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Q.(a) Give one chemical test as an evidence to show that [Co(NH3)5Cl]SO4[Co(NH_3)_5Cl]SO_4 and [Co(NH3)5(SO4)]Cl[Co(NH_3)_5(SO_4)]Cl are ionisation isomers.

(b) [NiCl4]2−[NiCl_4]^{2-} is paramagnetic while [Ni(CO)4][Ni(CO)_4] is diamagnetic though both are tetrahedral. Why ? (Atomic no. of Ni = 28)
(c) Write the electronic configuration of Fe(III) on the basis of crystal field theory when it forms an octahedral complex in the presence of
(i) strong field ligand, and
(ii) weak field ligand. (Atomic no. of Fe = 26)
CBSECBSE Class XII Board 2019Subjective· 3mImportance★★★★★
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Ionisation isomers differ in which anion is free in solution — a precipitation test with BaCl₂ or AgNO₃ distinguishes them. The paramagnetism of [NiCl4]2−[NiCl_4]^{2-} vs diamagnetism of [Ni(CO)4][Ni(CO)_4] arises from different oxidation states and ligand field strengths. For Fe(III) in an octahedral field, strong ligands give a low-spin t2g5t_{2g}^5 configuration, while weak ligands give a high-spin t2g3eg2t_{2g}^3 e_g^2 configuration.


(a) Chemical test for ionisation isomers

Ionisation isomers exchange a ligand inside the coordination sphere with an anion outside it. When dissolved, they release different ions into solution. The classic test uses precipitation reactions.

  1. Identify the free ions:

    [Co(NH3)5Cl]SO4[Co(NH_3)_5Cl]SO_4 will release SO42−SO_4^{2-} ions in solution.

    [Co(NH3)5(SO4)]Cl[Co(NH_3)_5(SO_4)]Cl will release Cl−Cl^- ions in solution.

  2. Choose a specific precipitating agent:

    Add aqueous BaCl2BaCl_2 to separate solutions of each isomer.

    • Ba2+Ba^{2+} reacts with SO42−SO_4^{2-} to form a white precipitate of BaSO4BaSO_4.
    • Ba2+Ba^{2+} does not react with Cl−Cl^-.
  3. Observe the result:

    • The isomer [Co(NH3)5Cl]SO4[Co(NH_3)_5Cl]SO_4 gives a white precipitate with BaCl2BaCl_2.
    • The isomer [Co(NH3)5(SO4)]Cl[Co(NH_3)_5(SO_4)]Cl gives no precipitate with BaCl2BaCl_2.
Tip

You could also use AgNO3AgNO_3 to test for free Cl−Cl^- ions — the first isomer gives no precipitate, the second gives a white precipitate of AgClAgCl. Either test works; the key is that the free anion is different.


(b) Paramagnetism of [NiCl4]2−[NiCl_4]^{2-} vs diamagnetism of [Ni(CO)4][Ni(CO)_4]

Both complexes are tetrahedral, but the nickel atom is in different oxidation states, leading to different numbers of d-electrons and different ligand field strengths.

  1. Determine the oxidation state and d-count:

    • In [NiCl4]2−[NiCl_4]^{2-}: Each Cl−Cl^- is −1-1, so x+4(−1)=−2⇒x=+2x + 4(-1) = -2 \Rightarrow x = +2. Ni(II) has electron configuration [Ar]3d8[Ar] 3d^8.
    • In [Ni(CO)4][Ni(CO)_4]: CO is a neutral ligand, so Ni is in the 0 oxidation state. Ni(0) has configuration [Ar]3d84s2[Ar] 3d^8 4s^2, but in complexes the 4s electrons are lost first, giving 3d103d^{10} (more on this below).
  2. Apply crystal field theory for tetrahedral geometry:

    In a tetrahedral field, the d-orbitals split into a lower-energy ee set (dxy,dxz,dyzd_{xy}, d_{xz}, d_{yz}) and a higher-energy t2t_2 set (dx2−y2,dz2d_{x^2-y^2}, d_{z^2}). The splitting energy Δt\Delta_t is much smaller than for octahedral complexes (roughly 4/94/9 of Δo\Delta_o).

  3. Analyse [NiCl4]2−[NiCl_4]^{2-}:

    • Cl−Cl^- is a weak field ligand, so Δt\Delta_t is small.
    • For d8d^8 in a tetrahedral field, the electrons fill according to Hund's rule: two electrons go into each of the three t2t_2 orbitals, and the remaining two go into the ee orbitals. This gives two unpaired electrons.
    • Hence, [NiCl4]2−[NiCl_4]^{2-} is paramagnetic.
  4. Analyse [Ni(CO)4][Ni(CO)_4]:

    • CO is a very strong field ligand. It also causes pairing of the 4s electrons into the 3d orbitals, effectively giving a 3d103d^{10} configuration for Ni(0).
    • In a tetrahedral field, d10d^{10} means all five d-orbitals are completely filled — no unpaired electrons.
    • Hence, [Ni(CO)4][Ni(CO)_4] is diamagnetic.
Watch out

A common mistake is to think both complexes have the same d-count because both are tetrahedral. Always check the oxidation state first — Ni(II) is d8d^8, Ni(0) is d10d^{10}. The ligand field strength then determines whether pairing occurs.


(c) Electronic configuration of Fe(III) in octahedral complexes …

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