Potential - pH (Pourbaix) Diagrams and Corrosion

-4 different regions

-3 different kind of behavior

- =>Immune (metal as stable phase
Þ corrosion (soluble ion as stable
phase) and
Þ passivation (oxide film or insoluble
ion as stable film)

-3 type of lines
-

-Al, an amphoteric material

 Potential - pH (Pourbaix) Diagram of water

Effect of water pH and dissolved oxygen on corrosion

a) No dissolved oxygen

(1)

=>Under standard conditions, e0=0

=>Under non-standard conditions, when [H+] concentration is different,

by applying Nernst's equation we will get:

(2)

EH+/H2= -0.059 pH
 Potential - pH (Pourbaix) Diagram of water

(2)

Above equation is for acid solution, what about for alkaline and
neutral solution??? No oxygen condition

=>For neutral solution (Ph=7):

(3)

E= -0.059 *7= -0.413 V

=>For alkaline solution (pH=14):

E= -0.059 *14= -0.826 V

 Potential - pH (Pourbaix) Diagram of water

We get Pourbaix diagram by plotting potential versus pH

No Oxygen Yet

EH+/H2 = 0 (pH=0)
Eq. condition

E= -0.059 *7 = -0.413 V

E= -0.059 *14 = -0.826 V

 Potential - pH (Pourbaix) Diagram of water

b) With dissolved oxygen

(4) O2 reduction in acid solution

After applying Nernst’s equation for different [H+] conc.

E= 1.229 - 0.059 pH (5)

 Potential - pH (Pourbaix) Diagram of water

b) With dissolved oxygen

(6)

O2 reduction in alkaline solution

After applying Nernst’s equation for different [H+] conc.

E= 0.401 - 0.059 pH (7)

 Potential - pH (Pourbaix) Diagram of water
We get Pourbaix diagram by plotting potential versus pH

with
Oxygen

E= 1.229
If pH=0 (Eq. condition)
 Potential - pH (Pourbaix) Diagram of water

  pourbaix diagram is a plot of reversible electrode potential and pH (pH measures the
oxidizing or reducing power of the solution);

O2

H2 evolution, if E is more negative

than Eq. potential of hydrogen
O2 evolution, if E is more positive
than Eq. potnetial of oxygen H2O
In between water is stable

H2