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Q.(a) Transition metals and their many compounds act as a good catalyst. Why?

(b) Why does light green Fe2+Fe^{2+} solution change to brown on exposure to air? OR Write down the steps involved in the preparation of KMnO4KMnO_4 from MnO2MnO_2.
Meghalaya MboseMBOSE Meghalaya Intermediate Board 2020Subjective· 2mImportance★★★★★
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Transition metals catalyse reactions via their variable oxidation states and vacant d-orbitals; Fe2+Fe^{2+} air-oxidises to the more stable Fe3+Fe^{3+}. (OR: KMnO4KMnO_4 is made from MnO2MnO_2 by alkaline oxidative fusion to manganate, then oxidation to permanganate.)

(a) Why transition metals/compounds are good catalysts.

Transition elements show variable oxidation states differing usually by one unit (e.g. Fe2+/Fe3+Fe^{2+}/Fe^{3+}, Mn2+/Mn3+/Mn4+Mn^{2+}/Mn^{3+}/Mn^{4+}…), which lets them readily form unstable intermediate compounds with the reacting molecules. The reaction then proceeds through this intermediate along a pathway of lower activation energy than the uncatalysed path, speeding up the reaction; the catalyst is regenerated at the end. Their large surface area (when finely divided) and availability of empty/partly filled d-orbitals to bind reactant molecules (in heterogeneous catalysis, e.g. Ni/Pt in hydrogenation) add to this effect.

(b) Why pale-green Fe2+Fe^{2+} turns brown in air.

Atmospheric oxygen oxidises Fe2+Fe^{2+} (pale green) to Fe3+Fe^{3+} (yellow-brown), because Fe3+Fe^{3+} (3d53d^5, half-filled d-subshell) is thermodynamically more stable than Fe2+Fe^{2+} (3d63d^6):

4Fe2+(aq)+O2(g)+4H+(aq)⟶4Fe3+(aq)+2H2O(l)4Fe^{2+}(aq) + O_2(g) + 4H^{+}(aq) \longrightarrow 4Fe^{3+}(aq) + 2H_2O(l)

Alternative (Or): Preparation of KMnO4KMnO_4 from MnO2MnO_2 (pyrolusite).

Step 1 — Oxidative alkaline fusion: MnO2MnO_2 is fused with KOHKOH in the presence of an oxidising agent (fused with air or KNO3KNO_3), giving dark-green potassium manganate:

2MnO2+4KOH+O2→Δ2K2MnO4+2H2O2MnO_2 + 4KOH + O_2 \xrightarrow{\Delta} 2K_2MnO_4 + 2H_2O

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