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Exercise · Q20

Q.For a strong electrolyte, Λm\Lambda_m is found to vary linearly with C\sqrt{C} (Debye-Huckel-Onsager behaviour: Λm=Λm0−AC\Lambda_m = \Lambda_m^{0} - A\sqrt{C}), while for a weak electrolyte it does not. Explain the physical reason behind this difference.

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The Debye-Huckel-Onsager equation, Λm=Λm0−AC\Lambda_m = \Lambda_m^{0} - A\sqrt{C}, is derived theoretically by modelling how the 'ionic atmosphere' around a moving ion distorts and retards it at a given ion concentration, and it is built on the explicit assumption that the number of ions per mole of electrolyte is fixed (i.e. dissociation is already complete) — only their mobility changes with concentration. This assumption is an excellent approximation for a strong electrolyte, which is indeed essentially fully ionized regardless of concentration, so its Λm\Lambda_m-vs-C\sqrt{C} data follows the predicted straight line closely. A weak electrolyte violates this core assumption: its degree of dissociation α\alpha is itself a strong, non-linear function of concentration, governed by its own dissociation equilibrium (the Ostwald dilution law, Ka=Cα2/(1−α)K_a = C\alpha^{2}/(1-\alpha) for a weak acid). Because the number of ions actually present changes dramatically and non-linearly with CC for a weak electrolyte, the mobility-only C\sqrt{C} relationship derived for …

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