21.

3 Electrolytic Cells >

Chapter 21
Electrochemistry

21.1 Electrochemical Cells

21.2 Half-Cells and Cell Potentials

21.3 Electrolytic Cells

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21.3 Electrolytic Cells > CHEMISTRY & YOU

How can an aluminum bottle be colored?

If an aluminum object
has a color other than
silver, it was anodized
before it was dyed. In
the anodizing process,
the aluminum object is
the anode in an
electrolytic cell.

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21.3 Electrolytic Cells > Electrolytic vs. Voltaic Cells

Electrolytic vs. Voltaic Cells

How do voltaic and electrolytic
cells differ?

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21.3 Electrolytic Cells > Electrolytic vs. Voltaic Cells

The process in which electrical energy is

used to bring about a chemical change
is called electrolysis.
• You are already
familiar with some
results of electrolysis,
such as gold-plated
jewelry,
chrome-plated
automobile parts, and
silver-plated dishes.
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21.3 Electrolytic Cells > Electrolytic vs. Voltaic Cells

The apparatus in which electrolysis is

carried out is an electrolytic cell.
• An electrolytic cell is an electrochemical
cell used to cause a chemical change
through the application of electrical energy.
• An electrolytic cell uses electrical energy
(direct current) to make a nonspontaneous
redox reaction proceed to completion.

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21.3 Electrolytic Cells > Electrolytic vs. Voltaic Cells
Voltaic Cell Electrolytic Cell Battery

e– e–

e– e–
Anode Cathode
(oxidation) (reduction)
Energy
Anode Cathode
(oxidation) (reduction)
Energy

In both voltaic and electrolytic cells,

electrons flow from the anode to the
cathode in the external circuit.

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21.3 Electrolytic Cells > Electrolytic vs. Voltaic Cells
Voltaic Cell Electrolytic Cell Battery

e– e–

e– e–
Anode Cathode
(oxidation) (reduction)
Energy
Anode Cathode
(oxidation) (reduction)
Energy

The key difference between voltaic and electrolytic

cells is that in a voltaic cell, the flow of electrons is the
result of a spontaneous redox reaction, whereas in an
electrolytic cell, electrons are caused to flow by an
outside power source, such as a battery.
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21.3 Electrolytic Cells > Electrolytic vs. Voltaic Cells
Voltaic Cell Electrolytic Cell Battery

e– e–

e– e–
Anode Cathode
(oxidation) (reduction)
Energy
Anode Cathode
(oxidation) (reduction)
Energy

• In a voltaic cell, the anode is the negative electrode

and the cathode is the positive electrode.
• In an electrolytic cell, the cathode is considered the
negative electrode.
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21.3 Electrolytic Cells > Driving Nonspontaneous
Processes

Driving Nonspontaneous Processes

What are some applications that
use electrolytic cells?

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21.3 Electrolytic Cells > Driving Nonspontaneous
Processes

Electrolysis of a solution or of a
melted, or molten, ionic compound
can result in the separation of
elements from compounds.
Electrolytic cells are also
commonly used in the plating,
purifying, and refining of metals.

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21.3 Electrolytic Cells > Driving Nonspontaneous
Processes

Electrolysis of Water
• When current is applied to two electrodes
immersed in pure water, nothing happens.
• When an electrolyte such as H2SO4 or
KNO3 in low concentration is added to the
pure water, the solution conducts an
electric current and electrolysis occurs.

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21.3 Electrolytic Cells > Driving Nonspontaneous
Processes

Electrolysis of Water
When an
electric current
is passed
through water,
the water O2 (g)

decomposes H2 (g)

into oxygen gas

and hydrogen
gas.

