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Eduqas A-level Chemistry (A410QS) · PI1 — Electrochemistry
Mini-Lesson

PI1 · Electrochemistry

Eduqas PI1 puts numbers on redox. You will assign oxidation numbers, build half-equations, measure standard electrode potentials against the hydrogen electrode, calculate cell and use it to judge feasibility — then apply it to fuel cells and redox titrations.

oxidation numbers E° and feasibility cells + titrations electrons moved, and how hard they push

Work through each screen, answer every question as you go — the multiple-choice checks, the calculations and the sorting games — and collect ⭐ stars. Press Start when you are ready.

PI1 · oxidation numbers

Oxidation numbers

Rules, applied in order of priority:

  • Uncombined element = 0. Simple ion = its charge.
  • Group 1 = +1; Group 2 = +2; F = −1 always.
  • H = +1 (but −1 in metal hydrides such as NaH).
  • O = −2 (but −1 in peroxides, and +2 in F₂O).
  • The sum equals 0 for a neutral compound, or the overall charge for an ion.
Worked example — sulfur in SO₄²⁻

x + 4(−2) = −2 → x − 8 = −2 → x = +6

Oxidation = loss of electrons = oxidation number increases. Reduction = gain = oxidation number decreases. An oxidising agent is itself reduced.

Calculate

Your turn — manganate(VII)

1What is the oxidation number of manganese in the manganate(VII) ion, MnO₄⁻ ?
(sign + number)
Hint: x + 4(−2) = −1, so x − 8 = −1.
Calculate

Your turn — dichromate(VI)

2What is the oxidation number of chromium in the dichromate(VI) ion, Cr₂O₇²⁻ ?
(sign + number)
Hint: 2x + 7(−2) = −2, so 2x − 14 = −2 and 2x = 12.
PI1 · half-equations

Building half-equations in acid

Balance a half-equation in this order — O, H, charge:

  • Balance the element being oxidised or reduced.
  • Balance O by adding H₂O.
  • Balance H by adding H⁺.
  • Balance the charge by adding electrons.
MnO₄⁻ + 8H⁺ + 5e⁻ → Mn²⁺ + 4H₂OO: 4 = 4 · H: 8 = 8 · charge: (−1) + (+8) + (−5) = +2 = the charge on Mn²⁺ ✓
Cr₂O₇²⁻ + 14H⁺ + 6e⁻ → 2Cr³⁺ + 7H₂OO: 7 = 7 · H: 14 = 14 · charge: (−2) + (+14) + (−6) = +6 = 2 × (+3) ✓

To combine two half-equations, scale them so the electrons cancel, then add.

Quick check

Check the half-equation

?Which is the correctly balanced half-equation for the reduction of MnO₄⁻ to Mn²⁺ in acid?
PI1 · electrode potentials

Standard electrode potentials

Every half-cell has an electrode potential, but you can only ever measure a difference. So all values are quoted against the standard hydrogen electrode (SHE), defined as exactly 0.00 V.

Standard conditions: 298 K, 100 kPa, all solutions at 1.00 mol dm⁻³, and an inert platinum electrode where there is no metal (e.g. for Fe³⁺/Fe²⁺).

Zn(s) | Zn²⁺(aq) ‖ Cu²⁺(aq) | Cu(s)cell notation: oxidation on the left, reduction on the right; ‖ is the salt bridge

A more negative E° means the system sits further to the left — it releases electrons more readily, so it is the better reducing agent. A more positive E° means it is the better oxidising agent.

PI1 · E cell

Calculating E°cell

cell = E°(reduced, positive electrode) − E°(oxidised, negative electrode)equivalently E°(right-hand electrode) − E°(left-hand electrode)
Worked example — the Daniell cell

Zn²⁺ + 2e⁻ ⇌ Zn, E° = −0.76 V · Cu²⁺ + 2e⁻ ⇌ Cu, E° = +0.34 V

Copper has the more positive E°, so copper is reduced and zinc is oxidised.

cell = (+0.34) − (−0.76) = +1.10 V

Never multiply an E° value by the number of electrons. E° is an intensive property — doubling the half-equation does not double the voltage.

Calculate

Your turn — E°cell

3Calculate E°cell for a cell made from Mg²⁺/Mg (E° = −2.37 V) and Ag⁺/Ag (E° = +0.80 V). Give the value for the spontaneous (feasible) direction.
V
Hint: silver has the more positive E°, so it is reduced. E°cell = (+0.80) − (−2.37).
Calculate

Your turn — a redox pair

4MnO₄⁻/Mn²⁺ has E° = +1.51 V and Fe³⁺/Fe²⁺ has E° = +0.77 V. Calculate E°cell when manganate(VII) oxidises iron(II).
V
Hint: MnO₄⁻ is reduced (more positive E°), so E°cell = (+1.51) − (+0.77).
Quick check

Is it feasible?

?What does a positivecell tell you about a reaction?
Sort it

Rank the redox systems

Tap a half-cell, then the box that describes it. Look only at the sign and size of E°.

