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Chapter 20 Petrucci
Chapter 20 Petrucci
Chapter 20 Petrucci
elec
= -zFE
cell
G = -zFE
cell
G = -zFE
cell
Michael Faraday 1791-1867
Slide 24 of 53
Combining Reduction Half-Equations
Copyright 2011 Pearson Canada Inc.
General Chemistry: Chapter 20
Fe
3+
(aq) + 3e
-
Fe(s) E
Fe
3+
/Fe
= ?
Fe
2+
(aq) + 2e
-
Fe(s) E
Fe
2+
/Fe
= -0.440 V
Fe
3+
(aq) + 1e
-
Fe
2+
(aq) E
Fe
3+
/Fe
2+ = 0.771 V
Fe
3+
(aq) + 3e
-
Fe(s)
G = +0.880 J
G = -0.771 J
G = +0.109 J E
Fe
3+
/Fe
= +0.331 V
G = +0.109 J = -nFE
E
Fe
3+
/Fe
= +0.109 J /(-3F) = -0.0363 V
but cannot simply add E
can add G
Slide 25 of 53
Spontaneous Change in
Oxidation-Reduction Reactions
Copyright 2011 Pearson Canada Inc.
General Chemistry: Chapter 20
G < 0 for spontaneous change.
Therefore E
cell
> 0 because G
cell
= -nFE
cell
E
cell
> 0
Reaction proceeds spontaneously as written.
E
cell
= 0
Reaction is at equilibrium.
E
cell
< 0
Reaction proceeds in the reverse direction spontaneously.
Slide 28 of 53
The Behavior or Metals Toward Acids
Copyright 2011 Pearson Canada Inc.
General Chemistry: Chapter 20
M(s) M
2+
(aq) + 2 e
-
E = -E
M
2+
/M
2 H
+
(aq) + 2 e
-
H
2
(g) E
H
+
/H
2
= 0 V
2 H
+
(aq) + M(s) H
2
(g) + M
2+
(aq)
E
cell
= E
H
+
/H
2
- E
M
2+
/M
= -E
M
2+
/M
When E
M
2+
/M
< 0, E
cell
> 0. Therefore G < 0.
Metals with negative reduction potentials react with acids.
Slide 30 of 53
Relationship Between E
cell
and K
eq
Copyright 2011 Pearson Canada Inc.
General Chemistry: Chapter 20
G = -RT ln K
eq
= -zFE
cell
E
cell
=
zF
RT
ln K
eq
E
cell
=
z
0.25693
ln K
eq
Slide 31 of 53
A summary of important thermodynamic, equilibrium and electrochemical
relationships under standard conditions.
FIGURE 20-8
Copyright 2011 Pearson Canada Inc.
General Chemistry: Chapter 20
Slide 33 of 53
20-4 E
cell
as a Function of Concentration
Copyright 2011 Pearson Canada Inc.
General Chemistry: Chapter 20
FIGURE 20-9
Variation of E
cell
with ion concentrations
G = G - RT ln Q
-zFE
cell
= -zFE
cell
- RT ln Q
E
cell
= E
cell
- ln Q
zF
RT
Convert to log
10
and calculate constants.
E
cell
= E
cell
- log Q
z
0.0592 V
The Nernst Equation
Slide 34 of 53
Concentration Cells
Copyright 2011 Pearson Canada Inc.
General Chemistry: Chapter 20
FIGURE 20-11
A concentration cell
Two half cells with identical electrodes but different ion concentrations.
2 H
+
(1 M) 2 H
+
(x M)
Pt|H
2
(1 atm)|H
+
(x M)||H
+
(1.0 M)|H
2
(1 atm)|Pt(s)
2 H
+
(1 M) + 2 e
-
H
2
(g, 1 atm)
H
2
(g, 1 atm) 2 H
+
(x M) + 2 e
-
E
cell
= E
H
+
/H
2
- E
H
+
/H
2
= 0
Slide 35 of 53
Copyright 2011 Pearson Canada Inc.
