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NCERT Exemplar · Q27

Q.Using crystal field theory, draw energy level diagram, write electronic configuration of the central metal atom/ion and determine the magnetic moment value in the following:

(i) [CoF6]3−[CoF_6]^{3-}, [Co(H2O)6]2+[Co(H_2O)_6]^{2+}, [Co(CN)6]3−[Co(CN)_6]^{3-}
(ii) [FeF6]3−[FeF_6]^{3-}, [Fe(H2O)6]2+[Fe(H_2O)_6]^{2+}, [Fe(CN)6]4−[Fe(CN)_6]^{4-}
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Crystal field theory explains how ligand field strength splits d-orbital energies, determining whether a complex is high-spin or low-spin. For each complex, we identify the metal ion's d-count, the ligand's field strength, fill the t2gt_{2g} and ege_g orbitals accordingly, and compute the magnetic moment using μ=n(n+2)\mu = \sqrt{n(n+2)} BM, where nn is the number of unpaired electrons.

Let’s work through each complex step by step. The key idea: ligands like CN⁻ are strong-field (large Δo\Delta_o, causing pairing), while F⁻ and H₂O are weak-field (small Δo\Delta_o, favouring high-spin). The geometry is octahedral for all.


(i) [CoF6]3−[CoF_6]^{3-}, [Co(H2O)6]2+[Co(H_2O)_6]^{2+}, [Co(CN)6]3−[Co(CN)_6]^{3-}

1. [CoF6]3−[CoF_6]^{3-}

  • Cobalt in +3 oxidation state: Co atomic number 27, so Co³⁺ has [Ar]3d6[Ar]3d^6 configuration.
  • F⁻ is a weak-field ligand → small Δo\Delta_o. Electrons fill according to Hund's rule: high-spin.
  • In octahedral field, the six d-electrons occupy: t2g4eg2t_{2g}^4 e_g^2 (four in t2gt_{2g}, two in ege_g).
  • Number of unpaired electrons: n=4n = 4 (two in ege_g are unpaired, and two of the t2gt_{2g} electrons are unpaired because of the fourth electron pairing one).
  • Magnetic moment: μ=4(4+2)=24≈4.90\mu = \sqrt{4(4+2)} = \sqrt{24} \approx 4.90 BM.
Watch out

A common mistake is to think Co³⁺ with weak field gives t2g3eg3t_{2g}^3 e_g^3 — that would be 3 unpaired, but the actual filling for d⁶ high-spin is t2g4eg2t_{2g}^4 e_g^2 with 4 unpaired electrons. Always apply Hund's rule to the t2gt_{2g} set first.

2. [Co(H2O)6]2+[Co(H_2O)_6]^{2+}

  • Cobalt in +2: Co²⁺ has [Ar]3d7[Ar]3d^7.
  • H₂O is intermediate but generally weak-field for Co²⁺ (it is borderline; for Co²⁺, H₂O acts as weak field). So high-spin.
  • d⁷ high-spin octahedral: t2g5eg2t_{2g}^5 e_g^2.
  • Unpaired electrons: n=3n = 3 (the ege_g has two unpaired, and the t2gt_{2g} has one unpaired because five electrons in three orbitals give one unpaired).
  • μ=3(3+2)=15≈3.87\mu = \sqrt{3(3+2)} = \sqrt{15} \approx 3.87 BM.

3. [Co(CN)6]3−[Co(CN)_6]^{3-}

  • Again Co³⁺, d⁶.
  • CN⁻ is a strong-field ligand → large Δo\Delta_o, electrons pair up in t2gt_{2g} before occupying ege_g.
  • Configuration: t2g6eg0t_{2g}^6 e_g^0 (all six electrons paired in the three t2gt_{2g} orbitals).
  • Unpaired electrons: n=0n = 0.
  • μ=0\mu = 0 BM (diamagnetic).
Tip

For d⁶, strong field gives t2g6t_{2g}^6 (low-spin, 0 unpaired), weak field gives t2g4eg2t_{2g}^4 e_g^2 (high-spin, 4 unpaired). The difference is dramatic — magnetic moment changes from 0 to ~4.9 BM.


(ii) [FeF6]3−[FeF_6]^{3-}, [Fe(H2O)6]2+[Fe(H_2O)_6]^{2+}, [Fe(CN)6]4−[Fe(CN)_6]^{4-}

4. [FeF6]3−[FeF_6]^{3-}

  • Iron in +3: Fe³⁺ has [Ar]3d5[Ar]3d^5.
  • F⁻ is weak-field → high-spin.
  • d⁵ high-spin octahedral: t2g3eg2t_{2g}^3 e_g^2 (Hund's rule: all five orbitals singly occupied).
  • Unpaired electrons: n=5n = 5.
  • μ=5(5+2)=35≈5.92\mu = \sqrt{5(5+2)} = \sqrt{35} \approx 5.92 BM.

5. [Fe(H2O)6]2+[Fe(H_2O)_6]^{2+}

  • Iron in +2: Fe²⁺ has [Ar]3d6[Ar]3d^6.
  • H₂O is weak-field for Fe²⁺ (it is borderline but generally considered weak for Fe²⁺). So high-spin. …

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