CIVL 6023 Redox Chemistry

Electron Exchange Reactions:

Use of pe = –log[e] as Master Variable

pe-pC Diagrams: Construction and Interpretation

pe-pH Diagram (phase stability) – for appreciation only

Interesting and Important Redox Environments

Oxidizing Environments
•Acid Mine Drainage Systems
•Epilimnion of Fresh Water Lakes
•Fast Moving Turbulent Rivers
•Surface Ocean
•Ozonation/Chlorination Processes

Reducing Environments
•Saturated High Organic Soils
•Sediments of Eutrophic Lakes and Rivers
•Peat Bogs
•Swamps and Wetlands
•Estuarine Sediments
•Hypolimnion of Statified Eutrophic Lakes
•Anaerobic Digestors

1
 Common Electron Exchange Reactions in Aquatic Systems
Consider the following electron exchange reactions:

logK
O2(g) + 4H+ + 4e = 2H2O 83.1

MnO2(s) + 4H+ + 2e = Mn2+ + 2H2O 43.6

NO3- + 10H+ + 8e = NH4+ + 3H2O 119.2

Fe(OH)3(s) + 3H+ + e = Fe2+ + 3H2O 16.0

SO42- + 9H+ + 8e = HS- + 4H2O 34.0

2H+ + 2e = H2(g) 0

CO2(g) + 8H+ + 8e = CH4(g) + 2H2O 23.0

Half Reactions Written as One Electron Exchanges

The reactions given as one electron exchanges are:

logK peº(w)
1/4O2(g) + H+ + e = 1/2H2O 20.75 13.75

1/2MnO2(s) + 2H+ + e = 1/2Mn2+ + H2O 21.8 7.8

1/8NO3- + 5/4H+ + e = 1/8NH4+ +3/8H2O 14.9 6.15

Fe(OH)3(s) 3H+ + e = Fe2+ + 3H2O 17.0 -4.0

1/8SO42- + 9/8H+ + e = 1/8HS- + 1/2H2O 4.25 -3.625

1/8CO2(g) + H+ + e = 1/8CH4(g) + 1/4H2O 2.875 -4.125

H+ + e = 1/2H2(g) 0.0 -7

2
 NO3-/NH4+ Redox Couple
1/8NO3- + 5/4H+ + e = 1/8NH4+ + 2/8H2O 14.9

K=
NH  + 1/ 8
= 10
4 14.9

NO  H  e
− 1/ 8
3
+ 5/ 4


1 K NO3− H +
=
  
1/ 8 5/ 4

e NH 4+  
1/ 8

pe = log K + 1 / 8 log
NO  + 5 / 4 logH 
−
+

NH 
3
+
4

14

NO3-/NH4+ Redox Couple

For solution conditions of pH 8 we can calculate the pe

where the [NO3-] = [NH4+]:

pe = 14.9 + 0 + 5/4(-8) = 4.9

Thus, the concentrations of NO3- and NH4+ will be equal

at pe = 4.9 and each will decrease on a 1/8 slope moving
away from the point of equal concentration on
a pe vs pC diagram.

These types of calculations allow us to identify the pe

range where the redox couples will be located under
different environmental conditions.

15

3
 Reductive Dissolution of Fe(OH)3(s)
An example reductive dissolution is ferrihydrite,
Fe(OH)3(s):

Fe(OH)3(s) + 3 H+ + e = Fe2+ + 3 H2O logK = 17.1 (1)

K=
Fe  = 10 2+
17.1

H  e
(2)
+ 3

at pH = 8 we have
K[H+]3 = 1017.1(10-8)3 = 10-6.9 = [Fe2+]/[e]
And
[e] = [Fe2+]106.9 and the equation for the ferrous ion line
is
Slope of 1, intercept
pFe2+ = pe + 6.9 at -6.9 for pFe = 0 16

16

[Fe+2]calc
pe
[FeT]
[Fe+2]
-14 -12 -10 -8 -6 -4 -2 0 2 4 6 8 10 12 14
0
Fe(OH)3(s)
5 FeT

