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Q.(a) Complete the reactions:

(i) MnO4- + S2- -->
(ii) Cr2O7 2- + NO2- + H+ -->
(b) Explain, with reason:
(i) The Cr2+ ion acts as a reducing agent and the Mn3+ ion acts as an oxidising agent, although both have a d4 electron configuration.
(ii) Between La(OH)3 and Lu(OH)3, which is more basic, and why? ((1+1)+(1+1)=4)
Tripura TbseHigher Secondary (+2 Stage) Examination 2025Subjective· 4mImportance★★★★★
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Two redox equations to balance, then two 'why' questions rooted in the extra stability of half-filled/related d-configurations and in lanthanide contraction.

(a)(i) MnO4- + S2- (acidic medium).

Mn: +7 -> +2 (gain of 5 electrons per Mn). S: -2 -> 0 (loss of 2 electrons per S, forming elemental sulfur). To balance electrons, take 2 Mn (10 e- gained) and 5 S (10 e- lost):

2MnO4- + 5S2- + 16H+ -> 2Mn2+ + 5S(down arrow) + 8H2O

(Charge check: LHS = 2(-1)+5(-2)+16(+1) = -2-10+16 = +4; RHS = 2(+2) = +4. Balanced.)

(a)(ii) Cr2O7^2- + NO2- (acidic medium).

Cr: +6 -> +3 (2 Cr atoms gain 3 e- each = 6 e- total). N: +3 (in NO2-) -> +5 (in NO3-), losing 2 e- per N. To balance 6 electrons, need 3 NO2-:

Cr2O7^2- + 3NO2- + 8H+ -> 2Cr3+ + 3NO3- + 4H2O

(Charge check: LHS = -2+3(-1)+8(+1) = -2-3+8 = +3; RHS = 2(+3)+3(-1) = 6-3 = +3. Balanced.)

(b)(i) Cr2+ as reducing agent, Mn3+ as oxidising agent, both d4.

Cr2+ (d4) loses one electron to become Cr3+ (d3). The d3 configuration (t2g^3, half-filled t2g set) has extra stability from favourable exchange energy, so Cr2+ readily gives up an electron to reach this more stable state - i.e. it behaves as a good reducing agent.

Mn3+ (d4) gains one electron to become Mn2+ (d5). The d5 configuration is exactly half-filled, which carries maximal exchange-energy stabilisation (the most stable arrangement among d-configurations), so Mn3+ readily accepts an electron to reach it - i.e. it behaves as a good oxidising agent.

So although both start as d4, one (Cr2+) is driven to lose an electron and the other (Mn3+) is driven to gain one, because each is moving toward a different, more stable neighbouring configuration (d3 vs d5).

(b)(ii) La(OH)3 vs Lu(OH)3 basicity. …

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