Environmental Chemistry

Part 3 Hydrospheric Chemistry

3.4 Oxidation and Reduction

SEVERAL CONCEPTS
pe and Eh
Nernst equation
Eh-pH diagrams
predominance areas
mineral stability fields
solubility contours
2

Questions?
K ---rG
K- Chemical Equilibrium Constant
rG Gibbs Free energy

Gibbs Free Energy

r G r G RT ln K
0

Standard state implies activity of the species

is/are equal to one
At equilibrium, rG=0

r G RT ln K 2.3026RT log K
0

Calculating rG
rG
0

0
f Gproducts

0
f G reac tan ts

rGo and K values are dependent on T and

P, so when calculating reactions you must
be careful what values of rGo you use

Hematite() Example
Dissolution of iron when hematite was in contact
with water
Differences when changing conditions, eg, pH
Important point was change in solubility with
acidity
Quantitative way of understanding reactions
between minerals and waters
6

Saturation State
log Q = log Klg[Red]/[Ox]
water is saturated with respect to mineral
log Q > log K
water is supersaturated with respect to mineral
log Q < log K
water is undersaturated with respect to mineral
7

Redox Reactions
Redox stands for reduction and oxidation
terms combined because they are always coupled in
chemical reactions

Reduction and oxidation relate to the valency

of an element, hence the charge of single
element ions.
e.g., Na+, Ca2+, Fe2+,Cl8

 Just as different aqueous species predominate in

acid - base reactions (e.g., Al3+, . . . Al(OH)4-),
different aqueous species predominate in redox
reactions (e.g., Fe2+, Fe3+)
Aqueous speciation and mineral solubilities can
depend on redox
9

Examples
Organisms reduce carbon dioxide to organic
carbon
Death and decay of organisms can lead to
oxygen-deficient water
Eutrophication()

Metal leaching and acid rock drainage

10

Eh

What is it?
Calculated using the Nernst equation(
)
log Q = log Klg[Red]/[Ox]

RT
0 + ne = Red

Ox
Eh E 2 . 3026
log Q
nF

nF

F=96500J/(V. mol)
1.00

11

Eh-pH Diagrams
Used to figure out what aqueous species and/or
minerals are predominant or stable at given EhpH conditions
Limits
predominance areas
mineral stability fields
solubility contours

12

 O2 + 4H+ + 4e- = 2H2O

E = E0 - 0.059 (1/n) log([H2O ]/[p ][H+]4)

=1.21 -(0.059/4) log(1/[H+]4)
=1.21
-0.059/4*{-4log[H+]}
=1
=1.21
=1 - 0.059 (-log[H+])
E =1.21
=1 - 0.059pH

13

+
2H
2H22O
O==O
O22++4H
4H+ ++4e
4eEquilibrium
Equilibriumpotential
potential
falls
fallsas
aspH
pHincreases
increases

Potential

The
-pH) Diagram

The Pourbaix
Pourbaix (E
(E-pH)
Diagram
2.0
1.6
1.2
0.8
0.4
0.0
-0.4
-0.8
-1.2
-1.6

EE=1.23
=1.23--0.059pH
0.059pH

O2 is stable+
2H
2H+++2e
2e-==HH22
Equilibrium
Equilibrium
potential
falls
as
potential
falls
as
H2O is stable
pH
pHincreases
increases

H2 is stable
+
pH
pH==--log
log[H
[H+]]
0

14
14

Pourbaix-diagram of iron to pH
Fe
Fe3+ + e- = Fe2+
E = constant

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

Fe2+ + 2H2O = Fe(OH)2 + 2H+
pH- variable, E not constant

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

E = E0 - 0.059 log([Fe2+]/[H+]3)
Fe(OH)3 + H+ + e- = Fe(OH)2 + H2O
E = E0 - 0.059 log(1/[H+])

15

Pourbaix Diagram for Zinc

Potential

Equilibrium
for
Equilibrium
for
2.0
2Zn(OH)
Zn(OH)22++2OH
2OH-
ZnO
ZnO222- ++2H
2H22O
O
1.6
Equilibrium
Equilibriumfor
for
1.2
2+
- - Zn(OH)
2+
Zn
+
2OH
+ 2OH Zn(OH)22
Zn Zn(OH)
0.8
stable
0.4
ZnO22for
solid Equilibrium
Equilibrium
for
2+
0.0
Zn stable
Equilibrium
for
stable
in
- - Zn(OH) + 2e- Equilibrium
for
Zn
+
2OH
Zn(OH)22 + 2e
Zn
+
2OH
2+
- - solution
-0.4
2+
+
2e
Zn

