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ASPECTS OF AQUATIC

REDOX CHEMISTRY
PART - I
REDOX CONDITIONS IN
NATURAL WATERS
Redox conditions in natural waters are controlled
largely by photosynthesis and bacterial respiration
processes
Oxidation Reduction Reactions

Oxidation - a process involving loss of electrons.


Reduction - a process involving gain of electrons.
Reductant - a species that loses electrons.
Oxidant - a species that gains electrons.
Free electrons do not accumulate in solution.
Electrons lost from one species in solution must
be immediately gained by another.
Ox1 + Red2 Red1 + Ox2
Reduction-Oxidation Potential
The potential that is generated between an
oxidation or reduction half cell and the
standard hydrogen electrode
In aqueous solutions, the reduction
potential is the tendency of the solution to
either gain or lose electrons
The potential abundance of electrons or
the electron activity
PHOTOSYNTHESIS
Synthesis of organic matter by photosynthesis

light
CO2 (g) H 2 O(aq) C(H 2 O) O 2 (g)

The average composition of the organic matter in plankton is approximately:


C106H263O110N16P1. Therefore, photosynthesis reaction can be
represented by the following and more complex reaction

106CO2 (g) 122H 2 O(aq) 16NO3 HPO 24 18H C106 H 263 O110 N16 P1 138O 2 (g)
light

algae

C : N : P 106 : 16 : 1
Redfield Ratio (Redfield et al., 1963)
Redfield Ratio Concept
RESPIRATION
In general, respiration involves the decomposition
of organic matter produced through photosynthesis
respiratio n
C(H 2O) O2 CO2 H 2O

During respiration, the organic matter is oxidized


and an electron acceptor is reduced
Example electron acceptors:

O2 NO3 MnO 2 Fe(OH)3 SO24 CO2


Respiration can occur under oxygenated (or aerobic)
conditions or in the absence of molecular oxygen
(anaerobic respiration).
RESPIRATION (contd)

In water containing excessive biomass (e.g.


during algal blooms), dead organic matter (OM)
is mineralized via microbial respiration in the
presence of terminal electron acceptors (TEA)
as illustrated in the following general reaction

respiratio n
OM TEA CO 2 H 2 O
Using CH2O as a general formula for OM and different TEA types, one obtains
(see next slide)
Progressive Microbial Respiration of OM in
Natural Waters and Thermodynamics
Re action .........................................................................................G 0w (kJ / equiv )
(1) Oxygen consumptio n
1 1 1 1
O 2 CH 2 O CO 2 H 2 O......................................................... 125.0
4 4 4 4
(2) Denitrific ation
1 1 1 1 7
NO3 CH 2 O H CO 2 N 2 H 2 O.............................. 119.0
5 4 4 10 20
(3) Formation of so lub le Mn (II) by reduction of Mn (IV) oxides
1 1 1 1 3
MnO 2 CH 2 O H CO 2 Mn 2 H 2 O............................. 85.0
2 4 4 2 4
(4) Formation of so lub le Fe(II) by reduction of Fe(III) (hydr )oxides
1 1 7
FeOOH CH 2 O 2H CO 2 Fe 2 H 2 O................................ 26.8
4 4 4
(5) Sulfate reduction
1 1 1 1 1 1
SO 24 CH 2 O H CO 2 HS H 2 O.............................. 26.0
8 4 8 4 8 4
(6) Methane formation (methanogen sis )
1 1 1 1
CO 2 CH 2 O CO 2 CH 2 ......................................................... 23.2
8 4 4 8
Redox Couples
For any half reaction, the oxidized/reduced
pair is the redox couple:
Fe2+ Fe3+ + e-
Couple: Fe2+/Fe3+

H2S + 4 H2O SO42- + 10 H+ + 8 e-


Couple: H2S/SO42-
Redox Ladder
Oxidized species (TEAs) 1 Reduced species

O2 H 2O

- 0.5
NO3 NO2-
-
NO2 NH4+
Mn+4 Mn+2
pE = Eh / 0.0591
FeOOH 0 Fe+2

SO4-2 HS-
CO2 CH4
H+ H2
HCOO- -0.5 CH2O
Eh (V)
Another Representation of The Redox Ladder
O2 Aerobes
Oxic H2O
NO3- Denitrifiers
N2 Manganese reducers
Sub-oxic MnO2
anaerobic Mn2+
Fe(OH)3 Iron reducers
Fe2+ SO42-
Sulfidic Sulfate reducers
H2S
CO2 Methanogens
CH4
Methanic H2O
H2

The redox-couples are shown on each stair-step, where the most energy is gained at
the top step and the least at the bottom step (i.e. the Gibbs free energy of reaction
becomes more positive going down the steps).
Half Reactions
Often split redox reactions in two:
oxidation half rxn e- leaves left, goes right
Fe2+ Fe3+ + e-
Reduction half rxn e- leaves left, goes right
O2 + 4 e- 2 H2O
SUM of the half reactions yields the total
redox reaction
4 Fe2+ 4 Fe3+ + 4 e-
O2 + 4 e- 2 H2O
4 Fe2+ + O2 4 Fe3+ + 2 H2O
Steps for Balancing Redox
Reactions
1. Indentify principle reactants and products

2. Balance atoms other than Hydrogen and


Oxygen

3. Balance oxygen using H2O

4. Balance H using H+

5. Balance Charge with electrons


7. Multiply each half cell by an integer so that
both half cells contain same number of
electrons

8. Add two balanced half cells

9. H+ may be present as product of reaction. If


the reaction is known to take place in an
alkaline solution, then add the reaction for
the dissociation of water to eliminate the H+
form the overall redox reaction
Examples

Write the half reactions corresponding to


each of these 2 reactions and show the
balanced overall redox reactions

Mn(IV) + H2S Mn2+ + S0 + H+

H2S + O2 S8 + H2O
Example Redox Impact on the Aquatic
Cycling of Iron
Efficiency of Thermodynamic Predictions

Measured Eh Vs Calculated Eh in Acid Mine Waters


ACS, 1979

0.95

0.9

0.85

0.8
Eh (volts)

0.75

0.7

0.65

0.6

0.55

0.5
0.5 0.55 0.6 0.65 0.7 0.75 0.8 0.85 0.9 0.95
Eh (mVolts)
Limitations of Thermodynamic Predictions
Measured Eh Vs Calculated Eh in Groundwaters
From Lindberg and Runells, 1984 (Science)