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…
Single correct option
A concentration cell at 298K is set up as Ag∣AgX(s),NaX(0.10M)∥Ag+(0.10M)∣Ag, where AgX is a sparingly soluble salt. Its emf is 0.413V. Take F2.303RT=0.059V. The solubility product of AgX and its molar solubility in pure water are respectively
A.1.0×10−8,1.0×10−4M
B.1.0×10−9,3.2×10−5M
C.1.0×10−10,1.0×10−5M
D.1.0×10−16,1.0×10−8M
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Answer:(B) 1.0×10−9,3.2×10−5M
The left electrode has [Ag+] fixed by the solubility equilibrium, the right one has 0.10M. For a one-electron concentration cell E=0.059log[Ag+]L0.10. So log[Ag+]L0.10=0.0590.413=7.0, giving [Ag+]L=1.0×10−8M. In the left compartment [X−]=0.10M (from NaX; the contribution of AgX is negligible), hence Ksp=[Ag+][X−]=1.0×10−8×0.10=1.0×10−9. In pure water s=Ksp=10−9=3.2×10−5M. The option with Ksp=10−8 forgets the X− concentration (and then takes s=Ksp); the other two pairs do not fit the measured emf. Note that the concentration cell has E∘=0, so only the ratio of the two silver ion concentrations matters and no standard potential data are needed.