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NCERT Exemplar · Q3

Q.When 0.1 mol CoCl3(NH3)5CoCl_3(NH_3)_5 is treated with excess of AgNO3AgNO_3, 0.2 mol of AgClAgCl are obtained. The conductivity of solution will correspond to

(i) 1:3 electrolyte
(ii) 1:2 electrolyte
(iii) 1:1 electrolyte
(iv) 3:1 electrolyte
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✓ Free question

The complex is [Co(NH3)5Cl]Cl2[Co(NH_3)_5Cl]Cl_2, which dissociates into 3 ions (1 Co complex cation + 2 Cl⁻ anions), so it behaves as a 1:2 electrolyte. The correct option is (ii).

Why Conductivity and Precipitation Tell the Same Story

When you dissolve a coordination compound in water, its conductivity depends on how many ions it releases. A 1:1 electrolyte (like NaCl) gives 2 ions, a 1:2 electrolyte (like CaCl₂) gives 3 ions, and so on. The precipitation experiment with AgNO₃ is a clever way to count how many chloride ions are free — because only free Cl⁻ ions react with Ag⁺ to form AgCl. Chloride ions that are tightly bound inside the coordination sphere (as ligands) do not precipitate.

So the two experiments — conductivity and precipitation — are two sides of the same coin. If you know how many Cl⁻ ions are free, you know the ionic formula of the complex, and from that you can predict how many total ions it will produce in solution.

Step-by-Step Reasoning

  1. Interpret the precipitation data.

    The reaction is:

    Ag++Cl−→AgCl↓\text{Ag}^+ + \text{Cl}^- \rightarrow \text{AgCl} \downarrow

    From 0.1 mol of the complex, we get 0.2 mol of AgCl. That means 0.2 mol of free Cl⁻ ions were present in the solution.

    So per mole of complex, the number of free Cl⁻ ions is:

    0.20.1=2\frac{0.2}{0.1} = 2

    Therefore, the complex must have two chloride ions outside the coordination sphere (as counter-ions) and the rest inside as ligands.

  2. Deduce the formula of the complex.

    The molecular formula is CoCl3(NH3)5CoCl_3(NH_3)_5. We have 3 Cl atoms total. Two are free (ionic), so the remaining one must be coordinated to cobalt inside the coordination sphere.

    Hence the correct structural formula is:

    [Co(NH3)5Cl]Cl2[Co(NH_3)_5Cl]Cl_2

    The square brackets enclose the coordination sphere: one Co³⁺ ion, five NH₃ molecules, and one Cl⁻ ligand. Outside the sphere, two Cl⁻ ions balance the +3 charge on the cobalt (since Co³⁺ + 5 neutral NH₃ + 1 Cl⁻ ligand gives a net +2 charge on the complex ion, which is neutralized by the two free Cl⁻ ions).

  3. Determine the number of ions in solution.

    When [Co(NH3)5Cl]Cl2[Co(NH_3)_5Cl]Cl_2 dissolves, it dissociates completely into:

    [Co(NH3)5Cl]2++2Cl−[Co(NH_3)_5Cl]^{2+} + 2Cl^-

    That is 3 ions per formula unit: one complex cation with charge +2, and two chloride anions.

  4. Classify the electrolyte type.

    An electrolyte that gives one cation of charge +2 and two anions of charge -1 is called a 1:2 electrolyte (the ratio of cation charge to anion charge is 1:2, but more commonly it refers to the number of ions: 1 cation : 2 anions).

    Option (ii) matches this.

Watch out

A common mistake is to think that all 3 chlorides are free because the formula shows 3 Cl atoms. Remember: only chlorides outside the coordination sphere precipitate with Ag⁺. The coordinated Cl⁻ is "invisible" to AgNO₃.

Tip

You can also work backwards from the conductivity: a 1:2 electrolyte gives a molar conductivity roughly double that of a 1:1 electrolyte (for similar ions), but here the precipitation data alone is sufficient — no need for actual conductivity values.

✓Final answer

The correct option is (ii) 1:2 electrolyte.

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