Eh - pH or Pourbaix Diagrams

Eh-pH or Pourbaix Diagrams are plots oI Eh versus pH showing

regions or Iields where dissolved species and precipitates are stable.
They can be used to quickly determine the equilibrium stability
Iields Ior aqueous species.
The eIIective overall boundaries oI the diagram are determined by
the stability Iield Ior water. One boundary is determined by the
stability oI water with respect to reduction to H
2
at 1 bar:
2 e
-
2 H
2
O (l) ------~ H
2
(g, 1 bar) 2 OH
-
(aq)
Writing the usual expression Ior the Gibb`s Iree energy change:
G G
o
R T ln | a
H
2
(g)
a
2
OH
-
(aq)
/ a
2
H
2
O (l)
|
We also have:
G - n F 1
where F, Faraday`s constant, is the charge on a mole oI electrons and
is equal to 96,570 C, and n is the number oI moles oI electrons
transIerred in the oxidation or reduction.
Using the Iact that the activities oI molecular hydrogen at 1 bar and
liquid water can be set equal to 1 gives:
- n F 1 G
o
2.303 R T log a
2
OH
-
(aq)
or:
1 - G
o
/ (n F) - (2.303 R T / (n F) log a
2
OH
-
(aq)
t 25
o
C:
2.303 R T / F 2.303 (8.314 J/mol K) (298.15 K) / (96,486.8 C)
0.05917 V
Thus:
1 - G
o
/ (n F) - ( 0.05917 V / n ) log a
2
OH
-
(aq)
- G
o
/ (2 F) - 2 ( 0.05917 V / 2 ) log a
OH
-
(aq)
- G
o
/ (2 F) - ( 0.05917 V ) log a
OH
-
(aq)
- G
o
/ (2 F) ( 0.05917 V ) pOH
- G
o
/ (2 F) ( 0.05917 V ) ( 14.0 pH )
G
o
can be calculated Irom standard tabulated Gibb`s Iree energies
oI Iormation at 298.15 K:
G
o
2 G
o
m, I, OH
-
(aq)
- 2 G
o
m, I, H
2
O (l)
2 ( - 157.300 kJ ) - 2 ( - 237.2 kJ )
159.8 kJ
1 - G
o
/ (2 F) ( 0.05912 V ) ( 14.0 pH )
- ( 159.8 10
3
J) / (2 (96,570 C) ) 0.8283 V
- ( 0.05911 V ) pH
~ 0 V - ( 0.05911 V ) pH
This equation can be plotted on an Eh-pH diagram to give one oI
the stablility boundaries Ior water:
Below this line water is unstable with respect to reductive
decomposition to H
2
(g) at 1 bar oI pressure.
How would this line change, iI the H
2
(g) pressure were set at 10
bar or 0.1 bar?
Eh - pH or Pourbaix Diagram
-1.10
-0.60
-0.10
0.40
0.90
1.40
0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0
pH
E
h

(
V
)
2 e
-
+ 2 H
2
O (I) ----> H
2
(g, 1 bar) + 2 OH
-
(aq)
With this background the stability boundary Ior the oxidative
decompostion oI water to O
2
(g) at 1 bar is relatively easily
calculated:
H
2
O (l) ------~ O
2
(g, 1 bar) 2 H

(aq) 2 e
-
Note Ior consistency in constructing the diagram this decomposition
must be written as a reduction:
O
2
(g, 1 bar) 2 H

(aq) 2 e
-
------~ 1 H
2
O (l)
1 - G
o
/ (n F) - ( 0.05911 V / n ) log | a
2
H
2
O (l)
/ a
O
2
(g)
a
2
H

(aq)
|
- G
o
/ (2 F) - ( 0.05911 V / 2 ) log a
-2
H

(aq)
- G
o
/ (2 F) - ( 0.05911 V ) pH
Calculating G
o
in this case gives:
G
o
1 G
o
m, I, H
2
O (l)
1 ( - 237.2 kJ )
- 237.2 kJ
gives:
1 - G
o
/ (2 F) - ( 0.05917 V ) pH
- (- 237.2 10
3
J / (2 (( 96,486.8 C )) - ( 0.05911 V ) pH
1.23 V - ( 0.05911 V ) pH
This equation can be plotted on an Eh-pH diagram to give the other
stablility boundary Ior water:
Eh - pH or Pourbaix Diagram
-1.10
-0.60
-0.10
0.40
0.90
1.40
0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0
pH
E
h

