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Q.(a) Conductivity of 2×10−32 \times 10^{-3} M methanoic acid is 8×10−58 \times 10^{-5} S cm−1^{-1}. Calculate its molar conductivity and degree of dissociation if Λm∘\Lambda^\circ_m for methanoic acid is 404 S cm2^2 mol−1^{-1}. (3 + 2)

(b) Calculate the ΔrG∘\Delta_rG^\circ and log KcK_c for the given reaction at 298 K : Ni(s)+2Ag+(aq)→Ni2+(aq)+2Ag(s)Ni(s) + 2Ag^+(aq) \rightarrow Ni^{2+}(aq) + 2Ag(s) Given : ENi2+/Ni∘=−0.25E^\circ_{Ni^{2+}/Ni} = -0.25 V, EAg+/Ag∘=+0.80E^\circ_{Ag^+/Ag} = +0.80 V 1F=965001F = 96500 C mol−1^{-1}.
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For part (a), we use the relation between conductivity and molar conductivity to find Λm\Lambda_m, then compare it with Λm∘\Lambda_m^\circ to get the degree of dissociation α\alpha. For part (b), we compute the standard cell potential, then use ΔrG∘=−nFEcell∘\Delta_r G^\circ = -nFE^\circ_{cell} and ΔrG∘=−2.303RTlog⁡Kc\Delta_r G^\circ = -2.303RT \log K_c to find ΔrG∘\Delta_r G^\circ and log⁡Kc\log K_c.

Part (a) — Methanoic acid conductivity

Concept first: Molar conductivity Λm\Lambda_m tells us how well a solution conducts electricity per mole of electrolyte. It is directly linked to the measured conductivity κ\kappa (kappa) by:

Λm=κ×1000C\Lambda_m = \frac{\kappa \times 1000}{C}

where CC is concentration in mol L−1^{-1}. The factor 1000 converts cm3^3 to L, because conductivity is in S cm−1^{-1} and we want Λm\Lambda_m in S cm2^2 mol−1^{-1}.

For a weak acid like methanoic acid, the degree of dissociation α\alpha is the fraction of molecules that have ionised. At a given concentration, the measured molar conductivity Λm\Lambda_m is less than the limiting molar conductivity Λm∘\Lambda_m^\circ (at infinite dilution) because not all molecules are dissociated. For weak electrolytes, Kohlrausch’s law gives:

α=ΛmΛm∘\alpha = \frac{\Lambda_m}{\Lambda_m^\circ}

Watch out

This relation α=Λm/Λm∘\alpha = \Lambda_m / \Lambda_m^\circ holds strictly only for weak electrolytes. For strong electrolytes, Λm\Lambda_m changes with concentration due to interionic attractions, not just dissociation — so this formula is not used there.

Step-by-step:

  1. Given data:

    κ=8×10−5\kappa = 8 \times 10^{-5} S cm−1^{-1}

    C=2×10−3C = 2 \times 10^{-3} M = 2×10−32 \times 10^{-3} mol L−1^{-1}

    Λm∘=404\Lambda_m^\circ = 404 S cm2^2 mol−1^{-1}

  2. Calculate molar conductivity Λm\Lambda_m:

Λm=κ×1000C=8×10−5×10002×10−3\Lambda_m = \frac{\kappa \times 1000}{C} = \frac{8 \times 10^{-5} \times 1000}{2 \times 10^{-3}}

Simplify stepwise:

8×10−5×1000=8×10−28 \times 10^{-5} \times 1000 = 8 \times 10^{-2}

Divide by 2×10−32 \times 10^{-3}:

Λm=8×10−22×10−3=4×101=40 S cm2 mol−1\Lambda_m = \frac{8 \times 10^{-2}}{2 \times 10^{-3}} = 4 \times 10^{1} = 40 \text{ S cm}^2 \text{ mol}^{-1}

  1. Calculate degree of dissociation α\alpha:

α=ΛmΛm∘=40404\alpha = \frac{\Lambda_m}{\Lambda_m^\circ} = \frac{40}{404}

Simplify:

α=0.0990(approximately 0.099)\alpha = 0.0990 \quad (\text{approximately } 0.099)

In percentage terms, about 9.9% dissociation.

Tip

Notice that Λm\Lambda_m (40) is much smaller than Λm∘\Lambda_m^\circ (404) — this is typical for a weak acid. The low α\alpha (~0.1) confirms methanoic acid is weakly dissociated at this concentration.


Part (b) — ΔrG∘\Delta_r G^\circ and log⁡Kc\log K_c for the cell reaction

Concept first: For any electrochemical cell, the standard Gibbs free energy change is related to the standard cell potential by:

ΔrG∘=−nFEcell∘\Delta_r G^\circ = -nFE^\circ_{cell}

where nn is the number of moles of electrons transferred in the balanced reaction, FF is Faraday’s constant (96500 C mol−1^{-1}), and Ecell∘E^\circ_{cell} is the standard cell potential.

The equilibrium constant KcK_c is related to ΔrG∘\Delta_r G^\circ via:

ΔrG∘=−2.303RTlog⁡Kc\Delta_r G^\circ = -2.303 RT \log K_c

At 298 K, 2.303RT=2.303×8.314×298≈57102.303 RT = 2.303 \times 8.314 \times 298 \approx 5710 J mol−1^{-1} (or 5.71 kJ mol−1^{-1}). Often we use the form:

log⁡Kc=nEcell∘0.0591(at 298 K, with E∘ in volts)\log K_c = \frac{n E^\circ_{cell}}{0.0591} \quad \text{(at 298 K, with } E^\circ \text{ in volts)}

because 2.303RTF=0.0591 \frac{2.303 RT}{F} = 0.0591 V at 298 K.

Step-by-step:

  1. Identify half-reactions and nn: Anode (oxidation): Ni(s)→Ni2+(aq)+2e−\text{Ni}(s) \rightarrow \text{Ni}^{2+}(aq) + 2e^- Cathode (reduction): 2Ag+(aq)+2e−→2Ag(s)2\text{Ag}^+(aq) + 2e^- \rightarrow 2\text{Ag}(s) Overall: Ni(s)+2Ag+(aq)→Ni2+(aq)+2Ag(s)\text{Ni}(s) + 2\text{Ag}^+(aq) \rightarrow \text{Ni}^{2+}(aq) + 2\text{Ag}(s) Number of electrons transferred: n=2n = 2. …

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