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Coordination Compounds question

2021 · 20 Jul · Shift 2 · Q23
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Coordination Compounds question

2021 · 20 Jul · Shift 2 · Q23

JEE MainChemistryCoordination CompoundsNumerical+4 / −1
An aqueous solution of NiCl2NiCl_2NiCl2​ was heated with excess sodium cyanide in presence of strong oxidizing agent to form [Ni(CN)6]2−[Ni(CN)_6]^{2-}[Ni(CN)6​]2−. The total change in number of unpaired electrons on metal centre is ‾\underline{\hspace{2cm}}​.
Numerical answer
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Correct answer: 2

  1. Find oxidation state and electronic configuration of metal in the reactant

In aqueous solution, NiCl2NiCl_2NiCl2​ contains Ni2+Ni^{2+}Ni2+.

Nickel atom: Z=28Z=28Z=28

Ni:[Ar]3d84s2Ni: [Ar]3d^8 4s^2Ni:[Ar]3d84s2

So,

Ni2+:[Ar]3d8Ni^{2+}: [Ar]3d^8Ni2+:[Ar]3d8

For free Ni2+Ni^{2+}Ni2+, the number of unpaired electrons in 3d83d^83d8 is 2.


  1. Determine oxidation state of Ni in the product

Given complex: [Ni(CN)6]2−[Ni(CN)_6]^{2-}[Ni(CN)6​]2−

Let oxidation state of Ni be xxx.

Since each CN−CN^-CN− has charge −1-1−1,

x+6(−1)=−2x + 6(-1) = -2x+6(−1)=−2 x−6=−2x - 6 = -2x−6=−2 x=+4x = +4x=+4

So metal centre is Ni4+Ni^{4+}Ni4+.

Now electronic configuration:

Ni4+:[Ar]3d6Ni^{4+}: [Ar]3d^6Ni4+:[Ar]3d6


  1. Nature of ligand and spin state

CN−CN^-CN− is a strong field ligand. Hence in octahedral complex [Ni(CN)6]2−[Ni(CN)_6]^{2-}[Ni(CN)6​]2−, electrons pair up to give a low-spin arrangement.

For octahedral low-spin d6d^6d6:

t2g6eg0t_{2g}^6 e_g^0t2g6​eg0​

All electrons are paired.

So number of unpaired electrons in [Ni(CN)6]2−[Ni(CN)_6]^{2-}[Ni(CN)6​]2− is 0.


  1. Calculate total change in number of unpaired electrons

Initial unpaired electrons on metal centre = 222

Final unpaired electrons on metal centre = 000

Therefore,

change=2−0=2\text{change} = 2 - 0 = 2change=2−0=2


  1. Final answer

The total change in number of unpaired electrons is:

2\boxed{2}2​


  1. Comparison with stored correct answer

Stored correct answer = 222

This matches the derived answer.

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