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Q.(a)(i) Account for the following:

(1) The melting and boiling points of Zn, Cd and Hg are low.
(2) Of the d4d^4 species, Cr2+Cr^{2+} is strongly reducing while Mn3+Mn^{3+} is strongly oxidizing.
(3) EoE^o value of Cu2+/CuCu^{2+}/Cu is +0.34+0.34 V.
(ii) Complete and balance the following chemical equations:
(1) KMnO4→heatKMnO_4 \xrightarrow{heat}
(2) Cr2O72−+6 I−+14 H+→Cr_2O_7^{2-} + 6\,I^- + 14\,H^+ \rightarrow (3+2=5)
(OR)
(b)(i) Out of Cu2Cl2Cu_2Cl_2 and CuCl2CuCl_2, which is more stable in aqueous solution and why?
(ii) Write the general electronic configuration of f-block elements.
(iii) Predict which of the following will be coloured in aqueous solution and why? Sc3+Sc^{3+}, Fe3+Fe^{3+}, Zn2+Zn^{2+} [Atomic number: Sc = 21, Fe = 26, Zn = 30]
(iv) How can you obtain potassium dichromate from sodium chromate?
(v) Why do transition metals and their compounds show catalytic activities? (5×1=5)
CBSECBSE Class XII Board 2024Subjective· 5mImportance★★★★★
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Part (a): Zn/Cd/Hg melt low because the full d¹⁰ shell gives weak metallic bonding; CrX2+\ce{Cr^2+} is reducing (→ stable d3d^3 CrX3+\ce{Cr^3+}) and MnX3+\ce{Mn^3+} oxidising (→ stable d5d^5 MnX2+\ce{Mn^2+}); ECuX2+/Cu∘E^\circ_{\ce{Cu^2+}/\ce{Cu}} is positive due to unfavourable enthalpies; 2 KMnOX4→KX2MnOX4+MnOX2+OX2\ce{2KMnO4 -> K2MnO4 + MnO2 + O2} and CrX2OX7X2−+6 IX−+14 HX+→2 CrX3++3 IX2+7 HX2O\ce{Cr2O7^2- + 6I- + 14H+ -> 2Cr^3+ + 3I2 + 7H2O}. Part (b): CuClX2\ce{CuCl2} is more stable (CuX+\ce{Cu+} disproportionates); f-block configs; only FeX3+\ce{Fe^3+} is coloured; chromate → dichromate → KX2CrX2OX7\ce{K2Cr2O7}; catalysis from variable oxidation states.

Part (a)

(i)(1) Low m.p./b.p. of Zn, Cd, Hg. These have the completely filled (n−1)d10ns2(n-1)d^{10}ns^2 configuration. The stable d¹⁰ electrons do not contribute to metallic bonding, so only the two ss-electrons bind the lattice — weak bonding, low melting and boiling points (Hg is liquid).

(2) CrX2+\ce{Cr^2+} reducing, MnX3+\ce{Mn^3+} oxidising (both d4d^4). CrX2+\ce{Cr^2+} readily loses an electron to become CrX3+\ce{Cr^3+} (d3d^3, exceptionally stable half-filled t2gt_{2g}), so it is a strong reducing agent. MnX3+\ce{Mn^3+} readily gains an electron to become MnX2+\ce{Mn^2+} (d5d^5, stable half-filled), so it is a strong oxidising agent.

(3) ECuX2+/Cu∘=+0.34E^\circ_{\ce{Cu^2+}/\ce{Cu}} = +0.34 V. The value is positive (unlike most 3d metals) because the high enthalpies of sublimation and ionisation of copper are not compensated by its hydration enthalpy, so Cu has little tendency to go into solution as CuX2+\ce{Cu^2+}.

(ii) Balanced equations.

2 KMnOX4→ΔKX2MnOX4+MnOX2+OX2\ce{2KMnO4 ->[\Delta] K2MnO4 + MnO2 + O2} …

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