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Q.When FeCr2O4FeCr_2O_4 is fused with Na2CO3Na_2CO_3 in the presence of air it gives a yellow solution of compound (A). Compound (A) on acidification gives compound (B). Compound (B) on reaction with KCl forms an orange coloured compound (C). An acidified solution of compound (C) oxidises Na2SO3Na_2SO_3 to (D). Identify (A), (B), (C) and (D).

CBSECBSE Class XII Board 2019Subjective· 2mImportance★★★★★
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This is a classic chromium extraction sequence: chromite ore (FeCr2O4FeCr_2O_4) is fused with soda ash in air to give yellow sodium chromate (A); acidification gives orange sodium dichromate (B); reaction with KCl precipitates orange potassium dichromate (C); and in acidic medium, (C) oxidises sulfite to sulfate (D).

The entire problem revolves around the chemistry of chromium in its +6 oxidation state. Chromite ore is a mixed oxide of iron(II) and chromium(III). When you fuse it with an alkali carbonate in the presence of oxygen, you are essentially performing an oxidative alkaline roast — the chromium(III) gets oxidised to chromium(VI), which is water-soluble as the yellow chromate ion. Iron remains behind as insoluble iron(III) oxide. This is the industrial first step in the manufacture of dichromates.

Let’s walk through each transformation step by step.

  1. Fusion of chromite with sodium carbonate in air The ore FeCr2O4FeCr_2O_4 contains chromium in the +3 state. In the presence of oxygen and molten Na2CO3Na_2CO_3, the chromium is oxidised to the +6 state, forming water-soluble sodium chromate. The iron is oxidised to Fe2O3Fe_2O_3, which is insoluble and can be filtered off. The balanced reaction is:

4FeCr2O4+8Na2CO3+7O2→8Na2CrO4+2Fe2O3+8CO24FeCr_2O_4 + 8Na_2CO_3 + 7O_2 \rightarrow 8Na_2CrO_4 + 2Fe_2O_3 + 8CO_2

The yellow solution obtained contains sodium chromate, Na2CrO4Na_2CrO_4. This is compound (A).

  1. Acidification of sodium chromate solution In neutral or alkaline solution, chromate ions (CrO42−CrO_4^{2-}) are stable and yellow. On adding acid, the equilibrium shifts to form dichromate ions (Cr2O72−Cr_2O_7^{2-}), which are orange. The reaction is:

2CrO42−+2H+⇌Cr2O72−+H2O2CrO_4^{2-} + 2H^+ \rightleftharpoons Cr_2O_7^{2-} + H_2O

So compound (B) is sodium dichromate, Na2Cr2O7Na_2Cr_2O_7, in solution.

Watch out

A common mistake is to think acidification gives chromic acid (H2CrO4H_2CrO_4). In aqueous solution, the dominant species at low pH is actually dichromate, not chromic acid — unless the solution is very concentrated or you evaporate it.

  1. Reaction of sodium dichromate with KCl This is a simple metathesis (double displacement) reaction. Potassium dichromate is less soluble than sodium dichromate, so it precipitates out as orange crystals. …

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