(
V
)
H
2
O (I) ----> 1/2 O
2
(g, 1 bar) + 2 H
+
(aq) + 2 e
-
bove this line water is unstable with respect to oxidative
decomposition to O
2
(g) at 1 bar oI pressure.
The regions within the stability Iield Ior water where Fe
3
and Fe
2
are stable can be determined by considering the reduction oI
iron (III) to iron (II):
Fe
3
(aq) ------~ Fe
2
(aq) e

G
o
G
o
m, I, Fe
2 - G
o
m, I, Fe
3
( - 78.87 kJ ) - ( - 4.6 kJ )
- 74.27 kJ
1 - G
o
/ (n F) - ( 0.05911 V / n ) log | a
Fe
2 / a
Fe
3 |
- ( -74.27 10
3
J / (1 (( 96,570 C ))
- ( 0.05911 V / 1 ) log | a
Fe
2 / a
Fe
3 |
0.769 V - ( 0.05911 V ) log | a
Fe
2 / a
Fe
3 |
To Iurther develop this equation requires making a choice about the
activities oI Fe
3
and Fe
2
. The usual choice is to take the activities
oI dissolved species as 10
-6
, although other choices can be made.
1 0.769 V - ( 0.05911 V ) log |10
-6
/ 10
-6
|
0.769 V
Notice that 1 is independent oI pH, because the reduction we were
considering did not involve, H

(aq) or OH
-
(aq) and will plot as a
straight line parallel to the pH axis on the Eh-pH diagram.
Eh - pH or Pourbaix Diagram
-1.10
-0.60
-0.10
0.40
0.90
1.40
0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0
pH
E
h

(
V
)
Fe
3+

(aq) ----> Fe
2+
(aq) + e
-
Fe
3+
(aq) stabIe
Fe
2+

(aq) stabIe
Note that the more oxidized species, in this case Fe
3
, is stable at
the higher Eh.
Now consider the relative stability oI Fe
3
(aq) and FeO(OH) (s), the
mineral goethite:
FeO(OH) (s) 3 H

(aq) ------~ Fe
3
(aq) 2 H
2
O (l)
Note that in this equilibrium no species is being oxidized or reduced.
G
o
G
o
m, I, Fe
3 2 G
o
m, I, H
2
O (l)
- G
o
m, I, FeO(OH) (s)
( - 4.6 kJ ) 2 ( - 237.2 kJ ) - ( - 488.57 kJ )
9.6 kJ
Why was G
o
m, I, H
not included in this calculation?
(n 0 ) 1 - G
o
/ F - ( 0.05911 V ) log | a
Fe
3 / a
FeO(OH) (s)
|
- ( 0.05911 V ) 3 pH
0 - ( 9.6 10
3
J ) / ( 96,570 C )
- ( 0.05911 V ) log | 10
-6
/ 1 |
- ( 0.05911 V ) 3 pH
( - 9.9
4
10
-5
V ) - 6 (- 0.05911 V ) - ( 0.1773 V ) pH
0.25
5
V - ( 0.1773 V ) pH
pH 1.44
Notice that when the equilibrium did not involve and oxidation or
reduction, pH is independent oI 1 and will plot as a straight line
parallel to the 1 axis on the Eh-pH diagram.
Eh - pH or Pourbaix Diagram
-1.10
-0.60
-0.10
0.40
0.90
1.40
0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0
pH
E
h

(
V
)
Fe
3+
Fe
2+
FeO(OH) (s)
pH = 1.44
Now consider the relative stability oI Fe
2
(aq) and FeO(OH) (s):
FeO(OH) (s) 3 H

(aq) e

------~ Fe
2
(aq) 2 H
2
O (l)
G
o
G
o
m, I, Fe
2 2 G
o
m, I, H
2
O (l)
- G
o
m, I, FeO(OH) (s)
( - 78.87 kJ ) 2 ( - 237.2 kJ ) - ( - 488.57 kJ )
- 64.7 kJ
1 - G
o
/ (n F) - ( 0.05911 V / n ) log | a
Fe
2 |
- ( 0.05911 V ) 3 pH
- ( - 64.7 10
3
J / (1 (( 96,570 C ))
- ( 0.05911 V / 1 ) log | 10
-6
|
- ( 0.05911 V ) 3 pH
0.670 V 0.355 V - ( 0.1773 V ) pH
1.025 V - ( 0.1773 V ) pH
Eh - pH or Pourbaix Diagram
-1.10
-0.60
-0.10
0.40
0.90
1.40
0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0
pH
E
h

