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Chemistry Question 63 – JEE-MAIN 2025

The correct order of the complexes [Co(NH3)5(H2O)]3+ (A), [Co(NH3)6]3+ (B), [Co(CN)6]3− (C) and [CoCl(NH3)5]2+ (D) in terms of wavelength of light absorbed is

The wavelength of light absorbed by a complex is inversely proportional to the crystal field splitting energy (Δo).

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Ninja Strategy•Extreme Ligand Strength Analysis

Identify the complexes with the strongest (CN− in C) and weakest (Cl− in D) ligand fields. The weakest field (D) will absorb the longest wavelength, and the strongest field (C) will absorb the shortest wavelength. This immediately eliminates options that place C at the longest wavelength end or D at the shortest wavelength end, and helps narrow down the choices.

Step 1: Determine Oxidation State and Ligand Field Strength✦ Active

All complexes have Co3+ as the central metal ion. The spectrochemical series for the ligands involved, from weakest to strongest field, is Cl−<H2O<NH3<CN−. The energy of light absorbed (Eabs) is directly proportional to the crystal field splitting energy (Δo), and inversely proportional to the wavelength of light absorbed (λabs). Thus, a weaker ligand field leads to smaller Δo and longer λabs.

Step 2: Order by Crystal Field Splitting Energy (Δo)○ Expand

Based on the ligand field strength, we can order the complexes by their Δo values:

[CoCl(NH3)5]2+(D)<[Co(NH3)5(H2O)]3+(A)<[Co(NH3)6]3+(B)<[Co(CN)6]3−(C)

This order reflects the increasing average ligand field strength: Cl− is the weakest, followed by H2O, then NH3, and finally CN− is the strongest.

Step 3: Order by Wavelength of Light Absorbed (λabs)○ Expand

Since λabs∝1/Δo, the order of wavelength absorbed will be the inverse of the Δo order:

λabs(D)>λabs(A)>λabs(B)>λabs(C)

This corresponds to option 4.

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