Electrolysis

Monday, 28 February 2022 12:06 PM

Electrolysis is defined as the breakdown of a compound via the passage of an electrical

current through it.

Metallic Conduction
In metallic structures, positive ions are packed closely together in a regular way,
'Free electrons' move randomly through the structure. When a power source is
attached to the metal, all the electrons move in one direction. We say an electric
current is flowing.

Electrolytic Conduction
An ionic substance consists of positive and negative ions held together by
electrostatic attraction . In the solid state, the ions are rigidly help in place. When
the substance is molten or dissolved, the ions become free to move about. These
mobile ions move randomly about, but if attached to a power supply they move in
one direction.

Electrolytes
Electrolytes are liquids that conduct electricity via the movement of mobile ions.

There are two types of electrolytes based on the degree of ionisation and
conductivity when in liquid state. These are:
• Strong Electrolytes - Substances which are completely ionised when
dissolved or molten, e.g. strong acids and salts like NaCl. These electrolytes
have high conductivity.
• Weak Electrolytes - Substances which are partially ionised when dissolved or
molten, e.g. weak acids and water. These electrolytes have a weak
conductivity.

Electrolytic Cell
In an electrolytic cell, the electrodes are pieces of metal which carry current into
the electrolyte. There are two electrodes:
• Anode - positive electrode which attracts the negative anions
• Cathode - negative electrode which attracts the positive cations

When the circuit is closed, the electrons in the battery nd wires begin to move,
causing the anode to become positively charged and the cathode negatively
charged.

At the cathode, the cations are attracted and move toward it. Here they gain
electrons and become neutral.
At the anode, the anions are attracted and move toward it. Here they lose
electrons and become neutral. The lost electrons flow through the circuit toward
the cathode.

The end result of electrolysis is the breakdown of a compound into its constituent
elements which are discharged or liberated at the electrodes. The products of
electrolysis depend on several factors which include:

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The end result of electrolysis is the breakdown of a compound into its constituent
elements which are discharged or liberated at the electrodes. The products of
electrolysis depend on several factors which include:
• The type of electrolyte - molten or aqueous
• The position of the ions in the electrochemical series
• The concentration of the solution - sometimes dilute solutions give different
products from concentrated solutions
• Type of electrode - Inert electrodes do not take part in the chemical changes
of electrolysis, e.g. carbon and platinum. Active electrodes take part in the
chemical changes of electrolysis, e.g. copper

Electrolysis of a Molten Solution Using Inert Electrodes

Molten lead (II) bromide - PbBr2
When the circuit is closed:

Br- ions migrate to the anode where they deposit electrons

Brown gas bubbles out as the bromine has been discharged.

The PB2+ travel to the cathode where they gain electrons.

As the lead has been discharged, a molted grey substance drips off the cathode

The Electrochemical Series Cations Anions

If a mixture of substances is used during electrolysis, then several ions will be K+ SO42-
attracted to a particular electrode. Only one type of ion can be discharged at a
time. The ion discharged depends on its position in the electrochemical series. Ca2+ NO3-
The electrochemical series is a listing that places ions in the order of ease of Na+ Cl-
electrical discharge. The lower an element is in the series, the easier it is to Al3+ Br-
discharge.
Zn2+ I-
When one ion is discharged in favour to another, preferential discharged is dais to
have occurred. Fe2+ OH-
Pb2+
H+
Cu2+
Ag+
Au+

Electrolysis of Dilute Sodium Chloride

In a solution of dilute sodium chloride, there are four types of ions present
Na+, Cl- from the solute
H+, OH- from water
During electrolysis:
Na+ and H+ move to the cathode. H+ is preferentially discharged as it is lower in
the electrochemical series.

Colourless gas bubbles out that gives a pop with a lit splint

Cl- and OH- move to the anode where OH- is preferentially discharged as it is lower
in the electrochemical series

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Colourless gas bubbles out that relights a glowing splint

Electrolysis of Concentrated Sodium Chloride

In a concentrated solution, the same ions are present as in the dilute solution.
However, the number of Na+ and Cl- ions is much greater than H+ and OH-. This
does not affect the reaction at the cathode.

Colourless gas is given off which gives a pop with a lit splint

However, it does affect the reaction at the anode. Cl- is discharged preferentially
to OH-, even though the latter is lower on the electrochemical series.

Colourless gas is given off which bleaches damp blue litmus paper.