💪 Powerful oxidising agent (E° > +1.0 V)

⚖️ Moderate oxidising agent (0 to +1.0 V)

🔋 Reducing agent (E° negative)

PI1 · limitations

The limitations of E° predictions

cell tells you whether a reaction can go, never whether it will. Three big caveats:

  • Kinetics: a large activation energy can make a feasible reaction immeasurably slow. Thermodynamics is silent about rate.
  • Non-standard conditions: real concentrations are rarely 1.00 mol dm⁻³, and changing them shifts the electrode potential (Le Chatelier applied to the half-cell equilibrium).
  • Temperature: E° values are only valid at 298 K.

The classic example: the oxidation of glucose by oxygen has a hugely positive E°cell, but sugar sits happily in a bowl for years — the activation energy is far too high without an enzyme.

Quick check

Feasible but nothing happens

?A reaction has E°cell = +1.20 V, yet no reaction is observed when the reagents are mixed at room temperature. What is the most likely explanation?
PI1 · fuel cells

Cells, batteries and fuel cells

In a hydrogen–oxygen fuel cell the reactants are fed in continuously, so it never goes flat.

In alkaline conditions:

Negative electrode: H₂ + 2OH⁻ → 2H₂O + 2e⁻
Positive electrode: ½O₂ + H₂O + 2e⁻ → 2OH⁻negative electrode charge: (−2) on the left = (−2) on the right ✓ · positive electrode: O 1 + 1 = 2 · H 2 = 2 · charge (−2) = (−2) ✓
Overall: 2H₂ + O₂ → 2H₂OH: 4 = 4 · O: 2 = 2 — the only product is water
  • Advantages: the only product is water; higher efficiency than a combustion engine; no CO₂ at the point of use.
  • Drawbacks: hydrogen is hard to store and transport; it is usually made from methane or by electrolysis, so the CO₂ may simply be moved elsewhere; expensive catalysts are needed.
Quick check

The fuel cell equation

?What is the overall equation for a hydrogen–oxygen fuel cell?
PI1 · redox titrations

Redox titrations

Manganate(VII) titrations are self-indicating: MnO₄⁻ is deep purple and Mn²⁺ is almost colourless, so the end point is the first permanent pale pink.

MnO₄⁻ + 8H⁺ + 5Fe²⁺ → Mn²⁺ + 4H₂O + 5Fe³⁺charge: (−1) + (+8) + (+10) = +17 · right: (+2) + (+15) = +17 ✓ — the ratio is 1 : 5

Acidify with dilute sulfuric acid — never with HCl (Cl⁻ would be oxidised to Cl₂) and never with nitric acid (it is itself an oxidising agent).

Iodine–thiosulfate titrations use starch, added near the end point, which turns blue-black then colourless:

I₂ + 2S₂O₃²⁻ → 2I⁻ + S₄O₆²⁻the ratio is 1 I₂ : 2 thiosulfate
Calculate

Your turn — manganate(VII) titration

525.0 cm³ of an Fe²⁺ solution needed 21.6 cm³ of 0.0200 mol dm⁻³ KMnO₄ for the first permanent pink. Using the 1 : 5 ratio, calculate the concentration of the Fe²⁺, to 3 significant figures.
mol dm⁻³
Hint: n(MnO₄⁻) = 0.0216 × 0.0200 = 4.32 × 10⁻⁴ mol. n(Fe²⁺) = 5 × that = 2.16 × 10⁻³ mol. Then ÷ 0.0250 dm³.
Calculate

Your turn — iodine and thiosulfate

6The iodine liberated in a flask needed 24.0 cm³ of 0.100 mol dm⁻³ sodium thiosulfate. Using I₂ + 2S₂O₃²⁻ → 2I⁻ + S₄O₆²⁻, calculate the amount of I₂ present, in millimoles (mmol).
mmol
Hint: n(S₂O₃²⁻) = 0.0240 × 0.100 = 2.40 × 10⁻³ mol = 2.40 mmol. The ratio is 2 : 1, so halve it.
Match it

Electrochemistry vocabulary

Tap a definition on the left, then the term on the right.

Definition
Term
Recap

The big ideas to know

Oxidation numbers: sum to 0 (compound) or to the charge (ion); O = −2, H = +1 (with exceptions)

Half-equations: balance O with H₂O, H with H⁺, then charge with electrons

E° values: measured against the SHE (0.00 V) at 298 K, 100 kPa, 1.00 mol dm⁻³

E°cell: E°(reduced) − E°(oxidised). Never multiply E° by the number of electrons

Feasibility: positive E°cell means feasible (ΔG negative) — but says NOTHING about rate

Fuel cells: 2H₂ + O₂ → 2H₂O; only water at the point of use

Titrations: MnO₄⁻/Fe²⁺ is 1 : 5, self-indicating, acidify with dilute H₂SO₄ · I₂/thiosulfate is 1 : 2

That is the whole of PI1. Press Finish to see your score.

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