Pourbaix diagrams

Plots of E vs pH
We will, as an example, derive the Pourbaix diagram for iron
Two Latimer diagrams pertain
In acid ([H+] = 1 M):
Fe
3+
Fe(OH)
2
Fe
0.77 V -0.44 V
In alkali ([OH
-
] = 1 M)
Fe
3+
Fe(OH)
2
Fe
-0.56 V -0.887 V
Pourbaix diagrams:
correlate Latimer diagrams at pH 0 and pH 14
take into account speciation or oxidation state of the element
The half reaction
Fe
3+
+ e Fe
2+
E
o
= 0.77 V
does not involve a proton so E
o
is independent of pH
Fe
3+
Fe(OH)
2
Fe
0.77 V -0.44 V
Fe
3+
+ e Fe
2+
Fe
3+
will precipitate out of solution as pH is increased. We can calculate the pH
at which this will occur from the K
SP
for Fe(OH)
3
.
Fe(OH)
3
(s) Fe
3+
+ 3OH

K
SP
= 4.11 x 10
-37
M
4
At what pH will [Fe
3+
] = 1.00 M?
K
SP
= 4.11 x 10
-37
M
4
= [Fe
3+
][OH

]
3
[OH

] = (4.11 x 10
-37
/1)
0.333
= 7.43 x 10
-13
M
So [H
+
] = 10
-14
/7.43 x 10
-13
= 1.35 x 10
-2
M
hence pH = 1.87
Fe(OH)
3
Fe
3+
+ 3OH
-
Vertical lines in a Pourbaix
diagram indicate where two
species of an element in the
same oxidation state are in
equilibrium
To calculate the
Fe(OH)
3
|Fe
2+
line...
Fe
3+
+ e Fe
2+
E
o
= 0.77 V G
o
= -74.3 kJ mol
-1
3OH
-
+ 3H
+
3H
2
O -239.7 kJ mol
-1
G
o
= -nFE
o
= -1 x 96485 x 0.77
Fe(OH)
3
Fe
3+
+ 3OH
-
207.6 kJ mol
-1
G
o
= -RT ln K
SP
= -8.315 x 298 x ln (4.11 x 10
-37
)
Fe(OH)
3
+ 3H
+
+ e Fe
2+
+ 3H
2
O -106.4 kJ mol
-1
= 106400/1 x 96485
= 1.10 V
G
o
= -nFE
o
E
o
= -G
o
/nF
Fe(OH)
3
+ 3H
+
+ e Fe
2+
+ 3H
2
O E
o
= 1.10 V
E = E
o
RT/nF ln Q
E = 1.10 3 x 0.0592 x pH
This must cross the Fe
3+
/Fe(OH)
3
line when
0.77 = 1.10 3(0.0592)pH
or pH = 1.87
which confirms the result we got from the K
SP
calclation
Fe
3+
Fe(OH)
2
Fe
0.77 V -0.44 V
1.1
Fe(OH)
3
+ 3H
+
+ e Fe
2+
+ 3H
2
O
1.1
Fe(OH)
3
+ 3H
+
+ e Fe
2+
+ 3H
2
O
From the K
SP
for Fe(OH)
2
Fe(OH)
2
Fe
2+
+ 2OH

K
SP
= 1.61 x 10
-15
M
3
At what pH will [Fe
2+
] = 1.00 M?
K
SP
= 1.61 x 10
-15
M
3
= [Fe
2+
][OH

]
2
[OH

] = (1.61 x 10
-15
/1)
0.5
= 4.01 x 10
-8
M
So [H
+
] = 10
-14
/4.01 x 10
-8
= 2.49 x 10
-7
M
hence pH = 6.61
1.1
Fe(OH)
2
Fe
2+
+ 2OH
-
The half reaction
Fe
2+
+ 2e Fe E
o
= -0.44 V
does not involve a proton so E
o
is independent of pH
1.1
Fe
2+
+ 2e Fe
An expression for the potential for the Fe(OH)
3
|Fe(OH)
2
couple can be derived
from the following data
Fe(OH)
3
+ 3H
+
+ e Fe
2+
+ 2H
2
O E
o
1.10 V G
o
-106.4 kJ mol
-1
3H
2
O 3H
+
+ 3OH
-
239.7 kJ mol
-1
Fe
2+
+ 2OH
-
Fe(OH)
2
-84.4 kJ mol
-1
Fe(OH)
3
+ e Fe(OH)
2
+ OH
-
E
o
-0.51 V G
o
48.9 kJ mol
-1
E = E
o
RT/nF ln Q
E = -0.51 + 0.0592 x pOH
E = -0.51 + 0.0592 x (14 pH)
E = 0.316 0.0592 x pH
1.1
0.316
Fe(OH)
3
+ e Fe(OH)
2
+ OH
-
...and finally the value of Fe(OH)
2
|Fe couple can be found by
similar considerations, and the Nernst equation applied.
E = -0.060 0.0592 x pH
Overlaying Pourbaix diagrams
The feasibility of a reaction can be predicted by overlaying the relevant
Pourbaix diagrams
stability field for As(V)
stability field for As(III)
9 5.5
At pH < 5.5 and at
pH > 9, Fe
3+
has the
potential to oxidise
As
3+
to As
5+
For example
2
0.65
0.45
Fe(OH)
3
+ e + 3H
+
Fe
2+
+ 3H
2
O E = 0.65
As
3+
As
5+
+ 2e E = -0.45
As
3+
+ 2Fe(OH)
3
+ 6H
+
2Fe
2+
+ 6H
2
O + As
5+
E = 0.20 V
For 5.5 < pH < 9
As
5+
will oxidise Fe
2+
to Fe
3+
The effect of complex formation on E
o
values
The E
o
value of a metal ion is very dependent on the ligands of the ion
Example, for the Fe
3+
|Fe
2+
couple
Ligand E
o
/V
phenanthroline 1.14
H
2
O 0.77
CN
-
0.36
N N
Fe
N
N N
N
N
N
N N
Fe
back bonding from
metal to phen ligand
stabilises Fe(II)
Ligand E
o
/V
phenanthroline 1.14
H
2
O 0.77
CN
-
0.36
Ligand E
o
/V
phenanthroline 1.14
H
2
O 0.77
CN
-
0.36
Fe
-
NC
-
NC CN
-
CN
-
CN
-
CN
-
Negatively charged ligands favour the
higher positive charge of Fe(III)
Co
H
3
N
H
3
N NH
3
NH
3
NH
3
NH
3
Co
H
2
O
H
2
O OH
2
OH
2
OH
2
OH
2
Co
3+
|Co
2+
0.11 V
1.84 V
NH
3
is a better
donor ligand than
H
2
O and so stablises
Co(III)