ELECTROLYSIS| CHAPTER 10

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 ELECTROLYSIS| CHAPTER 10

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 ELECTROLYSIS| CHAPTER 10

Conductivity in Ionic Compounds

Ionic compounds like sodium chloride and potassium iodide do not conduct electricity as solids
because their ions are fixed in a rigid lattice structure. However, when melted or dissolved in
water, the ions are free to move, allowing them to conduct electricity.

Conductivity in Covalent Compounds

Covalent molecular compounds like hexane, methane, and carbon dioxide do not conduct
electricity in any state because they consist of neutral molecules with no free-moving charged
particles. Their electrons are tightly bound and cannot move freely to carry current.
However, some exceptions exist—certain covalent compounds can form ions when they react
with water. For example, ammonia reacts with water as follows:
𝑁𝐻3 (𝑔) + 𝐻2 𝑂 ⇌ 𝑁𝐻4+ (𝑎𝑞) + 𝑂𝐻 − (𝑎𝑞)
In this case, ammonia solution can conduct electricity because the reaction produces ions that
are free to move.

Electrolysis
Electrolysis is a chemical process in which electric current is passed through an electrolyte to
cause a non-spontaneous chemical reaction. It is commonly used to decompose compounds,
such as splitting water into hydrogen and oxygen.

Electrolyte
An electrolyte is a substance that conducts electricity when molten or dissolved in water. It
contains free-moving ions that allow the flow of electric current. Examples: sodium chloride
(NaCl) solution, sulfuric acid (H₂SO₄), or molten lead bromide (PbBr₂).

Cathode and Anode

The cathode is the negative electrode where reduction takes place. Positively charged ions,
known as cations, are attracted to the cathode. When they reach the cathode, they gain
electrons from the external power supply and become neutral atoms or molecules. On the
other hand, the anode is the positive electrode where oxidation occurs. Negatively charged
ions, called anions, move toward the anode and lose electrons, which are then transferred to
the external circuit.

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Electrolysis of Molten Substances

Electrolysis of Lead Bromide (PbBr₂)

Lead(II) bromide is made up of positively charged lead ions (Pb²⁺) and negatively charged
bromide ions (Br⁻), arranged in a rigid crystal lattice when solid. In this solid state, the ions are
tightly held and cannot move, which is why solid PbBr₂ does not conduct electricity. However,
when it is heated until it melts, the lattice breaks down and the ions become free to move. This
allows the molten compound to conduct electricity and undergo electrolysis.

Role of Electrodes and Power Supply

✓ When a power source is connected to molten
lead (II) bromide, electric current flows
through the liquid.
✓ Electrons are pulled away from the left-hand
electrode, making it positively charged — this
is the anode.
✓ Electrons flow to the right-hand electrode,
making it negatively charged — this is the
cathode.
✓ In the molten electrolyte, Pb²⁺ ions move
toward the cathode (negative electrode).
✓ At the cathode, each Pb²⁺ ion gains two electrons (reduction) to become a neutral lead
atom.
✓ These lead atoms collect as molten metal at the bottom of the container.

This can be represented by a half-equation:

𝑃𝑏²⁺ + 2𝑒⁻ → 𝑃𝑏

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✓ Negatively charged bromide ions (Br⁻)

are attracted to the positively charged
anode.
✓ At the anode, each Br⁻ ion loses one
electron (oxidation) to become a neutral
bromine atom.
✓ These bromine atoms pair up to form
bromine gas (Br₂).
✓ The bromine gas bubbles off at the
surface of the electrolyte.

𝐵𝑟⁻ → 𝐵𝑟 + 𝑒⁻
Br joins in pairs to make bromine molecules
2𝐵𝑟 ⟶ 𝐵𝑟2
Overall,
2𝐵𝑟 − ⟶ 𝐵𝑟2 + 2𝑒 −
Overall, the electrolysis of lead (II) bromide results in the decomposition of the ionic compound
into its elements: metallic lead is collected at the cathode, and bromine gas is released at the
anode. This process clearly illustrates the roles of the anode and cathode, and how electric
current drives the movement of ions and the chemical changes at the electrodes.

Half Equations
At the cathode (reduction):
𝑃𝑏²⁺ + 2𝑒⁻ → 𝑃𝑏

At the anode (oxidation):

2𝐵𝑟 − ⟶ 𝐵𝑟2 + 2𝑒 −

Overall Equation
Add the above two half-equations,
𝑃𝑏𝐵𝑟2 (𝑙) → 𝑃𝑏 (𝑙) + 𝐵𝑟2 (𝑔)

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Oxidation
Oxidation is the loss of electrons by a substance.

Reduction
Reduction is the gain of electrons by a substance.

Electrolysis of Other Molten Substances

➢ Electrolysis of molten sodium chloride (NaCl)
Electrolysis of molten sodium chloride breaks it down into its elements using electricity. The
molten form contains free-moving Na⁺ and Cl⁻ ions, allowing conduction and electrochemical
reactions.

Half Equations
• At the cathode (-):
Sodium ions (Na⁺) gain electrons and form liquid sodium metal.

