OXIDATION/

REDUCTION IN
AQUATIC
CHEMISTRY

OXIDATION/REDUCTION REACTIONS
Oxidation/reduction

reactions are
reactions involving changes of
oxidation states of reactants.

OXIDATION/REDUCTION REACTIONS
Reduction

half-reaction:

Oxidation half-reaction:

4.1 THE SIGNIFICANCE OF

OXIDATION/REDUCTION
Oxidation-reduction phenomena are
significant in the environmental
chemistry of natural waters and
wastewaters.

4.1 THE SIGNIFICANCE OF

OXIDATION/REDUCTION
Bacterially mediated oxidation of

biomass depletes oxygen

{CH2O} + O2 CO2 + H2O
Bacterially mediated reduction of

solid iron oxides and hydroxides puts

soluble iron in water
Fe(OH)3(s) + 3H+ + e- Fe2+(aq) + 3H2O
Microbially mediated oxidation of

ammonium nitrogen produces nitrate,

which can be assimilated by algae
NH4+ + 2O2 NO3- + 2H+ + H2O

4.1 THE SIGNIFICANCE OF

OXIDATION/REDUCTION
Two important points regarding
oxidation/reduction in water:
Most such reactions catalyzed by
microorganisms
Close relationship with acid-base,
analogies between e- and H+

Figure 4.1 Predominance of various chemical

species in a stratified body of water
O2

CO2

2SO
4
NO3

Fe(OH)3

Oxidizing, high pE

Reducing, low pE
+
H2SCH NH4
4

MnO2

Very low O2
2+ Mn2+
Fe

4.2 THE ELECTRON AND REDOX

REACTIONS
Reduction-oxidation reactions can be
viewed as the transfer of electrons
between species.

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4.2 THE ELECTRON AND REDOX

REACTIONS
2Fe3+ + H2 2Fe2+ + 2H+
pE

Closingthis switch allows

electron flow so that
reaction occurs

Measureof voltage
(reaction tendency)

H2

Salt bridge

Half reaction:
2H+ + 2e- H2

Half reaction:
Fe3+ + e- Fe2+

Pt
+

Fe3+

Fe2+

Pt

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4.2 THE ELECTRON AND REDOX

REACTIONS
The left electrode is the standard
hydrogen electrode, SHE
Half-reaction:
2H+ + 2e-

H2

E0 = 0.00 volts

When all reaction participants are at

unit activity (essentially [H+] = 1.00
mol/L, pressure of H2 = 1.00 atm), the
potential of the SHE (E0) is assigned
a value of 0.00 volt

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4.2 THE ELECTRON AND REDOX

REACTIONS
The potential of the right electrode vs.
SHE is the electrode potential, E.
When Fe3+ and Fe2+ are at unit
activity, E is the standard electrode
potential, E0
Fe3+ + e- Fe2+

E0 = 0.77 volts

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4.3 ELECTRON ACTIVITY AND pE

Conceptually

the negative log of

electron activity, pE , expresses
this activity over many orders of
magnitude
(at 25 C)

(at 25 C)

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4.4 THE NERNST EQUATION

The

Nernst equation is used to account

for the effect of different
activities upon electrode potential.

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4.4 THE NERNST EQUATION

Fe3+ + e- Fe2+ E0 = 0.77 volts
For the [Fe3+]/[Fe2+] electrode, which
expresses pE as a function of species
concentration, is

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4.4 THE NERNST EQUATION

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4.4 THE NERNST EQUATION

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4.4 THE NERNST EQUATION

For example, the value of [Fe3+] is
2.35 X 10-3M and [Fe2+] = 7.85 X 10-5M,
the value of pE is

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4.5 REACTION TENDENCY:

WHOLE REACTION FROM HALFREACTIONS

pE0 = 13.35

pE0 = 13.20

pE0 =

5.71

pE0 =

0.00

pE0 = -2.13

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4.5 REACTION TENDENCY:

WHOLE REACTION FROM HALFREACTIONS
A solution of Cu2+ flows through a
lead pipe and the lead acquires a
layer of copper metal through the
reaction

4.5 REACTION TENDENCY:

WHOLE REACTION FROM HALFREACTIONS

-(

24

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4.5 REACTION TENDENCY:

