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Salt Analysis question

2024 · Shift 2 · Q17
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Salt Analysis question

2024 · Shift 2 · Q17

JEE AdvancedChemistrySalt AnalysisNumerical+3 / −1
When potassium iodide is added to an aqueous solution of potassium ferricyanide, a reversible reaction is observed in which a complex P\mathbf{P}P is formed. In a strong acidic medium, the equilibrium shifts completely towards P\mathbf{P}P. Addition of zinc chloride to P\mathbf{P}P in a slightly acidic medium results in a sparingly soluble complex Q.The number of zinc ions present in the molecular formula of Q\mathbf{Q}Q is ‾\underline{\hspace{2cm}}​.
Numerical answer
View written solutionFree

Correct answer: 3OR2

  1. Identify the reaction between potassium iodide and potassium ferricyanide

Potassium ferricyanide is K3[Fe(CN)6]K_3[Fe(CN)_6]K3​[Fe(CN)6​], containing the complex ion [Fe(CN)6]3−[Fe(CN)_6]^{3-}[Fe(CN)6​]3−.

On adding iodide ions, a reversible redox reaction occurs:

2[Fe(CN)6]3−+2I−⇌2[Fe(CN)6]4−+I22[Fe(CN)_6]^{3-} + 2I^- \rightleftharpoons 2[Fe(CN)_6]^{4-} + I_22[Fe(CN)6​]3−+2I−⇌2[Fe(CN)6​]4−+I2​

In excess iodide, the iodine formed combines with iodide to give triiodide:

I2+I−⇌I3−I_2 + I^- \rightleftharpoons I_3^-I2​+I−⇌I3−​

So the overall reversible reaction becomes:

2[Fe(CN)6]3−+3I−⇌2[Fe(CN)6]4−+I3−2[Fe(CN)_6]^{3-} + 3I^- \rightleftharpoons 2[Fe(CN)_6]^{4-} + I_3^-2[Fe(CN)6​]3−+3I−⇌2[Fe(CN)6​]4−+I3−​

Thus the complex/species PPP formed in solution is essentially the ferrocyanide-containing system, i.e. [Fe(CN)6]4−[Fe(CN)_6]^{4-}[Fe(CN)6​]4− produced in acidic medium as the equilibrium shifts to the right.

  1. Why strong acid shifts equilibrium toward PPP

In strong acidic medium, the iodine/triiodide side is favored and the redox process proceeds essentially completely, generating ferrocyanide ion [Fe(CN)6]4−[Fe(CN)_6]^{4-}[Fe(CN)6​]4−.

So for the precipitation step, the relevant anion is:

[Fe(CN)6]4−[Fe(CN)_6]^{4-}[Fe(CN)6​]4−

  1. Reaction with zinc chloride in slightly acidic medium

Zinc ion gives a sparingly soluble zinc ferrocyanide with ferrocyanide ion. The known insoluble zinc ferrocyanide is:

Zn2[Fe(CN)6]Zn_2[Fe(CN)_6]Zn2​[Fe(CN)6​]

because charge balance requires:

2×(+2)+(−4)=02 \times (+2) + (-4) = 02×(+2)+(−4)=0

Hence the precipitate QQQ is zinc ferrocyanide, containing 2 zinc ions per formula unit.

  1. Answer

The number of zinc ions in the molecular formula of QQQ is:

2\boxed{2}2​

  1. Comparison with stored answer

The stored correct answer is given as 3 OR 2. My derived answer is 2, which matches one of the accepted answers.

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