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Question 21

How would you account for the following:

(i) Of the d4 species, Cr2+ is strongly reducing while manganese (III) is strongly oxidising.

(ii) Cobalt (II) is stable in aqueous solution but in the presence of complexing reagents it is easily oxidised.

(iii) The d1 configuration is very unstable in ions.

Answer

(i) Cr2+ is strongly reducing in nature. It has a d4 configuration. While acting as a reducing agent, it gets oxidized to Cr3+ (electronic configuration, d3). This d3 configuration can be written as t32g configuration, which is a more stable configuration. In the case of Mn3+(d4), it acts as an oxidizing agent and gets reduced to Mn2+(d5). This has an exactly half-filled d-orbital and is highly stable.



 

(ii) Co(II) is stable in aqueous solutions. However, in the presence of strong field complexing reagents, it is oxidized to Co (III). Although the 3rdionization energy for Co is high, but the higher amount of crystal field stabilization energy (CFSE) released in the presence of strong field ligands overcomes this ionization energy.

 

(iii) The ions in d1 configuration tend to lose one more electron to get into stable d0 configuration. Also, the hydration or lattice energy is more than sufficient to remove the only electron present in the d-orbital of these ions. Therefore, they act as reducing agents

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