Redox and

pE pH Diagrams

OCN 623 Chemical Oceanography

Reading: Libes, Chapter 7

 Redox Equations Worth Knowing
G = nFE
0. 0592 oxid a

E=E + log b
n reduc
1 oxid a

Equations are

pE = pE + log b written as
n reduc
REDUCTIONS!!
F
pE = Eh
2.3RT
1
pE = log K
n
G
pE =
2.3nRT

This lecture will go briefly over the principles involved in

deriving and using these equations. These principles
are all based on electrochemical cells.
 Electrochemical Cells
Consider the following simple electrochemical cell
operating at 25C, used to measure the electrochemical
potential of this reaction: Cu2+(aq) Cu0(s)

ions
 We arbitrarily assign a potential of 0 to
the reaction in the left cell:
2H+(aq) + 2e- H2(g) E= 0.000 V

Then the potential for the reaction in

the right cell is:
Cu2+(aq) + 2e- Cu0(s) E= 0.337 V
(always write as a reduction)

The standard potentials for all redox reactions are similarly

determined against the standard hydrogen electrode:
= E = EH
An electrochemical cell is capable of doing work by
driving electrons across a potential difference.
This can be measured as a change in free energy:
Gr = -nFE
where
n = number of moles of electrons (equivalents) involved in
the reaction
F = Faraday constant = 23.1 kcal V-1 equiv-1
E = the cell potential (V) at standard state

For the general case: Gr = -nFE

 Nernst Equation
We know from a previous class:
{ products }x reduced species
G = G + RT ln
{reactants } y oxidized species

Substituting G = -nFE, we get the Nernst Equation:

RT { products } x
E = E ln
nF {reactants } y
Or:
y
RT {reactants }
E = E + ln
nF { products }x
At 298K:
y
0.0592 {reactants }
E = E + log
n { products } x
Important points:

Geochemists usually use the symbol EH instead of E

(indicating the hydrogen scale is being used)

The Nernst Equation relates the EH of a cell to the

standard EH and to the activities of reactants and
products under given conditions

When at standard state (all activities = 1), EH = E

We can use EH as an indicator of the state of natural

waters:
 Example #1: Use Eh values to
Calculate Vanadium Speciation
3+ 2+
V +e V
What species of V dominates in seawater with
measured Eh = 0.729 V? 3+
0 . 059 V
Eh = Eh + log 2 +
1 V
1. From Table 7.1: Eh= -0.26 V 3+
0.729 = 0.26 + 0.059 log 2 +
V
2. Plug into equation:
V 3+
0.989 = 0.059 log 2+
V
V 3+
V3+ dominates 16.8 = log 2+
V
V 3+
2+ = 6x10
16

V
 Definition of pE
a(oxidized-species) + ne- b(reduced-species)

From equilibrium theory:

K=
{reduc}
b

{oxid }a { e }n

1
=K
{oxid }
a

{e }
n
{reduc}b

Take the log :

1
n log = log K + log
{oxid }
a

{ }
e {reduc}b
 but : log = log{e } pE
1
{e } and divide by n

1 1
pE = log K + log
{oxid }
a

n n {reduc}b

1
but : pE = log K
n

1
pE = pE + log
{oxid }
a

n {reduc}b
 Example #2: Calculation of pE
Assume:
pE in a given environment is controlled by this reaction:
Fe3+ + e- Fe2+ 1 oxid
pE = pE + log
(n = 1) n reduc

{Fe3+} = 10-5
log (K ) = 13 . 0
{Fe2+} = 10-3 Table 7.1 pE =
n

5
10
pE = 13 . 0 + log 3
= 11 . 0
10

{ e } = 10
11
 Example #3: Effect of Atmospheric O2
Assume: Natural water at pH 7.5 in equilibrium with the atmosphere
PO2 = 0.21atm { O2 } = 0.21

1 1
O2 ( g ) + H + (aq ) + e H 2O(l )
4 2

pE = 20.75 (Table 7.3, Libes)

