Chapter 21: Electrochemistry

Batteries serve as power sources for all

types of gadgets
The energy in a battery comes from a
spontaneous redox reaction where the
electron transfer is forced to take place
through a wire
The apparatus that provides electricity in
this way is called a galvanic or voltaic cell

A galvanic cell. The cell consists of two half-cells
where the oxidation and reduction half-reactions
take place. The salt bridge is required for electrical
neutrality. The overall cell reaction is:
2Ag
+
(aq)+Cu(s) 2Ag(s)+Cu
2
+(aq)
Cell reactions are obtained by adding the
half-reactions
Half-reactions are balanced using the ion-
electron method (see Section 6.2)
The electrodes are assigned the name anode
or cathode
Reduction (electron gain) occurs at the cathode
Electrons appear as reactants in the half-reaction
Oxidation (electron loss) occurs at the anode
Electrons appear as products in the half-reaction

Changes that take
place at the anode
and cathode of a
copper-silver
galvanic cell. At the
anode, Cu
2+
ions
enter the solution
when copper atoms
are oxidized. At the
cathode, Ag
+
ions
leave solution and
become silver
atoms.
There are two types of electrical conduction
in a galvanic cell
Metallic conduction occurs when electrons move
through the wires
Electrolytic conduction occurs through the liquid by
movement of ions, not electrons
The movement of ions through the salt
bridge and in solution is required for charge
neutrality
Cations move in the general direction of the cathode
Anions move in the general direction of the anode
The anode has negative polarity because the
electrons left behind by the Cu
2+
ions give it a
slightly negative charge
The cathode has positive polarity because of the
Ag
+
ions joining the electrode give it a slightly
positive charge
For convenience, a standard cell notation has
been developed by chemists
Anode half-cell is specified on the left
Cathode half-cell is specified on the right
Phase boundaries are indicated using |
The salt bridge separates the anode and cathode and is
indicated using ||
The cell diagram for the copper-silver
galvanic cell is
Cu(s)|Cu
2+
(aq)||Ag
+
(aq)|Ag(s)
(anode) (cathode)
Galvanic cells can push electrons through a
wire
The magnitude of this ability is expressed as
a potential
The maximum potential a given cell can
generate is called the cell potential, E
cell
The cell potential depends on the
temperature and composition
The standard cell potential, E
o
cell
, is the
cell potential measured at 298 K (25
o
C)
with all ion concentration 1.00 M
Standard cell potentials are rarely more than
a few volts
E
o
cell
for the copper-silver galvanic cell is 0.46 V
E
o
cell
for a single cell in a car battery is about 2 V
The tendency for a species to gain electrons
and be reduced is its reduction potential
When measured at standard condition, it is
called the standard reduction potential, E
o

When two half-cells are are connected:
The one with the larger reduction potential will
acquire electrons and undergo reduction
The half-cell with the lower reduction potential
will give up electrons and undergo oxidation
The difference in the two standard reduction
potentials gives the standard cell potential



It is not possible to measure the reduction
potential of an isolated half-cell
A reference electrode, called the standard
hydrogen electrode, has been assigned the
potential of exactly 0 V
|
|
|
.
|

\
|

|
|
|
.
|

\
|
=
oxidized substance
the of potential
reduction standard
reduced substance
the of potential
reduction standard
o
cell
E

The standard
hydrogen
electrode.
Hydrogen gas at 1
atm is passed over
finely divided
platinum. The
solution contains
1.00 M hydrogen
ion. The reduction
potential is exactly
0 V at 298 K
(25
o
C).
Using a hydrogen half-cell, other reduction
potentials can be measured
A galvanic cell
comprised of
copper and
hydrogen half-cells.
The reaction is
Cu
2+
(aq)+H
2
(g)
Cu(s)+2H
+
(aq)
Cell notation:
Pt(s), H
2
(g)|H
+
(aq)||Cu
2+
(aq)|Cu(s)
Table 21.1 and Appendix C lists the
standard reduction potentials for a number
of species
Calculated cell potentials can be used to
identify spontaneous reactions
For any pair of reduction potentials ordered
most reactive to least reactive:
The higher (more positive) reduction potential will
occur as a reduction
The lower (more negative) reduction potential will
be reversed and occur as an oxidation
In a galvanic cell, the calculated cell
potential for the spontaneous reaction is
always positive
If the calculated cell potential is negative,
the cell is spontaneous in the reverse
direction
The free energy change for a system can
also be used to predict if a reaction is
spontaneous
Free energy changes and cell potentials are
related
The maximum useful work that can be
obtained from a reaction is:

