Electrolysis of Aqueous Sodium Chloride (Brine)
Brine is a concentrated solution of sodium chloride (NaCl) in water.
Electrodes used
● Inert electrodes: carbon (graphite) or platinum
(They do not react during electrolysis.)
Ions present in brine
From sodium chloride:
● Na⁺ (sodium ions)
● Cl⁻ (chloride ions)
From water:
● H⁺ (hydrogen ions)
● OH⁻ (hydroxide ions)
What happens during electrolysis?
● Electricity passes through the solution
● Gases are released at both electrodes
● A solution remains in the container
At the negative electrode (cathode)
● H⁺ ions are discharged
● Sodium ions are more reactive, so they are not discharged
● H⁺ ions gain electrons to form hydrogen gas
Half-equation (cathode):
2H++2e−→H2
Hydrogen gas is produced
At the positive electrode (anode)
● Cl⁻ ions are discharged
● Chloride ions lose electrons to form chlorine gas
Half-equation (anode):
2Cl−→Cl2+2e−
Chlorine gas is produced
Solution left behind
● Na⁺ and OH⁻ ions remain
● They form sodium hydroxide (NaOH) solution
Products of brine electrolysis
Product Where formed Uses
Hydrogen (H₂) Cathode Making margarine, fuel
Chlorine (Cl₂) Anode Making bleach, disinfectants
Sodium hydroxide (NaOH) Solution Soap, detergents
Electrolysis of Dilute Sulfuric Acid
Dilute sulfuric acid is used to electrolyse water.
Electrodes used
● Inert electrodes: carbon (graphite) or platinum
Ions present
From sulfuric acid:
● H⁺
● SO₄²⁻ (sulfate ions)
From water:
● H⁺
● OH⁻
What happens during electrolysis?
● Gas bubbles form at both electrodes
● Hydrogen and oxygen gases are produced
At the negative electrode (cathode)
● H⁺ ions gain electrons
● Hydrogen gas is formed
Half-equation (cathode):
2H++2e−→H2
Hydrogen gas is produced
At the positive electrode (anode)
● OH⁻ ions lose electrons
● Oxygen gas and water are formed
Half-equation (anode):
4OH−→O2+2H2O+4e−
Oxygen gas is produced
Volume of gases
● Twice as much hydrogen is produced as oxygen
● Ratio = 2 : 1 (H₂ : O₂)
(This can be seen using a Hoffmann voltameter.)
Electrolysis of Aqueous Solutions
Key idea
An aqueous solution always contains water (H₂O).
So during electrolysis, ions from the compound AND ions from water compete to be
discharged.
Water partially dissociates into ions:
H2O⇌H++OH−
Ions present in aqueous electrolysis
● From the solute (e.g. Na⁺, Cl⁻, Cu²⁺, SO₄²⁻)
● From water (H⁺ and OH⁻)
Which ion is discharged depends on:
● Reactivity of the element
● Concentration of the solution
● Type of electrode (inert or active)
At the Anode (Positive Electrode)
Attracted ions:
● OH⁻ ions
● Non-metal (negative) ions such as Cl⁻, Br⁻, I⁻
Rule for the anode
1. If halide ions (Cl⁻, Br⁻, I⁻) are present:
○ The halogen gas is produced
○ Example: Cl⁻ → Cl₂
2. If no halide ions are present:
○ Oxygen gas is produced from OH⁻ ions
Half-equations at the anode
● Halide ions:
2Cl−→Cl2+2e−
● Hydroxide ions:
4OH−→O2+2H2O+4e−
Effect of Concentration at the Anode
Solution Product at Anode Reason
Concentrated halide Halogen gas Halide ions discharged
Dilute halide Oxygen gas OH⁻ ions discharged
Example: Barium chloride (BaCl₂)
● Concentrated: Chlorine gas formed
● Dilute: Oxygen gas formed
At the Cathode (Negative Electrode)
Attracted ions:
● H⁺ ions
● Metal ions (e.g. Na⁺, Cu²⁺)
Rule for the cathode
● If the metal is more reactive than hydrogen → Hydrogen gas is produced
