pE

The concept of pE can be used to describe the redox nature of natural waters. pE is defined as the
negative logarithm of the electron activity:

pE = –log {e–}.

Note the similarity with the definition of pH, where pH = –log{H+}. (Remember the earlier
discussion on ionic strength and activity? In fresh waters, generally [H+] = {H+} – the curly
brackets denote the activity of the H+).

Note – there are no free electrons in solution! There are no bare protons (H+) in solution either.
Chemists use this as a convenient way of illustrating the actual situation.

A large negative pE value indicates that there is a large electron activity in the solution, so that
reducing conditions exist. Conversely, a high positive pE value indicates a low electron activity in
the solution, and hence oxidising conditions exist. (Because few electrons are available to
participate in reduction reactions). In practice, the pE values in water range from about –12 to 25.

Calculating pE

For the general reaction

aA + bB + ne − ←
→ cC + dD

the equilibrium constant can be stated as

{C}c {D}d
K eq =
{A}a {B}b {e− }n

1 {A}a {B}b
= K ×
{e − }n
eq
{C}c {D}d

Redox chemistry in natural waters 5

Taking the log of both sides of the equation*

1
log − n
= log(1) − n log{e − }
LHS: {e }

= − n log{e − }

Remember the definition of pE: pE = – log {e-}. So,

– n log {e-} = n pE

LHS = n pE

 {A}a {B}b   {A}a {B}b 

RHS: log  K eq ×  = log K + log 
 {C}c {D}d 
{C}c {D}d 
eq
  

 {A}a {B}b 
RHS = logK eq + log  c d 
 {C} {D} 

Therefore, since LHS = RHS:

 {A}a {B}b 
n pE = log K eq + log  c d 
 {C} {D} 

and therefore,

 {A}a {B}b 
pE = 1 n log K eq + 1 n log  c d  -- Eq 1
 {C} {D} 

*
log(A/B) = log A – log B
log (A*B) = log A + log B
log (Aa) = a log A

Redox chemistry in natural waters 6

From thermodynamics:
∆Go = –2.303 RT log Keq = –nFEo

we can rewrite this as

nFE o
log K eq =
2.303RT

where T = 298 K, the gas constant, R = 8.314 J K-1 mol-1 and the Faraday constant,
F = 96485 C mol-1, we have

nE o
log K eq =
0.0591

We can now return to the pE equation (Eqn. 1) and substitute for log Keq:

1 nE o 1  {A}a {B}b 
pE = × + log  c d 
n 0.0591 n  {C} {D} 

Eo 1  {A}a {B}b 
pE = + log  c d  -- Eq. 2
0.0591 n  {C} {D} 

Eo
Now, under standard conditions, pE = pE o = .
0.0591

Eo
So to finish this derivation, we return to Eq. 2, and substitute for :
0.0591

1  {A}a {B}b 
pE = pE + log 
o

n  {C}c {D}d 
 

By using this equation with standard pEo values (readily obtainable from chemical tables) and
approximating the activities of the chemical species by their concentrations (remember this is okay
for dilute solutions), you can calculate the pE value for a specific environmental case.

Need an example? Check the Action Menu for this page – pE examples 1 and 2 cover this.
Going through them should help you internalise the concept.

Redox chemistry in natural waters 7

Using pE to predict redox speciation

The redox condition of a natural water body is one of the factors that controls the type of species
that will be present. This is of particular interest to the environmental chemist, because the form or
the species that a chemical exhibits in the environment will determine its behaviour. In
environmental studies, the behaviour we are often most interested in is the toxicity of the substance.

Here’s a famous example: chromium is a common contaminant in cooling water from power plants
(anybody seen Erin Brockovitch?). However, it is the +6 oxidation state ( Cr2 O 72− ) that is toxic to
humans. Chromium in the +3 oxidation state (Cr3+) is non-toxic. Therefore, analysing for the total
chromium concentration may not be very helpful. What would be more useful, would be some
indication of the speciation of the chromium – in other words, how much is Cr(VI) and how much
is Cr(III). pE calculations can help us to determine whether toxic species exist, and in what
proportions.

The redox chemistry of the water is controlled by the dominant redox equilibrium. Therefore, if
you know the dominant reaction, you can calculate its pE value, and so determine the equilibrium
position for all other redox reactions.

When there is a lot of oxygen dissolved in the water, oxidising conditions prevail (as you might
expect) and pE will be positive. For natural waters, this would be a pE value of about 12 or 13.
The way we can use this information is that the pE value for any other redox reaction will be equal
to the pE value for the dominant redox reaction.

So for example, to determine what would be the distribution of inorganic nitrogen in a well aerated
water body, you would first determine the pE value for the oxygen half reaction under the given
conditions (see pE examples 1 and 2). Then you would determine the pE value for the half reaction
for the conversion of nitrate to ammonia. Since the system is at equilibrium,
pEOxygen = pENitrate/Ammonia. Once these pE expressions are equated, you can determine the ratio of
nitrate ion to ammonia in the water. If the ratio is large, then the concentration of nitrate would be
much higher than that of ammonia. If the ratio is small, then the opposite is true. A ratio close to a
value of one (1) indicates more or less equal concentrations of each inorganic nitrogen species.

Need an example? Check the Action Menu – pE example 3 covers this last topic – using pE
calculations to predict the species distribution for given environmental conditions. You can go
through the example, and try the self-test questions to make sure you have this concept down.