In electrical systems, work is supplied by
the current as it is pushed along by the
potential of the cell
maximum work = nF
n = number of moles of electrons transferred
F = Faraday constant = 96,485 C/mol e
= cell potential in volts
work maximum = A G
o
cell
E
o
cell
E
Equating:


The cell potential can be related to the
equilibrium constant K



Cell potentials depend on concentrations
) conditions (standard
) conditions rd (nonstanda
o o
cell
cell
nFE G
nFE G
= A
= A
RT nFE
cell
cell
cell
e K K
nF
RT
E
nFE K RT G
/ o
o o
o
or ln
thus ln
= =
= = A




The last expression is a form of the Nernst
equation which relates ion concentrations to
the cell potential
Use molar concentrations (M) for ions and
partial pressures of gases in atmospheres
when calculating Q
Q
nF
RT
E E
Q RT nFE nFE
Q RT G G
cell cell
cell cell
ln
or ln
thus ln
o
o
0
=
+ =
+ A = A
Example: In a certain zinc-copper cell,
Zn(s)+Cu
2+
(aq)Zn
2+
(aq)+Cu(s)
the ion concentrations are [Cu
2+
]=0.0100 M and
[Zn
2+
]=1.0 M. What is the cell potential at 298
K?
From Table 21.1

For this two electron change at 298 K
V 1.10 V 0.76) ( V 0.34
o o o
2 2
= = =
+ +
Zn Cu
cell
E E E
V 04 . 1
] [
] [
ln
2
2
2
o
= =
+
+
Cu
Zn
F
RT
E E
cell cell
Galvanic cells, commonly called batteries,
can be classified as either primary or
secondary cells
Primary cells are not designed to be recharged
Secondary cells are able to be recharged
A battery is usually a collection of cells
connected in series
When connected in series, the voltage of
each cell is added to provide the total
voltage of the battery





Lead Storage Battery

Three 2 V cells
connected in series. The
cell voltages are added.
The total voltage
provided is 6 V.
A 12 V lead storage battery, like
those used in automotive
applications, consist of six cells
like the one shown here. Heavy
duty plates are used so the
current produced is sufficient to
start a car.
The anode of each cell consists of lead plates
The cathode consist of another set of plates
holding PbO
2
The electrolyte is sulfuric acid
During discharge, the reactions are
O H s PbSO aq HSO aq H s Pb s PbO
e aq H s PbSO aq HSO s Pb
O H s PbSO e aq HSO aq H s PbO
2 4 4 2
4 4
2 4 4 2
2 ) ( 2 ) ( 2 ) ( 2 ) ( ) (
: Overall
2 ) ( ) ( ) ( ) (
: anode At the
2 ) ( 2 ) ( ) ( 3 ) (
: cathode At the
+ + + +
+ + +
+ + + +
+
+
+
As the battery discharges the sulfuric acid
concentration decreases and the density of the
electrolyte changes
The condition of the battery can be checked by
using a hydrometer to determine the electrolyte
density
The lead storage battery is a secondary cell
because it can be recharged
The zinc-manganese dioxide cell
These are the ordinary dry cells and deliver
1.5 V

A cutaway view of a
zinc-manganese dioxide
dry cell. The anode
reaction is the oxidation
of zinc:
Zn(s)Zn
2+
(aq)+2e
-

