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Practical Chemistry

JEE Main · Chemistry · Practical Chemistry

A student is given an aqueous mixture containing Fe^ 3+ and Mg^ 2+...

A student is given an aqueous mixture containing Fe3+\mathrm{Fe}^{3+} and Mg2+\mathrm{Mg}^{2+} ions. Upon adding solid NH4Cl\mathrm{NH_4Cl} followed by excess NH4OH\mathrm{NH_4OH} solution, a brown precipitate forms, but Mg2+\mathrm{Mg}^{2+} remains in the solution. The combined thermodynamic and equilibrium reason why Mg2+\mathrm{Mg}^{2+} does not precipitate under these specific conditions is that :

Options

  1. Athe common ion effect of NH4+\mathrm{NH_4^+} keeps [OH−][\mathrm{OH}^{-}] low, which fails to exceed the higher KspK_{\mathrm{sp}} of Mg(OH)2\mathrm{Mg(OH)_2}
  2. BMg(OH)2\mathrm{Mg(OH)_2} has a lower KspK_{\mathrm{sp}} than Fe(OH)3\mathrm{Fe(OH)_3}, preventing its precipitation in basic medium
  3. Cthe common ion effect of Cl−\mathrm{Cl}^{-} suppresses the dissociation of the mixture, preventing the precipitation of MgCl2\mathrm{MgCl_2}
  4. DMg2+\mathrm{Mg}^{2+} forms a highly soluble ammine complex [Mg(NH3)4]2+[\mathrm{Mg(NH_3)_4}]^{2+} with excess ammonia

Correct answer

A. the common ion effect of NH4+\mathrm{NH_4^+} keeps [OH−][\mathrm{OH}^{-}] low, which fails to exceed the higher KspK_{\mathrm{sp}} of Mg(OH)2\mathrm{Mg(OH)_2}

Step-by-step solution

Ammonium hydroxide (NH4OH\mathrm{NH_4OH}) is a weak base, and its ionization is suppressed by the addition of the strong electrolyte ammonium chloride (NH4Cl\mathrm{NH_4Cl}) due to the common ion effect of NH4+\mathrm{NH_4^+} ions.

NH4OH⇌NH4++OH−\mathrm{NH_4OH} \rightleftharpoons \mathrm{NH_4^+} + \mathrm{OH}^{-}
NH4Cl→NH4++Cl−\mathrm{NH_4Cl} \rightarrow \mathrm{NH_4^+} + \mathrm{Cl}^{-}

This suppression keeps the concentration of OH−\mathrm{OH}^{-} ions very low in the solution. The solubility product (KspK_{\mathrm{sp}})ofFe(OH)3of \mathrm{Fe(OH)_3} is much lower (around 10−3810^{-38}) compared to that of Mg(OH)2\mathrm{Mg(OH)_2} (around 10−1110^{-11}). The low [OH−][\mathrm{OH}^{-}] is sufficient to make the ionic product of Fe(OH)3\mathrm{Fe(OH)_3} exceed its KspK_{\mathrm{sp}}, leading to its precipitation. However, the ionic product of Mg(OH)2\mathrm{Mg(OH)_2} does not exceed its relatively higher KspK_{\mathrm{sp}}, so Mg2+\mathrm{Mg}^{2+} remains dissolved in the solution.

Answer: the common ion effect of NH4+\mathrm{NH_4^+} keeps [OH−][\mathrm{OH}^{-}] low, which fails to exceed the higher KspK_{\mathrm{sp}} of Mg(OH)2\mathrm{Mg(OH)_2}
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