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JEE Advanced 2019 Paper 1 · Chemistry · d- and f-Block Elements and Metallurgy · medium

Regarding the chemistry of manganese and chromium oxoanions, the correct statement(s) is(are)

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Regarding the chemistry of manganese and chromium oxoanions, the correct statement(s) is(are)
  1. A. Manganate MnO42−\mathrm{MnO_4^{2-}} disproportionates in acidic medium to MnO4−\mathrm{MnO_4^-} and MnO2\mathrm{MnO_2}.
  2. B. The conversion of orange dichromate to yellow chromate on adding alkali is a redox reaction.
  3. C. The purple colour of MnO4−\mathrm{MnO_4^-} arises from dd-dd transitions of Mn(VII)\mathrm{Mn(VII)}.
  4. D. The spin-only magnetic moment of MnO42−\mathrm{MnO_4^{2-}} is zero.
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Answer: A

(A) Manganate(VI), d1d^1, is stable only in strongly alkaline solution. In acid it disproportionates: 3MnO42−+4H+→2MnO4−+MnO2+2H2O3\mathrm{MnO_4^{2-}}+4\mathrm{H^+}\to2\mathrm{MnO_4^-}+\mathrm{MnO_2}+2\mathrm{H_2O}; Mn goes from +6 to +7 and +4, so (A) is true. (B) The equilibrium Cr2O72−+2OH−⇌2CrO42−+H2O\mathrm{Cr_2O_7^{2-}+2OH^-\rightleftharpoons2CrO_4^{2-}+H_2O} keeps Cr at +6 on both sides, so it is an acid-base process, not redox; false. (C) Mn(VII) is d0d^0, so no dd-dd transitions are possible; the intense purple colour is due to ligand-to-metal charge transfer from oxygen to manganese; false. (D) Mn(VI)\mathrm{Mn(VI)} is d1d^1 with one unpaired electron, so μ=1⋅3=1.73\mu=\sqrt{1\cdot3}=1.73 BM, not zero; false. Only A is correct.
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