The cathode reaction is
complicated and a
mixture of products are
formed. One of the major
reactions is:
2MnO
2
(s)+2NH
4
+
(aq)+2e
-
Mn
2
O
3
(s)+2NH
3
(aq)+H
2
O
The dry cell is a primary cell.
Alkaline battery or alkaline dry cell
Has longer shelf-life and can deliver more
current than the less expensive dry cell

A simplified diagram of an
alkaline zinc-manganese
dioxide dry cell. The anode
reaction is:
Zn(s)+2OH-(aq)
ZnO(s)+H
2
O+2e
-
The cathode reaction is:
2MnO
2
(s)+H
2
O+2e
-

Mn
2
O
3
(s)+2OH
-
(aq)

Net cell reaction: Zn(s)+2MnO
2
(s)ZnO(s)+Mn
2
O
3
(s)
It is also a primary cell.
The nickel-cadmium storage cell
The nicad battery is a secondary cell that
produces a potential of about 1.4 V
Cutaway view of the construction
of a nickel-cadmium battery. The
anode reaction is:
Cd(s)+2OH
-
(aq)Cd(OH)
2
(s)+2e
-

The cathode reaction is:
NiO
2
(s)+2H
2
O+2e
-

Ni(OH)
2
(s)+2OH
-
(aq)
The net cell reaction is:
Cd(s)+ NiO
2
(s)+2H
2
O
Ni(OH)
2
(s)+ Cd(OH)
2
(s)+
The silver oxide battery
This primary cell generates a potential of about
1.5 V and is relatively expensive because it
contains silver
The silver oxide battery was
developed to replace earlier
mercury batteries. The reaction at
the anode is:
Zn(s)+2OH
-
(aq)Zn(OH)
2
(s)+2e
-

The reaction at the cathode is:
Ag
2
O(s)+H
2
O+2e
-

2Ag(s)+2OH
-
(aq)
The net cell reaction is:
Zn(s)+ Ag
2
O(s)+H
2
O
Zn(OH)
2
(s)+2Ag(s)
A number of properties are important for
batteries, including:
Shelf-life, rate of energy output
Energy density (the ratio of available energy to
battery volume)
Specific energy (the ratio of available energy to
weight)
We will look at two modern high-
performance batteries
Nickel-hydride battery
Secondary cells often referred to as Ni-MH
batteries, where MH is used to represent a
metal hydride
Certain alloys, such as Mg
2
Ni, have the ability
to absorb and hold substantial amounts of
hydrogen
The term metal hydride has come to be used
to describe these hydrogen-holding alloy
Ni-MH batteries have a relatively high energy
density and produce about 1.35 V

Cutaway view of a nickel-metal
hydride cell. The electrode
sandwich is rolled up jelly roll
style which gives it a large
effective electrode area. This
enables the cell to deliver large
amounts of energy. The anode
reaction is:
NH(s)+OH
-
(aq)M(s)+H
2
O+e
-
Where MH represents the metal
hydride. The cathode reaction is:
NiO(OH)(s)+H
2
O+e
-

Ni(OH)
2
(s)+OH
-
(aq)

The cell reaction is:
NH(s)+NiO(OH)(s)
Ni(OH)
2
(s)+M(s)
Lithium batteries
Lithium has the potential to used in batteries
with high specific energy (because of its low
molar mass) and high energy density (because
of its very negative reduction potential)
They can be either non-rechargeable (primary
cells) or rechargeable (secondary cells)
Lithium-manganese dioxide battery
Accounts for about 80% of the primary lithium
cells

Uses a solid lithium anode and a cathode made
from heat treated manganese(IV) oxide
The electrolyte is a lithium salt dissolved in an
organic solvent




manganese) the of numbers oxidation the are ts superscrip (The
) ( : reaction Overall
) ( : reaction Cathode
: reaction Anode
2 2
2 2
+
+ +
+
+
+ +
+
Li O Mn O Mn Li
Li O Mn e Li O Mn
e Li Li
III IV
III IV
These batteries have a shelf-life of about 7
years and produce a voltage during use of about
2.8 V
Lithium ion cells
These secondary cells dont actually involve
true oxidation and reduction
Li
+
ions can slip between layers of atoms in
solids such as graphite (a process called
intercalation)
The Li
+
ion battery is based on the transport of
Li
+
ions


Lithium ion cell. (a) During charging, an external voltage forces
electrons through an external circuit and causes lithium ions to travel
from the LiCoO
2
to the graphite electrode. (b) During discharge, the
lithium ions spontaneously migrate back to the LiCoO
2
electrode.
Electrons flow through the external circuit to balance the charge.

