Lecture 7a - Redox Process and Equilibrium K23

LECTURE 7.
Redox processes
Why be interested in redox processes?
Determine the fate of pollutants;

Nitrate leaching from agricultural fields
Contaminants leaching from landfills, industrial spills etc.
Exert an important control on the concentration of O2, Fe2+, SO42-,

CH4 etc in groundwater
2Fe2+ + MnO2 + 2 H2O

2 FeOOH + Mn2+ + 2H+
2e-
2Fe2+ + MnO2 + 4H+ 2Fe3+ + Mn2+ + 2 H2O
Reductant
Reducing agent
Electron donor
Is oxidised
Oxidant
Oxidising agent
Electron acceptor
Is reduced
2Fe2+ + MnO2 + 4H+ 2Fe3+ + Mn2+ + 2H2O
ree n s
f
No ctro
ele
Fe
(II)
Fe
(II)
Mn
(IV) Mn(
IV)
Fe
(II)
Mn(
IV)
Fe
(II)
Fe2+ Fe3+ + e-
Mn2+ + 2H2O
MnO2 + 4H+ + 2e-
The Nernst equation

bBred + cCox dDox + gGred
Gibbs free energy:
G = nFE
E0: Standard potential; [i] = 1; 25C; 1 atm
Redox Cell
E0 when
[Fe2+] = [Fe3+] = 1
Standard state
conditions
H2 2H+ + 2e-
Fe2+ Fe3+ + e-
E0 for oxidation of Fe2+ to Fe3+

2Fe2+ + 2H+ 2Fe3+ + H2(g)
The Nernst equation:
Fe P
RT
ln
2 F Fe H
3 2
E E0
H2
2 2
PH2 = 1 and [H+] = 1 :
RT
Fe 3
Eh E
ln
1F , Fe 2
0
For the half-reaction:
Fe2+ Fe3+ + e-
PH2 = 1; [H+] = 1
E0: The tendency to release or accept electrons

For a given Eh the distribution of all other redox
couples is fixed
The pe concept
Fe2+ Fe3+ + e-
Definition:
pe = -log([e-])
~ pH = -log([H+])
Log(K) = log([Fe3+]) pe - log([Fe2+]) = -13.05
at 25C:
Eh = 0.059 pe
Standard Potentials
Red. agents
Ox. agents
Overall reaction E0 = 0.77V 1.23V = -0.46V
Eh measurements
HS-/SO42-
O2/H2O
Fe3+/Fe2+
Example 1.
Calculation of redox speciation with the Nernst equation
A water sample contains [Fe2+] = 10-4.95 and [Fe3+] = 10-2.29 with a
pH=3.5 at 250C. What would be [Mn2+] if this water sample were in
equilibrium with sediment containing MnO2?
Answer 1:
For [Fe3+]/[Fe2+]:
with pe = -log[e-]
Fe2+ Fe3+ + e-
logK = log[Fe3+] pe log[Fe2+] = -13.05

Subsituting values gives: pe = -(-13.05) + (-2.29) (-4.95) = 15.71
For MnO2/Mn2+: Mn2+ + H2O MnO2 + 4H+ + 2e-
with K = 10-41.52
log[Mn2+] = -logK 4pH -2pe

Substituting logK, pH and the pe calculated above yields
log[Mn2+] = -(-41.52) -4*3.5 2*15.71 = -3.90
Answer 2.
For Fe3+/Fe2+:
Eh = 0.77 + 0.059(log[Fe 3+] log[Fe2+])
Substitute iron activities

Eh = 0.77 + 0.059(-2.29 (-4.95)) = 0.927 Volt
Next for MnO2/Mn2+:
Eh = 1.23 + 0.03(-4pH-log[Mn2+])
log[Mn2+] = (1/0.03)(1.23 Eh 0.12pH)
Substitute the given pH and the Eh calculated from Fe 3+/Fe2+ couple
log[Mn2+] = 33.33(1.23-0.927-0.42)=-3.9
[Mn2+] = 10-3.90
Thus, for any lower [Fe3+]/[Fe2+] ratio, or lower pH value, the [Mn 2+] will
increase and vice versa. The example illustrates that once the Eh is
evaluated from one redox couple, the distribution of all other redox
couples is fixed.
The stability of H2O

Oxidation of O2- in water
H2O 2e- + 2H+ + O2
Log(K) = log([PO2]) 2pe 2pH = -41.55
Atmosphere: PO2 = 0.2
pe = 20.6 - pH
Reduction of H+ in water
H2 H+ + eLog(K) = -pH pe -log(PH2) = 0
At max PH2 = 1
pe = -pH
pH/pe diagrams
pe = 20.6 - pH
pe = -pH
Stability of dissolved species: Arsenic
Boundary between As(V) species:
log([HAsO42-]) - pH log[H2AsO4-] = -6.76
At pH = 6.76:
H2AsO4- = HAsO42-
pH = 6.76
V
III
III
Boundary between H2AsO4- and H3AsO3:

H3AsO3 + H2O H2AsO4- + 3H+ + 2elog([H2AsO4-]) - 3pH 2pe - log([H3AsO3) = -21.14
If [H2AsO4-] = [H3AsO3]:
2pe = -3pH + 21.14
pH = 6.76
V
III
2pe = -3pH + 21.14
III
Equal activities
N2 + 2.5O2 + H2O
2NO3- + 2H+
PN2 = 0.77
[NO3-] = [NH4+] = 10-3
Sulfur
Carbon
Stability of minerals: Iron

