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JEE Advanced 2016 Paper 1 · Chemistry · Electrochemistry · medium

A concentration cell at 298 K is set up as Ag | AgX(s), NaX (0.10 M) \| Ag^+ (0.10 M) | Ag, where AgX is a sparingly soluble salt. Its emf is 0.413…

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A concentration cell at 298 K298\ \mathrm{K} is set up as Ag ∣ AgX(s), NaX (0.10 M) ∥ Ag+ (0.10 M) ∣ Ag\mathrm{Ag\,|\,AgX(s),\ NaX\,(0.10\ M)\,\|\,Ag^{+}\,(0.10\ M)\,|\,Ag}, where AgX\mathrm{AgX} is a sparingly soluble salt. Its emf is 0.413 V0.413\ \mathrm{V}. Take 2.303RTF=0.059 V\dfrac{2.303RT}{F}=0.059\ \mathrm{V}. The solubility product of AgX\mathrm{AgX} and its molar solubility in pure water are respectively
  1. A. 1.0×10−8, 1.0×10−4 M1.0\times10^{-8},\ 1.0\times10^{-4}\ \mathrm{M}
  2. B. 1.0×10−9, 3.2×10−5 M1.0\times10^{-9},\ 3.2\times10^{-5}\ \mathrm{M}
  3. C. 1.0×10−10, 1.0×10−5 M1.0\times10^{-10},\ 1.0\times10^{-5}\ \mathrm{M}
  4. D. 1.0×10−16, 1.0×10−8 M1.0\times10^{-16},\ 1.0\times10^{-8}\ \mathrm{M}
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Answer: (B) 1.0×10−9, 3.2×10−5 M1.0\times10^{-9},\ 3.2\times10^{-5}\ \mathrm{M}

The left electrode has [Ag+][\mathrm{Ag^+}] fixed by the solubility equilibrium, the right one has 0.10 M0.10\ \mathrm{M}. For a one-electron concentration cell E=0.059log⁡0.10[Ag+]LE=0.059\log\dfrac{0.10}{[\mathrm{Ag^+}]_L}. So log⁡0.10[Ag+]L=0.4130.059=7.0\log\dfrac{0.10}{[\mathrm{Ag^+}]_L}=\dfrac{0.413}{0.059}=7.0, giving [Ag+]L=1.0×10−8 M[\mathrm{Ag^+}]_L=1.0\times10^{-8}\ \mathrm{M}. In the left compartment [X−]=0.10 M[\mathrm{X^-}]=0.10\ \mathrm{M} (from NaX; the contribution of AgX is negligible), hence Ksp=[Ag+][X−]=1.0×10−8×0.10=1.0×10−9K_{sp}=[\mathrm{Ag^+}][\mathrm{X^-}]=1.0\times10^{-8}\times0.10=1.0\times10^{-9}. In pure water s=Ksp=10−9=3.2×10−5 Ms=\sqrt{K_{sp}}=\sqrt{10^{-9}}=3.2\times10^{-5}\ \mathrm{M}. The option with Ksp=10−8K_{sp}=10^{-8} forgets the X−\mathrm{X^-} concentration (and then takes s=Ksps=\sqrt{K_{sp}}); the other two pairs do not fit the measured emf. Note that the concentration cell has E∘=0E^\circ=0, so only the ratio of the two silver ion concentrations matters and no standard potential data are needed.
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