Fuel cells are electrochemical cells in which
electrode reactants are continuously
supplied
Early hydrogen-oxygen fuel
cell. The net reaction is the
conversion of hydrogen and
oxygen into water. Typically,
a gas or diesel engine is only
about 20 30% efficient.
Fuel cells have efficiencies
as high as 75%.
Electricity can be used to make
nonspontaneous redox reactions to occur
The process is called electrolysis
Electrolysis occurs in an electrolysis or
electrolytic cell
These cells require a source of direct
current, possibly one of the batteries just
discussed, to provide electrical energy

Electrolysis of molten
sodium chloride. The
passage of an electric
current through
molten sodium
chloride decomposes
the material into
molten sodium and
chlorine gas. The
products must be kept
separated because
they react on contact
to re-form NaCl.

A microscopic view of the changes at the anode in the electrolysis
of molten NaCl. The positive charge of the electrode attracts Cl
-

ions. At the surface of the electrode electrons are pulled from the
ions yielding neutral Cl atoms with combine to form Cl
2

molecules that rise to the surface as a gas.
Sodium is a liquid at the melting point of
sodium chloride (801
o
C)
Reaction at the cathode:
Na
+
(l) + e
-
Na(l)
Reaction at the anode:
2Cl
-
(l) Cl
2
(g) + 2e
-

Cell reaction:
2Na
+
(l) + 2Cl
-
(l) 2Na(l) + Cl
2
(g)
The electrode polarities are reversed in
electrolytic cells relative to those in
galvanic cells


In both types of cells oxidation occurs at the
anode and reduction occurs at the cathode
Electrolysis in aqueous solutions often
involves water molecules
This is often unintended and called a
competing reaction
Electrolytic Cell
Cathode is negative (reduction)
Anode is positive (oxidation)
Galvanic Cell
Cathode is positive (reduction)
Anode is negative (oxidation)

Electrolysis of an aqueous solution of potassium sulfate.
The products of the electrolysis are H
2
and O
2
gas, not
the expected products solid K and S
2
O
8
2-
.
The competing reactions at the cathode are:
K
+
(aq)+e
-
K(s) E
o
K
+
= -2.92 V
2H
2
O(l)+2e
-
H
2
(g)+2OH
-
(aq) E
o
H2O
= -0.83 V

Water has a less negative reduction potential
than the potassium ion so it it easier to reduce
When electrolysis is performed, the more easily
reduced substance is reduced and H
2
is
observed to form
A similar situation occurs at the anode
The competing reactions at the anode are:


The standard cell potential tells us that S
2
O
8
2-
is
more easily reduced than O
2

This means that the product SO
4
2-
is harder to
oxidize than water
When electrolysis is performed the more easily
oxidized substance is oxidized and O
2
is
observed to form at the anode
V 23 . 1 2e ) ( O ) ( 4H O 2H
V 01 . 2 2e ) ( O S ) ( SO
o
O 2 2
o
O S
- 2
8 2
- 2
4
2
- 2
8 2
+ = + +
+ = +
+

E g aq
E aq aq
-
The net change is then
2H
2
O2H
2
(g)+O
2
(g)
This is the sort of analysis that needs to be
done to anticipate the products of
electrolysis
Sometimes the predicted products are still
not obtained
The reasons are beyond the scope of this
book but serve as a reminder to be cautious
about predicting the products of electrolysis
solely on the basis of reduction potentials
Michael Faraday discovered that the amount
of chemical change is directly proportional
to the amount of electrical charge passed
through an electrolysis cell
For example, the equation:
Cu
2+
(aq)Cu(s)+2e
-

says that to deposit 1 mol of Cu, 2 mol of
electrons are required

The SI unit of electrical current is the
ampere (A) and the SI unit of charge is the
coulomb (C)
A coulomb is the amount of charge that
passes a given point in a wire when an
electrical current of 1 ampere flows for 1
second