𝑁𝑎+ + 𝑒 − ⟶ 𝑁𝑎 (𝑙)
• At the anode (+):
Chloride ions (Cl⁻) lose electrons and form chlorine gas (Cl₂).
2𝐶𝑙 − ⟶ 𝐶𝑙2 (𝑔) + 2𝑒 −

Overall Equation
2𝑁𝑎𝐶𝑙 (𝑙) → 2𝑁𝑎 (𝑙) + 𝐶𝑙2 (𝑔)

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➢ Electrolysis of Aluminium Oxide (Al₂O₃)

Electrolysis of aluminium oxide extracts aluminium metal using electricity. Aluminium oxide is
first dissolved in molten cryolite to lower its melting point and allow ion movement. The melt
contains free Al³⁺ and O²⁻ ions.

Half Equations
• At the Cathode (−):
Aluminium ions gain electrons (reduction):
𝐴𝑙 3+ + 3𝑒 − → 𝐴𝑙 (𝑙)
• At the Anode (+):
Oxide ions lose electrons and form oxygen gas (oxidation):
2𝑂2− → 𝑂2 (𝑔) + 4𝑒 −

Overall Equation
2𝐴𝑙2 𝑂3 (𝑙) → 4𝐴𝑙 (𝑙) + 3𝑂2 (𝑔)

➢ Electrolysis of Zinc Chloride (ZnCl₂)

Electrolysis of molten zinc chloride breaks it down into its elements using electricity. In the
molten state, Zn²⁺ and Cl⁻ ions are free to move and conduct electricity.

Half Equations
• At the Cathode (−):
Zinc ions gain electrons (reduction):
𝑍𝑛2+ + 2𝑒 − → 𝑍𝑛 (𝑙)
• At the Anode (+):
Chloride ions lose electrons and form chlorine gas (oxidation):

2𝐶𝑙 − → 𝐶𝑙2 (𝑔) + 2𝑒 −

Overall Equation
𝑍𝑛𝐶𝑙2 (𝑙) → 𝑍𝑛 (𝑙) + 𝐶𝑙2 (𝑔)

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Electrolysis of Aqueous Solutions

Electrolysis of aqueous Sodium Chloride (NaCl) Solution
The electrolysis of sodium chloride solution, commonly
known as brine, is an important industrial process used
to produce three valuable substances: hydrogen gas,
chlorine gas, and sodium hydroxide. When sodium
chloride (NaCl) dissolves in water, it dissociates into
sodium ions (Na⁺) and chloride ions (Cl⁻). Water itself
also partially ionizes into hydrogen ions (H⁺) and
hydroxide ions (OH⁻). Thus, the solution contains four
types of ions: Na⁺, Cl⁻, H⁺, and OH⁻.
During electrolysis, an electric current is passed through
this solution using two inert electrodes (typically
graphite or platinum). At the cathode (negative
electrode), positively charged ions are attracted. Here,
both Na⁺ and H⁺ ions are present, but H⁺ ions are preferentially discharged because hydrogen is
less reactive than sodium. As a result, hydrogen gas (H₂) is released at the cathode through the
reduction half-equation:
2𝐻 + + 2𝑒 − → 𝐻2 (𝑔)
At the anode (positive electrode), negatively charged ions (Cl⁻ and OH⁻) are attracted. Although
both ions are present, chloride ions (Cl⁻) are more easily oxidized and are discharged in
preference to hydroxide ions. This produces chlorine gas (Cl₂) at the anode, according to the
oxidation half-equation:
2𝐶𝑙 − → 𝐶𝑙2 (𝑔) + 2𝑒 −
The overall reaction for the electrolysis of brine is:
2𝑁𝑎𝐶𝑙 (𝑎𝑞) + 2𝐻2 𝑂 (𝑙) → 𝐻2 (𝑔) + 𝐶𝑙2 (𝑔) + 2𝑁𝑎𝑂𝐻 (𝑎𝑞)
After the gases are removed, sodium ions (Na⁺) and hydroxide ions (OH⁻) remain in the
solution, combining to form sodium hydroxide (NaOH). Thus, this process yields three useful
products: hydrogen gas at the cathode, chlorine gas at the anode, and sodium hydroxide in
solution, all of which have important industrial uses such as in soap making, bleach production,
and water treatment.

