Module A10 · CSEC Chemistry
Electro-chemistry

Electrochemical series, conductors & electrolytes, electrolysis of molten and aqueous solutions, Faraday calculations, and four industrial applications.

Section 1 — The Electrochemical Series

The series ranks metals by ease of losing electrons (ionising). A higher metal is a stronger reducing agent and displaces any metal below it from a salt solution.

Metals — Reactivity Series

MetalIon
Potassium KK⁺↑ Strongest reducer
Calcium CaCa²⁺↑ Easier to ionise
Sodium NaNa⁺
Magnesium MgMg²⁺
Aluminium AlAl³⁺
Zinc ZnZn²⁺
Iron FeFe²⁺
Lead PbPb²⁺
Hydrogen HH⁺Reference
Copper CuCu²⁺
Silver AgAg⁺↓ Weakest reducer
⚡ Displacement RuleA metal HIGHER in the series displaces a metal LOWER from its salt solution. Higher = stronger reducing agent = donates electrons more readily.
📋 Example: Mg + CuSO₄Mg(s) + CuSO₄(aq) → MgSO₄(aq) + Cu(s)
Observations: Mg gets smaller · Blue fades · Pink Cu deposits · Temperature rises.

Non-Metals (Oxidising Power)

Ranked by ease of gaining electrons. Higher = stronger oxidising agent and displaces those below from their compounds.

F₂ > Cl₂ > Br₂ > I₂ Cl₂ + 2KI → 2KCl + I₂ (Cl above I)

Section 2 — Electrical Conduction & Electrolytes

Metallic ConductionCarried by mobile electrons through the metal lattice. Metal remains chemically UNCHANGED. Examples: all metals, graphite.
Electrolytic ConductionCarried by mobile ions through the liquid/solution. Electrolyte DECOMPOSES — a chemical change occurs.
TypeIonisationBulbExamples
Strong electrolyteFully ionised → single arrowBrightHCl(aq), H₂SO₄(aq), NaOH(aq), NaCl(aq)
Weak electrolytePartially ionised ⇌DimCH₃COOH(aq), NH₃(aq), H₂CO₃(aq)
Non-electrolyteDoes not ioniseNo glowEthanol, glucose, sugar solution, wax

Section 3 — Electrolysis

Definition — ElectrolysisThe chemical change that occurs when an electric current passes through an electrolyte (molten or aqueous). The electrolyte decomposes at the electrodes.
ANODE (+) Connected to POSITIVE terminal Anions (−) migrate here Anions LOSE electrons → discharged OXIDATION occurs — OIL Aⁿ⁻ → A + ne⁻
CATHODE (−) Connected to NEGATIVE terminal Cations (+) migrate here Cations GAIN electrons → discharged REDUCTION occurs — RIG Cⁿ⁺ + ne⁻ → C
🧠 MemoryANiONs → ANode. CATions → CAThode. Anode = (+) = Oxidation (OIL). Cathode = (−) = Reduction (RIG). "An CAT is always negative!"

Molten PbBr₂ — Worked Example

Ions present: Pb²⁺(l) and Br⁻(l) ANODE (+): 2Br⁻(l) → Br₂(g) + 2e⁻ Brown/orange bromine vapour evolved CATHODE (−): Pb²⁺(l) + 2e⁻ → Pb(l) Molten lead collects at base

Aqueous Solutions — Which Ion Is Discharged?

ElectrodeFactorRule
ANODEAnion series positionLower in series = easier to discharge. OH⁻ > I⁻ > Br⁻ > Cl⁻ > NO₃⁻ > SO₄²⁻ > F⁻
ANODEConcentrationConcentrated Cl⁻, Br⁻, I⁻ overrides position. Dilute NaCl → O₂; Conc. NaCl (brine) → Cl₂
ANODEElectrode typeINERT (graphite/Pt): normal discharge. ACTIVE (e.g. Cu): anode metal ionises instead
CATHODECation series positionLower in series = easier to discharge. Cu²⁺ below H⁺ → Cu deposits. Na⁺ above H⁺ → H₂ instead
ElectrolyteElectrodesAnodeCathodeElectrolyte Change
Dilute H₂SO₄InertO₂H₂More concentrated
Dilute NaClInertO₂H₂More concentrated
Conc. NaCl (brine)InertCl₂H₂Becomes alkaline (NaOH)
CuSO₄Inert graphiteO₂Cu (pink)Paler blue, more acidic
CuSO₄Active copperCu dissolvedCu (pink)Unchanged

Section 4 — Quantitative Electrolysis (The Faraday)

Faraday Constant F = 96,500 C mol⁻¹One mole of electrons carries 96,500 coulombs of charge. Formula: Q = I × t (Q in C, I in A, t in s).

5-Step Method

  • 1Calculate Q = I × t — convert minutes to seconds first!
  • 2Write the half-equation at the relevant electrode.
  • 3Find moles of electrons per mole of product from the half-equation.
  • 4n(product) = Q ÷ (n(e⁻) × 96,500)
  • 5Convert: mass = n × M, or volume = n × Vₘ.
Worked Example — Mass of Pb from molten PbBr₂ I = 5.0 A, t = 16 min 5 s = 965 s Step 1: Q = 5.0 × 965 = 4825 C Step 2: Pb²⁺(l) + 2e⁻ → Pb(l) Step 3: 2 mol e⁻ per mol Pb Step 4: n(Pb) = 4825 ÷ (2 × 96500) = 0.025 mol Step 5: m(Pb) = 0.025 × 207 = 5.175 g ✅

Section 5 — Industrial Applications

1 — Metal Extraction (Al)

Al is too high in the series for carbon reduction. Extracted by electrolysis of molten Al₂O₃ dissolved in cryolite.

