Pourbaix diagram for Iron

The Pourbaix diagram for redox chemistry is a type of combination redox/pH predominance diagram
developed by the French electrochemistry Pourbaix. These diagrams are closely related to the stability field
for waterincluding either the main E/pH lines from the water diagram, or both the main and overpotential
lines. What these diagrams add are the relationships between the redox activity and the Brnsted acidity of
the elements. They are thus related both to Latimer diagrams, and to predominance diagrams for
acid/base reactions.

The vertical axis plots the standard reduction potential, and the horizontal the pH. Remember what
a predominance diagram was: simple vertical boundaries where the most abundant species altered.
Consider as an example the Pourbaix diagram for iron. Note that some of the lines from the stability field
of water are drawn into this diagram, since this diagram applies to aqueous solutions of iron compounds.
(a) The bottom of the diagram refers to reduced species, i.e. Fe(s), or to the type of conditions that
lead to reduction.
(b) The top of the diagram to oxidized species and/or oxidizing conditions.
(c) Vertical lines indicate changes in acid base chemistry independent of E, e.g. Fe3+/Fe(OH)3.
(d) Horizontal lines indicate redox changes unaffected by pH, e.g. Fe2+/Fe below pH 6.45.
(e) In the more general case, the lines slope, since both E and [H +] or [OH-] affect the redox process.

22-

FeO4 /Fe(OH)3

2-

FeO4 (aq)
1.5

E / Volts

0.5

3+

3+

Fe (aq)
4H +(aq
)+O (g
)+4e -=2
2
H O(l)
2
Fe(OH)3(s)

1.0
2+

Fe (aq)

With ov
er p

otentia

-1.0
-1.5

With overpotential

Fe(OH) (s
2 )

2e =H (g
)
2

Fe(s)

With ov
er p

pH
2

2+

Fe /Fe
Fe(OH)2/Fe
with overpotential
H2O/H2

0.0

Fe(OH)3/Fe(OH)2

O2/H2O

2+

2H +(aq)+

2+

Fe /Fe
2+
Fe(OH)3/Fe

Fe /Fe(OH)2

-0.5

3+

FeO4 /Fe

3+

Fe /Fe(OH)3

2.0

10

otentia

12

14

pH

The Pourbaix Diagram for Iron

O 2 (g) + 4 H + (aq) + 4 e- 2 H 2 O(l) E= +1.23 V

0.0592 p(O 2 )][H + ]4
E=E+
lg
= 1.23 0.0592 pH
4
1
2H + (aq) + 2e = H 2 ( g )
E = 0 V
E=E+

0.0592 [H + ]2
lg
= 0.0592 pH
2
p(H 2 )]

O/H2O 0.5V H2O/H2 0.5V Pourbaix

 0.5V
2
+
3+
(1) FeO 4 (aq) + 8 H (aq) + 3 e- Fe + 4 H 2 O(l) E= +1.90 V
0.0592 [FeO 24 ][H + ]8
0.0592 8
lg
= 1.9
pH
3+
3
3
[Fe ]
= 1.9 0.158 pH

E=E+

(2)

FeO 24 (aq) + 4 H 2 O(l) + 3 e- Fe(OH)3 + 5 H 2 O (aq)

E=E+

0.0592 [FeO24 ][H + ]8

0.0592 [FeO 24 ][H + ]8 [OH ]3
lg
=
E

+
lg
3
3
K sp
[Fe3+ ]

0.0592 ( K w )3 0.0592 5
= 1.9 +
lg

pH
3
K sp
3
= 1.8 0.099 pH
(3) Fe (aq) + e- Fe 2 + E= +0.77 V
3+

[Fe3+ ]
= 0.77
[Fe 2+ ]
2+

(4) Fe(OH)3 (s) + e- Fe (aq) + 3OH ( aq )

K sp (Fe(OH)3 )
[Fe3+ ]
E=E+0.0592 lg
= E+0.0592 lg
2+
[Fe ]
[OH - ]3
E=E+0.0592 lg

= E+0.0592 lg

K sp (Fe(OH)3 )[H + ]3
(K w ) 3

=0.77+0.0592(37.4 + 42) 0.0592 3 pH

= 1.04 0.178 pH
Fe(OH) 2 (s ) + OH ( aq)
K sp (Fe(OH)3 )
[Fe3+ ]
E=E+0.0592 lg
= E+0.0592 lg
2+
[Fe ]
K sp (Fe(OH) 2 )[OH - ]

(5) Fe(OH)3 (s) + e-

= E+0.0592 lg

K sp (Fe(OH)3 )[H + ]
K sp (Fe(OH) 2 )K w

=0.77+0.0592(37.4 + 15.1 + 14) 0.0592 pH

= 0.28 0.0592 pH
(6) Fe 2 + (aq) + 2e- Fe E= 0.44 V
0.0592
E=E+
lg[Fe 2+ ] = 0.44
2

(7) Fe(OH) 2 (s ) + 2e- Fe(s ) + 2OH ( aq )

0.0592
0.0592 K sp (Fe(OH) 2 )
E=E+
lg[Fe 2+ ] = E+
lg
2
2
[OH - ]2
= E+

+ 2
0.0592 K sp (Fe(OH) 2 )[H ]
0.0592
lg
=-0.44+
(15.1 + 28) 0.0592 pH
2
2
2
(K w )

= 0.058 0.0592 pH
(8) Fe(OH)3 (s)

[Fe3+ ] =

Fe3+ (aq) + 3OH ( aq)

K sp (Fe(OH)3 )
- 3

[OH ]

(9) Fe(OH) 2 (s )

2+

, [OH - ] =

K sp (Fe(OH)3 )

Fe (aq) + 2OH ( aq)

3+ 3

[Fe ]

= 3.4 10 13 M , pH=1.53

[Fe 2+ ] =

K sp (Fe(OH) 2 )
- 2

[OH ]

, [OH - ] =

K sp (Fe(OH) 2 )
[Fe 2+ ]

= 2.8 10 8 M , pH=6.45