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Role of Oxidation/Reduction in Water Bodies

Why the Oxidation/Reduction in the Natural Environment is so important?

To understand the changes in chemicals/nutrients, it is essential to know the


oxidation and reduction chemistry of species in the water bodies.

Here, we are examining the effect o oxidizing media on species in water.

Why the oxidation state is important ?

Hg, HgCH 3 +, and Hg(CH 3 ) 2

Methyl Mercury (both forms) is much more toxic than mercury metal;

Chromium VI is more toxic than other forms of chromium (i.e. Cr3+).

Philosophy: Thermodynamics vs. Kinetics

Remember: Oxidation states

Hydrogen is always +1

Oxygen is always -2

Alkali +1, Alkane earths +2

Element in its natural state is defined to equal zero

Look at Nitrogen, Sulfur, Carbon

N 2 , NH 3 , NO 3 -, NO 2 , NO, NO 2 -, H 2 S, S,

SO 2 , SO 3 2-, SO 4 2-, CH 4, , CH 2 O, CO, CO 2

Reduction is defined as the gain of electrons

Oxidation is defined as the loss of electrons


The hydrogen is defined to be zero and everything is relative to this standard.

The more positive the potential, the greater the tendency for the reaction to proceed as
written.

∆G0 = -nFE 0

∆G0 = -2.303 nRT pE

Since we do not know about ALL of the species present in any particular sample of
natural water, we can not write the arrive any balanced redox reaction that suppose to
occur.

Hence, we are now defining a quantity termed as pE:

pE = -log a e-

Here, A e- is the term referring the activity of an electron

According to the Nerst’s Equation:


Low pE is reducing

Figure 1. Different Nitrogen in the Natural Environment

pE diagrams tell us the most thermodynamic stable form in certain water environments.

pE of water in equilibrium with the air = + 13.58

Many times the form of a species in water is a function of both pH and pE

These ideas can be incorporated into one concise diagram -pE - pH

Oxidizing limit for water pE = 20.75 - pH

Reducing limit for water pE = 0.0 - pH

The common forms of nitrogen in the aqueous environment are:


Transformations between these nitrogen oxidation states are managed by the
following equations:
Table 2. Apply this data to construct a pE/pH Diagram for Nitrogen (in water):

Boundry pH pE

O 2 /H 2 O 0 20.75

O 2 /H 2 O 10 10.75

H 2 /H 2 O 0 0

H 2 /H 2 O 10 -10

NO 3 -/NO 2 - 0 14.15

NO 3 -/NO 2 - 10 4.15

NO 3 -/NH 4 + 0 14.90

NO 3 -/NH 4 + 10 2.40

NO 2 -/NH 4 + 0 15.14

NO 2 -/NH 4 + 10 1.81
Figure 2. pE/pH Diagram for Nitrogen (N-O-H System)

What about the presence of Carbon in aqueous system?


Figure 3. pH-pE Diagram for Nitrogen, Sulfur and Carbon