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NEET CHEMISTRYHard

The KspK_{sp} of Ag2CrO4Ag_2CrO_4, AgClAgCl, AgBrAgBr and AgIAgI are, respectively, 1.1×10121.1 \times 10^{-12}, 1.8×10101.8 \times 10^{-10}, 5.0×10135.0 \times 10^{-13}, and 8.3×10178.3 \times 10^{-17}. The salt that precipitates last if AgNO3AgNO_3 solution is added to the solution containing equal moles of NaClNaCl, NaBrNaBr, NaINaI and Na2CrO4Na_2CrO_4 is:

A

AgIAgI

B

AgClAgCl

C

AgBrAgBr

D

Ag2CrO4Ag_2CrO_4

Step-by-Step Solution

Let the concentration of ClCl^-, BrBr^-, II^-, and CrO42CrO_4^{2-} be cc. The concentration of Ag+Ag^+ required to precipitate each salt is calculated as follows: For AgClAgCl: [Ag+]=Ksp[Cl]=1.8×1010c[Ag^+] = \frac{K_{sp}}{[Cl^-]} = \frac{1.8 \times 10^{-10}}{c} For AgBrAgBr: [Ag+]=Ksp[Br]=5.0×1013c[Ag^+] = \frac{K_{sp}}{[Br^-]} = \frac{5.0 \times 10^{-13}}{c} For AgIAgI: [Ag+]=Ksp[I]=8.3×1017c[Ag^+] = \frac{K_{sp}}{[I^-]} = \frac{8.3 \times 10^{-17}}{c} For Ag2CrO4Ag_2CrO_4: [Ag+]=Ksp[CrO42]=1.1×1012c[Ag^+] = \sqrt{\frac{K_{sp}}{[CrO_4^{2-}]}} = \sqrt{\frac{1.1 \times 10^{-12}}{c}} Assuming c=0.1 Mc = 0.1\text{ M} for comparison: [Ag+][Ag^+] for AgI=8.3×1016 MAgI = 8.3 \times 10^{-16}\text{ M} [Ag+][Ag^+] for AgBr=5.0×1012 MAgBr = 5.0 \times 10^{-12}\text{ M} [Ag+][Ag^+] for AgCl=1.8×109 MAgCl = 1.8 \times 10^{-9}\text{ M} [Ag+][Ag^+] for Ag2CrO4=1.1×10113.32×106 MAg_2CrO_4 = \sqrt{1.1 \times 10^{-11}} \approx 3.32 \times 10^{-6}\text{ M} The salt that requires the highest concentration of Ag+Ag^+ to exceed its ionic product over KspK_{sp} will precipitate last. Here, Ag2CrO4Ag_2CrO_4 requires the maximum [Ag+][Ag^+], so it will precipitate last.

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