Notes Lecture 04b Redox

Pourbaix Diagrams
+1.0
+0.75
PbO2
+0.5
Pb2+
a.
+0.25
E (V)
more oxidized
species
Pb(OH)2
0.25
more reduced
species
0.5
Pb
0.75
1.0
7
pH
aquo species
11
14
hydroxo species
Pourbaix Diagrams
+1.0
+0.75
PbO2
+0.5
Pb2+(H2O)6
a.
+0.25
E (V)
more oxidized
species
Pb(OH)2
0.25
more reduced
species
0.5
Pb
0.75
1.0
aquo species
7
pH
11
hydroxo species
14
Pourbaix Diagrams
+1.0
+4
+0.75
PbO2
+0.5
Pb2+(H2O)6
a.
+0.25
E (V)
more oxidized
species
+2
Pb(OH)2
0.25
0.5
more reduced
species
Pb
0.75
1.0
7
pH
aquo species
11
14
hydroxo species
Pourbaix Diagrams
+1.0
+4
+0.75
PbO2
+0.5
= predominant
more oxidized
species over this
species
potential and pH
a. range
+2
Pb2+
+0.25
E (V)
Pb(OH)2
0.25
0.5
more reduced
species
Pb
0.75
1.0
aquo species
7
pH
11
hydroxo species
14
Pourbaix Diagrams
pH ! 3.8
+1.0
+0.75
PbO2
+0.5
Pb2+
a.
+0.25
E (V)
+1.0V ! E1/2
! 0.23 V
Pb(OH)2
0.25
more reduced
species
0.5
Pb
0.75
1.0
7
pH
aquo species
11
14
hydroxo species
Pourbaix Diagrams
+1.0
+0.75
PbO2
+0.5
Pb2+
a.
+0.25
E (V)
more oxidized
species
dominate
under more
basic
conditions
Pb(OH)2
0.25
more reduced
species
0.5
Pb
0.75
1.0
aquo species
7
pH
11
hydroxo species
14
Pourbaix Diagrams
+1.0
+0.75
PbO2
+0.5
Pb2+
a.
+0.25
E (V)
more reduced
species dominate
under more
acidic conditions
0.25
0.5
Pb(OH)2
more reduced
species
Pb
0.75
1.0
pH
aquo species
under acidic conditions

higher potentials are
required in order to maintain
the higher oxidation state
14
11
hydroxo species
Pourbaix Diagrams
pH ! 3.8
+1.0
+0.75
PbO2
+0.5
Pb2+
a.
+0.25
E (V)
+1.0V ! E1/2
! 0.23 V
Pb(OH)2
0.25
more reduced
species
0.5
Pb
0.75
1.0
aquo species
7
pH
11
hydroxo species
14
Pourbaix Diagrams
What form of lead

would you expect to
find at pH= 7, and a
potential of 0 V?
+1.0
+0.75
PbO2
+0.5
Pb2+
a.
+0.25
E (V)
Pb(OH)2
0.25
0.5
Pb
0.75
1.0
11
14
pH
Pourbaix Diagrams
What form of lead

would you expect to
find at pH= 7, and a
potential of 0 V?
+1.0
+0.75
PbO2
+0.5
Pb2+
a.
+0.25
E (V)
the solution would

predominantly
consist of
Pb(OH)2, with a
small amount of
Pb2+
Pb(OH)2
0.25
0.5
Pb
0.75
1.0
7
pH
11
14
Pourbaix Diagrams
What does the solution
consist of at pH= 6.9, and
0.25 < E1/2 < +0.6 V
ie, on the dotted blue
line?
+1.0
+0.75
PbO2
+0.5
Pb2+
a.
+0.25
0
E (V)
Pb(OH)2
0.25
0.5
Pb
0.75
1.0
11
14
pH
Pourbaix Diagrams
What does the solution
consist of at pH= 6.9, and
0.25 < E1/2 < +0.6 V
ie, on the dotted blue
line?
+1.0
+0.75
PbO2
+0.5
Pb2+
E (V)
the solution would

consist of exactly
50% Pb(OH)2, and
50% Pb2+
a.
+0.25
0
Pb(OH)2
0.25
0.5
Pb
0.75
1.0
7
pH
11
14
Pourbaix Diagrams
What about along this

dotted blue line?
+1.0
+0.75
PbO2
+0.5
Pb2+
a.
+0.25
E (V)
Pb(OH)2
0.25
0.5
Pb
0.75
1.0
11
14
pH
Pourbaix Diagrams
What about along this

dotted blue line?
+1.0
+0.75
PbO2
+0.5
Pb2+
E (V)
the solution would

consist of exactly
50% PbO2, and
50% Pb2+
a.
+0.25
0
Pb(OH)2
0.25
0.5
Pb
0.75
1.0
7
pH
11
14
Pourbaix Diagrams
+1.0
+0.75
+0.5
Pb2+
a.
+0.25
E (V)
more oxidized
species
PbO2
+2
Pb(OH)2
0.25
as the potential
is raised above
this line Pb+2 is
oxidized to
Pb+4
0.5
Pb
0.75
more reduced
species
1.0
pH
aquo species
11
14
hydroxo species
Pourbaix Diagrams
pH ! 3.8
+1.0
+0.75
+0.5
+0.25
E (V)
0.25
PbO2
as the pH is raised
Pb2+
more oxidized
species
a.
above this line

