MODULE A10

Electrochemistry

Electrolysis, electrode reactions, industrial applications, electroplating — electricity meets chemistry! ⚡🔋

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1. Electrolysis — Core Concepts

Electrolysis is the decomposition of an ionic compound (electrolyte) using electricity. It requires a direct current (DC) supply, two electrodes, and an electrolyte (molten or dissolved ionic compound).

ComponentDefinitionRule
CathodeNegative electrodeCations (+) attracted here → Reduction (gains electrons)
AnodePositive electrodeAnions (−) attracted here → Oxidation (loses electrons)
ElectrolyteIonic compound that conducts electricity in solution or when moltenMust contain free-moving ions
🧠 Memory aid: ANode = OXidation = ANOX. CAThode = REDuction = CATRED (or remember: RED CAT — reduction at the cathode!).
Cations are positive and go to the negative cathode. Anions are negative and go to the positive anode.

2. Electrolysis of Specific Electrolytes

A. Molten NaCl (sodium chloride)

Only Na⁺ and Cl⁻ ions present. Simple — no competition.

ElectrodeIon dischargedHalf-equationProduct
Cathode (−)Na⁺Na⁺ + e⁻ → NaSodium metal (liquid)
Anode (+)Cl⁻2Cl⁻ → Cl₂ + 2e⁻Chlorine gas

B. Aqueous NaCl (brine) — electrolysis of brine

Brine contains Na⁺, Cl⁻, H⁺, and OH⁻ ions (from water). Competition occurs at each electrode.

ElectrodeCompeting ionsIon discharged & whyProduct
Cathode (−)Na⁺ and H⁺H⁺ discharged — lower in reactivity series (H₂ preferred over Na metal)Hydrogen gas (H₂)
Anode (+)Cl⁻ and OH⁻Cl⁻ discharged — higher concentration effectChlorine gas (Cl₂)
Solution left behindNa⁺ + OH⁻Remaining ions form NaOHSodium hydroxide (NaOH)
🏭 Industrial importance of brine electrolysis (Chlor-alkali process):
H₂ → fuel cells, margarine production, rocket fuel
Cl₂ → PVC plastic, bleach (NaOCl), disinfecting water supplies
NaOH → soap, paper, drain cleaners, food processing

C. Aqueous CuSO₄ with inert (carbon/platinum) electrodes

ElectrodeIon dischargedHalf-equationProduct
Cathode (−)Cu²⁺ (preferred over H⁺ — Cu is lower in reactivity series)Cu²⁺ + 2e⁻ → CuPink copper deposits on cathode
Anode (+)OH⁻ / H₂O (preferred over SO₄²⁻)2H₂O → O₂ + 4H⁺ + 4e⁻Oxygen gas

D. Aqueous CuSO₄ with copper electrodes (electroplating setup)

ElectrodeHalf-equationWhat happens
Cathode (−) — object to be platedCu²⁺ + 2e⁻ → CuCopper deposits — cathode gets heavier
Anode (+) — pure copperCu → Cu²⁺ + 2e⁻Copper dissolves — anode gets lighter

The Cu²⁺ concentration in solution stays constant — copper dissolves from anode at the same rate it deposits on the cathode!

3. Discharge Order (Which Ion is Discharged?)

When multiple ions compete, the one discharged depends on position in the reactivity series and concentration.

At the Cathode (reduction — cations)At the Anode (oxidation — anions)
Less reactive metal ions discharged first.
Order: Cu²⁺ > H⁺ > Zn²⁺ > Na⁺
(Cu²⁺ most easily reduced)
OH⁻ / halide ions (Cl⁻, Br⁻, I⁻) discharged in preference to SO₄²⁻, NO₃⁻.
At high conc. of Cl⁻ → Cl₂
At low conc. or no Cl⁻ → O₂

4. Extraction of Aluminium — Hall-Héroult Process

Aluminium cannot be extracted by reduction with carbon (too high reactivity) so electrolysis is used.

5. Electroplating

Electroplating deposits a thin layer of metal onto an object for protection, appearance, or conductivity.

ComponentWhat to useWhy
CathodeObject to be platedMetal ions deposit here (reduction)
AnodePure metal being plated (e.g. copper, silver)Dissolves to replenish ions in solution
ElectrolyteSolution of the plating metal's saltProvides ions; e.g. CuSO₄ for copper plating, AgNO₃ for silver plating
🔩 Real-world uses: Chrome-plated car bumpers (corrosion resistance + appearance). Silver-plated cutlery (cheaper than solid silver). Copper plating of circuit boards. Zinc galvanising (protects iron/steel from rust).

6. Faraday's Laws (Quantitative Electrolysis)

First Law: The mass of substance deposited/released is proportional to the quantity of electricity (charge) passed.

Second Law: The mass deposited is inversely proportional to the charge of the ion (i.e. doubly-charged ions need twice the charge per mole).

Key formulas:
Q = I × t    charge (coulombs) = current (A) × time (s)
moles of e⁻ = Q / 96500    (Faraday constant F = 96500 C/mol)
moles of substance = moles of e⁻ / n    (n = charge on ion)
mass = moles × Mᵣ
📝 Example: A current of 2A is passed through CuSO₄ for 965 seconds. Mass of Cu deposited?
Q = 2 × 965 = 1930 C | n(e⁻) = 1930/96500 = 0.02 mol
Cu²⁺ + 2e⁻ → Cu: n(Cu) = 0.02/2 = 0.01 mol | mass = 0.01 × 64 = 0.64 g

⚡ Electrolytic Cell Simulator

Select an electrolyte and watch ions migrate to the correct electrode, products appear, and half-equations update live.

