Question:medium

The violet colour of \(KMnO_4\) solution is due to:

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Compounds having \(d^0\) or \(d^{10}\) configuration generally do not show \(d-d\) transitions. Their colour usually arises from charge transfer transitions.
Updated On: Jun 3, 2026
  • \(d-d\) transition
  • Charge transfer transition
  • Presence of unpaired electrons
  • Hybridization
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The Correct Option is B

Solution and Explanation

Step 1: Understanding the Concept:
In coordination chemistry, the intense colors of transition metal complexes typically arise from electronic transitions within the visible light spectrum. While many transition metal compounds owe their colors to $d-d$ transitions, certain complexes exhibit vivid colors despite having empty $d$-orbitals. This requires an alternative electronic mechanism known as charge transfer.
Step 2: Key Formula or Approach:
Let's determine the oxidation state and electronic configuration of the central metal atom in potassium permanganate ($\text{KMnO}_4$): - In the permanganate ion ($\text{MnO}_4^-$), oxygen has an oxidation state of $-2$. - Let $x$ be the oxidation state of Manganese ($\text{Mn}$): $$ x + 4(-2) = -1 \implies x - 8 = -1 \implies x = +7 $$ - The ground-state electronic configuration of atomic Manganese ($Z=25$) is $[\text{Ar}] 3d^5 4s^2$. - For the $\text{Mn}^{7+}$ ion, all 7 valence electrons are removed: $$ \text{Mn}^{7+} = [\text{Ar}] 3d^0 4s^0 $$
Step 3: Detailed Explanation:
Let's analyze why $d-d$ transition cannot explain the color, and why charge transfer is responsible: 1. Rule out $d-d$ transitions: Because the $\text{Mn}^{7+}$ central ion possesses a completely empty $d$-orbital configuration ($3d^0$), there are no electrons available in lower $d$-orbitals to absorb light and jump to higher $d$-orbitals. This rules out options (A) and (C). 2. Mechanism of Charge Transfer: The intense deep-violet color is caused by a Ligand-to-Metal Charge Transfer (LMCT) transition. 3. An electron absorbs a photon of visible green-yellow light and momentarily shifts from a filled $p$-orbital of an oxide ligand ($\text{O}^{2-}$) into an empty, low-lying $3d$-orbital of the central $\text{Mn}^{7+}$ ion. 4. Because this transition is Laporte-allowed and spin-allowed, it is highly probable, creating an exceptionally intense color absorption compared to weak, forbidden $d-d$ transitions. The absorbed light falls in the green-yellow region, causing our eyes to perceive the complementary deep violet color. This corresponds to option (B).
Step 4: Final Answer:
The violet color of $\text{KMnO}_4$ is due to a charge transfer transition.
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