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Q.Explain Kohlrausch's law. If Λm∘\Lambda^{\circ}_m for NaCl, HCl and NaAc are 126.4, 425.9 and 91.0 S cm2^2 mol−1^{-1}. Calculate Λ∘\Lambda^{\circ} for HAc.

Uttar Pradesh UpmspUP Board (UPMSP) Intermediate 2026Subjective· 4mImportance★★★★★
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Kohlrausch's law: Λm∘\Lambda^{\circ}_m is the sum of separate ion conductivities. For acetic acid, Λ∘(HAc)=Λ∘(HCl)+Λ∘(NaAc)−Λ∘(NaCl)=390.5\Lambda^{\circ}(HAc) = \Lambda^{\circ}(HCl) + \Lambda^{\circ}(NaAc) - \Lambda^{\circ}(NaCl) = 390.5 S cm2^2 mol−1^{-1}.

Kohlrausch's law of independent migration of ions. At infinite dilution, when dissociation is complete, each ion migrates independently of the others and makes its own definite contribution to the total molar conductivity, irrespective of the nature of the ion it is paired with. Thus the limiting molar conductivity of an electrolyte is the sum of the limiting molar conductivities of its cation and anion:

Λm∘=u+ λ+∘+u− λ−∘\Lambda^{\circ}_m = u_+\,\lambda^{\circ}_+ + u_-\,\lambda^{\circ}_-

This allows Λm∘\Lambda^{\circ}_m of a weak electrolyte (like acetic acid, HAc), which cannot be found by extrapolation, to be calculated from strong-electrolyte values.

Calculation for acetic acid (HAc):

Λ∘(HAc)=λH+∘+λAc−∘\Lambda^{\circ}(HAc) = \lambda^{\circ}_{H^+} + \lambda^{\circ}_{Ac^-}

We can build this from the given strong electrolytes: …

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