📈 Electrode Products vs Electrolyte & Conditions

An interactive reference chart. Click any cell to get the full explanation for that combination.

👆 Click a cell to see the explanation

🃏 Flashcards — Electrochemistry

Click to flip!

Answer
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❓ Quiz — Electrochemistry

🔢 Worked Example — Faraday's Laws Calculation

Problem: A steady current of 3.0 A is passed through a solution of silver nitrate (AgNO₃) for 1608 seconds using platinum electrodes. Calculate the mass of silver deposited at the cathode. (Aᵣ: Ag = 108, F = 96500 C/mol)

Step 1: Calculate charge passed (Q)

Use Q = I × t. Current = 3.0 A, time = 1608 s.

Step 2: Calculate moles of electrons transferred

Use n(e⁻) = Q / F = 4824 / 96500.

Step 3: Moles of Ag deposited

Half-equation: Ag⁺ + e⁻ → Ag. Ag⁺ has a +1 charge so 1 mole of e⁻ deposits 1 mole of Ag. Moles of Ag = ?

Step 4: Mass of Ag deposited

Use m = n × Mᵣ. n(Ag) = 0.05 mol, Mᵣ(Ag) = 108 g/mol.

🔗 Matching — Electrochemistry

Term

Definition / Description

📝 CSEC-Style Questions

Q1. Concentrated sodium chloride solution (brine) is electrolysed using inert electrodes. (a) Name the product at each electrode. (b) Write a half-equation for each electrode. (c) Name the substance left in solution and state one industrial use of each product. [8 marks]+
Mark Scheme

1 (a) Cathode: hydrogen (H₂) ✓ | Anode: chlorine (Cl₂) ✓

2 (b) Cathode: 2H⁺ + 2e⁻ → H₂ ✓ | Anode: 2Cl⁻ → Cl₂ + 2e⁻ ✓

3 (c) Sodium hydroxide (NaOH) left in solution ✓

4 H₂: used as a fuel / making margarine / rocket propellant ✓

5 Cl₂: used to disinfect water supplies / making PVC plastic / bleach production ✓

6 NaOH: soap manufacture / paper production / drain cleaners ✓ [Award any 2 for 2 marks]

Q2. Copper is electroplated onto a metal spoon using copper sulfate solution. (a) What is connected to the cathode? (b) What is connected to the anode? (c) Why does the anode lose mass during the process? (d) Write the half-equation at the cathode. [5 marks]+
Mark Scheme

1 (a) The metal spoon (object to be plated) ✓

2 (b) Pure copper (the plating metal) ✓

3 (c) The copper anode is oxidised and dissolves into solution as Cu²⁺ ions: Cu → Cu²⁺ + 2e⁻. This replenishes the Cu²⁺ used at the cathode, keeping the electrolyte concentration constant. ✓✓

4 (d) Cu²⁺(aq) + 2e⁻ → Cu(s) ✓

Q3. In the electrolysis of dilute H₂SO₄, hydrogen gas is produced at the cathode and oxygen gas at the anode. (a) Write the half-equation for each electrode. (b) If 2 mol of H₂ are produced, how many moles of O₂ are produced? Explain using the half-equations. [5 marks]+
Mark Scheme

1 (a) Cathode: 2H⁺ + 2e⁻ → H₂ ✓

2 Anode: 2H₂O → O₂ + 4H⁺ + 4e⁻ ✓

3 (b) To produce 2 mol H₂: 2 × (2e⁻) = 4 mol e⁻ used ✓

4 At the anode, 4e⁻ released produces 1 mol O₂ ✓

5 So 2 mol H₂ : 1 mol O₂. The volume ratio H₂:O₂ = 2:1 — this matches the electrolysis of water. ✓

Q4. A current of 5.0 A is passed through molten lead bromide (PbBr₂) for 1930 seconds. (a) Name the products at each electrode. (b) Calculate the mass of lead deposited. (Aᵣ: Pb = 207, F = 96500 C/mol) [5 marks]+
Mark Scheme

1 (a) Cathode: lead (Pb) ✓ | Anode: bromine (Br₂) ✓

2 (b) Q = I × t = 5.0 × 1930 = 9650 C ✓

3 n(e⁻) = 9650 / 96500 = 0.1 mol ✓

4 Pb²⁺ + 2e⁻ → Pb: n(Pb) = 0.1/2 = 0.05 mol ✓

5 m(Pb) = 0.05 × 207 = 10.35 g

⭐ Key Concepts & Formulas

Electrode Rules

Cathode (−) = Reduction Anode (+) = Oxidation RED CAT | AN OX

Brine Products

Cathode: H₂ (2H⁺+2e⁻→H₂) Anode: Cl₂ (2Cl⁻→Cl₂+2e⁻) Solution: NaOH

Faraday Formulas

Q = I × t n(e⁻) = Q / 96500 n = n(e⁻) / ion charge m = n × Mᵣ

Electroplating

Cathode = object (gains mass) Anode = plating metal (loses mass) Electrolyte = metal salt solution

CuSO₄ (inert)

Cathode: Cu²⁺+2e⁻→Cu (pink) Anode: O₂ from H₂O Solution loses Cu²⁺, paler

Al Extraction

Al₂O₃ dissolved in cryolite Cathode: Al³⁺+3e⁻→Al Anode burns away as CO₂

📚 Resources