Zn
Zn Zn + 2e
in
solution
Equilibrium
for
Equilibrium
for
-0.8
2-Zn
ZnO
2H
++2e
Zn++4OH
4OH-

ZnO
222- +
+
2H
22O
O
2e
-1.2
Zn metal stable
-1.6
0
7
14
2

16

Pourbaix Diagram for Iron

Will
Will iron
iron
Yes
corrode
in
Yes--there
there
corrode
inisisaa
reasonably
reasonablywide
wide
acid?
acid?
range
of
range
ofpotentials
potentials

2.0
1.6
1.2
Fe3+
0.8
0.4
Fe oxides
Yes
can
Yes--although
althoughiron
iron
stable
0.0can
form
neutral
forman
anoxide
oxidein
in-0.4
neutralFe2+ stable
solution,
solution,itittends
tendsnot
notto
to
-0.8
form
on
metal,
iron
forms
formdirectly
directlyNo
on-the
metal,
No
-the
iron
formsaasolid
solid
Feand
metal stable
as
too
low,
oxide
at
all
asthe
thepotential
potential
is
too
low,
oxideis
at-1.2
allpotentials,
potentials,
and
therefore
not
will
passivate
-1.6
thereforeititisis
not
will
passivate
0
7
protective.
protective.
Potential

Will
iron
corrode
Will
iron
corrode
Will
iron
Will iron corrode
corrode in
in
in
neutral
waters?
inalkaline
neutral
waters?
solution?
alkaline solution?

where
wherehydrogen
hydrogencan
can
be
beevolved
evolvedand
andiron
iron
dissolved
dissolved

14
17

Effect of pH and potential on rate of

hydrogen oxidation
Oxidation
Faster

Reduction
Slower

Potential
Oxidation
Slower Reduction
Rates equal
Faster Electrochemical
Equilibrium
pH
18

Limitations of Pourbaix Diagrams

Tell us what can happen, not necessarily what will
happen
No information on rate of reaction
Can only be plotted for pure metals and simple
solutions, not for alloys

19

Two-variable Systems
Pourbaix diagram generally used in
hydrosphere pE against pH
pE is defined as the negative logarithm of
electron activity():
pE = -log ae
A large negative value of pE indicates large
value for electron activity reducing conditions
20

Pe ----ph

21

pE/pH Diagrams
Large positive value for pE indicates small value
for electron activity oxidizing conditions (
)
pE values in water vary from -12 to 25

22

REDOX BUFFERING
The sequence of redox reactions
described above does not yield a
continuous variation in pe values.
Rather, at each step in the process,
pe is held at a nearly constant value
until the current electron acceptor is
used up. Then, the pe will change
rapidly until the value associated
with the next redox reaction in the
sequence is attained.

23

pe

Eh (V)
0.9

Redox Reactions
Aerobic respiration
(oxygen reduction)
Anaerobic respiration

0.3

reactions

0
Fermentation

Nitrate (NO3) reduction

Mn4+ reduction
Ferric iron (Fe3+) reduction
Sulfate (SO42) reduction
CO2 reduction
(methanogenesis)

0.6

0.3

0.6

Approximate pe values at which various redox reactions occur

in
24
water at pH 7 and 25C (Drever, 1997)

Calculations of pE

Fe3+(aq)

+ e-

= Fe2+(aq)

K eq

a Fe 2
a Fe 3 a e

Rearrange and draw log on both sides:

pE log a e log K eq log

a Fe 3
a Fe 2

A
25

Calculations of pE
It is known that Go=-2.303RTlogKeq and
Go=nFEo (where n=number of electrons that
are transferred in the half-reaction at 298 K
)(R=8.314JK-1mol-1, F=96 485 C mol-1)
Therefore
o

log K eq

nFE
nE

2 . 303 RT
0 . 0591
26

Calculations of pE
In this case n=1
Substitute for Keq in equation A, then
o

a Fe 3
E
log
pE
0 .0591
a Fe 2

The general form of this equation is:

b
1
[
B
]
pE pE o log Q where Q
n
[ A]a
27

Calculations of pE
For the half-reaction pE can be calculated by
substituting standard pEo value as well as the
activities (approximated by concentration) of Fe3+
and Fe2+ into the equation

