Académique Documents
Professionnel Documents
Culture Documents
THERMODYNAMIC OF
CORROSION:
POURBAIX DIAGRAM
STABILITY OF WATER
Water
2H 2e H 2 ( g )
or, in neutral or alkaline solution as
H 2O 2e H 2 ( g ) 2OH
These
EH / H E
2
H / H2
0.0592
H2
log
2
2
H
0.0592
EE
2 pH
2
E E 0.0592 pH
As
O2 4H 4e 2H 2O
in acid
O2 2H 2O 4e 4OH
in neutral or alkali
And
0.0592
H 2O
E O2 / H 2O
log
4
O2 H
EO2 / H 2O
E E 0.0592 pH
So
These
It
The
Any
a)
M M
b)
ne
Oxidation to hydroxide/oxide
M nH 2O M OH n nH ne
c)
M nH 2O MOn
2nH ne
Copper
Gold
applications include:
1. Formulation of corrosion control methods
(use of cathodic protection, anodic protection,
corrosion inhibitors etc.)
2. Identification of possible corroding states of
the metal-H2O system (regions of immunity,
passivation, corrosion or cracking)
3. Prediction of most likely corrosion products
(Fe2+ or Fe3+ ) for the metal-H2O system.
Some
1.
2.
3.
4.
5.
8.6
Line 3
Line 5
Al3+
Al2O3
AlO2Line 1
Line 2
Al
Line 4
E 1.66V
3
0
.
0592
Al
E Al / Al 3 E
log
n
Al
0.0592
3
E Al / Al 3 1.66
log Al
3
[ Al 3 ] 106 , n 3
b)
2 Al 3H 2O Al 2O3 6H 6e E 1.55V
E Al / Al 2O3
E Al / Al 2O3
Al 2O3 H
0.0592
E
log
2
n
Al
0.0592
1.55
6 log H
6
Slope 0.0592
Intersection
2 Al
3H 2O Al 2O3 6H
Al 10
3
[H ]
Al
3 2
10
11.4
6 pH 2 logAl
log K log Al
pH
6
3
11.4 6 3.9
6
c)
Al 2H 2O AlO2 4H 3e
E 1.26V
0.0592
AlO H
E Al / AlO E
log
2
Al
n
0.0592
E Al / AlO 1.26
[log AlO2 4 pH ]
2
3
E Al / AlO
2
0.0592
4
1.26
log AlO2 0.0592 pH
3
3
Al 2O3 H 2O 2 AlO2 2H
There
[ AlO2 ] 10
When
pH 8.6
Conclusion of Water-Aluminium
diagram
The
alkaline solutions:
Al 2H 2O AlO2 4H 3e
Corrosion/oxidation
is favoured in most
natural conditions.
Corrosion can be made thermodynamically
impossible with cathodic protection by moving
the potential into the range of immunity.
In the intermediate pH range between 4 and 8,
Al2O3 provides a protective film with that the
corrosion rate is low in all electrolytes.
At high and low pH, where the oxide is soluble,
the corrosion rate may be high depending
other ions present.