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Chapter 21: Electrochemistry

Lesson 21.3: Electrolytic Cells
- The process in which electrical energy is used to bring about such a chemical change is called
electrolysis.
- 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.

- In both voltaic and electrolytic cells, electrons flow from the anode to the cathode in the external
circuit.
- 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.
- The redox process in the voltaic cell is spontaneous; in the electrolytic cell, the redox process is
nonspontaneous.
- 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 to be the negative electrode because it is
connected to the negative electrode of the battery. The anode in the electrolytic cell is considered
to be the positive electrode because it is connected to the positive electrode of the battery.
- 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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Electrolysis of Water

- When a current is applied to two electrodes immersed in pure water, nothing happens. There is
no current flow and no electrolysis. However, when an electrolyte such as H2SO4 or NO3 in low
concentration is added to the pure water, the solution conducts an electric current and electrolysis
occurs. This process is illustrated in Figure 21.12.
- The products of the electrolysis of water are hydrogen gas and oxygen gas.
- This process is sometimes used to produce hydrogen gas for fuel cells.
Water is oxidized at the anode according to the following oxidation half-reaction:

- Water is reduced to hydrogen at the cathode according to the following reduction half-reaction:

- The region around the anode turns acidic due to an increase in H+ ions.
- The region around the cathode turns basic due to the production of OH- ions.
- The overall cell reaction is obtained by adding the half-reactions (after doubling the reduction
half-reaction equation to balance electrons).

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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.
- This process simultaneously produces three important industrial chemicals:
1. chlorine gas.
2. hydrogen gas.
3. sodium hydroxide.

- When the sodium hydroxide solution is about 10 percent (mass/volume), it is removed from the
cell and processed further.
Electrolysis of Molten Sodium Chloride

- Both sodium and chlorine are commercially important. Sodium is used in sodium vapor lamps
and as the coolant in some nuclear reactors. Chlorine, a greenish-yellow gas, is used to sterilize
drinking water and is important in the manufacture of polyvinyl chloride (PVC) and various
pesticides. These two elements are produced through the electrolysis of pure molten sodium
chloride, rather than an aqueous solution of NaCl. Chlorine gas is produced at the anode, and
molten sodium collects at the cathode. The half-reactions for the electrolysis of molten sodium
chloride are as follows:

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- The electrolytic cell in which this commercial process is carried out is called the Downs cell and
is shown in Figure 21.14.
- The cell operates at a temperature of 801°C so that the sodium chloride is maintained in the
molten state.
- A perforated iron screen separates the circular cathode from the graphite anode. The sodium,
with a melting point of 97.8°C, remains in liquid form. The liquid sodium floats on the more
dense molten sodium chloride and is drawn off as it is formed. The chlorine gas is collected after
it bubbles up and out of the molten salt. The design of the Downs cell allows fresh sodium chlo-
ride to be added as required. The design also separates the products so they will not recombine to
reform sodium chloride.

Using Electrolysis in Metal Processing

- Electroplating is the deposition of a thin layer of a metal on an object in an electrolytic cell.

- An object may be electroplated to protect the surface of the base metal from corrosion or to make
it more attractive.
- 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, and the electrolyte is a solution of a silver salt, such as
silver cyanide. When a direct current is applied, silver ions move from the anode to the object to
be plated.

- The net result is that silver transfers from the silver anode to the object being plated.

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- Electroforming is a process in which an object is reproduced by making a metal mold of it at the

cathode of a cell. For example, 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. This coating can then be stripped
off of the mold.
- Electroforming is used to make jewelry and tubing for chemical instrumentation, such as gas
chromatographs.
- In 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.
- In electropolishing, the surface of an object at the anode is dissolved selectively to give it a high
polish.
- In electro machining, 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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