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21.3 Electrolytic Cells > Driving Nonspontaneous
Processes

Electrolysis of Water
• Water is oxidized at the anode.
Oxidation: 2H2O(l) → O2(g) + 4H+(aq) + 4e–

• Water is reduced to hydrogen at the

cathode.
Reduction: 2H2O(l) + 2e– → H2(g) + 2OH–(aq)

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21.3 Electrolytic Cells > Driving Nonspontaneous
Processes

Electrolysis of Water
The overall cell reaction is obtained by
adding the half-reactions (after doubling the
reduction half-reaction equation to balance
electrons).
Oxidation: 2H2O(l) → O2(g) + 4H+(aq) + 4e–
Reduction: 2[2H2O(l) + 2e– → H2(g) + 2OH–(aq)]
6H2O(l) → 2H2(g) + O2(g) + 4H+(aq) + 4OH–(aq)

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21.3 Electrolytic Cells > Driving Nonspontaneous
Processes

Electrolysis of Water
• The ions produced tend to recombine to
form water.
4H+(aq) + 4OH–(aq) → 4H2O(l)

• Therefore, the net reaction can be written

as follows:
2H2O(l) → 2H2(g) + O2(g)

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21.3 Electrolytic Cells > Driving Nonspontaneous
Processes

Electrolysis of Brine
If the electrolyte in an aqueous solution is
more easily oxidized or reduced than water,
then the products of electrolysis will be
substances other than hydrogen and oxygen.
• An example is the electrolysis of brine, a
concentrated aqueous solution of sodium chloride.
• This process simultaneously produces three
important industrial chemicals: chlorine gas,
hydrogen gas, and sodium hydroxide.

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21.3 Electrolytic Cells > Driving Nonspontaneous
Processes

Electrolysis of Brine
• Chloride ions are oxidized to produce chlorine
gas at the anode.
• Water is reduced to produce hydrogen gas at the
cathode.

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21.3 Electrolytic Cells > Driving Nonspontaneous
Processes

Electrolysis of Brine
• Sodium ions are not reduced to sodium metal
because water molecules are more easily
reduced than are sodium ions.

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21.3 Electrolytic Cells > Driving Nonspontaneous
Processes

Electrolysis of Brine
• The reduction of water also produces hydroxide
ions.
– The electrolyte in solution becomes sodium hydroxide.

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21.3 Electrolytic Cells > Driving Nonspontaneous
Processes

Electrolysis of Brine
• The half-reactions are as follows:
Oxidation: 2Cl–(aq) → Cl2(g) + 2e–
Reduction: 2H2O(l) + 2e– → H2(g) + 2OH–(aq)

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21.3 Electrolytic Cells > Driving Nonspontaneous
Processes

Electrolysis of Brine

• The overall ionic equation is the sum of

the two half-reactions.
Oxidation: 2Cl–(aq) → Cl2(g) + 2e–
Reduction: 2H2O(l) + 2e– → H2(g) + 2OH–(aq)
2Cl–(aq) + 2H2O(l) → Cl2(g) + H2(g) + 2OH–(aq)

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21.3 Electrolytic Cells > Driving Nonspontaneous
Processes

Electrolysis of Brine

• The spectator ion Na+ can be included in

the equation to show the formation of
sodium hydroxide during the electrolytic
process.
2NaCl(aq) + 2H2O(l) → Cl2(g) + H2(g) + 2NaOH(aq)

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21.3 Electrolytic Cells > Driving Nonspontaneous
Processes

Electrolysis of Molten Sodium Chloride

Sodium and chlorine are produced
through the electrolysis of pure molten
sodium chloride, rather than an aqueous
solution of NaCl.
• Chlorine gas is produced at the anode.
• Molten sodium collects at the cathode.

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21.3 Electrolytic Cells > Driving Nonspontaneous
Processes

Electrolysis of Molten Sodium Chloride

• The half-reactions are as follows:
Oxidation: 2Cl–(l) → Cl2(g) + 2e–
Reduction: 2Na+(l) + 2e– → 2Na(l)

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21.3 Electrolytic Cells > Driving Nonspontaneous
Processes

Electrolysis of Molten Sodium Chloride

• The overall equation is the sum of the two

half-reactions:
Oxidation: 2Cl–(l) → Cl2(g) + 2e–
Reduction: 2Na+(l) + 2e– → 2Na(l)
2NaCl(l) → 2Na(l) + Cl2(g)

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21.3 Electrolytic Cells > Driving Nonspontaneous
Processes

Electrolysis of Molten Sodium Chloride

The electrolytic cell in which this
commercial process is carried out is
called the Downs cell.
• The cell operates
at a temperature
of 801°C so that
the sodium
chloride is
maintained in the
molten state.
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21.3 Electrolytic Cells > Driving Nonspontaneous
Processes

Using Electrolysis in Metal Processing

Electrolysis has many important
applications in the field of metallurgy.
• Many of the shiny metallic objects you see
every day—such as chrome-plated fixtures
or nickel-plated coins—were manufactured
with the help of electrolytic processes.