This occurs in cases where both ions are close together on the electrochemical
series. The large numbers of Cl- ions give it the advantage over the OH-.
Concentration is an important factor to consider in the electrolysis of aqueous
solutions of al halides, e.g. HI, HCl, CuCl2, and NaBr.

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Electrodes
Wednesday, March 16, 2022 2:46 PM

Electrolysis of Copper Sulphate Using Inert Electrodes (Carbon Electrodes)

The ions present in the solution are H+, Cu2+, OH-, and So42-

At the Anode:
OH- and SO42- ions move here. The OH- is preferentially discharged.

Colourless gas is produced

At the Cathode:
Cu2+ and H+ ions move here. The Cu2+ is preferentially discharged.

Pink solid is produced

Electrolysis of Copper Sulphate Using Active Electrodes (Copper Electrodes)

The ions present are H+, Cu2+, OH- and SO42-

At the Cathode:
H+ and Cu2+ move there where Cu+ is preferentially discharged

Pink solid is formed

Anode:
OH- and SO42- move to the anode where neither are discharged. Something totally
different happens. Cu from the electrode loses its electrons and goes into solution.
This occurs because it is energetically than the discharge of OH-. The anode loses
mass.

There is always reduction at the cathode, and oxidization at the anode

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Uses of Electrolysis
Wednesday, March 16, 2022 5:07 PM

Metal / Non-Metal Extraction

Elements extracted by electrolysis include:
• Aluminum from aluminum oxide (bauxite)
• Chlorine from sodium chloride (brine)
• Sodium from sodium chloride

The Down's process is used to produce sodium. In this process, molten sodium chloride is
electrolysed between a graphite anode and iron cathode. Calcium chloride is added to lower
the melting point of sodium chloride. Sodium is discharged at the cathode and is collected in a
circular inverted trough from where it is sent to a storage tank. Although the process is used
primarily for the production of sodium, chlorine is also a useful byproduct.

Electrofining
Sometimes metals exist in mixtures with other substances. One method that can
be used to purify such metals utilises electrolysis in the process called
electrofining. One metal that can be purified in this way is copper.
Impure copper is made the anode in an electrolytic cell. The cell uses a pure strip
of copper as the cathode and aqueous copper sulphate as the electrolyte. The
process essentially employs 'electrolysis of copper sulphate using active
electrodes'
Copper from the impure solid, which forms the anode, goes into solution via the
reaction

Pure copper accumulates on the copper strip that forms the cathode.

Impurities from the anode drop to the bottom of the cell

Electroplating
This process employs electrolysis to form a thin metal coating on an object

Some objects electroplated are:

• Jewellery electroplated with gold
• Steel electroplated with tin to form 'tin cans'
• Cutlery, car bumpers and taps electroplated with nickel or chrome

Some reasons for electroplating objects are to:

• Make them more attractive. Gold plated jewellery looks like real gold
• Prevent coating by coating with an inert material. Tin protects the steel from
rusting in tin plated cans.
• Save expensive metal. Pure chrome or nickel articles would use a lot of
metal. Electroplating uses a small fraction of this amount.

During electroplating, the object being electroplated is the cathode of the cell. I n
gold platin, the anode is made of the electroplating metal, gold, and the
electrolyte is a solution of the electroplating metal, aqueous gold nitrate.
At the anode, gold goes into solution.

At the cathode, the object is coated with gold

Anodising

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Anodising
Aluminum is naturally protected by a thin aluminum oxide layer on its surface.
This layer must be penetrated in order for aluminum to react. The oxide layer
makes aluminum corrosion resistant. It also readily adsorbs dyes so aluminum can
be easily attractively coloured. Anodising thickens this layer.
Objects made of aluminum, e.g. window frames and aircraft bodies, are anodised
by making them the anode in an electrolytic cell. The electrolyte used is dilute
sulphuric acid and the other electrode is inert. At the anode, oxygen is produced,
which penetrates the outer layers of the object and react with it, increasing the
thickness of the aluminum oxide layer.

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Calculations
Wednesday, March 16, 2022 8:43 PM

The scientist Michael Faraday developed two laws concerning the quantitative
aspect of electrolysis. Faraday's laws are:
1. The mass of a substance produced or dissolved at an electrode is
proportional to the electric charge passed through the electrolyte
m∝Q
○ Q = It - Q is charge measured in coulombs (C); I is electrical current
measured in amperes (A); t is time in seconds
○ m∝It
2. One mole of electrons had a charge of 96500 coulombs or 1 Faraday. This
is also called Faraday's constant. The number of Faradays required to
discharge 1 mole of a substance is equal to the charge on its ion.

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