General Chemistry: Chapter 20 Slide 35 of 54
E
cell
= E
cell
- log
z
0.0592 V x
2
1
2
E
cell
= 0 - log
2
0.0592 V x
2
1
E
cell
= - 0.0592 V log x
E
cell
= (0.0592 V) pH
2 H
+
(1 M) 2 H
+
(x M)
E
cell
= E
cell
- log Q
z
0.0592 V
E
cell
= E
H
+
/H
2
- E
H
+
/H
2
= 0
but we can calculate
using the Nernst Equation
Slide 38 of 53
Measurement of K
sp
Copyright 2011 Pearson Canada Inc.
General Chemistry: Chapter 20 Slide 38 of 54
FIGURE 20-12
A concentration cell for determining K
sp
of AgI
Ag
+
(0.100 M) Ag
+
(satd M)
Ag|Ag
+
(satd AgI)||Ag
+
(0.10 M)|Ag(s)
Ag
+
(0.100 M) + e
-
Ag(s)
Ag(s) Ag+(satd) + e
-
Work Example 20-11 as an exercise
to understand the process.
Slide 40 of 53
Schematic diagrams of some common electrodes
FIGURE 20-13
Copyright 2011 Pearson Canada Inc.
General Chemistry: Chapter 20 Slide 40 of 54
0.22233 V
0.2680 V (satd KCl)
or
0.2412 V (1 M KCl)
Slide 41 of 53
The Glass Electrode and the Electrochemical
Measurement of pH
Copyright 2011 Pearson Canada Inc.
General Chemistry: Chapter 20
Ag|AgCl(s)|Cl
-
(1.0M),H
+
(1.0M)|glass membrane|H
+
(unknown)|| Cl
-
(1.0 M)|AgCl(s)|Ag(s)
Ag(s) + Cl
-
AgCl(s) + e
-
H
+
(1.0 M) H
+
(unknown)
AgCl(s) + e
-
Ag(s) + Cl
-
(aq)
G = G(unknown) G(1.0M)
= G + RTln[unknown] G - RTln(1.0)
=RTln[unknown]
E
cell
= -RTln[unknown]/zF
pH = -log[unknown]=zFE
cell
/RT
Slide 42 of 53
20-5 Batteries: Producing Electricity Through
Chemical Reactions
Primary Cells (or batteries).
Cell reaction is not reversible.
Secondary Cells.
Cell reaction can be reversed by passing
electricity through the cell (charging).
Flow Batteries and Fuel Cells.
Materials pass through the battery which converts
chemical energy to electric energy.
Copyright 2011 Pearson Canada Inc.
General Chemistry: Chapter 20
Slide 43 of 53
The Leclanch (dry) cell
FIGURE 20-14
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General Chemistry: Chapter 20
Slide 44 of 53
The Leclanch Dry Cell
Copyright 2011 Pearson Canada Inc.
General Chemistry: Chapter 20
Zn(s) Zn
2+
(aq) + 2 e
-
Oxidation:
2 MnO
2
(s) + H
2
O(l) + 2 e
-
Mn
2
O
3
(s) + 2 OH
-
Reduction:
NH
4
+
+ OH
-
NH
3
(g) + H
2
O(l)
Acid-base reaction:
NH
3
+ Zn
2+
(aq)
+ Cl
-
[Zn(NH
3
)
2
]Cl
2
(s)
Precipitation reaction:
Slide 45 of 53
Copyright 2011 Pearson Canada Inc.
General Chemistry: Chapter 20
Zn
2+
(aq)
+ 2 OH
-
Zn (OH)
2
(s)
Zn(s) Zn
2+
(aq) + 2 e
-
Oxidation reaction can be thought of in two steps:
2 MnO
2
(s) + H
2
O(l) + 2 e
-
Mn
2
O
3
(s) + 2 OH
-
Reduction:
Zn
(s)
+ 2 OH
-
Zn (OH)
2
(s) + 2 e
-
The alkaline cell
Slide 46 of 53
The Lead-Acid (Storage) Battery
Copyright 2011 Pearson Canada Inc.