WHOLE REACTION FROM HALFREACTIONS

pE
Salt bridge

2+

Cu

Cu
NO 3

Pb2+

NO3-

Pb

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4.6 THE NERNST EQUATION AND

CHEMICAL EQUILIBRIUM

pE
Salt bridge

2+

Cu

Cu
NO 3

Pb2+

NO3-

Pb

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4.6 THE NERNST EQUATION AND

CHEMICAL EQUILIBRIUM

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4.7 THE RELATIONSHIP OF pE TO FREE

ENERGY

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4.8 REACTIONS IN TERMS OF ONE

ELECTRON-MOLE
Writing oxidation/reduction reactions
on the basis of one electron-mole
enables their comparison on a common
basis

33

4.8 REACTIONS IN TERMS OF ONE

ELECTRON-MOLE
Consider

the reaction

The N atom changes oxidation state

from -3 to +5 corresponding to a
transfer of 8 electrons, so the
reaction in terms of 1 mole of
electrons is

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4.8 REACTIONS IN TERMS OF ONE

ELECTRON-MOLE
A comparison of pE0 values provide a
direct comparison of G0 values.

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4.8 REACTIONS IN TERMS OF ONE

ELECTRON-MOLE
For

a redox reaction involving n

electrons, pE0 is related to the
equilibrium constant by

which for a one electron-mole

reactions becomes simply

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4.8 REACTIONS IN TERMS OF ONE

ELECTRON-MOLE

The equilibrium-constant expression

for this reaction is,

or

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4.9 THE LIMITS OF pE IN WATER

Water

may be both oxidized:

Or it may be reduced:

39

4.9 THE LIMITS OF pE IN WATER

The

condition under which oxygen from

the oxidation of water has a
pressure of 1.00 atm can be regarded
as the oxidizing limit of water.

40

4.9 THE LIMITS OF pE IN WATER

The

condition under which hydrogen

from the reduction of water has a
pressure of 1.00 atm may be regarded
as the reducing limit of water.

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4.9 THE LIMITS OF pE IN WATER

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4.10 pE VALUES IN NATURAL WATER

SYSTEMS
Consider

pH 7.00 water in equilibrium

with atmospheric oxygen (0.21atm
partial pressure)
PO2 = 0.21 and [H+] = 1.00 X 10-7 M
Substituting,

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4.10 pE VALUES IN NATURAL WATER

SYSTEMS
Consider

anoxic water at pH 7.00 in

which the pressures of CH4 and CO2
are equal
PCO2 = PCH4 and [H+] = 1.00 X 10-7 M

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4.10 pE VALUES IN NATURAL WATER

SYSTEMS

Substituting,

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4.11 pE-pH DIAGRAMS

pE-pH diagram for an iron system in
which maximum soluble iron =
1.00X10-5 mol/L
20

Fe3+

15

O2

10
pE

Fe(OH)3

Fe2+

0
-5
H2

-10

Fe(OH)2

-15
0 1 2 3 4 5

7 8 9 10 1
pH

12 13 14

48

4.11 pE-pH DIAGRAMS

13.2

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4.11 pE-pH DIAGRAMS

Dashed lines are thermodynamic limits
of water stability

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4.11 pE-pH DIAGRAMS

Fe3+ is stable in a small region at
high pE and low pH

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4.11 pE-pH DIAGRAMS

(independent of pH)

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4.11 pE-pH DIAGRAMS

At pE exceeding 13.2, as the pH

increases from very low values,
Fe(OH)3 precipitates from a solution
of Fe3+. [Fe3+] = 1.00 X 10-5 M

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4.11 pE-pH DIAGRAMS

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4.11 pE-pH DIAGRAMS

The boundary between Fe2+ and solid

Fe(OH)2 may be defined.
[Fe2+] = 1.00 X 10-5 M

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4.11 pE-pH DIAGRAMS

The boundary between Fe2+ and Fe(OH)3
depends upon both pE and pH.

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4.11 pE-pH DIAGRAMS

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4.11 pE-pH DIAGRAMS

The boundary between Fe(OH)2 and
Fe(OH)3 also depends upon both pE
and pH.

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4.11 pE-pH DIAGRAMS

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4.11 pE-pH DIAGRAMS

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4.12 CORROSION
Corrosion

is defined as the
destructive alteration of metal
through interactions with its
surroundings.
Corrosion takes place when an
electrochemical cell is set up on
the surface of a metal, M.

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4.12 CORROSION
Several

cathodic reactions are

possible.
Oxygen may also be involved in
cathodic reactions.