Chapter 20 Petrucci

Slide 1 of 53
Copyright 2011 Pearson Canada Inc.

General Chemistry: Chapter 20 Slide 1 of 53
PHILIP DUTTON
UNIVERSITY OF WINDSOR
DEPARTMENT OF CHEMISTRY AND
BIOCHEMISTRY
TENTH EDITION
GENERAL CHEMISTRY
Principles and Modern Applications
PETRUCCI HERRING MADURA BISSONNETTE
Electrochemistry
20
Slide 2 of 53
Spontaneous Change:
Entropy and Gibbs Energy

CONTENTS
19-1 Electrode Potentials and Their
Measurement
19-2 Standard Electrode Potentials
19-3 E
cell
, G, and K

19-4 E
cell
as a function of
Concentrations
19-5 Batteries: Producing Electricity
Through Chemical Reactions
19-6 Corrosion: Unwanted Voltaic
Cells
19-7 Electrolysis: Causing
Nonspontaneous Reactions to
Occur
19-8 Industrial Electrolysis Processes
Slide 3 of 53
20-1 Electrode Potentials and Their Measurement
FIGURE 20-1
Behaviour of Ag
+
(aq) and Zn
+
(aq) in the presence of copper
Cu(s) + 2Ag
+
(aq)
Cu
2+
(aq) + 2 Ag(s)
Cu(s) + Zn
2+
(aq)
No reaction
Slide 4 of 53
An electrochemical half cell
FIGURE 20-2
General Chemistry: Chapter 20
Anode
Cathode
Slide 5 of 53
Measurement of the electromotive force of an electrochemical cell
FIGURE 20-3
Copyright 2011 Pearson Canada Inc. General Chemistry: Chapter 20
Slide 6 of 53
The reaction Zn(s) + Cu
2+
(aq) Zn
2+
(aq) + Cu(s) in an electrochemical cell
FIGURE 20-4
Zn(s) + Cu
2+
(aq) Zn
2+
(aq) + Cu(s)
E
cell
= 1.103 V
Slide 7 of 53
Cell Diagrams and Terminology
Electromotive force, E
cell

The cell voltage or cell potential.
Cell diagram

Shows the components of the cell in a symbolic way.
Anode (where oxidation occurs) on the left.
Cathode (where reduction occurs) on the right.
Boundary between phases shown by |.
Boundary between half cells
(commonly a salt bridge) shown by ||.
Slide 8 of 53
The reaction Zn(s) + Cu
2+
(aq) Zn
2+
(aq) + Cu(s) in an electrochemical cell
FIGURE 20-4
Zn(s) | Zn
2+
(aq) || Cu
2+
(aq) | Cu(s)
E
cell
= 1.103 V
Slide 9 of 53
Galvanic (or voltaic) cells
Produce electricity as a result of spontaneous reactions.
Electrolytic cells
Non-spontaneous chemical change driven by electricity.
Couple, M|M
n+

A pair of species related by a change in number of e
-
.
Slide 12 of 53
20-2 Standard Electrode Potentials
Cell voltages, the potential differences
between electrodes, are among the most
precise scientific measurements.
The potential of an individual electrode is
difficult to establish.
Arbitrary zero is chosen.
The Standard Hydrogen Electrode (SHE)
Slide 13 of 53
The standard hydrogen electrode (SHE)
FIGURE 20-5
2 H
+
(a = 1) + 2 e
-
H
2
(g, 1 bar) E = 0
V
Pt|H
2
(g, 1 bar)|H
+
(a = 1)
Slide 14 of 53
Standard Electrode Potential, E
E
cell
= E
cathode
(right) E
anode
,(left)
The tendency for a reduction process to occur at an electrode.
All ionic species present at a=1 (approximately 1 M).
All gases are at 1 bar (approximately 1 atm).
Where no metallic substance is indicated, the potential is
established on an inert metallic electrode (ex. Pt).

Slide 15 of 53
Cu
2+
(1M) + 2 e
-
Cu(s) E
Cu
2+
/Cu
= ?
Pt|H
2
(g, 1 bar)|H
+
(a = 1) || Cu
2+
(1 M)|Cu(s) E
cell
= 0.340 V
Standard cell potential: the potential difference of a
cell formed from two standard electrodes.
E
cell
= E
cathode
-

E
anode
cathode anode
Slide 16 of 53
Pt|H
2
(g, 1 bar)|H
+
(a = 1) || Cu
2+
(1 M)|Cu(s) E
cell
= 0.340 V
E
cell
= E
cathode
-

E
anode
E
cell
= E
Cu
2+
/Cu
-

E
H
+
/H
2
0.340 V = E
Cu
2+
/Cu
-

0 V

E
Cu
2+
/Cu
= +0.340 V
H
2
(g, 1 atm) + Cu
2+
(1 M) H
+
(1 M) + Cu(s) E
cell
= 0.340
V
Slide 17 of 53
Measuring standard reduction potential
FIGURE 20-6
anode anode cathode cathode
Slide 18 of 53
TABLE 20.1 Some Selected Standard Electrode (Reduction)
Potentials at 25C
Reduction Half-Reaction E, V
Acidic Solution
Slide 19 of 53
Potentials at 25C (continued)
Acidic Solution
Slide 20 of 53
Potentials at 25C (continued)
Acidic Solution
Basic Solution
Slide 23 of 53
20-3 E
cell
, G, and K
eq

Faraday constant,
F = 96,485 C mol
-1
When products are in their
standard states
elec
= -zFE
cell

G = -zFE
cell

G = -zFE
cell

Michael Faraday 1791-1867
Slide 24 of 53
Combining Reduction Half-Equations
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
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
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

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
Slide 33 of 53
20-4 E
cell
as a Function of Concentration
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
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
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

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
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
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.

Slide 43 of 53
The Leclanch (dry) cell
FIGURE 20-14
Slide 44 of 53
The Leclanch Dry Cell
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
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
FIGURE 20
The lead-acid (storage) cell
Slide 47 of 53
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
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
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
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
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
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
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
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
Slide 57 of 53
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
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
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.

Slide 61 of 53
Quantitative Aspects of Electrolysis
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
The refining of copper by electrolysis.
Slide 65 of 53
Electrorefining
Electroplating
Electrosynthesis
A rack of metal parts being lifted from the
electrolyte solution after electroplating.
Slide 66 of 53
Chlor-Alkali Process
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.

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