General Chemistry: Chapter 20
FIGURE 20
The lead-acid (storage) cell
Slide 47 of 53
Copyright 2011 Pearson Canada Inc.
General Chemistry: Chapter 20
PbO
2
(s) + 3 H
+
(aq) + HSO
4
-
(aq) + 2 e
-
PbSO
4
(s) + 2 H
2
O(l)
Oxidation:
Reduction:
Pb (s) + HSO
4
-
(aq) PbSO
4
(s) + H
+
(aq) + 2 e
-
PbO
2
(s) + Pb(s) + 2 H
+
(aq) + HSO
4
-
(aq) 2 PbSO
4
(s) + 2 H
2
O(l)
E
cell
= E
PbO
2
/PbSO
4
- E
PbSO
4
/Pb
= 1.74 V (-0.28 V) =
2.02 V
Slide 48 of 53
The Silver-Zinc Cell: A Button Battery
Copyright 2011 Pearson Canada Inc.
General Chemistry: Chapter 20
FIGURE 20-16
The silver-zinc button (miniature) cell
Zn(s) + Ag
2
O(s) ZnO(s) + 2 Ag(s) E
cell
= 1.8 V
Zn(s),ZnO(s)|KOH(satd)|Ag
2
O(s),Ag(s)
Slide 49 of 53
The Nickel-Cadmium Cell: A Rechargeable
Battery
Copyright 2011 Pearson Canada Inc.
General Chemistry: Chapter 20
Cd(s) + 2 NiO(OH)(s) + 2 H
2
O(L) 2 Ni(OH)
2
(s) + Cd(OH)
2
(s)
A rechargeable nickel-cadmium cell, or nicad battery
Slide 50 of 53
The Lithium-Ion Battery
Copyright 2011 Pearson Canada Inc.
General Chemistry: Chapter 20 Slide 50 of 53
FIGURE 20-17
The electrodes of a lithium-ion battery
The positive electrode consists of lithium cobalt(III) oxide, LiCoO
2
, and the
negative electrode is highly crystallized graphite. To complete the battery an
electrolyte is needed, which can consist of an organic solvent and ions, such as
LiPF
6
. The structure of LiCoO
2
, and graphite electrode is illustrated in Figure 20-
17.
In the charging cycle at the positive electrode, lithium ions are released into
the electrolyte solution as electrons are removed from the electrode. To
maintain a charge balance, one cobalt(III) ion is oxidized to cobalt(IV) for
each lithium ion released.
LiCoO
2
(s)+Li
(1-x)
= 2CoO
2
(s) + xLi
+
(solvent) + x e-
C(s) + xLi
+
(solvent) + x e- = Li
x
C(S)
The layered graphite electrode is shown with lithium ions (violet) intercalated. The
LiCoO
2
is shown as a face-centered cubic lattice, with the oxygen atoms (red)
occupying the corners and the faces, the cobalt atoms (pink) occupying half of the
edges, and the lithium atoms occupying half of the edges and the central octahedral
hole. This arrangement leads to planes of oxygen, cobalt, oxygen, lithium, oxygen,
cobalt, and oxygen atoms, as indicated in the figure.
Slide 52 of 53
Fuel Cells
Copyright 2011 Pearson Canada Inc.
General Chemistry: Chapter 20
FIGURE 20-18
A hydrogen-oxygen fuel cell
O
2
(g) + 2 H
2
O(l) + 4 e
-
4 OH
-
(aq)
2{H
2
(g) + 2 OH
-
(aq) 2 H
2
O(l) + 2 e
-
}
2H
2
(g) + O
2
(g)
2 H
2
O(l)
E
cell
= E
O
2
/OH
- - E
H
2
O/H
2
= 0.401 V (-0.828 V) = 1.229 V
= G/ H =
0.83
Slide 53 of 53
Air Batteries
Copyright 2011 Pearson Canada Inc.