28

Determining pEo
c. Use

log K eq

nE

npE
0 . 0591

which can be rearranged to

log K eq
0
pE
n
when Eo value is not available, but Keq is known
29

Determining pEo
Sometimes several reactions must be combined
to produce an overall half reaction
No tabulated value for the following is available:

aq

2
aq

Fe(OH)3 3H3O e Fe 6H2O

30

Determining pEo
a. Tables environmentally important values

b. Use

pE

Eo

0 . 0591

if a tabulated Eo value is available

31

Determining pEo
The reaction is the sum of:
Fe ( OH ) 3 Fe
Fe

3
aq

Fe

3 H 3 O aq 3 OH

aq

3
aq

3 OH

aq

2
aq

6 H 2O

If we now calculate K values for the 3 reactions

and add them all up, we find the value for pEo
32

Determining pEo
Using values of G from thermodynamic tables
can also calculate pEo:
Use
o
pE

2 . 303 RTn

33

pE/pH Diagrams
Two-dimensional plot of pE (ordinate , yaxis) versus pH (abscissa, x axis) areas
define regions where particular species is dominant
must define conditions at boundaries
Gas and liquid boundary condition is Po=101325
Pa = 1 atm
34

pE/pH Diagrams
Water stability with respect to reduction: pE= -pH
Water stability with respect to oxidation: pE = 20.80
pH
Can draw lines on graph above upper line: water in
oxidized with evolution of oxygen, under lower line
water is reduced with evolution of hydrogen

35

Measurement of pE
Non-equilibrium conditions make reading of pE in
environment very difficult
Need indicator electrode (small platinum
electrode) inert develops potential
Reference electrode (saturated calomel)
indicated potential can be measured against
known value
36

Measurement of pE
Potential of SCE = +0.242
E against NHE = 0.713 + 0.242 = 0.955V
Calculate value of pE:
pE = 0.955/0.0591 = 16.23 (Oxidizing)
Mostly only possible to determine approximate
value
37

NATURAL WATERS

38

LEARNING OBJECTIVES
Learn to construct and use pe-pH (Eh-pH)
diagrams.

39

pe-pH (Eh-pH) DIAGRAMS

Diagrams that display relationships between oxidized
and reduced species and phases.
They are a type of activity-activity diagram!
Useful to depict general relationships, but difficulties of
using field-measured pe (Eh) values should be kept in
mind.
Constructed by writing half reactions representing the
boundaries between species/phases.
40

UPPER STABILITY LIMIT OF WATER

(pe-pH)

The following half reaction defines the conditions

under which water is oxidized to oxygen:
1/2O2(g) + 2e- + 2H+ H2O
The equilibrium constant for this reaction is given by
1
K 12 2 2
pO 2 a e a H
log K

log p O 2 2 log a e 2 log a H

log K

log p O 2 2 pe 2 pH

41

Solving for pe we get

pe

2 log K

log p O 2 pH

This equation contains three variables, so it cannot be

plotted on a two-dimensional diagram without making
some assumption about pO2. We assume that pO2 = 1
atm. This results in
pe 1 2 log K pH
We next calculate log K using
Gr = -237.1 kJ mol-1
237 ,100 J mol 1
log K
41 .53
1
1
2 . 303 ( 8 . 314 J K mol )(298.15 K )

pe 20 . 77 pH

42

LOWER STABILITY LIMIT OF

WATER (pe-pH)

At some low pe, water will be reduced to hydrogen by

the reaction
pH
K
H+ + e- 1/2H2(g)
a a
1

log K

log p H 2 pe pH

pe pH
We set pH2 = 1 atm. Also, Gr = 0, so log K = 0.

43

T = 25 o C
p H = 1 atm

20

16

H O
2

12

p O = 1 atm

pe

Water stable

4
0

H O
2
H

-4

-8
-12
0

pH

10

12

14

A pe-pH diagram
showing the stability
limits of water. At
conditions above the top
dashed line, water is
oxidized to O2; at
conditions below the
bottom dashed line,
water is reduced to H2.
No natural water can
persist outside these
stability limits for any
length of time.
44

UPPER STABILITY LIMIT OF

WATER (Eh-pH)

To determine the upper limit on an Eh-pH diagram, we

start with the same reaction
1/2O2(g) + 2e- + 2H+ H2O
but now we employ the Nernst eq.

