

2.0
No - hydrogen
1.6
evolution only
Cu oxides
1.2
occurs below the
stable
0.8 Cu2+ stable
potential for copper
corrosion
0.4
in solution
Usually it will0.0
just
passivate,-0.4
but
corrosion can-0.8
occur
Cu metal stable
in slightly acid
-1.2
solutions
-1.6
0
7
14

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.

Will iron
corrode in
acid?

2.0
1.6
Yes - there is a
1.2
reasonably wide
Fe3+
0.8
range of potentials
0.4
Fe oxides where hydrogen
stable can be evolved and
0.0can
Yes - although iron
iron dissolved
form an oxide in-0.4
neutral
Fe2+ stable
solution, it tends-0.8
not to
No - iron forms a solid
form directly on
the
Fe metal stable
-1.2
oxide at all potentials,
metal, as the potential
and-1.6
will passivate
is too low.
0
7
14
Potential

WillWill
ironiron
corrode
corrode
in
in alkaline
neutral
waters?
solution?

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

Potential

2.0
1.6 C
1.2
0.8
0.4
0.0
-0.4
-0.8
-1.2
-1.6
0

Passivity
C
corrode
Gold Gold
metalcant
stable
with oxygen reduction
Immunity
or hydrogen evolution

14