Mistake Master
Home Unit 9 · Applications of Thermodynamics 9.1·9.2·9.3·9.4·9.5·9.6·9.7·9.8·9.9·9.10·9.11 Lesson
Skill Check 0 / 10 complete

Galvanic and electrolytic cells

An electrochemical cell splits a redox reaction in two and makes the electrons travel through a wire to get from one half to the other. Which way they travel — and whether they need a push — is the whole story.

§1

Two cells, one set of rules.

A cell separates a redox reaction into two half-reactions at two electrodes. A galvanic (voltaic) cell runs a spontaneous reaction (ΔG < 0) to produce electrical energy; an electrolytic cell uses an external power source to drive a nonspontaneous one (ΔG > 0).

In both, the rules for the electrodes are the same: oxidation happens at the anode, reduction at the cathode ("an ox, red cat"). Electrons flow through the external wire from anode to cathode.

The salt bridge carries ions, not electrons, to keep each half-cell electrically neutral. Electrons never travel through the salt bridge — they go through the wire.

UNIT 9 TOPIC 9.8 • GALVANIC AND ELECTROLYTIC CELLS GALVANIC AND ELECTROLYTIC CELLS GALVANIC (VOLTAIC) CELL Spontaneous · ΔG < 0 · E°cell > 0 chemical energy → electrical energy V e⁻ flow salt bridge anions ← | → cations Zn Cu Zn²⁺ Cu²⁺ ANODE (−) CATHODE (+) oxidation (anode): Zn(s) → Zn²⁺(aq) + 2e⁻ reduction (cathode): Cu²⁺(aq) + 2e⁻ → Cu(s) Anions (Cl⁻) migrate toward the anode. Cations (K⁺) migrate toward the cathode. COMPARISON GALVANIC ELECTROLYTIC Spontaneity Spontaneous Nonspontaneous Thermodynamics ΔG < 0, E° > 0 ΔG > 0, E° < 0 Energy change chem → elec elec → chem Driven by itself (redox) external source Terminals anode −, cath + anode +, cath − Net result makes voltage needs voltage ELECTROLYTIC CELL Nonspontaneous · ΔG > 0 · E°cell < 0 electrical energy → chemical energy + e⁻ e⁻ power source electrolyte: NaCl(aq) ANODE (+) CATHODE (−) oxidation (anode): 2Cl⁻(aq) → Cl₂(g) + 2e⁻ reduction (cathode): 2H₂O(l) + 2e⁻ → H₂(g) + 2OH⁻(aq) Anions (Cl⁻) migrate toward the anode (+). Cations (Na⁺) migrate toward the cathode (−). KEY IDEAS e⁻: anode → cathode external circuit, both cells Anode = oxidation Cathode = reduction (always) Ions balance charge cations→cathode, anions→anode Voltage galvanic out, electrolytic in AP Chemistry · Unit 9 · Applications of Thermodynamics
Fig. 9.8.1 A galvanic cell makes electricity from a spontaneous reaction; an electrolytic cell drives a nonspontaneous one with a power source. In both, oxidation is at the anode and reduction at the cathode; electrons flow through the wire (anode → cathode), ions through the salt bridge.
§2

Wiring the cell.

Assign each role, then route the charge.

  1. Split the redox reaction. One half-reaction oxidizes, the other reduces.
  2. Assign the electrodes. Oxidation at the anode, reduction at the cathode (in both cell types).
  3. Route the electrons. Through the external wire, from anode to cathode.
  4. Route the ions. Through the salt bridge, to keep each half-cell neutral.
  5. Check for a power source. Galvanic runs on its own; electrolytic needs an external supply.
§3

The pieces you'll meet.

The parts of an electrochemical cell.

galvanic
Galvanic cell
Spontaneous; makes electrical energy.
electrolytic
Electrolytic cell
Nonspontaneous; needs a power source.
anode
Anode
Where oxidation occurs.
cathode
Cathode
Where reduction occurs.
wire
External wire
Carries electrons, anode → cathode.
bridge
Salt bridge
Carries ions, not electrons.
§4

Worked example: tracing a galvanic cell.

Anode. The metal being oxidized (losing electrons) is the anode — say Zn → Zn²⁺ + 2e⁻.

Cathode. The reduction half (gaining electrons) is the cathode — say Cu²⁺ + 2e⁻ → Cu.

Electrons. Flow through the external wire from the Zn anode to the Cu cathode.

Ions. The salt bridge lets ions migrate to balance charge; no electrons pass through it. Because the reaction is spontaneous, no power source is needed — this is galvanic.

§5

Mistakes that cost real points.

Pitfall · 01

"Electrons travel through the salt bridge."

Electrons flow through the external wire; the salt bridge carries ions to keep the half-cells neutral. Routing electrons through the salt bridge misrepresents how the circuit works — the wire is the electron path.

Fix. Send electrons through the wire and ions through the salt bridge.

Pitfall · 02

"Reduction happens at the anode."

Oxidation happens at the anode and reduction at the cathode, in both galvanic and electrolytic cells ("an ox, red cat"). Swapping the electrode roles reverses the entire analysis. Anode = oxidation, cathode = reduction.

Fix. Fix the roles: oxidation at the anode, reduction at the cathode.

Pitfall · 03

"An electrolytic cell runs on its own, like a battery."

An electrolytic cell drives a nonspontaneous reaction (ΔG > 0), so it requires an external power source to push the electrons. Only a galvanic cell runs spontaneously. Assuming electrolysis is self-driving misses the required power supply.

Fix. Remember electrolytic cells need an external power source; only galvanic cells are spontaneous.

§6

Skill Check.

Ten scenarios. Pick the chips that match your answer, then check. A scenario marks complete the first time every part is right. Progress saves on this device.

0 of 10 scenarios complete