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Salt Analysis question

2011 · Shift 1 · Q19
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Salt Analysis question

2011 · Shift 1 · Q19

JEE AdvancedChemistrySalt AnalysisMCQ+3 / −1
When a metal rod M is dipped into an aqueous colourless concentrated solution of compound N, the solution turns light blue. Addition of aqueous NaClNaClNaCl to the blue solution gives a white precipitate O. Addition of aqueous NH3NH_3NH3​ dissolves O and gives an intense blue solution.The compound N is
  1. A
    AgNO3AgNO_3AgNO3​
  2. B
    Zn(NO3)2Zn(NO_3)_2Zn(NO3​)2​
  3. C
    Al(NO3)3Al(NO_3)_3Al(NO3​)3​
  4. D
    Pb(NO3)2Pb(NO_3)_2Pb(NO3​)2​
View written solutionFree

Correct answer: A

Step-by-Step Solution:

  1. Analyze the first observation: A metal rod M is dipped into a colorless concentrated solution of compound N, and the solution turns light blue.

    • The light blue color in aqueous solution is characteristic of the hydrated copper(II) ion, [Cu(H2O)6]2+[Cu(H_2O)_6]^{2+}[Cu(H2​O)6​]2+. This strongly suggests that the metal rod M is copper (Cu) and it gets oxidized to Cu2+Cu^{2+}Cu2+ ions.
    • For this reaction to occur, the metal M (Copper) must be more reactive than the metal cation present in compound N. The reaction is a displacement reaction: M(s)+[cationextfromN]n+(aq)→Mm+(aq)+[metalextfromN](s)M(s) + [cation ext{ from } N]^{n+}(aq) \rightarrow M^{m+}(aq) + [metal ext{ from } N](s)M(s)+[cationextfromN]n+(aq)→Mm+(aq)+[metalextfromN](s) Assuming M is Cu, the reaction is: Cu(s)+[cationextfromN]n+(aq)→Cu2+(aq)+[metalextfromN](s)Cu(s) + [cation ext{ from } N]^{n+}(aq) \rightarrow Cu^{2+}(aq) + [metal ext{ from } N](s)Cu(s)+[cationextfromN]n+(aq)→Cu2+(aq)+[metalextfromN](s)
    • Let's examine the options based on the reactivity series (or standard electrode potentials). Copper can displace metals that are less reactive than it. The relevant part of the reactivity series is: ...>Pb>H>Cu>Ag>...... > Pb > H > Cu > Ag > ......>Pb>H>Cu>Ag>....
      • A: AgNO3AgNO_3AgNO3​: Silver (AgAgAg) is less reactive than copper (CuCuCu). So, CuCuCu can displace AgAgAg from AgNO3AgNO_3AgNO3​ solution. The reaction is spontaneous. Cu(s)+2Ag+(aq)→Cu2+(aq)+2Ag(s)Cu(s) + 2Ag^+(aq) \rightarrow Cu^{2+}(aq) + 2Ag(s)Cu(s)+2Ag+(aq)→Cu2+(aq)+2Ag(s)
      • B: Zn(NO3)2Zn(NO_3)_2Zn(NO3​)2​: Zinc (ZnZnZn) is more reactive than CuCuCu. No reaction.
      • C: Al(NO3)3Al(NO_3)_3Al(NO3​)3​: Aluminum (AlAlAl) is more reactive than CuCuCu. No reaction.
      • D: Pb(NO3)2Pb(NO_3)_2Pb(NO3​)2​: Lead (PbPbPb) is more reactive than CuCuCu. No reaction.
    • Based on the first observation alone, compound N must be AgNO3AgNO_3AgNO3​.
  2. Analyze the second observation: Addition of aqueous NaClNaClNaCl to the blue solution gives a white precipitate O.

    • The blue solution contains Cu(NO3)2Cu(NO_3)_2Cu(NO3​)2​ and possibly unreacted AgNO3AgNO_3AgNO3​ (since the initial solution was concentrated). So, the ions present are Cu2+Cu^{2+}Cu2+, Ag+Ag^+Ag+, and NO3−NO_3^-NO3−​.
    • When NaClNaClNaCl is added, Na+Na^+Na+ and Cl−Cl^-Cl− ions are introduced.
    • The possible precipitates are AgClAgClAgCl and CuCl2CuCl_2CuCl2​. CuCl2CuCl_2CuCl2​ is soluble in water. AgClAgClAgCl is a well-known white precipitate. Ag+(aq)+Cl−(aq)→AgCl(s) (white precipitate O)Ag^+(aq) + Cl^-(aq) \rightarrow AgCl(s) \text{ (white precipitate O)}Ag+(aq)+Cl−(aq)→AgCl(s) (white precipitate O)
    • This observation is consistent with the solution containing Ag+Ag^+Ag+ ions, which confirms that N is AgNO3AgNO_3AgNO3​.
  3. Analyze the third observation: Addition of aqueous NH3NH_3NH3​ dissolves O and gives an intense blue solution.

    • This observation involves two simultaneous reactions.
    • First, the white precipitate O (AgClAgClAgCl) dissolves in aqueous ammonia to form a soluble, colorless complex, diamminesilver(I) chloride. AgCl(s)+2NH3(aq)→[Ag(NH3)2]+(aq)+Cl−(aq)AgCl(s) + 2NH_3(aq) \rightarrow [Ag(NH_3)_2]^+(aq) + Cl^-(aq)AgCl(s)+2NH3​(aq)→[Ag(NH3​)2​]+(aq)+Cl−(aq)
    • Second, the light blue Cu2+Cu^{2+}Cu2+ ions in the solution react with aqueous ammonia to form the tetraamminecopper(II) complex ion, [Cu(NH3)4]2+[Cu(NH_3)_4]^{2+}[Cu(NH3​)4​]2+, which has a characteristic deep, intense blue color. Cu2+(aq)+4NH3(aq)→[Cu(NH3)4]2+(aq) (intense blue solution)Cu^{2+}(aq) + 4NH_3(aq) \rightarrow [Cu(NH_3)_4]^{2+}(aq) \text{ (intense blue solution)}Cu2+(aq)+4NH3​(aq)→[Cu(NH3​)4​]2+(aq) (intense blue solution)
    • This final observation perfectly matches the expected reactions for a system containing both Ag+Ag^+Ag+ and Cu2+Cu^{2+}Cu2+ ions.

Conclusion:

All three observations consistently point to compound N being AgNO3AgNO_3AgNO3​. The metal M is Cu. The precipitate O is AgClAgClAgCl. The intense blue color is due to the [Cu(NH3)4]2+[Cu(NH_3)_4]^{2+}[Cu(NH3​)4​]2+ complex.

Therefore, the correct option is A.

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