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Q.The following question is a case-based question. Read the case carefully and answer the questions that follow. Werner's coordination theory in 1893 was the first attempt to explain the bonding in coordination complexes. It must be remembered that this theory was put forward before the electron had been discovered by J.J. Thomson in 1897, and before the electronic theory of valency. Werner did not have any of the modern instrumental techniques and all his studies were made using simple experimental techniques. Werner was able to explain the nature of bonding in complexes and he concluded that in complexes, the metal shows two different sorts of valency : primary and secondary. Primary valences are normally ionisable whereas secondary valences are non-ionisable. Answer the following questions :

(a) One mole of CrCl3⋅4H2OCrCl_3 \cdot 4H_2O precipitates one mole of AgCl when treated with excess of AgNO3AgNO_3 solution. Write
(i) the structural formula of the complex, and
(ii) the secondary valency of Cr.
(b) What is the difference between a complex and a double salt ?
(c)
(i) Arrange the following complexes in the increasing order of conductivity of their solution : [Cr(NH3)3Cl3][Cr(NH_3)_3Cl_3], [Cr(NH3)6]Cl3[Cr(NH_3)_6]Cl_3, [Cr(NH3)5Cl]Cl2[Cr(NH_3)_5Cl]Cl_2
(OR)
(c)
(ii) Write two differences between primary and secondary valences in coordination compounds.
CBSECBSE Class XII Board 2025Subjective· 4mImportance★★★★★
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Part (a): [Cr(H2O)4Cl2]Cl[\text{Cr(H}_2\text{O})_4\text{Cl}_2]\text{Cl}, secondary valency 6; a complex keeps its identity in solution while a double salt dissociates fully; conductivity increases with the number of free ions: [Cr(NH3)3Cl3]<[Cr(NH3)5Cl]Cl2<[Cr(NH3)6]Cl3[\text{Cr(NH}_3)_3\text{Cl}_3] < [\text{Cr(NH}_3)_5\text{Cl}]\text{Cl}_2 < [\text{Cr(NH}_3)_6]\text{Cl}_3. Part (c): primary valency = ionisable oxidation state; secondary valency = non‑ionisable coordination number.

Werner's key idea: only chloride outside the coordination sphere is ionisable and precipitates with AgNO3_3; chloride bonded to the metal (inside the sphere) does not.

Part (a)

(a) Formula and secondary valency.

  1. CrCl3⋅4H2O\text{CrCl}_3\cdot 4\text{H}_2\text{O} has 3 Cl. Only 1 mol AgCl forms per mole, so one Cl−^- is ionisable; the other two Cl−^- are inside the sphere.
  2. Cr3+^{3+} has coordination number 6, filled by 2 Cl−^- + 4 H2_2O.
  3. Structural formula: [Cr(H2O)4Cl2]Cl[\text{Cr(H}_2\text{O})_4\text{Cl}_2]\text{Cl} — the single outer Cl−^- is the counter‑ion that precipitates.
  4. Secondary valency (coordination number) = 6.
Watch out

All four water molecules are coordinated here (no water of crystallisation), and only the one outer Cl−^- precipitates.

(b) Complex vs double salt.

FeatureComplexDouble salt
Identity in solutionretains the complex ion, e.g. [Fe(CN)6]4−[\text{Fe(CN)}_6]^{4-}breaks into all simple ions
Bondingcoordinate bonds hold the inner sphereonly ionic interactions
ExampleK4[Fe(CN)6]\text{K}_4[\text{Fe(CN)}_6]KAl(SO4)2⋅12H2O\text{KAl(SO}_4)_2\cdot 12\text{H}_2\text{O}

A double salt gives tests for all its ions; a complex does not give tests for the metal/ligands locked inside the sphere.

(c)(i) Increasing conductivity. Conductivity rises with the number of ions released:

  • [Cr(NH3)3Cl3][\text{Cr(NH}_3)_3\text{Cl}_3]: all Cl inside → 0 ions (non‑electrolyte).
  • [Cr(NH3)5Cl]Cl2[\text{Cr(NH}_3)_5\text{Cl}]\text{Cl}_2: → [Cr(NH3)5Cl]2++2Cl−[\text{Cr(NH}_3)_5\text{Cl}]^{2+} + 2\text{Cl}^- = 3 ions.
  • [Cr(NH3)6]Cl3[\text{Cr(NH}_3)_6]\text{Cl}_3: → [Cr(NH3)6]3++3Cl−[\text{Cr(NH}_3)_6]^{3+} + 3\text{Cl}^- = 4 ions. …

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