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Q.(a)

(i) From the given data of E∘E^{\circ} values, answer the following questions : EM2+/M∘E^{\circ}_{M^{2+}/M} (in V): V =−1.18= -1.18 | Cr =−0.91= -0.91 | Mn =−1.18= -1.18 | Fe =−0.44= -0.44 | Co =−0.28= -0.28 | Ni =−0.25= -0.25 | Cu =+0.34= +0.34 (I) Why EM2+/M∘E^{\circ}_{M^{2+}/M} show irregular trend in the above values ? (II) Why is ECu2+/Cu∘E^{\circ}_{Cu^{2+}/Cu} value exceptionally positive ? (III) Why EMn2+/Mn∘E^{\circ}_{Mn^{2+}/Mn} value is highly negative ?
(ii) Write the ionic equations for the oxidising action of potassium permanganate for its reaction with I−I^- in both acidic and alkaline solutions.
(OR)
(b) Answer the following questions :
(i) Name a member of the lanthanoid series (I) which exhibits +4 oxidation state (II) which exhibits +2 oxidation state.
(ii) Why transition metals act as good catalyst ?
(iii) Why Cr has higher melting point than Mn ?
(iv) What happens when acidic solution of potassium permanganate is allowed to stand for sometime ? Give the equation involved. What is this type of reaction called ?
CBSECBSE Class XII Board 2026Subjective· 5mImportance★★★★★
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Part (a): the EM2+/M∘E^\circ_{M^{2+}/M} trend is irregular (sublimation+ionisation+hydration enthalpies); Cu is exceptionally positive, Mn highly negative (stable half-filled Mn2+Mn^{2+}); KMnO4KMnO_4 oxidises I−I^- to I2I_2 (acidic) or IO3−IO_3^- (alkaline).

Part (b): Ce shows +4, Eu +2; transition metals catalyse via variable states/vacant d-orbitals; Cr melts higher than Mn; acidified KMnO4KMnO_4 decomposes (4MnO4−+4H+→4MnO2+3O2+2H2O4MnO_4^-+4H^+\to4MnO_2+3O_2+2H_2O) — an auto-oxidation.


Part (a)

(i) Interpreting the EM2+/M∘E^\circ_{M^{2+}/M} values

EM2+/M∘E^\circ_{M^{2+}/M} is governed by ΔHsub+(IE1+IE2)+ΔHhyd\Delta H_{sub} + (IE_1+IE_2) + \Delta H_{hyd}, none of which vary smoothly.

  • (I) Irregular trend: the three enthalpies vary irregularly, and extra stability of half-filled (Mn2+Mn^{2+} d5d^5) or the special hydration/ionisation of Cu2+Cu^{2+} distort the values (V and Mn both −1.18-1.18, Cr −0.91-0.91, Cu +0.34+0.34).
  • (II) Cu2+/CuCu^{2+}/Cu exceptionally positive (+0.34+0.34 V): the very high (IE1+IE2)(IE_1+IE_2) of copper is not compensated by its enthalpy of atomisation and hydration, so Cu2+Cu^{2+} is readily reduced to Cu (Cu is a poor reducing metal — it does not liberate H2H_2 from acids).
  • (III) Mn2+/MnMn^{2+}/Mn highly negative (−1.18-1.18 V): Mn2+Mn^{2+} has a stable half-filled 3d53d^5 configuration; it forms easily from Mn and resists reduction back to Mn, giving a strongly negative potential.

(ii) Oxidising action of KMnO4KMnO_4 with I−I^-

  • Acidic medium (MnO4−→Mn2+MnO_4^- \rightarrow Mn^{2+}, I−→I2I^- \rightarrow I_2):

2MnO4−+16H++10I−→2Mn2++8H2O+5I22MnO_4^- + 16H^+ + 10I^- \rightarrow 2Mn^{2+} + 8H_2O + 5I_2

  • Alkaline medium (MnO4−→MnO2MnO_4^- \rightarrow MnO_2, I−→IO3−I^- \rightarrow IO_3^-): …

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