● If the metal is less reactive than hydrogen → Metal is produced
Half-equations at the cathode
● Hydrogen formation:
2H++2e−→H2
● Metal deposition (example):
Cu2++2e−→Cu
Electrolysis of Aqueous Copper(II) Sulfate (CuSO₄)
Ions present
● Cu²⁺, SO₄²⁻ (from CuSO₄)
● H⁺, OH⁻ (from water)
Using Graphite (Inert) Electrodes
Observations
● Cathode: Pink-brown copper deposited
● Anode: Colourless oxygen gas bubbles
● Blue solution becomes paler
Products
● Cathode: Copper metal
● Anode: Oxygen gas
Half-equations
● Cathode:
Cu2++2e−→Cu
● Anode:
4OH−→O2+2H2O+4e−
Using Copper (Active) Electrodes
Observations
● Cathode gains mass (copper deposited)
● Anode loses mass (copper dissolves)
● Blue colour remains unchanged
Explanation
● Copper is transferred from anode → cathode
● Cu²⁺ concentration in solution stays constant
Half-equations
Cathode:
Cu2++2e−→Cu
Anode:
Cu→Cu2++2e−
Products of Common Aqueous Solutions
Aqueous Solution Product at Anode Product at Cathode
Concentrated NaCl Chlorine gas Hydrogen gas
Dilute NaCl Oxygen gas Hydrogen gas
CuSO₄ (aq) Oxygen gas Copper
Dilute H₂SO₄ Oxygen gas Hydrogen gas
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Ionic Half-Equations
What is electrochemistry?
Electrochemistry is the study of electron transfer in chemical reactions.
Because electrons are involved:
● Oxidation and reduction are defined using electrons, not oxygen.
Key Definitions
● Oxidation = loss of electrons
● Reduction = gain of electrons
Remember: OIL RIG
Oxidation Is Loss
Reduction Is Gain
What happens at the electrodes?
When ions reach an electrode:
● They gain or lose electrons
● They form neutral substances
● These substances are discharged as products
At the electrodes:
● Anode (positive electrode)
○ Negative ions lose electrons
○ Oxidation occurs
● Cathode (negative electrode)
○ Positive ions gain electrons
○ Reduction occurs
Memory trick:
RED CAT → REDuction at the CAThode
AN OX → ANode for OXidation
What are ionic half-equations?
● They show only one part of a redox reaction
● One half-equation shows oxidation
● The other shows reduction
● Atoms and charges must be balanced
Writing Ionic Half-Equations
1. Metals (Reduction)
Metal ions are positive ions (e.g. Li⁺, Cu²⁺, Al³⁺).
When metals are formed during electrolysis:
● Metal ions gain electrons
● The metal ion is reduced
The charge on the ion tells you how many electrons are gained.
Examples:
● Li⁺ + e⁻ → Li
● Cu²⁺ + 2e⁻ → Cu
● Al³⁺ + 3e⁻ → Al
2. Hydrogen Ion (Reduction)
Hydrogen ion (H⁺) is a positive ion.
When hydrogen gas is produced:
● Two H⁺ ions gain two electrons
● Hydrogen ions are reduced
Half-equation:
2H++2e−→H2
3. Halide Ions → Halogens (Oxidation)
Halide ions are negative ions (Cl⁻, Br⁻, I⁻).
When a halogen is produced:
● Halide ions lose electrons
● Halide ions are oxidised
General half-equation:
2X−→X2+2e−
Example:
2Cl−→Cl2+2e−
4. Hydroxide Ions → Oxygen (Oxidation)
This is the most challenging half-equation and often tested.
● Hydroxide ions lose electrons
● Oxygen gas and water are formed
● Hydroxide ions are oxidised
Half-equation:
4OH−→O2+2H2O+4e−
✔ Atoms balanced
✔ Charges balanced
Common Half-Equations in Electrolysis
Electrolysis of Anode (Oxidation) Cathode (Reduction)
Molten lead(II) bromide 2Br⁻ → Br₂ + 2e⁻ Pb²⁺ + 2e⁻ → Pb
(PbBr₂)
Concentrated aqueous NaCl 2Cl⁻ → Cl₂ + 2e⁻ 2H⁺ + 2e⁻ → H₂
Dilute sulfuric acid 4OH⁻ → O₂ + 2H₂O + 4e⁻ 2H⁺ + 2e⁻ → H₂