Electric Work

• Energy drives all changes including chemical

reactions. In a redox reaction, the energy released
in a reaction due to movement of charged particles
give rise to a potential difference. The maximum
potential differenc is called the electromotive
force, (EMF), E and the maximum electric work W
is the product of charge q in Coulomb (C), and the
potential ΔE in Volt (= J / C) or EMF.

W =qΔE

• Note that the EMF ΔE is determined by the nature

of the reactants and electrolytes, not by the size of
the cell or amounts of material in it. The amount of
reactants is proportional to the charge and available
energy of the galvanic cell.
 Gibb's Free Energy
• The Gibb's free energy DG is the negative value of
maximum electric work,

ΔG = - W
    = - q ΔE

• A redox reaction equation represents definite

amounts of reactants in the formation of also definite
amounts of products. The number (n) of electrons in
such a reaction equation, is related to the amount of
charge trnasferred when the reaction is completed.
Since each mole of electron has a charge of 96485 C
(known as the Faraday's constant, F),

q=nF

and,
ΔG = - n F DE

At standard conditions,

DG° = - n F DE°
 Nerst Equation

• The general Nernst equation correlates the

Gibb's Free Energy DG and the EMF of a
chemical system known as the galvanic cell. For
the reaction

aA+bB=cC+dD
[C]c [D]d
Q = ---------
[A]a [B]b

ΔG = ΔG° + R T ln Q
and

ΔG = - n F ΔE .
Therefore

- n F DE = - n F DE° + R T ln Q

where R, T, Q and F are the gas constant (8.314 J

mol-1 K-1), temperature (in K), reaction quotient,
and Faraday constant (96485 C) respectively.
Thus, we have
 Nerst Equation
RT [C]c [D]d
ΔE = ΔE° - ----- ln ---------
nF [A]a [B]b

This is known as the Nernst equation. The

equation allows us to calculate the cell
potential of any galvanic cell for any
concentrations. Some examples are given
in the next section to illustrate its
application. It is interesting to note the
relationship between equilibrium and the
Gibb's free energy at this point. When a
system is at equilibrium, ΔE = 0, and
Therefore, we have,

RT [C]c [D]d
ΔE° = ----- ln ---------
nF [A]a [B]b
 Nerst Equation

• At any specific
temperature, the Nernst
equation derived above can
be reduced into a simple
form. For example, at the
standard condition of 298 K
(25°), the Nernst equation
becomes

0.059 [C]c [D]d

ΔE = ΔE° - ----- log ---------
n [A]a [B]b
 Nerst Equation

For the cell

Zn | Zn2+ || H+ | H2 | Pt

we have a net chemical reaction of

Zn(s) + 2 H+ = Zn2+ + H2(g)

and the standard cell potential ΔE° = 0.763.

If the concentrations of the ions are not 1.0 M, and the

H2 pressure is not 1.0 atm, then the cell potential
ΔE may be calculated using the Nernst equation:

0.0592 V P(H2) [Zn2+]

ΔE = ΔE° - ------- log ------------
n [H+]2
 Eh – pH or Pourbaix Diagrams
Eh-pH or Pourbaix Diagrams are plots of Eh versus pH showing
regions or fields where dissolved species and precipitates are stable.
They can be used to quickly determine the equilibrium stability
fields for aqueous species.
The effective overall boundaries of the diagram are determined by
the stability field for water. One boundary is determined by the
stability of water with respect to reduction to H2 at 1 bar:

2 e- + 2 H2O (l) ------> H2 (g, 1 bar) + 2 OH- (aq)

Writing the usual expression for the Gibb’s free energy change:
o
G = G + R T ln [ a H2 (g) a2 OH- (aq) / a2 H2O (l) ]

We also have:

G = - n F 
where F, Faraday’s constant, is the charge on a mole of electrons
and is equal to 96,570 C, and n is the number of moles of electrons
transferred in the oxidation or reduction.
Using the fact that the activities of molecular hydrogen at 1 bar and
liquid water can be set equal to 1 gives:

- n F  = Go + 2.303 R T log a2 OH- (aq)

or:

 o
= - G / (n F) - (2.303 R T / (n F) log a2 OH- (aq)
 o
At 25 C:
2.303 R T / F = 2.303 (8.314 J/mol K) (298.15 K) / (96,486.8 C)
= 0.05917 V
Thus:

 = - Go / (n F) - ( 0.05917 V / n ) log a2 OH- (aq)

o
= - G / (2 F) - 2 ( 0.05917 V / 2 ) log a OH- (aq)
o
= - G / (2 F) - ( 0.05917 V ) log a OH- (aq)

= - Go / (2 F) + ( 0.05917 V ) pOH

= - Go / (2 F) + ( 0.05917 V ) ( 14.0 – pH )

o
G can be calculated from standard tabulated Gibb’s free energies
of formation at 298.15 K:
o
G = 2 Go m, f, OH- (aq) - 2 Go m, f, H O (l)
2

= 2 ( - 157.300 kJ ) - 2 ( - 237.2 kJ )
= + 159.8 kJ

 o
= - G / (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 of
the stablility boundaries for water:

Eh - pH or Pourbaix Diagram

1.40

0.90

0.40
Eh (V)

2 e - + 2 H2O (l) ----> H2 (g, 1 bar) + 2 OH - (aq)

-0.10

-0.60

-1.10
0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0
pH

Below this line water is unstable with respect to reductive

decomposition to H2 (g) at 1 bar of pressure.
How would this line change, if the H2 (g) pressure were set at 10
bar or 0.1 bar?
With this background the stability boundary for the oxidative
decompostion of water to O2 (g) at 1 bar is relatively easily
calculated:

H2O (l) ------> ½ O2 (g, 1 bar) + 2 H+ (aq) + 2 e-

Note for consistency in constructing the diagram this decomposition
must be written as a reduction:

½ O2 (g, 1 bar) + 2 H+ (aq) + 2 e- ------> 1 H2O (l)

 o
= - G / (n F) - ( 0.05911 V / n ) log [ a2 H2O (l) / a O2 (g) a2H+ (aq) ]
o
= - G / (2 F) - ( 0.05911 V / 2 ) log a-2H+ (aq)

= - Go / (2 F) - ( 0.05911 V ) pH

Calculating Go in this case gives:

o o
G = + 1 G m, f, H2O (l) = + 1 ( - 237.2 kJ )

= - 237.2 kJ
gives:

 = - Go / (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 for water:

Eh - pH or Pourbaix Diagram

1.40

0.90

0.40
H2O (l) ----> 1/2 O2 (g, 1 bar) + 2 H + (aq) + 2 e -
Eh (V)

-0.10

-0.60

-1.10
0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0
pH

Above this line water is unstable with respect to oxidative

decomposition to O2 (g) at 1 bar of pressure.
The regions within the stability field for water where Fe3+ and Fe2+
are stable can be determined by considering the reduction of
iron (III) to iron (II):
Fe3+ (aq) ------> Fe2+ (aq) + e –

o
G = Gom, f, Fe2+ - Go m, f, Fe3+
= ( - 78.87 kJ ) - ( - 4.6 kJ )
= - 74.27 kJ

 o
= - G / (n F) - ( 0.05911 V / n ) log [ a Fe2+ / a Fe3+ ]
= - ( -74.27 10+3 J / (1 (( 96,570 C ))
- ( 0.05911 V / 1 ) log [ a Fe2+ / a Fe3+ ]
= + 0.769 V - ( 0.05911 V ) log [ a Fe2+ / a Fe3+ ]
To further develop this equation requires making a choice about the
activities of Fe3+ and Fe2+. The usual choice is to take the activities
of dissolved species as 10-6, although other choices can be made.

 = + 0.769 V - ( 0.05911 V ) log [10-6 / 10-6 ]

= + 0.769 V

Notice that  is independent of 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

1.40

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

0.90 3+
Fe (aq) stable

2+
0.40 Fe (aq) stable
Eh (V)

-0.10

-0.60

-1.10
0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0
pH

Note that the more oxidized species, in this case Fe 3+, is stable at
the higher Eh.
Now consider the relative stability of Fe 3+ (aq) and FeO(OH) (s), the
mineral goethite:
FeO(OH) (s) + 3 H+ (aq) ------> Fe3+ (aq) + 2 H2O (l)
Note that in this equilibrium no species is being oxidized or reduced.
o
G = Gom, f, Fe3+ + 2 Gom, f, H O (l) - Go m, f, FeO(OH) (s)
2

= ( - 4.6 kJ ) + 2 ( - 237.2 kJ ) - ( - 488.57 kJ )

= + 9.6 kJ
Why was Gom, f, H+ not included in this calculation?

