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?