O2 } {H + }
1

pE = pE + 1
log
{ 4
{H } = 10
+ 7.5
1
n {H 2O}2 1

pE = 13.08 { }
e = 1013.08

Conclusion: This environment has lower electron activity than

Example #2, and is thus more oxidizing
Redox Reactions Have Characteristic pE Values
F
pE = EH
2.3RT

G
pE =
2.3nRT
 Thus, if an environment is characterized by a
certain redox reaction, it has a characteristic pE

O2 + H+ + e- H2O

H2O + e- H2 + OH-

Garrels & Christ (1965)

 pE-pH Diagrams
pE-pH stability field diagrams show in a comprehensive
way how protons (pH) and electrons (pE)
simultaneously shift equilibria of reactions under various
conditions
These diagrams also indicate which species predominate
under any given condition of pE and pH

Two equations are used to produce the diagrams:

1
pE = pE + log
{oxid }
o

n {reduc}r
1
pE = log K
n
Oxidizing limit of diagrams: O2 + H+ + e- H2O
pE = +20.75 (Table 7.3) 1
pE = pE + log
{
1
{ }
O2 } 4 H+
{H 2O} 2
n=1 1
n
pH = -log{H+}
Set limit: {O2} = 1 pE = 20.75 pH

Reducing limit of diagrams: H2O + e- H2 + OH-

OH- + H+ H2O
H+ + e- H2
pE = 0.0 (Table 7.3) 1
pE = pE + log
{ }
H+
{H 2 } 2
n=1 1
n
pH = -log{H+}
Set limit: {H2} = 1 pE = pH
Oxidizing limit of diagrams:
O2 + H+ + e- H2O
pE = 20.75 pH

Reducing limit of diagrams:

H+ + e- H2
pE = pH
 Phase-boundary lines on a
pE-pH diagram indicate stability
field boundaries defined as
lines where activities of both
adjacent dominant species are
equal.
Lines are defined by reactions
between adjacent dominant
species
Reactions must have known
log K or pE values.
Construction of pE-pH Diagrams
Acid-base reactions with no pE dependency

2
6. HSO 4 SO 4 + H+ logK = 2.0

K =
{ SO }{ H }
2 +

{ HSO }
4

4

log K = 2.0 = log

{ SO }
pH
2

{ HSO }
4

4

{
When SO4
2
}= { HSO }, 4

pH = 2.0
Redox reactions of dissolved species
2
5. SO 4 + 9H + + 8e HS + 4H 2 O log K = 34.0

1
pE = pE + log
SO4 { H + 2
}{ } 9

8 {
HS {H 2O}}
4

=1

1 34
pE = log K =
n 8

pE =
34 1
+ log
SO4 { 2
} 9
8 8 HS { } 8
pH

{
When SO4
2
} = { HS },

pE =
34
8
9
pH
8
Redox reactions of dissolved and solid species

2
1. SO 4 + 8H + + 6e S(s ) + 4H 2 O log K = 36.2

pE =
36.2
+
1
log
SO4 {H+
2
}{ }
8

6 6 { S(s )}{ H 2O }4 =1

pE =
36.2
6
1
+ log SO4
6
2 8
{
pH
6
}

When SO4{ 2
} = 10 2
, pE = 5.70
8
6
pH

Activity of dissolved
species must be given
SI
Homework Due Thurs, Jan. 24, 2013
1) Write a balanced equation for the nitrification of NH4+ to
NO3- (oxidation by O2).

2) Calculate the Eh at 25C for this reaction in offshore

Hawaiian seawater at 100 m depth. Assume [NH4+] = 1 M,
[NO3- ] = 150 nM, and the partial pressure of O2 = 0.21 atm;
assume the activity coefficients for NH4+ and NO3- are 0.7 .
(Hint: calculate G and then Eh.)

3) In which direction would the reaction proceed in an

environment with an Eh of -200 mV? Why?