Redox chemistry in natural waters 8

Using pE/pH diagrams

The preceding sections introduced the concept of pE, and how this can be used to describe, and
indeed predict, the type of species that would be present in a body of water, under given conditions.
This kind of information is vital to environmental chemists, because it is impossible to analyse for
every single different chemical species in a lake or river. The ability to predict or model the
composition of the lake or river is very helpful to understanding the chemical processes that are
taking place.

Up until this point, we have examined fairly simple systems, considering only two redox reactions
at any one time. However, you can bet there are many more than two reactions occurring in a river
– and all at the same time! In order to deal with this, we will now examine a more complex system,
which will include more information, for more chemical species.

A pE/pH diagram is a plot of pE versus pH, and the different areas on the diagram indicate the
conditions under which a particular redox species is dominant. The lines on the diagram which
separate these areas, constitute the boundaries between different dominant species. These
boundaries are defined by the different redox reactions that can occur in the water body.

As a simple example of how this works, we will examine a redox pair that must be included in any
aquatic system – we will consider the reactions in pure water.

Water has a limited range of pE and pH values – outside of that range, water is unstable, and may
be oxidised (to oxygen) or reduced (to hydrogen). Under highly oxidising conditions, the following
reaction occurs.

½ H2O
H+(aq) + ¼ O2 (g) + e–

pE = pE o + log PO24 [H + ]

1
pE expression*:
 

pE = pE o + log PO24 [H + ] − pH

1

 

Boundary condition: PO2 = 1 atm

E° = 1.229 V; pE° = 20.8

pE/pH relationship for pE = 20.8 – pH

*
NOTE!! Although this reaction is an oxidation, it is IUPAC convention that all E, Eo, pE, pEo data is defined as for
the REVERSE reaction – so the pE expression above is for the reduction reaction.

Redox chemistry in natural waters 9

oxidising conditions:

For highly reducing conditions, the following reaction occurs.

H2O + e– 
→ ½ H2 (g) + OH–(aq)

 1 
pE expression: pE = pE o + log 1 
 P 2 [OH −] 
 H2 

pE = pE° – ½ log (PH2) – log [OH-]

pE = pE° + ½ log (PH2) + pOH

Note that: pH + pOH = 14; so pOH = 14 – pH

pE = pE° + ½ log (PH2) + 14 – pH

Boundary condition: PH2 = 1 atm

E° = – 0.828 V; pE° = – 14.0

pE = – 14.0 + 14 – pH

pE/pH relationship for pE = – pH

reducing conditions:

The two equations we have developed are the

stability boundaries for water. To produce the 20
pE/pH diagram for water, the pH values are varied O2 (g)
from 0 to 14, and the associated pE values are 12
pE = 20.8 - pH
calculated. These two lines are then plotted on a
pE

graph. Figure 1 shows such a plot. 4 H2O (l)

-4 pE = - pH
If you examine Figure 1, you can see how you can H2 (g)
use a pE/pH diagram. In the region above the top -12
line, pE is high and positive, oxidising conditions 0 2 4 6 8 10 12 14
prevail and water may be oxidised to oxygen. pH
Similarly, in the region below the lower line, pE is
Figure 1. pE/pH diagram for water
low and negative, reducing conditions prevail and
water may be reduced to hydrogen.

Redox chemistry in natural waters 10

Therefore, it is clear that for any water body, the area of interest on the pE/pH diagram must be
between these two lines, because outside of these lines, water may decompose.

The method undertaken to produce Figure 1 can be done for any redox reactions in water. In the
example above, it was extremely simple, with only three species of interest, H2O, O2, and H2.
Under environmental conditions in a river, however, you can expect that a large number of different
cations and anions exist, and so the number of different species that could be included in a pE/pH
diagram could be quite large. Figure 2 is an example of such a complicated, and more realistic,
pE/pH diagram.

FIGURE 2 HERE.

Let us now examine the way in which

you can use such a pE/pH diagram to 20
make reasonable predictions about the
Fe 3+
oxidation state of chemical species in
water. We will use a simplified 12
pE/pH diagram for iron in water
(Figure 3). The diagram is simplified
pE

because it only considers soluble iron 4 Fe2+ Fe(OH)3

and its neutral hydroxides, and not
any of the other species that could
exist (sulphides, carbonates, etc.). -4

Fe(OH)2
In general, Figure 3 illustrates that as -12
pH decreases (acidic conditions), the 0 2 4 6 8 10 12 14
2+ 3+
soluble iron species Fe and Fe pH
predominate. This is hardly Figure 3. Simplified pE/pH diagram for iron in water.
surprising – metals are more soluble
in acidic media. To determine which
of these two species would be dominant, you would have to include pE information. At high pE
levels, Fe3+ would dominate. Again, this is expected – under extreme oxidising conditions, you
would expect to find iron in its highest oxidation state.

A similar argument can be made as pH increases. Under alkaline conditions (as [OH–] increases)
you would expect the iron hydroxides to be dominant. Again, pE can be used to distinguish which
iron hydroxide is dominant.

Okay, these general statements seem reasonable. But what do you do if you have a specific water
body to make predictions about?

Redox chemistry in natural waters 11

That is easy. Simply determine the pH and pE conditions for your given water body, draw the
corresponding lines on the pE/pH diagram, and see where they intersect. The point at which these
lines intersect on the diagram will tell you what the major species is for the specified conditions.
It is important that you recognise that each prediction is for a specific set of conditions, and should
the water conditions change, your prediction may change as well.

Need an example? Check the Action Menu. pE example 4 illustrates the use of the pE/pH
diagram.

Redox chemistry in natural waters 12