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21.3 Electrolytic Cells > Driving Nonspontaneous
Processes

Electroplating and Electroforming

Electroplating is the deposition of a thin
layer of a metal on an object in an
electrolytic cell.
• An object that is to be silver-plated is made
the cathode in an electrolytic cell.
• The anode is the metallic silver that is to be
deposited.
• The electrolyte is a solution of a silver salt,
such as silver cyanide.
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21.3 Electrolytic Cells > Driving Nonspontaneous
Processes

Electroplating and Electroforming

When direct current is applied, silver ions
move from the anode to the object to be
plated.
Reduction: Ag+(aq) + e– → Ag(s) (at cathode)

This figure shows

statuettes that were
electroplated with
copper, nickel, and
24-carat gold.
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21.3 Electrolytic Cells > Driving Nonspontaneous
Processes

Electroplating and Electroforming

Electroforming is a process in which an
object is reproduced by making a metal
mold of it at the cathode of a cell.
• A mold of an object can be coated with metal
so it will conduct a current.
• It is then electroplated with a thick coating of
metal.
• Electroforming is used to make jewelry and
tubing for chemical instrumentation.
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21.3 Electrolytic Cells > Driving Nonspontaneous
Processes

Electrowinning and Electrorefining

In a process called electrowinning, impure
metals can be purified in electrolytic cells.
• The cations of molten salts or aqueous
solutions are reduced at the cathode to give
very pure metals.

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21.3 Electrolytic Cells > Driving Nonspontaneous
Processes

Electrowinning and Electrorefining

A common use of electrowinning is in the
extraction of aluminum from its ore, bauxite.
• Bauxite is impure alumina (Al2O3).
• In the Hall-Heroult process, purified alumina is
dissolved in molten cryolite (Na3AlF6) and heated to
above 1000°C in a carbon-lined tank.
• The carbon lining, connected to a direct current, serves
as the cathode.
• The anode consists of carbon rods dipped into the tank.

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21.3 Electrolytic Cells > Driving Nonspontaneous
Processes

Electrowinning and Electrorefining

A common use of electrowinning is in the
extraction of aluminum from its ore, bauxite.
• At the cathode, Al3+ ions are reduced,
forming molten aluminum.
• At the anode, carbon is oxidized, forming
carbon dioxide gas.
• The overall reaction is as follows:
2Al2O3(l) + 3C(s) → 4Al(l) + 3CO2(g)
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21.3 Electrolytic Cells > Driving Nonspontaneous
Processes

Electrowinning and Electrorefining

In the process of electrorefining, a piece of
impure metal is made the anode of the cell.
• It is oxidized to the cation and then reduced
to the pure metal at the cathode.
• This technique is used to obtain ultrapure
silver, lead, and copper.

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21.3 Electrolytic Cells > Driving Nonspontaneous
Processes

Other Processes
Other electrolytic processes are centered on
the anode rather than the cathode.
• In electropolishing, the surface of an object
at the anode is dissolved selectively to give
it a high polish.
• In electromachining, a piece of metal at the
anode is partially dissolved until the
remaining portion is an exact copy of the
object at the cathode.
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21.3 Electrolytic Cells > CHEMISTRY & YOU

In the process of anodizing aluminum, the

aluminum object serves as the anode. To
which electrode of the power source is
the anode connected?
In any electrolytic
cell, the anode is
connected to the
positive electrode of
the power source.

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21.3 Electrolytic Cells > LessonCheck

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21.3 Electrolytic Cells > LessonCheck

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21.3 Electrolytic Cells >

END OF 21.3

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