Several different iron oxides:
Ferrihydrite: Fe(OH)3
Lepidocrocite: -FeOOH
Goethite: -FeOOH
Hematite: -Fe2O3
-FeOOH
Lepidocrocite
-FeOOH
Goethite
logKs for reactions among Fe

Reaction
log K
FeOH2+
Fe3+ + H2O FeOH2+ + H+
-2.4
Fe(3)/Fe(2)
Fe2+ Fe3+ + e-
-13.05
Ferrihydrite
Fe(OH)3(s) + 3H+ Fe3+ + 3H2O
3.7
Siderite
FeCO3 Fe2+ + CO32-
-10.45
Fe(OH)2
Fe(OH)2(s) + 2H+ Fe2+ + 2H2O
13.9
Dissociation of iron oxides

Ferrihydrite:
Fe(OH)3 Fe3+ + 3OHLepidocrocite and goethite:
FeOOH + H2O Fe3+ + 3OHHematite:
Fe2O3 + 3/2H2O Fe3+ + 3OH-
K = [Fe3+][OH-]3
Stability range of iron oxides
TIC = 10-2.5
Log(Kferrihydrite) = 38.3
Redox Processes: I- Arsenic and pe

Dan Phuong ca 30 km upstream of Hanoi along the Red
River.
Sample
Depth m pH
As(3)
mol/l
As(5)
mol/l
B1-01
7.76
1.24
0.70
B1-06
7.22
4.09
0.24
B1-16
16
7.09
0.61
0.07
Redox Processes: I- Arsenic and pe

Dan Phuong ca 30 km upstream of Hanoi along the Red
River.
Sample
pe
pH
As(3)
mol/l
As(5)
mol/l
B1-01
-1.71
7.76
1.24
0.70
B1-06
-1.17
7.22
4.09
0.24
B1-16
-0.78
7.09
0.61
0.07
log([H2AsO4-]) - 3pH 2pe - log([H3AsO3) = -21.14
Exercise 1.
Groundwater sample from wells in the Nadia district of West Bengal show
the following composition ( Mukherjee et al., 2000). Concentrations are in
micrograms per liter.
Sample
pH
Eh/mV
As(3)
As(5)
S1
6.90
-152
84.7
88.3
a. How do these sample compare with drinking water limits

b. Calculate the Eh from dissolved arsenic
Exercise 2.
Construct a pe-pH diagram for Pb2+ with the following data:
1) PbO2 + 4H+ + 2e- 2H2O + Pb2+
2) Pb2+ + 2e- Pb
3) PbO + 2H+ Pb2+ + H2O
4) Pb2+ + 3H2O Pb(OH)3- + 3H+
(1)
(2)
(3)
(4)
Log K = 49.2
Log K = -4.26
Log K = 12.7
Log K = -28.1
Use activity levels of Pb2+ and Pb(OH)3- at the solid/solution boundaries.
Exercise 3.
a. Calculate the amount of MnCO3 (rhodochrosite) that can dissolve in
water, if PCO2 = 10-1.5
MnCO3 Mn2+ + CO32- k= 10-9.3
b. Which type of rhodochrosite dissolution in expected in a well-aerated
soil: congruent dissolution or incongruent dissolution? Which mineral(s) will
form? What is the effect on the PCO2?

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LECTURE 7.

Why be interested in redox processes?

Determine the fate of pollutants;

Exert an important control on the concentration of O2, Fe2+, SO42-,

2Fe2+ + MnO2 + 2 H2O

2Fe2+ + MnO2 + 4H+ 2Fe3+ + Mn2+ + 2 H2O

2Fe2+ + MnO2 + 4H+ 2Fe3+ + Mn2+ + 2H2O

The Nernst equation

E0: Standard potential; [i] = 1; 25C; 1 atm

E0 for oxidation of Fe2+ to Fe3+

The Nernst equation:

PH2 = 1 and [H+] = 1 :

For the half-reaction:

E0: The tendency to release or accept electrons

Log(K) = log([Fe3+]) pe - log([Fe2+]) = -13.05

Overall reaction E0 = 0.77V 1.23V = -0.46V

logK = log[Fe3+] pe log[Fe2+] = -13.05

For MnO2/Mn2+: Mn2+ + H2O MnO2 + 4H+ + 2e-

log[Mn2+] = -logK 4pH -2pe

Eh = 0.77 + 0.059(log[Fe 3+] log[Fe2+])

Substitute iron activities

The stability of H2O

Stability of dissolved species: Arsenic

Boundary between As(V) species:

log([HAsO42-]) - pH log[H2AsO4-] = -6.76

Boundary between H2AsO4- and H3AsO3:

Stability of minerals: Iron

logKs for reactions among Fe

Fe3+ + H2O FeOH2+ + H+

Fe(OH)3(s) + 3H+ Fe3+ + 3H2O

FeCO3 Fe2+ + CO32-

Fe(OH)2(s) + 2H+ Fe2+ + 2H2O

Dissociation of iron oxides

Stability range of iron oxides

Redox Processes: I- Arsenic and pe

Redox Processes: I- Arsenic and pe

log([H2AsO4-]) - 3pH 2pe - log([H3AsO3) = -21.14

a. How do these sample compare with drinking water limits

Use activity levels of Pb2+ and Pb(OH)3- at the solid/solution boundaries.

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