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Part of PC-07 — Redox Reactions & Electrochemistry

Redox Reactions & Electrochemistry: Formula Reference Sheet

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Cell Potential

Standard cell EMF: Ecell∘=Ecathode∘−Eanode∘E^\circ_{cell} = E^\circ_{cathode} - E^\circ_{anode}

Nernst equation (general form): E=E∘−RTnFln⁡QE = E^\circ - \frac{RT}{nF}\ln Q

Nernst equation at 25°C (298 K): E=E∘−0.0592nlog⁡QE = E^\circ - \frac{0.0592}{n}\log Q

Note: 2.303RTF∣298K=2.303×8.314×29896485=0.05916≈0.0592 V\frac{2.303RT}{F}\bigg|_{298K} = \frac{2.303 \times 8.314 \times 298}{96485} = 0.05916 \approx 0.0592 \text{ V}

Equilibrium and Thermodynamics

At equilibrium (E = 0, Q = K): E∘=0.0592nlog⁡K⇔log⁡K=nE∘0.0592E^\circ = \frac{0.0592}{n}\log K \quad \Leftrightarrow \quad \log K = \frac{nE^\circ}{0.0592}

Gibbs energy and EMF: ΔG∘=−nFE∘\Delta G^\circ = -nFE^\circ ΔG=−nFE=ΔG∘+RTln⁡Q\Delta G = -nFE = \Delta G^\circ + RT\ln Q

Faraday constant: F=96485≈96500 C mol−1F = 96485 \approx 96500 \text{ C mol}^{-1}

Faraday's Laws

Mass deposited (Faraday's combined law): w=ZIt=MItnFw = ZIt = \frac{MIt}{nF}

Electrochemical equivalent: Z=MnF (g C−1)Z = \frac{M}{nF} \text{ (g C}^{-1}\text{)}

Charge = current × time: Qcharge=It (in Coulombs, t in seconds)Q_{charge} = It \text{ (in Coulombs, t in seconds)}

Conductance

Specific conductance: κ=1ρ=G×lA[S cm−1]\kappa = \frac{1}{\rho} = G \times \frac{l}{A} \quad [\text{S cm}^{-1}]

Molar conductivity: Λm=κ×1000M[S cm2mol−1]\Lambda_m = \frac{\kappa \times 1000}{M} \quad [\text{S cm}^2 \text{mol}^{-1}]

where M = molarity in mol/L.

Debye-Hückel-Onsager (strong electrolytes): Λm=Λm∘−AC\Lambda_m = \Lambda^\circ_m - A\sqrt{C}

Kohlrausch's law (limiting molar conductivity): Λm∘=ν+λ+∘+ν−λ−∘\Lambda^\circ_m = \nu_+\lambda^\circ_+ + \nu_-\lambda^\circ_-

Degree of dissociation (weak electrolytes): α=ΛmΛm∘\alpha = \frac{\Lambda_m}{\Lambda^\circ_m}

Acid dissociation constant from conductance: Ka=Cα21−α≈Cα2 (if α≪1)K_a = \frac{C\alpha^2}{1-\alpha} \approx C\alpha^2 \text{ (if } \alpha \ll 1\text{)}

Key Numerical Values

ConstantValue
Faraday constant F96500 C/mol
0.0592/n factor (n=1, 25°C)0.0592 V/decade
0.0592/n factor (n=2, 25°C)0.0296 V/decade
ΔG\Delta G° for Daniell cell−212.3 kJ/mol
log K for Daniell cell37.2

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