(
V
)
Fe
3+
Fe
2+
FeO(OH) (s)
FeO(OH) (s) + 3 H
+
(aq) + e
-
--> Fe
2+
(aq) + 2 H
2
O (l)
ny oxidation or reduction equilibrium that involves H

(aq) or
OH
-
(aq) will plot as a sloped line on these Eh-pH diagrams.
Now consider the relative stability oI FeO(OH) (s) and Fe
3
O
4
(s),
magnetite:
3 FeO(OH) (s) H

(aq) e

------~ Fe
3
O
4
(s) 2 H
2
O (l)
G
o
G
o
m, I, Fe
3
O
4
(s)
2 G
o
m, I, H
3
O (l)
- 3 G
o
m, I, FeO(OH) (s)
( - 1015 kJ ) 2 ( - 237.2 kJ ) - 3 ( - 488.57 kJ )
- 24.
13
kJ
1 - G
o
/ (n F) - ( 0.05911 V ) 1 pH
- ( - 24.
13
10
3
J / (1 (( 96,570 C ))
- ( 0.05911 V ) 1 pH
0.25
0
V - ( 0.05911 V ) pH
Eh - pH or Pourbaix Diagram
-1.10
-0.60
-0.10
0.40
0.90
1.40
0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0
pH
E
h

(
V
)
Fe
3+
Fe
2+
FeO(OH) (s)
3 FeO(OH) (s) + H
+
(aq) + e
-
--> Fe
3
O
4
(s) + 2 H
2
O (l)
Fe3O4 (s)
Now consider the relative stability oI Fe
2
(aq) and Fe
3
O
4
(s),
magnetite:
Fe
3
O
4
(s) 8 H

(aq) 2 e

------~ 3 Fe
2
(aq) 4 H
2
O (l)
G
o
3 G
o
m, I, Fe
2 4 G
o
m, I, H
2
O (l)
- G
o
m, I, Fe
3
O
4
(s)
3 ( - 78.87 kJ ) 4 ( - 237.2 kJ ) - ( - 1015 kJ )
- 170 kJ
1 - G
o
/ (n F) - ( 0.05911 V / n ) log | a
3
Fe
2 |
- (( 0.05911 V ) 8 / 2 ) pH
- ( - 170 10
3
J / (2 ( 96,570 C )))
- 3 ( 0.05911 V / 2 ) log | 10
-6
|
- (( 0.05911 V ) 8 / 2 ) pH
0.880 V 0.532 V - ( 0.1773 V ) pH
1.025 V - ( 0.2364 V ) pH
Eh - pH or Pourbaix Diagram
-1.10
-0.60
-0.10
0.40
0.90
1.40
0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0
pH
E
h

(
V
)
Fe
3+
Fe
2+
FeO(OH) (s)
Fe
3
O
4
(s) + 8 H
+
(aq) + 2 e
-
--> 3 Fe
2+
(aq) + 4 H
2
O (l)
Fe
3
O
4
(s)
Note that Fe
2
(aq) - Fe
3
O
4
(s) line meets the intersection oI the
FeO(OH) (s) - Fe
3
O
4
(s) and Fe
2
(aq) - FeO(OH) (s) lines, as, oI
course, it should. These expectations can be used to reduce the
eIIort required to construct these diagrams.
Based on the above diagram what iron species and what iron
equilibria would you expect to dominate natural waters containing
iron?
How does the Eh-pH diagram change iI activities oI the aquesous
ions involved in the various equilibria are changed by a Iactor oI 10
in either direction Irom the 10
-6
values that have been used so Iar?
Using the result Ior the Fe
2
(aq) and Fe
3
O
4
(s) equilibria
previously derived Ior a
Fe
2 10
-6
:
1 0.880 V - 3 ( 0.05911 V / 2 ) log | 10
-6
| - ( 0.1773 V ) pH
equations can be quickly derived Ior:
a
Fe
2 10
-5
:
1 0.880 V - 3 ( 0.05911 V / 2 ) log | 10
-5
| - ( 0.1773 V ) pH
1.323 V - ( 0.1773 V ) pH
and Ior a
Fe
2 10
-7
:
1 0.880 V - 3 ( 0.05911 V / 2 ) log | 10
-7
| - ( 0.1773 V ) pH
1.500 V - ( 0.1773 V ) pH
The positions oI the other lines oI equilibria can relatively quickly
established based on the intersections oI the above lines with lines
that don`t shiIt and the Iact the changing these activities does not
aIIect the slope oI the lines.
Eh - pH or Pourbaix Diagram
-1.10
-0.60
-0.10
0.40
0.90
1.40
0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0
pH
E
h

