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Part of PC-07 — Redox Reactions & Electrochemistry

Master Reference — Electrochemistry Core Concepts

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Cue Column | Note Column

What is a galvanic cell? | Spontaneous electrochemical cell (ΔG\Delta G < 0, E°cell > 0). Chemical energy → Electrical energy. Anode is NEGATIVE, cathode is POSITIVE.

What is an electrolytic cell? | Non-spontaneous cell requiring external power (ΔG\Delta G > 0). Electrical energy → Chemical energy. Anode is POSITIVE, cathode is NEGATIVE.

E°cell formula? | E°cell = E°cathode − E°anode (always cathode MINUS anode)

Nernst equation at 25°C? | E=E0.0592nlogQE = E^\circ - \frac{0.0592}{n}\log Q

At equilibrium? | E = 0, Q = K, therefore: E=0.0592nlogKE^\circ = \frac{0.0592}{n}\log K

ΔG\Delta G° and E°cell? | ΔG=nFE\Delta G^\circ = -nFE^\circ where F = 96500 C/mol

Faraday's law? | w=MItnFw = \frac{MIt}{nF} where M = molar mass, I = current (A), t = time (s), n = electrons

Molar conductivity? | Λm=κ×1000M\Lambda_m = \frac{\kappa \times 1000}{M} units: S·cm2cm^{2}/mol

Kohlrausch's law? | Λm=ν+λ++νλ\Lambda^\circ_m = \nu_+ \lambda^\circ_+ + \nu_- \lambda^\circ_-

Degree of dissociation? | α=ΛmΛm\alpha = \frac{\Lambda_m}{\Lambda^\circ_m}

Corrosion? | Anode (anodic spot): Fe → Fe2+Fe^{2+} + 2ee^{-}; Cathode: O2O_{2} + $2H_{2}O+4 + 4e^{-}4 → 4OH^{-}Rust:→ Rust:Fe_{2}O_{3}x·xH_{2}O$

Summary

The core equations are: E°cell = E°cath − E°an; Nernst E = E° − (0.0592/n)log Q; ΔG\Delta G° = −nFE°; w = MIt/(nF). Galvanic = spontaneous (anode negative); Electrolytic = non-spontaneous (anode positive). In BOTH, oxidation is at anode, reduction at cathode.$

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