Question
Give the octahedral as well as tetrahedral field electronic configuration for the Cr3+ and Mn2+
ions. Which site will be preferred by these ions, octahedral or tetrahedral? Justify your answer.
Answer :
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The crystal field electronic configurations of Cr³⁺ and Mn²⁺ can be understood from their d-electron configurations and the splitting of d-orbitals in octahedral and tetrahedral ligand fields. In both cases, Cr³⁺ has a 3d³ configuration, while Mn²⁺ has a 3d⁵ configuration. For Cr³⁺, the electronic configuration of the free ion is [Ar]3d³. In an octahedral field, the five d-orbitals split into a lower-energy t₂g set and a higher-energy e_g set. The three d-electrons occupy the three t₂g orbitals singly according to Hund’s rule. Thus, the octahedral configuration is t₂g³e_g⁰. There are three unpaired electrons. The crystal field stabilization energy (CFSE) is 3(−0.4Δ₀) = −1.2Δ₀, or 1.2Δ₀ stabilization. In a tetrahedral field, the splitting is reversed in energy. The lower-energy orbitals are e, while the higher-energy orbitals are t₂. Since Cr³⁺ has three d-electrons, they occupy the lower e orbitals first and then the t₂
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