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Electrolysis of Copper(ll) Sulphate Solution Using Inert

Electrodes
The electrolysis of copper(II) sulfate (CuSO₄) solution is a
common laboratory and industrial process used to
purify copper metal. When copper sulfate dissolves in
water, it dissociates into copper ions (Cu²⁺) and sulfate
ions (SO₄²⁻). Additionally, water itself ionizes slightly to
form hydrogen ions (H⁺) and hydroxide ions (OH⁻).
Therefore, the solution contains four types of ions: Cu²⁺,
SO₄²⁻, H⁺, and OH⁻.
During electrolysis, an electric current is passed through
the solution using inert electrodes such as graphite or
platinum. At the cathode (negative electrode), positively
charged ions are attracted. Both Cu²⁺ and H⁺ ions are present in the solution, but Cu²⁺ ions are
preferentially discharged because copper is less reactive than hydrogen. As a result, copper
metal is deposited at the cathode through the following reduction half-equation:
𝐶𝑢2+ + 2𝑒 − → 𝐶𝑢 (𝑠)
This forms a layer of pure copper on the cathode.
At the anode (positive electrode), negatively charged ions are attracted. Here, both SO₄²⁻ and
OH⁻ ions are present, but OH⁻ ions are discharged preferentially, leading to the formation of
oxygen gas (O₂) and water. The oxidation half-equation is:
4𝑂𝐻 − → 𝑂2 (𝑔) + 2𝐻2 𝑂 (𝑙) + 4𝑒 −
The overall reaction for the electrolysis of copper (II) sulfate solution is:
2𝐶𝑢𝑆𝑂4 (𝑎𝑞) + 2𝐻2 𝑂 (𝑙) → 2𝐶𝑢 (𝑠) + 𝑂2 (𝑔) + 2𝐻2 𝑆𝑂4 (𝑎𝑞)
As the reaction proceeds, copper is deposited on the cathode while oxygen bubbles off at the
anode, and the solution gradually becomes more acidic due to the formation of sulfuric acid
(H₂SO₄). If instead of inert electrodes, a copper anode is used, the copper atoms from the
anode are oxidized and go into the solution as Cu²⁺ ions, keeping the concentration of Cu²⁺
constant. This setup is used in industry for electrorefining of copper, where impure copper is
used as the anode, and pure copper is collected at the cathode.

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Electrolysis of Dilute Sulfuric Acid Solution Using Inert

Electrodes
The electrolysis of dilute sulfuric acid (H₂SO₄) is a well-known
laboratory method to produce hydrogen and oxygen gases.
When sulfuric acid is diluted in water, it dissociates into
hydrogen ions (H⁺) and sulfate ions (SO₄²⁻). In addition, water
itself also ionizes slightly into hydrogen ions (H⁺) and
hydroxide ions (OH⁻). Therefore, the solution contains the
following ions: H⁺, SO₄²⁻, and OH⁻.
During electrolysis, an electric current is passed through the
solution using two inert electrodes (typically graphite or
platinum). At the cathode (negative electrode), positively
charged ions move towards the electrode. Both H⁺ and metal
ions (if any) may be present, but in the case of dilute sulfuric
acid, only H⁺ is relevant. These H⁺ ions gain electrons and are
reduced to form hydrogen gas (H₂) according to the following
half-equation:
2𝐻 + + 2𝑒 − → 𝐻2 (𝑔)
At the anode (positive electrode), negatively charged ions are
attracted. Both OH⁻ and SO₄²⁻ are present, but OH⁻ ions from water are more easily oxidized.
As a result, oxygen gas (O₂) is released at the anode along with the formation of water, as
represented by the oxidation half-equation:
4𝑂𝐻 − → 𝑂2 (𝑔) + 2𝐻2 𝑂(𝑙) + 4𝑒 −
The overall reaction for the electrolysis of dilute sulfuric acid is:
2𝐻2 𝑂(𝑙) → 2𝐻2 (𝑔) + 𝑂2 (𝑔)
In this process, hydrogen gas is produced at the cathode, and oxygen gas is released at the
anode, with the ratio of hydrogen to oxygen being 2:1 by volume. Sulfate ions (SO₄²⁻) are not
discharged and remain in the solution, making the solution remain acidic throughout the
process. This method is widely used to demonstrate electrolysis and the composition of water,
as well as to generate small amounts of gases in a lab setup.

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Understanding Electrolysis and the Reactivity Series

What Happens at the Cathode (Negative Electrode)?
• If the metal is more reactive than hydrogen (e.g.,
potassium, sodium, calcium, etc. from the top of the
reactivity series), the metal does not get deposited.
Instead, hydrogen gas is produced from the reduction
of H⁺ ions in the solution.
• If the metal is less reactive than hydrogen (e.g.,
copper, silver, gold), the metal ions in the solution will
be reduced, and the pure metal will be deposited at
the cathode.

What Happens at the Anode (Positive

Electrode)?
• If the solution contains halide ions (like Cl⁻, Br⁻, or I⁻ from chloride, bromide, or iodide
salts), the halogen gas (chlorine, bromine, or iodine) is released at the anode.
• If the solution contains common negative ions that are not halides (like sulfate SO₄²⁻,
nitrate NO₃⁻, or hydroxide OH⁻), oxygen gas is released instead.

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Suggested Problems
1.

2.

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3.

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4.

5.

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References
➢ Edexcel International GCSE (9-1) Chemistry Student Book

Disclaimer
❖ These notes contain the information that serves as a student’s aid for Edexcel
International GCSE (9-1) Chemistry Student book.
❖ The notes only cover the theoretical part for the exam, for practicals and for more in-
depth knowledge students must consult the textbook.
❖ Consequently, these notes cannot replace the textbook.

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