7.
3 — Reactions at the Electrodes
What happens during electrolysis?
Electrolysis happens when electricity passes through a molten (melted) ionic compound or
an ionic solution.
● Ions move because electricity is flowing.
● Opposite charges attract.
○ Positive ions → go to the cathode (–)
○ Negative ions → go to the anode (+)
Remember:
● OIL RIG
Oxidation Is Loss of electrons
Reduction Is Gain of electrons
● RACI
Reduction At Cathode, Oxidation at Anode
Molten Lead(II) Bromide (PbBr₂)
When PbBr₂ is melted, its ions are free to move.
At the cathode (–):
Positive lead ions (Pb²⁺) gain 2 electrons → lead metal forms.
Half-equation:
Pb²⁺ + 2e⁻ → Pb
This is reduction (gain of electrons).
At the anode (+):
Negative bromide ions (Br⁻) lose electrons → bromine gas forms.
Half-equation:
2Br⁻ → Br₂ + 2e⁻
This is oxidation (loss of electrons).
Electrolysis of Concentrated Sodium Chloride
Solution (Brine)
The solution contains:
● Na⁺
● Cl⁻
● H⁺
● OH⁻
At the cathode (–):
Hydrogen ions (H⁺) gain electrons because hydrogen is less reactive than sodium.
2H⁺ + 2e⁻ → H₂
Hydrogen gas forms.
At the anode (+):
Chloride ions (Cl⁻) lose electrons more easily than OH⁻.
2Cl⁻ → Cl₂ + 2e⁻
Chlorine gas forms.
What is left in solution?
Na⁺ and OH⁻ → sodium hydroxide (NaOH)
Electrolysis of Dilute Sodium Chloride Solution
The solution has more water and less NaCl, so results change.
Cathode:
Hydrogen is still produced:
2H₂O + 2e⁻ → H₂ + 2OH⁻
(or 4H⁺ + 4e⁻ → 2H₂)
Anode:
Not enough Cl⁻ ions, so oxygen is released from OH⁻:
4OH⁻ → O₂ + 2H₂O + 4e⁻
What remains in solution?
More NaCl solution (since water breaks down instead).
Half-Equations (How to Write Them)
1. Identify the ion and its charge.
2. Decide if it gains or loses electrons.
3. Balance electrons with the ion’s charge.
4. Add state symbols if needed.
Example: Electrolysis of Molten Magnesium
Chloride (MgCl₂)
Ions present:
Mg²⁺, Cl⁻
Cathode (reduction):
Mg²⁺ + 2e⁻ → Mg
Anode (oxidation):
2Cl⁻ → Cl₂ + 2e⁻
Important Questions
1. At which electrode does reduction always happen? Why?
Reduction always happens at the cathode (–)
→ because positive ions are attracted to the negative electrode and gain electrons.
2. Half-equations at the anode for molten:
a) Potassium chloride (KCl)
KCl → K⁺ + Cl⁻
Anode:
2Cl⁻ → Cl₂ + 2e⁻
b) Calcium oxide (CaO)
CaO → Ca²⁺ + O²⁻
Anode:
O²⁻ → ½O₂ + 2e⁻
(or 2O²⁻ → O₂ + 4e⁻)
3. Why does hydrogen form instead of sodium in NaCl solution?
Because hydrogen ions (from water) are easier to reduce than sodium ions.
Sodium is very reactive and does not gain electrons easily in water.
Hydrogen comes from the water, not from the salt.
Compare concentrated vs dilute NaCl solutions:
Solution Cathode Anode What’s left?
Concentrated H₂ gas Cl₂ gas NaOH solution
Dilute H₂ gas O₂ gas NaCl solution
Predict the products:
a) Concentrated CuCl₂ solution
Ions: Cu²⁺, Cl⁻, H⁺, OH⁻
● Cathode: Copper forms
Cu²⁺ + 2e⁻ → Cu
● Anode: Chlorine forms
2Cl⁻ → Cl₂ + 2e⁻
6a Concentrated HCl solution
Ions: H⁺, Cl⁻
● Cathode:
2H⁺ + 2e⁻ → H₂
● Anode:
2Cl⁻ → Cl₂ + 2e⁻
6b Dilute NaOH solution
Ions: Na⁺, OH⁻, H⁺ from water
● Cathode: Hydrogen forms
2H₂O + 2e⁻ → H₂ + 2OH⁻
● Anode: Oxygen forms
4OH⁻ → O₂ + 2H₂O + 4e⁻
6c Dilute CuCl₂ solution
Ions: Cu²⁺, Cl⁻, H⁺, OH⁻
● Cathode: Copper forms (easily reduced)
Cu²⁺ + 2e⁻ → Cu
● Anode: Oxygen forms (because solution is dilute)
4OH⁻ → O₂ + 2H₂O + 4e⁻
—---------------------------------------------------------------------------------------------------------
7.4 Electroplating
What is electroplating?
Electroplating means using electricity to coat one metal with another metal.
Examples:
● Steel taps coated with shiny chromium
● Steel food cans coated with tin
● Plastic car parts coated with nickel
● Cheap jewellery coated with silver or gold
Electroplating makes objects:
● look better (shiny, attractive)
● last longer (no rusting)
Electrolysis of Copper(II) Sulfate Solution (CuSO₄)
A CuSO₄ solution contains these ions:
● Cu²⁺ (copper ions – blue colour)
● SO₄²⁻
● H⁺ and OH⁻ (from water)
Results depend on the electrodes you use.
A. Using Carbon Electrodes (Inert)
Carbon electrodes do not react.
Cathode (–):
Cu²⁺ ions gain electrons → copper metal sticks to the cathode.
Cu²⁺ + 2e⁻ → Cu (solid)
Anode (+):
OH⁻ ions lose electrons → oxygen gas forms.
4OH⁻ → O₂ + 2H₂O + 4e⁻
What happens to the solution?
● Copper ions are removed from solution
● So the blue colour fades
✔ Reason: Cu²⁺ ions are used up and changed into copper metal.
B. Using Copper Electrodes (Not Inert)
Now the electrodes do react.
Cathode (–):
Copper forms and coats the electrode (same as before):
Cu²⁺ + 2e⁻ → Cu
Anode (+):
Anode dissolves:
Cu → Cu²⁺ + 2e⁻
What happens to the solution?
● Copper ions leave the anode
● Copper ions go to the cathode
● Overall: number of Cu²⁺ ions in solution stays the same
● So the blue colour remains
✔ Copper moves from anode → cathode
Metal Refining (Purifying Copper)
Electrolysis can make copper 99.9% pure.
● Anode: impure copper
● Cathode: pure copper
● Electrolyte: CuSO₄ solution
What happens?
● Anode dissolves: copper goes into solution
● Cathode gains pure copper
● Impurities fall to the bottom as sludge
Sludge contains valuable metals like silver and gold.
Electroplating Process (How it Works)
To electroplate a steel jug with silver:
● Cathode: the object (steel jug)
● Anode: pure silver metal
● Electrolyte: silver nitrate (AgNO₃) solution
Reactions:
At anode:
Ag → Ag⁺ + e⁻ (silver dissolves)
At cathode:
Ag⁺ + e⁻ → Ag (silver sticks to jug)
The jug becomes coated with shiny silver.
How to Set Up Electroplating (General Rule)
To coat an object with metal X:
● Cathode: the object
● Anode: metal X
● Electrolyte: solution of a soluble compound of X
(example: silver plating → use silver nitrate)