(n = 0 )  = - Go / F - ( 0.05911 V ) log [ a Fe3+ / 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
= ( - 9.94 10-5 V ) - 6 (- 0.05911 V ) - ( 0.1773 V ) pH
= + 0.255 V - ( 0.1773 V ) pH

pH = 1.44
Notice that when the equilibrium did not involve and oxidation or
reduction, pH is independent of  and will plot as a straight line
 Eh - pH or Pourbaix Diagram

1.40

3+
Fe FeO(OH) (s)
0.90

pH = 1.44

0.40 Fe2+
Eh (V)

-0.10

-0.60

-1.10
0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0
pH
Now consider the relative stability of Fe 2+ (aq) and FeO(OH) (s):

FeO(OH) (s) + 3 H+ (aq) + e- ------> Fe2+ (aq) + 2 H2O (l)

o
G = Gom, f, Fe2+ + 2 Gom, f, H O (l) - Go m, f, FeO(OH) (s)
2

= ( - 78.87 kJ ) + 2 ( - 237.2 kJ ) - ( - 488.57 kJ )

= - 64.7 kJ

 = - Go / (n F) - ( 0.05911 V / n ) log [ a Fe2+ ]

- ( 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

1.40

3+
Fe
0.90

FeO(OH) (s)
2+
0.40 Fe
Eh (V)

+ - 2+
FeO(OH) (s) + 3 H (aq) + e --> Fe (aq) + 2 H2O (l)

-0.10

-0.60

-1.10
0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0
pH

Any 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 of FeO(OH) (s) and Fe3O4 (s),
magnetite:

3 FeO(OH) (s) + H+ (aq) + e- ------> Fe3O4 (s) + 2 H2O (l)

o
G = Go m, f, Fe O + 2 Go m, f, H O (l) - 3 Go m, f, FeO(OH) (s)
3 4 (s) 3

= ( - 1015 kJ ) + 2 ( - 237.2 kJ ) - 3 ( - 488.57 kJ )

= - 24.13 kJ

 o
= - G / (n F) - ( 0.05911 V ) 1 pH
= - ( - 24.13 10+3 J / (1 (( 96,570 C ))
- ( 0.05911 V ) 1 pH
= + 0.250 V - ( 0.05911 V ) pH
 Eh - pH or Pourbaix Diagram

1.40

Fe3+
0.90

FeO(OH) (s)

0.40 Fe2+
Eh (V)

-
3 FeO(OH) (s) + H+ (aq) + e --> Fe3O4 (s) + 2 H2O (l)

-0.10

Fe3O4 (s)

-0.60

-1.10
0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0
pH
Now consider the relative stability of Fe 2+ (aq) and Fe3O4 (s),
magnetite:

Fe3O4 (s) + 8 H+ (aq) + 2 e- ------> 3 Fe2+ (aq) + 4 H2O (l)

o o o o
G = 3 G m, f, Fe2+ + 4 G m, f, H2O (l) - G m, f, Fe3O4 (s)

= 3 ( - 78.87 kJ ) + 4 ( - 237.2 kJ ) - ( - 1015 kJ )

= - 170 kJ

 o
= - G / (n F) - ( 0.05911 V / n ) log [ a3 Fe2+ ]
- (( 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

1.40

0.90 Fe3+

0.40 2+
Fe
FeO(OH) (s)
Eh (V)

-0.10

Fe3O4 (s)
-0.60
-
Fe3O4 (s) + 8 H+ (aq) + 2 e --> 3 Fe2+ (aq) + 4 H2O (l)

-1.10
0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0
pH

Note that Fe2+ (aq) - Fe3O4 (s) line meets the intersection of the
FeO(OH) (s) - Fe3O4 (s) and Fe2+ (aq) - FeO(OH) (s) lines, as, of
course, it should. These expectations can be used to reduce the
effort 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 if activities of the aquesous
ions involved in the various equilibria are changed by a factor of 10
in either direction from the 10-6 values that have been used so far?