Cathode: Al³⁺(l) + 3e⁻ → Al(l) Anode: 2O²⁻(l) → O₂(g) + 4e⁻

Graphite anodes corrode and must be replaced regularly.

2 — Electrorefining

Purifies impure Cu: impure metal = anode, pure metal = cathode, CuSO₄ = electrolyte.

Anode: Cu(s) → Cu²⁺(aq) + 2e⁻ Cathode: Cu²⁺(aq) + 2e⁻ → Cu(s)

Impurities sink as sludge. Electrolyte unchanged.

3 — Electroplating

Deposits a thin metal coat on an object (corrosion protection, appearance).
Object = cathode; plating metal = anode; metal salt solution = electrolyte.

Cr³⁺(aq) + 3e⁻ → Cr(s) [on cathode]
4 — Anodising Al

Thickens Al₂O₃ protective layer. Al article = anode; dilute H₂SO₄ = electrolyte.

Al(s) → Al³⁺ + 3e⁻ [anode] Al³⁺ + O²⁻ → Al₂O₃ [thick layer]

More corrosion-resistant; can be dyed attractive colours.

🌍 Chlor-Alkali IndustryElectrolysis of concentrated brine produces: Cl₂ at the anode (bleach, PVC), H₂ at the cathode (fuel), and NaOH in the electrolyte (soap, paper). Three essential products from one cell!

Section 6 — Resources

Section 7 — CSEC Practice Questions

Question 1 — Displacement
Predict whether iron reacts with CuSO₄(aq). Write a balanced equation and ionic equation. Give two observations.
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1 Fe is above Cu in the electrochemical series → Fe is a stronger reducing agent → reaction occurs.

2 Fe(s) + CuSO₄(aq) → FeSO₄(aq) + Cu(s)

3 Ionic: Fe(s) + Cu²⁺(aq) → Fe²⁺(aq) + Cu(s)

✅ Observations: Iron nail coated in pink/brown copper. Blue solution fades; pale green FeSO₄ solution forms.
Question 2 — Brine Electrolysis
For electrolysis of concentrated NaCl (brine) with inert electrodes: (a) name ions present, (b) write half-equations at each electrode, (c) explain why Cl₂ not O₂ forms at the anode.
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a Ions present: Na⁺(aq), Cl⁻(aq), H⁺(aq), OH⁻(aq)

b Cathode: 2H⁺(aq) + 2e⁻ → H₂(g)
Anode: 2Cl⁻(aq) → Cl₂(g) + 2e⁻

c Although OH⁻ is lower in the anion series, in concentrated NaCl the Cl⁻ concentration is very high. The concentration factor overrides position — Cl⁻ is preferentially discharged.

✅ Electrolyte becomes alkaline as NaOH forms (Na⁺ + OH⁻ remain in solution).
Question 3 — Faraday Calculation
A current of 3.0 A flows for 40 minutes through CuSO₄ with copper electrodes. (a) Calculate Q. (b) Find moles of Cu deposited. (c) Find mass of Cu. (d) What happens at the anode?
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a t = 40 × 60 = 2400 s. Q = 3.0 × 2400 = 7200 C

b Half-equation: Cu²⁺ + 2e⁻ → Cu (2 mol e⁻ per mol Cu)
n(Cu) = 7200 ÷ (2 × 96500) = 0.0373 mol

c m(Cu) = 0.0373 × 63.5 = 2.37 g

d Active copper anode dissolves: Cu(s) → Cu²⁺(aq) + 2e⁻. Solution colour stays constant as Cu²⁺ is replenished.

✅ (a) 7200 C (b) 0.0373 mol (c) 2.37 g (d) Anode Cu dissolves; solution unchanged.
Question 4 — Aluminium Extraction
Why can't Al be extracted by carbon reduction? Describe how it is extracted industrially with electrode equations.
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1 Al is very high in the electrochemical series. Its Al³⁺ ions are so stable that carbon (coke) cannot reduce them — C is not a strong enough reducing agent.

2 Al is extracted by electrolysis of molten Al₂O₃ (bauxite) dissolved in molten cryolite (which lowers the melting point from ~2000°C to ~950°C).

3 Cathode: Al³⁺(l) + 3e⁻ → Al(l) [molten Al sinks]
Anode: 2O²⁻(l) → O₂(g) + 4e⁻ [O₂ attacks graphite → CO₂ → anodes corrode and must be replaced]

✅ Hall–Héroult process. Cryolite lowers melting point. Graphite anodes replaced regularly due to oxidation.
Question 5 — Inert vs Active Electrodes
Describe the difference when CuSO₄ is electrolysed with (a) graphite electrodes vs (b) copper electrodes. What happens to the blue colour each time?
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a Graphite (inert): Anode: 4OH⁻ → O₂ + 2H₂O + 4e⁻ [O₂ evolved]. Cathode: Cu²⁺ + 2e⁻ → Cu [pink deposits]. Cu²⁺ removed but not replaced → solution gets paler blue.

b Copper (active): Anode: Cu → Cu²⁺ + 2e⁻ [anode dissolves]. Cathode: Cu²⁺ + 2e⁻ → Cu [pink deposits]. Cu²⁺ consumed = Cu²⁺ produced → solution colour stays the same.

✅ Inert: blue fades (Cu²⁺ decreasing). Active: colour unchanged (Cu²⁺ constant). Active electrode = basis of electroplating and electrorefining.