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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
light
CO2 (g) H 2 O(aq) C(H 2 O) O 2 (g)
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
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+
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
4. Balance H using H+
H2S + O2 S8 + H2O
Example Redox Impact on the Aquatic
Cycling of Iron
Efficiency of Thermodynamic Predictions
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)