Using the result for the Fe2+ (aq) and Fe3O4 (s) equilibria previously
derived for aFe2+ = 10-6:

 = + 0.880 V - 3 ( 0.05911 V / 2 ) log [ 10-6 ] - ( 0.1773 V ) pH

equations can be quickly derived for:

aFe2+ = 10-5:

 = + 0.880 V - 3 ( 0.05911 V / 2 ) log [ 10-5 ] - ( 0.1773 V ) pH

= 1.323 V - ( 0.1773 V ) pH

and for aFe2+ = 10-7:

 = + 0.880 V - 3 ( 0.05911 V / 2 ) log [ 10-7 ] - ( 0.1773 V ) pH

= 1.500 V - ( 0.1773 V ) pH

The positions of the other lines of equilibria can relatively quickly

established based on the intersections of the above lines with lines
that don’t shift and the fact the changing these activities does not
affect the slope of the lines.
 Eh - pH or Pourbaix Diagram

1.40

3+
0.90 Fe
-7
a = 10

-6
a = 10
2+
0.40 Fe
FeO(OH) (s)
Eh (V)

-5
a = 10

-0.10

Fe3O4 (s)
-0.60

-1.10
0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0
pH

Note that where the aqueous ionic species is in the products of the
equilibria used to derive these lines, decreasing that ionic species
activity increases it’s stability field.
Where does elemental iron occur in this Eh-pH diagram?

Consider the reduction of Fe2+ (aq) to Fe (s):

Fe2+ (aq) + 2 e – ------> Fe (s)

o
G = Gom, f, Fe (s) - Go m, f, Fe2+
= ( 0 kJ ) - ( - 78.87 kJ )
= + 78.87 kJ

 = - Go / (n F) - ( 0.05911 V / n ) log [ 1 / a Fe2+ ]

= - ( +78.87 10+3 J / (2 (( 96,570 C ))
- ( 0.05911 V / 2 ) log [ 1 / a Fe2+ ]
= - 0.4084 V - ( 0.05911 V / 2 ) log [ 1 / 10-6 ]
= - 0.4084 V - 0.1773 V
= - 0.5857 V
Also consider the reduction of magnetite to elemental iron:

Fe3O4 (s) + 8 H+ (aq) + 8 e- ------> 3 Fe (s) + 4 H2O (l)

o o o
G = 4 G m, f, H2O (l) - G m, f, Fe3O4 (s)

= 4 ( - 237.2 kJ ) - ( - 1015 kJ )
= + 66.2 kJ

 = - Go / (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:

Eh - pH or Pourbaix Diagram

1.40

0.90 Fe3+

0.40 Fe2+
FeO(OH) (s)
Eh (V)

-0.10

Fe3O4 (s)
-0.60

Fe (s)

-1.10
0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0
pH

Would you expect to find elemental iron in a wet oxygen rich

environment?

Under what conditions of Eh and pH is siderite, FeCO3 (s), stable?

To answer this question assume that PCO2 (g) is 10-3.47 bar, roughly the
global average value for the partial pressure of carbon dioxide.
The iron – oxygen diagram that we have developed is a strong
function of the species considered and would look differently, if
other species were taken into account, e.g. FeOH2+ (aq), Fe(OH)2+,
etc. For example, if hematite, Fe2O3 (s), had been considered, it
would occupy the entire stability field 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 formation
of iron precipitates.

An Atlas of Eh pH Diagrams, Intercomparison of Thermodynamic

Databases, Geological Survey of Japan, Open File Report No. 419,
National Institute of Advanced Industrial Science and Technology
Research Center for Deep Geological Environments Naoto
TAKENO, May 2005 is available on the web at:
http://www.gsj.jp/GDB/openfile/files/no0419/openfile419e.pdf
Pages 101 to 103 of this reference cover the iron oxygen system.

There are a number of commercial software packages that will

generate Eh pH diagrams, notably STABCAL:
http://www.mtech.edu/hhuang/predominance.htm
developed by Hsin-Hsiung Huang of the Metallurgical
Engineering Department at Montana Tech.

These comments just point out that these diagrams should be used
with caution.