Fe2+
10

15 pH 6
pH 7 FeT = 1.x 10-5 M pFe2+ = pe + 0.9
pC

pH 7
20

25
pFe2+ = pe + 3.9
30
Fe(OH)3(s) + 3 H+ + e = Fe2+ + 3 H2OpH 8
35 pFe2+ = pe + 6.9

pe-pC diagram for Fe(OH)3(s) / Fe+2

17

17

4
 Anoxic Water-Sulfate/Sulfide Couple
Anoxic systems where reducing conditions are such that
Both sulfate and bisulfide coexist:

1/8SO42- + 9/8H+ + e = 1/8HS- + 1/2H2O pe° = 4.25

[ HS − ]1/ 8
K= 2 − 1/ 8 + 9/8
= 104.25
[ SO4 ] [ H ] [e]
Taking the logs of the variables gives

[ SO42− ]1/ 8 [ H + ]9 / 8
pe = pe + log


[ HS − ]1/ 8
20

20

To plot the SO42-/HS- couple on a pe-pC diagram we need

To set the ratio of [SO42-]/[HS-] = 1

pe = logK + 9/8log[H+] + 1/8log([SO42-]/[HS-])

For pH 8

pe = logK + 9/8(-8) + 1/8log([SO42-]/[HS-])

pe = 4.25 – 9 + 0 = -4.75

Thus, the two species are equal at pe = -4.75 and will change
On a slope of 8 after the transition (8 electron exchange).

21

21

5
 [SO4-2]
pe
-4.75 [HS-]

-14 -12 -10 -8 -6 -4 -2 0 2 4 6 8 10 12 14 16 18 20

0

5
HS- SO42-
10

15 pH 8
pC

20 ST = 1 x10-3 M
25 SO42- HS-
30

35

pe-pC diagram for SO4-2 / HS-

22

22

Methane Formation in Sediments and Soils

Typical conditions in high organic soils and sediments can
lead to the formation of methane from carbon dioxide.
consider the following reaction:

1/8CO2(g) + H+ + e = 1/8CH4(g) + 1/4H2O pe° = 2.87

Where the mass action expression is:

1/ 8
PCH
K= 1/ 8
4
+
= 102.87
P [ H ][e]
CO2

Converting to pe notation gives

1  PCO2 
pe = log K + log  − pH
8  PCH 4 

23

23

6
 To plot the CO2/CH4 couple on a pe-pC diagram we need
to set the ratio of PCO2/PCH4 = 1. Thus, for a pH of 8
we would have the following pe:

1  PCO2 
pe = log K + log  − pH
8  PCH 4 


pe = 2.87 – 8 + 0 = -5.13

The concentrations of CO2 and CH4 will decrease by with

a slope of 8 going past the point of equal concentrations.

24

24

[PCO2]
pe
-5.13 [PCH4]

-14 -12 -10 -8 -6 -4 -2 0 2 4 6 8 10 12 14 16 18 20

0

5
PCH4 PCO2
10

15
pC

20

PCH4
25

30 PCO2
35

pe-pC diagram for CO2(g)/ CH4(g)

25

25

7
 Spacial and Temporal Separation
of Redox Environments

Photosynthesis

Oxidizing
Conditions

Redox Boundary

Reducing Conditions Respiration

Algae CO2
Sediment/Water
Interface

30

30

Eutrophic Stratified Lake

In temperate climates where the winter season leads to

temperatures below freezing, many lakes and ponds have
two annual turnovers and two periods of stratification.
Consider a eutrophic stratified lake with the
following composition:

pH 7
Alk = 2x10-3 eq (CT = 2.4x10-3 M)
[SO42-] = 1x10-3 M
[NO3-] = 1x10-5 M
FeT = 1x10-5 M
MnT = 3x10-6 M
[O2] = 2.5x10-4 M (8 mg/l)
31

31

8
 Eutrophic Statified Lake

32

32

Electron Equivalent Capacity

The capacity of each subsystem is the electron equivalents

contained in each electron acceptor concentration:

O2: (2.5x10-4) x 4e = 1x10-3 at pe = 13.75

MnO2(s): (3x10-6) x 2e = 6x10-6 at pe = 7.8

NO3-: (1x10-4) x 8e = 0.8 x 10-3 at pe = 6.15

Fe(OH)3(s): (1x10-5) x 1e = 1x10-5 at pe = 1

SO42-: (1x10-3) x 8e = 8 x 10-3 at pe = -3.63

33

33

9
 34

34

10