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Q.(a) Describe the preparation of potassium permanganate from pyrolusite ore. Write the chemical equation for one reaction to show the oxidising nature of potassium permanganate. OR

(b) Explain the following:
(i) the effect of increasing pH on a solution of potassium dichromate.
(ii) Manganese shows maximum number of oxidation states in 3d series of transition metals.
Manipur CohsemCOHSEM Manipur Higher Secondary Board 2024Subjective· 5mImportance★★★★★
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This question offers a choice between the industrial preparation of KMnO₄ from pyrolusite (primary) or two short reasoning questions on chromium/manganese chemistry (the alternative). Both are answered below.

(Primary) — Preparation of KMnO4KMnO_4 from pyrolusite:

Step 1 — Fusion: Pyrolusite ore (MnO2MnO_2) is fused with potassium hydroxide (KOH) in the presence of an oxidising agent (air/O2O_2 or KNO3KNO_3), converting it to dark green potassium manganate:

2MnO2+4KOH+O2→fuse2K2MnO4+2H2O2MnO_2 + 4KOH + O_2 \xrightarrow{fuse} 2K_2MnO_4 + 2H_2O

Step 2 — Oxidation: The manganate(K2MnO4K_2MnO_4, containing Mn in +6 state) is then oxidised — either electrolytically (anodic oxidation) or chemically (with Cl2Cl_2 or O3O_3) — to permanganate (MnO4−MnO_4^-, Mn in +7):

2K2MnO4+Cl2→2KMnO4+2KCl2K_2MnO_4 + Cl_2 \rightarrow 2KMnO_4 + 2KCl

(Electrolytic oxidation: 2MnO42−→anode2MnO4−+2e−2MnO_4^{2-} \xrightarrow{anode} 2MnO_4^- + 2e^-.)

Reaction showing the oxidising nature of KMnO4KMnO_4: In acidic medium, KMnO4KMnO_4 oxidises oxalic acid to CO2CO_2, itself being reduced from +7 to +2:

2KMnO4+3H2SO4+5H2C2O4→K2SO4+2MnSO4+10CO2+8H2O2KMnO_4 + 3H_2SO_4 + 5H_2C_2O_4 \rightarrow K_2SO_4 + 2MnSO_4 + 10CO_2 + 8H_2O

OR (b) — reasoning questions:

(i) Effect of increasing pH on potassium dichromate solution: The dichromate ion (Cr2O72−Cr_2O_7^{2-}, orange) exists in equilibrium with the chromate ion (CrO42−CrO_4^{2-}, yellow), which is pH-dependent: Cr2O72−+H2O⇌2CrO42−+2H+Cr_2O_7^{2-} + H_2O \rightleftharpoons 2CrO_4^{2-} + 2H^+. Increasing the pH (making the solution more basic) shifts this equilibrium to the right, converting the orange dichromate to the yellow chromate ion.

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