0 . 0592
1
log 1 2 2
Eh E
n
pO 2 a H
0

45

0
G

( 237 . 1)
0
r
E

1 . 23 volts
n
( 2 )( 96 . 42 )

Eh 1 . 23 0 . 0296 log p O 2 a
1

2
H

Eh 1 . 23 0 . 0148 log p O 2 0 . 0592 pH

As for the pe-pH diagram, we assume that pO2 = 1

atm. This results in
Eh 1 . 23 0 . 0592 pH

This yields a line with slope of -0.0592.

46

LOWER STABILITY LIMIT OF WATER

(Eh-pH)
Starting with
H+ + e- 1/2H2(g)
we write the Nernst equation
1

2
p
0
.
0592
H2
0
Eh E
log
1
aH

We set pH2 = 1 atm. Also, Gr = 0, so E0 = 0. Thus,

we have

Eh 0 . 0592 pH

47

1.4

T = 25 o C
p H = 1 atm

1.2

1.0

H O
2

0.8

Eh-pH diagram showing

the stability limits of
water at 25C and 1
bar. Note the similarity
to the pe-pH diagram.

p O = 1 atm

Eh (volts)

0.6
0.4
0.2
0.0

H O
2
H

-0.2
-0.4

-0.6
-0.8
-1.0
0

10

12

14

pH
48

Range of Eh-pH
conditions in
natural
environments
based on data of
Baas-Becking et
al. (1960) Jour.
Geol. 68: 243-284.

49

Fe-O2-H2O SYSTEM
Species

-1

-1

G r(kJ m ol )

Species

G r(kJ m ol )

Fe

2+

-90.0

Fe(OH) 2 (s)

-486.5

Fe

3+

-16.7

Fe(OH) 3 (s)

-696.5

H 2O

-237.1

50

Fe

3+

Fe

Fe(OH)3(s)

2+

A preliminary
mapping of the species
and phases in pe-pH
space.

Fe(OH)2(s)

pH
51

Fe(OH)3/Fe(OH)2 BOUNDARY
First we write a reaction with one phase on each side,
and using only H2O, H+ and e- to balance, as
necessary
Fe(OH)3(s) + e- + H+ Fe(OH)2(s) + H2O(l)
Next we write the mass-action expression for the
reaction
1
K

ae a H

Taking the logarithms of both sides and rearranging

log K log a e log a H pe pH
we get

52

pe log K pH
And then
Next, we calculate rG and log K.
Gr = GfFe(OH)2 + GfH2O - GfFe(OH)3
Gr = (-486.5) + (-237.1) - (-696.5)
Gr = -27.1 kJ mol-1
1

27 ,100 J mol
log K
4 . 75
1
1
2 . 303 ( 8 . 314 J K mol )(298.15 K )
pe 4 . 75 pH

So now we have
This is a line with slope -1 and intercept 4.75.

53

T = 25 o C
p H = 1 atm

20

Our first Fe boundary is

shown plotted here. This
boundary will surely intersect
another boundary and be
truncated, but at this point we
dont know where this
intersection will occur. So for
now, the boundary is drawn in
lightly and is shown stretching
across the entire Eh-pH
diagram.

16

H O
2

12

p O = 1 atm

pe

8
4
0

Fe

H O
2
H

-4

Fe

(O

(O

H)

H)

3 (s )

2 (s )

-8
-12
0

10

12

14

pH
54

Fe(OH)2/Fe2+ BOUNDARY
Again we write a balanced reaction
Fe(OH)2(s) + 2H+ Fe2+ + 2H2O(l)
Note that, no electrons are required to balance this
reaction. The mass-action expression is:
K

a Fe 2
a H2

log K log a Fe 2 2 pH
pH

log K

log a Fe 2

55

Gr = GfFe2+ + 2GfH2O - GfFe(OH)2

Gr = (-90.0) + 2(-237.1) - (-486.5)
Gr = -77.7 kJ mol-1
1

77 ,700 J mol
log K
13 . 61
1
1
2 . 303 ( 8 . 314 J K mol )(298.15 K )

pH

2 (13 . 61 )

2 log a Fe 2 6 . 81

log a Fe 2

To plot this boundary, we need to assume a value for Fe

a Fe2+ m Fe2+.
pH 6 . 81

( 6 ) 9 . 81

56
6
1
This choice is arbitrary - here we choose Fe =10 mol L . Now we have

T = 25 o C
p H = 1 atm

20

16

H O
2

12

p O = 1 atm

pe

8
4
0

H O
2
H

-4

Fe
Fe2+

-8

Fe = 10

-12
0

-6

m ol L

Fe

(O

(O

H)

pH

10

(s )

(s )

H)

-1

12

14

This diagram illustrates the

plotting of the second
boundary required for this
diagram. Note that the portion
of the Fe(OH)3(s) /Fe(OH)2(s)
boundary from about pH 10 to
pH 0 was erased as it is
metastable(). Also, the
portion of the Fe2+ /Fe(OH)2
boundary at high pe is also
metastable and has been
erased. It is clear that the
next boundary to be
calculated is the Fe(OH)3(s)
57
/Fe2+ boundary.