(
V
)
Fe
3+
Fe
2+
FeO(OH) (s)
Fe3O4 (s)
a = 10
-7
a = 10
-5
a = 10
-6
Note that where the aqueous ionic species is in the products oI the
equilibria used to derive these lines, decreasing that ionic species
activity increases it`s stability Iield.
Where does elemental iron occur in this Eh-pH diagram?
Consider the reduction oI Fe
2
(aq) to Fe (s):
Fe
2
(aq) 2 e

------~ Fe (s)
G
o
G
o
m, I, Fe (s)
- G
o
m, I, Fe
2
( 0 kJ ) - ( - 78.87 kJ )
78.87 kJ
1 - G
o
/ (n F) - ( 0.05911 V / n ) log | 1 / a
Fe
2 |
- ( 78.87 10
3
J / (2 (( 96,570 C ))
- ( 0.05911 V / 2 ) log | 1 / a
Fe
2 |
- 0.4084 V - ( 0.05911 V / 2 ) log | 1 / 10
-6
|
- 0.4084 V - 0.1773 V
- 0.5857 V
lso consider the reduction oI magnetite to elemental iron:
Fe
3
O
4
(s) 8 H

(aq) 8 e

------~ 3 Fe (s) 4 H
2
O (l)
G
o
4 G
o
m, I, H
2
O (l)
- G
o
m, I, Fe
3
O
4
(s)
4 ( - 237.2 kJ ) - ( - 1015 kJ )
66.
2
kJ
1 - G
o
/ (n F - (( 0.05911 V ) 8 / 8 ) pH
- ( 66.
2
10
3
J / (8 ( 96,570 C )))
- ( 0.05911 V ) pH
- 0.086 V - ( 0.05911 V ) pH
Plotting these lines on the Eh-pH diagram gives:
Would you expect to Iind elemental iron in a wet oxygen rich
environment?
Under what conditions oI Eh and pH is siderite, FeCO
3
(s), stable?
To answer this question assume that P
CO2 (g)
is 10
-3.47
bar, roughly the
global average value Ior the partial pressure oI carbon dioxide.
Eh - pH or Pourbaix Diagram
-1.10
-0.60
-0.10
0.40
0.90
1.40
0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0
pH
E
h

(
V
)
Fe
3+
Fe
2+
FeO(OH) (s)
Fe3O4 (s)
Fe (s)
The iron oxygen diagram that we have developed is a strong
Iunction oI the species considered and would look diIIerently, iI
other species were taken into account, e.g. FeOH
2
(aq), Fe(OH)
2

,
etc. For example, iI hematite, Fe
2
O
3
(s), had been considered, it
would occupy the entire stability Iield now occupied by geothite,
FeO(OH) (s) and since hematite is thermodynamically more
stable, it would be the species represented on the diagram.
Geothite is a precursor to hematite and kinetically it takes several
months to convert geothite to hematite and so the diagram
developed in these notes would apply to the short time Iormation
oI iron precipitates.
n tlas oI Eh pH Diagrams, Intercomparison oI Thermodynamic
Databases, Geological Survey oI Japan, Open File Report No. 419,
National Institute oI dvanced Industrial Science and Technology
Research Center Ior Deep Geological Environments Naoto
TKENO, May 2005 is available on the web at:
http://www.gsi.ip/GDB/openIile/Iiles/no0419/openIile419e.pdI
Pages 101 to 103 oI this reIerence cover the iron oxygen system.
There are a number oI commercial soItware packages that will
generate Eh pH diagrams, notably STBC:
http://www.mtech.edu/hhuang/predominance.htm
developed by Hsin-Hsiung Huang oI the Metallurgical
Engineering Department at Montana Tech.
These comments iust point out that these diagrams should be used
with caution.