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Q.(i) Solution of [Ni(H2O)6]2+[Ni(H_2O)_6]^{2+} is green, but solution of [Ni(CN)4]2−[Ni(CN)_4]^{2-} is colourless. Explain.

(ii) [Cr(NH3)6]3+[Cr(NH_3)_6]^{3+} is paramagnetic, while [Ni(CN)4]2−[Ni(CN)_4]^{2-} is diamagnetic. Explain.
Uttar Pradesh UpmspUP Board (UPMSP) Intermediate 2024Subjective· 4mImportance★★★★★
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Colour and magnetism follow from crystal-field theory: weak-field H2OH_2O leaves unpaired electrons and a small Δ\Delta (green, absorbs visible), strong-field CN−CN^- pairs electrons and widens Δ\Delta (colourless, diamagnetic); Cr3+Cr^{3+} (d3d^3) keeps three unpaired electrons (paramagnetic).

(i) Colour of the two nickel complexes.

  • [Ni(H2O)6]2+[Ni(H_2O)_6]^{2+}: Ni2+=d8Ni^{2+}=d^8, octahedral, and H2OH_2O is a weak-field ligand → small splitting Δo\Delta_o. Electrons are available for d–d transitions whose energy falls in the visible region; the complex absorbs part of visible light and transmits the complementary colour, so it appears green.
  • [Ni(CN)4]2−[Ni(CN)_4]^{2-}: CN−CN^- is a strong-field ligand → it forces a square-planar d8d^8 arrangement in which all eight electrons are paired and the energy gap to the empty dx2−y2d_{x^2-y^2} orbital is large. The corresponding absorption lies in the UV, not the visible, so no visible light is absorbed → the complex is colourless.

(ii) Magnetic behaviour.

  • [Cr(NH3)6]3+[Cr(NH_3)_6]^{3+}: Cr3+=[Ar]3d3Cr^{3+}=[Ar]3d^3. In the octahedral field the three dd-electrons occupy separate t2gt_{2g} orbitals singly (t2g3t_{2g}^3) → three unpaired electrons → paramagnetic (spin-only moment μ=3(3+2)=3.87 BM\mu=\sqrt{3(3+2)}=3.87\ \text{BM}). …

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