Fe(OH)3/Fe2+ BOUNDARY
Again we write a balanced reaction
Fe(OH)3(s) + 3H+ + e- Fe2+ + 3H2O(l)
a Fe
The mass-action expression is:
K
2

a e a H3

log K log a Fe 2 pe 3 pH
pe log K log a Fe 2 3 pH
58

Gr = GfFe2+ + 3GfH2O - GfFe(OH)3

Gr = (-90.0) + 3(-237.1) - (-696.5)
Gr = -104.8 kJ mol-1
1

104 ,800 J mol

log K
18 . 36
1
1
2 . 303 ( 8 . 314 J K mol )(298.15 K )
pe 18 . 36

log a Fe 2 3 pH

To plot this boundary, we again need to assume a value for

Fe a Fe2+ m Fe2+. We must now stick with the choice
pe 18 . 36 ( 6 )-6 3 pH -1 24 . 36 3 pH
made earlier, i.e., Fe =10 mol L . Now we have
59

T = 25 o C
p H = 1 atm

20

16

H O
2

12

p O = 1 atm

The third boundary is now

plotted on the diagram. This
boundary will probably intersect
the Fe2+/Fe3+ boundary, but at
this point, we do not yet know
where the intersection will be.
Thus, the line is shown
extending throughout the
diagram.

pe

8
4

Fe 2+
0

H O
2
H

-4

Fe

Fe

-8

Fe = 10

-12
0

-6

m ol L

(O

(O

H)

10

(s )

(s )

H)

-1

12

14

pH
60

3+
2+
Fe /Fe

BOUNDARY

We write
Fe3+ + e- Fe2+
Note that this boundary will be pH-independent.
K

a Fe 2

a Fe 2

a e a Fe 3

a Fe 3

pe log K

Gr = GfFe2+ - GfFe3+
Gr = (-90.0) - (-16.7) = -73.3 kJ mol-1
73 ,300 J mol 1
log K
12 . 84
1
1
2 .303 ( 8 . 314 J K mol )(298.15 K )

pe 1261. 8

T = 25 o C
p H = 1 atm

20
16

Fe

3+

H O
2

12

The Fe2+/Fe3+ boundary now

truncates the Fe2+/Fe(OH)3
boundary as shown. There
remains just one boundary to
calculate - the Fe(OH)3(s) /Fe3+
boundary. Because the reaction
for the Fe2+/Fe3+ boundary does
not include any protons, this
boundary is horizontal, i.e., pHindependent.

p O = 1 atm

pe

Fe 2+

Fe(OH) 3 (s)

H O
2
H

-4

Fe

-8

Fe = 10

-12
0

-6

m ol L

(O

H)

-1

10

12

(s )
14

pH
62

Fe(OH)3/Fe3+ BOUNDARY
Fe(OH)3(s) + 3H+ Fe3+ + 3H2O(l)

log K log a Fe 3 3 pH

a Fe 3
a

pH

3
H

log K

log a Fe 3

Gr = GfFe3+ + 3GfH2O - GfFe(OH)3

Gr = (-16.7) + 3(-237.1) - (-696.5) = -31.5 kJ mol-1
31 ,500 J mol 1
log K
5 . 52
1
1
2 . 303 ( 8 . 314 J K mol )(298.15 K )
pH

3 ( 5 . 52 )

3 ( 6 ) 3 . 84

63

T = 25 o C
p H = 1 atm

20
16

Fe

3+

H O
2

12

p O = 1 atm

pe

Fe 2+

Fe(OH) 3 (s)

H O
2
H

-4

Fe

-8

Fe = 10

-12
0

-6

m ol L

(O

H)

-1

10

12

(s )
14

Final pe-pH diagram for the FeO2-H2O system. Note that the
solubility of iron phases is
greater when the dissolved iron
species is the reduced Fe2+. In
other words, Fe is more soluble
under reducing conditions.
Because most natural waters
have pH values in the range 5.58.5, they will not contain much
iron unless redox conditions are
relatively reducing.

pH
64