Pb+2(H2O)6 is
converted to
Pb+2(OH)2
+2
Pb(OH)2
more reduced
species
0.5
Pb
0.75
1.0
aquo species
7
pH
11
hydroxo species
14
1. Vertical lines:
separate species of the same oxidation state
pH-dependent acid/base rxns occur across
2. Horizonal lines:
separate species of different oxidation states
a redox rxn occurs as you cross this line
w/ a pH-independent redox potential
3. Diagonal lines:
separate species of different oxidation states
a pH-dependent redox rxn occurs as you cross
this line
Is PbO2 a better oxidizing agent at pH= 5 or pH= 11?

at pH= 5 PbO2 has a redox
potential of ~ +0.88 V
+1.0
PbO2 is reduced to Pb2+
+0.75
PbO2 is reduced to Pb2+(OH)2
PbO2
+0.5
Pb2+
a.
+0.25
E (V)
Pb(OH)2
0.25
0.5
Pb
0.75
1.0
Thus, it is a better
oxidant at pH= 5
11
pH
E(pH= 5)= ~ +0.88 V

E(pH= 11)= ~ +0.12 V
14
Is Pb0 a better reducing agent at pH= 0 or pH= 14?

+1.0
Pb0 is oxidized to Pb2+

Pb0 is
oxidized to
+0.75
Pb2+(OH)2
PbO2
+0.5
Pb2+
a.
+0.25
E (V)
Pb(OH)2
0.25
0.5
Pb
0.75
1.0
Thus, it is a better
reductant at pH= 14
11
14
pH
E(pH= 0)= ~ 0.25 V

E(pH= 11)= ~ 1.1V
What is the approximate redox

potential of Pb2+ at pH= 4?
+1.0
Pb2+ is reduced to Pb0

Pb2+
is oxidized to
+0.75
Pb4+O
PbO2
+0.5
Pb2+
a.
+0.25
E (V)
Pb(OH)2
0.25
Pb2+ is converted to Pb2+(OH)2 0.5
Pb
0.75
1.0
11
pH
E(pH= 4)= ~ 0.25 V
14

+1.0
Pb2+(OH)2 is reduced to Pb0
+0.75
PbO2
Pb2+(OH)2 is oxidized to Pb4+O2
+0.5
Pb2+
a.
+0.25
E (V)
Pb(OH)2
0.25
Pb2+(OH)2 is converted to Pb2+ 0.5
Pb
0.75
1.0
11
pH
E(pH= 11)= ~ 0.6 V

Pb2+(OH)2 is reduced to Pb0

+1.0
+0.75
PbO2
+0.5
Pb2+
a.
+0.25
E (V)
Pb(OH)2
0.25
0.5
Pb
0.75
1.0
11
14
pH
E(pH= 11)= ~ + 0.12 V

14
What reaction occurs across the line labeled a

at pH= 9? Write a balanced eqn.
+1.0
+0.75
PbO2
+0.5
Pb2+
a.
+0.25
0
E (V)
Pb(OH)2
0.25
0.5
Pb
0.75
1.0
Pb4+O2 is reduced to Pb2+(OH)2
11
14
pH
2H2O + Pb4+O2
+ 2e
Pb2+(OH)2 + 2OH

Notes Lecture 04b Redox

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Notes Lecture 04b Redox

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Pourbaix Diagrams

under acidic conditions

What form of lead

What form of lead

the solution would

the solution would

What about along this

What about along this

the solution would

above this line

Is PbO2 a better oxidizing agent at pH= 5 or pH= 11?

PbO2 is reduced to Pb2+

PbO2 is reduced to Pb2+(OH)2

E(pH= 5)= ~ +0.88 V

Is Pb0 a better reducing agent at pH= 0 or pH= 14?

Pb0 is oxidized to Pb2+

E(pH= 0)= ~ 0.25 V

What is the approximate redox

Pb2+ is reduced to Pb0

Pb2+ is converted to Pb2+(OH)2 0.5

E(pH= 4)= ~ 0.25 V

What is the approximate redox

Pb2+(OH)2 is reduced to Pb0

Pb2+(OH)2 is oxidized to Pb4+O2

Pb2+(OH)2 is converted to Pb2+ 0.5

E(pH= 11)= ~ 0.6 V

What is the approximate redox

E(pH= 11)= ~ + 0.12 V

What reaction occurs across the line labeled a

Pb4+O2 is reduced to Pb2+(OH)2

Pb2+(OH)2 is oxidized to Pb4+O2

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