General Chemistry: Chapter 20
FIGURE 20-19
A simplified aluminum-air battery
4 Al(s) + 3 O
2
(g) + 6 H
2
O(l) + 4 OH
-
4 [Al(OH)
4
](aq)
Slide 54 of 53
20-6 Corrosion: Unwanted Voltaic Cells
Copyright 2011 Pearson Canada Inc.
General Chemistry: Chapter 20
O
2
(g) + 2 H
2
O(l) + 4 e
-
4 OH
-
(aq)
2 Fe(s) 2 Fe
2+
(aq) + 4 e
-
2 Fe(s) + O
2
(g)
+
2 H
2
O(l)
2 Fe
2+
(aq) + 4 OH
-
(aq)
E
cell
= 0.841 V
E
O
2
/OH
- = 0.401 V
E
Fe/Fe
2+ = -0.440 V
I n neutral solution:
I n acidic solution:
O
2
(g) + 4 H
+
(aq) + 4 e
-
4 H
2
O (aq) E
O
2
/OH
- = 1.229 V
Slide 55 of 53
Demonstration of corrosion and methods of corrosion protection
FIGURE 20-20
Copyright 2011 Pearson Canada Inc.
General Chemistry: Chapter 20
The pink color
results from the
indicator
phenolphthalein in
the presence of base.
The dark blue color
results from the
formation of
Turnbulls blue
KFe[Fe(CN)
6
].
Zn
Cu
Slide 56 of 53
Protection of iron against electrolytic corrosion
FIGURE 20-21
Copyright 2011 Pearson Canada Inc.
General Chemistry: Chapter 20
Slide 57 of 53
Copyright 2011 Pearson Canada Inc.
General Chemistry: Chapter 20
The small cylindrical bars of magnesium attached to the steel ship
provide cathodic protection against corrosion.
Magnesium sacrificial anodes
Slide 58 of 53
20-7 Electrolysis: Causing Non-spontaneous
Reactions to Occur
Copyright 2011 Pearson Canada Inc.
General Chemistry: Chapter 20
Voltaic Cell:
Zn(s) + Cu
2+
(aq) Zn
2+
(aq) + Cu(s) E
O
2
/OH
- = 1.103 V
Electolytic Cell:
Cu(s) + Zn
2+
(aq) Cu
2+
(aq) + Zn(s) E
O
2
/OH
- = -1.103 V
Slide 59 of 53
Predicting Electrolysis Reaction
Copyright 2011 Pearson Canada Inc.
General Chemistry: Chapter 20
FIGURE 20-22
An electrolytic cell
An Electrolytic Cell
e
-
is the reverse of the
voltaic cell.
The battery must have a
voltage in excess of 1.103
V in order to force the
non-spontaneous reaction.
Slide 60 of 53
Complications in Electrolytic Cells
Overpotential.
Competing reactions.
Non-standard states.
Nature of electrodes.
Copyright 2011 Pearson Canada Inc.
General Chemistry: Chapter 20
Slide 61 of 53
Quantitative Aspects of Electrolysis
Copyright 2011 Pearson Canada Inc.
General Chemistry: Chapter 20
n
e
- =
I t
F
1 mol e
-
= 96485 C
Charge (C) = current (C/s) time (s)
Slide 64 of 53
20-8 Industrial Electrolysis Processes
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General Chemistry: Chapter 20
The refining of copper by electrolysis.
Slide 65 of 53
Electrorefining
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General Chemistry: Chapter 20
Electroplating
Electrosynthesis
A rack of metal parts being lifted from the
electrolyte solution after electroplating.
Slide 66 of 53
Chlor-Alkali Process
Copyright 2011 Pearson Canada Inc.
General Chemistry: Chapter 20
FIGURE 20-24
A diaphragm chlor-alkali cell
FIGURE 20-25
The mercury-cell chlor-alkali process
Slide 67 of 53
End of Chapter Questions
Dont just read examples, work them!!
If you write:
Information is going through your fingers,
Your muscles,
Your nerves,
Directly to your brain.
Physically experience the solution.
Your eyes and ears are not enough.
Copyright 2011 Pearson Canada Inc.
General Chemistry: Chapter 20