The charge carried by 1 mol of electrons is
the basis for the Faraday constant (96,485
C/mol e)
This provides a way to measure the amount
of chemical change in the laboratory
1s A 1 C 1 =
Example: What current must be supplied to
deposit 3.00 g Au from a solution of AuCl
3
in
200.0 s?




Electroplating is a procedure in which
electrolysis is used to apply a thin coating
of one metal over another
There are many industrial applications
A 22.0 s C 22.0
s 0 . 200
1
mol 1
C 485 , 96
Au mol 1
mol 3
Au g 197
Au mol 1
Au g 00 . 3
) ( 3 ) ( : Reduction
1
3
= =

+

+
e
e
s Au e aq Au

Apparatus for
electroplating
silver. Silver
dissolves at the
anode where it is
oxidized to Ag
+
.
Silver is
deposited at the
cathode (the
fork) where Ag
+

is reduced.
Aluminum does not occur as a free metal in
nature because it is so reactive
It is obtained from the electrolysis of Al
2
O
3
at high temperatures
Al
3+
+ 3e
-
Al(l) (cathode)
2O
2-
O
2
(g) + 2e
-
(anode)
4 Al
3+
+ 6O
2-
4Al(l) + 3 O
2
(g) (net cell)
Production of Al requires lots of electricity and heat
Recycling of Al costs only a small fraction of what
it costs to produce Al from the ore bauxite

Production of aluminum by electrolysis. Al
2
O
3
is dissolved in
cryolite, Na
3
AlF
6
. The Al
3+
is reduced to Al(l) and the O
2-

oxidized to O
2
, which reacts with the carbon anode to produce
CO
2
. Molten aluminum is periodically drawn off and additional
Al
2
O
3
is added. The carbon anodes must occasionally be
replaced as they are consumed by the reaction with oxygen.
Magnesium is used in many light weight
structural applications
A major source of magnesium is seawater
Seawater is made basic causing Mg
2+
to precipitate
as Mg(OH)
2

The precipitate is separated by filtration and
dissolved in hydrochloric acid:
Mg(OH)
2
(s)+2HCl(aq)MgCl
2
(aq)+2H
2
O
The resulting solution is evaporated to give solid
MgCl
2
, which is melted and electrolyzed:
MgCl
2
(l)Mg(l)+Cl
2
(g)

Commercial electrolysis
of molten NaCl. The
cathode is a circular ring
that surrounds the anode.
The electrodes are
separated by an iron
screen. Molten Na
collects at the top of the
cathode compartment and
is periodically drained.
Cl
2
bubbles out of the
anode compartment and
is collected.
An interesting and economical application
of electrolysis is the purification or refining
of metallic copper
Purification of copper
by electrolysis. The
impure copper anode
dissolves and the Cu is
deposited on the
cathode. The sludge
often contains enough
silver, gold, and
platinum to pay almost
all the refining costs.
Brine is a concentrated aqueous solution of
of sodium chloride
The electrolysis of brine produces hydrogen and chlorine
gas. The solution becomes basis as the reaction progresses.

A diaphragm cell
used in the
commercial
production of NaOH
by the electrolysis of
aqueous NaCl. This is
a cross section of a
cylindrical cell in
which NaCl solution
is surrounded by an
asbestos diaphragm
supported by a steal
mesh cathode.

Electrolysis of brine using
a mercury cell. At the
anode, chloride ions are
oxidized to chlorine. At
the cathode, sodium ions
are reduced to sodium
atoms, which dissolve in
the mercury. The mercury
is pumped into a separate
compartment and exposed
to water. The dissolved
sodium reacts with the
water to form H
2
and
NaOH.