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CMT555

THERMODYNAMIC OF
CORROSION:

POURBAIX DIAGRAM

STABILITY OF WATER
Water

can be converted to its component


elemental gases, H2 and O2 through the
application of an external voltage.
The reduction reaction of water can be written
either as

2H 2e H 2 ( g )
or, in neutral or alkaline solution as
H 2O 2e H 2 ( g ) 2OH

These

two reactions are equivalent and follow


the same Nernst equation

EH / H E
2

H / H2

0.0592
H2

log
2

2
H

Assuming H2 gas is 1 atm; log 1/[H+] = pH

0.0592
EE
2 pH
2

E E 0.0592 pH

As

potential becomes more positive or noble, water


can be decomposed into its other constituent (i.e.
oxygen).
The equations representing respectively the acidic
form and neutral or basic form of this equilibrium
are written as:

O2 4H 4e 2H 2O
in acid

O2 2H 2O 4e 4OH
in neutral or alkali

And

again these equivalent equations can be


used to develop a Nernst expression of the
potential in standard conditions of temperature
and oxygen pressure:

0.0592
H 2O
E O2 / H 2O
log

4
O2 H

EO2 / H 2O

Assuming [H2O] = 1 and [O2] = 1atm;


log 1/[H+] = pH

E E 0.0592 pH

So

the E vs. pH plots for both processes have


identical slopes and yield the stability diagram
for water shown below:
water can be oxidized and form oxygen

water is thermodynamically stable

water can be reduced to form hydrogen gas

These

diagram is divided into three regions.

In the upper one, water can be oxidized


and form oxygen (the stability of oxygen).
2. In the lower one, it can be reduced to form
hydrogen gas (the stability of hydrogen).
3. In the intermediate region, water is
thermodynamically stable (the stability of
water).
1.

It

is common practice to superimpose these two


lines (a) and (b) on Pourbaix diagrams to mark
the water stability boundaries.

E-PH OR POURBAIX DIAGRAMS


These

diagrams are graphical representations of


thermodynamic information appropriate to
electrochemical reactions (available for almost
all metals).
The objectives of the construction of the
diagram:
To predict whether or not corrosion can occur
To estimate the composition of the corrosion
product form
To predict environmental changes which will
prevent or reduce corrosion attack

The

parameters in Pourbaix diagrams are:


1. pH is plotted on the x-axis
2. Electrode potential (E) vs SHE is plotted on
the y-axis
There are three kinds of region/domain on the
diagram:
Region of immunity in which the metal itself
is the stable species and is immune to corrosion.
2. Region of corrosion in which the stable
species is a soluble ion and the metal is expected
to corrode.
3. Region of passivity in which the stable species
is insoluble (e.g. oxide, hydroxide or salt of the
metal) and the metal is resistant to corrosion.
1.

Any

point on the diagram will give the


thermodynamically most stable form of that
element at a given potential and pH condition.
Strong oxidizing agents and oxidizing
conditions are found only at the top of Pourbaix
diagram.
Reducing agents and reducing conditions are
found at the bottom of a diagram.
The are three general reactions by which a metal,
M may react anodically in the presence of water:

a)

Oxidation to aqueous cations

M M
b)

ne

Oxidation to hydroxide/oxide

M nH 2O M OH n nH ne

c)

Oxidation to aqueous anions

M nH 2O MOn

2nH ne

(These three reactions are used to construct


the Pourbaix diagram)

SAMPLE OF POURBAIX DIAGRAMS


Iron

Copper

Gold

APPLICATION AND LIMITATION


Its

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.

limitations of such diagrams include:


No information on corrosion kinetics is
provided by these thermodynamically derived
diagrams.
The diagrams are derived for specific
temperature and pressure conditions.
The diagrams are derived for selected
concentrations of ionic species (10-6 M).
Most diagrams consider pure substances only
for example the diagram applies to pure
water and pure metal only. Additional
computations must be made if other species
are involved.

5.

In area where a Pourbaix diagram shows


oxides to be thermodynamically stable, these
oxides are not necessarily of a protective
(passivating) nature.

Calculation and Construction


of E-pH diagram
Identify

all possible chemical and


electrochemical reactions in the given system
Apply Nernst equation to each possible reaction
Determine the relationship between the
potential (E) and the pH of the system
Draw the potential as a function of pH in a chart
[Mn+] = 10-6 M is assumed as borderline for
corrosion and non-corrosion region
The chart is divided into different region
representing different corroding conditions.

POURBAIX DIAGRAM FOR


ALUMINIUM
3.9

8.6

Line 3
Line 5
Al3+
Al2O3
AlO2Line 1
Line 2
Al

Line 4

CONSTRUCTION FOR ALUMINIUM


(WATER ALUMINIUM SYSTEM)
a)

Oxidation to Aluminium cation


Al Al 3 3e

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

(dependent on [Al3+], independent of


pH produce line 1)

b)

Oxidation to Aluminium oxide

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

E Al / Al 2O3 1.55 0.0592 pH

Slope 0.0592

(dependent of pH produce line 2)

Intersection

between line 1 and line 2


straight line (line 3)

2 Al

3H 2O Al 2O3 6H

(No electron transfer is required,


independent of potential but dependent on
concentrations of product & reactant)
The

equilibrium pH where line 1 and line 2


intersect may be calculated from the known
value of the equilibrium constant of K;

Al 10
3

[H ]

Al

3 2

10

11.4

6 pH 2 logAl

log K 6 log H 2 log Al

log K log Al
pH

6
3

At above 3.9 : Al2O3 is stable


below 3.9 : Al3+ is stable

11.4 6 3.9
6

when potential is sufficiently high

c)

Oxidation to Aluminium anion

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

1.26 0.020 log AlO2 0.079 pH

(Dependent on both pH and [AlO2-] produce


line 4) Slope = -0.079
At

some high pH the oxide Al2O3 dissolves as


the aluminate anion (AlO2-).

Al 2O3 H 2O 2 AlO2 2H
There

is no charge transfer, and the reaction is


independent of potential produce line 5.
(calculation as similar as shown for line 3)
o At above 8.6 ; AlO2- is stable
below 8.6 ; Al2O3 is stable

pH 14.6 log[ AlO2 ]

[ AlO2 ] 10
When

pH 8.6

potential is sufficiently high Al2O3 is


stable below pH 8.6 and AlO2- is stable above
pH 8.6.

Conclusion of Water-Aluminium
diagram
The

cathodic reduction reaction during


corrosion in the absence of dissolved oxygen
will be the evolution of hydrogen.
The anodic oxidation reaction:
In acid solutions:
Al Al 3 3e
In nearly neutral solutions:
2 Al 3H 2O Al 2O3 6H
In

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.

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