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JEE Chemistry 2023 Question with Solution

Which of the following statements are correct?

(A) The M3+/M2+\mathrm{M}^{3+}/\mathrm{M}^{2+} reduction potential for iron is greater than manganese. (B) The higher oxidation states of first-row d-block elements get stabilized by oxide ion. (C) Aqueous solution of Cr2+\mathrm{Cr}^{2+} can liberate hydrogen from dilute acid. (D) Magnetic moment of V2+\mathrm{V}^{2+} is observed between 4.4-5.2BM4.4\text{-}5.2\,\mathrm{BM}.

  • A

    (C) , (D) only

  • B

    (B) , (C) only

  • C

    (A) , (B), (D) only

  • D

    (A) , (B) only

Answer

Correct answer:B

Step-by-step solution

Standard Method

Given: Four statements about reduction potential, stabilization of oxidation states, reducing behaviour of Cr2+\mathrm{Cr}^{2+}, and magnetic moment of V2+\mathrm{V}^{2+} are to be checked.

Find: Which statements are correct.

For statement (A), compare the standard reduction potentials:

EMn3+/Mn2+=+1.57V,EFe3+/Fe2+=+0.77VE^\circ_{\mathrm{Mn}^{3+}/\mathrm{Mn}^{2+}} = +1.57 \, \text{V}, \quad E^\circ_{\mathrm{Fe}^{3+}/\mathrm{Fe}^{2+}} = +0.77 \, \text{V}

Since the value for manganese is greater than that for iron, statement (A) is incorrect.

For statement (B), higher oxidation states of first-row d-block elements are stabilized by oxide ion because strong metal-oxygen bonds are formed. Hence statement (B) is correct.

For statement (C), Cr2+\mathrm{Cr}^{2+} acts as a reducing agent and can reduce H+\mathrm{H}^+ to hydrogen:

Cr2++H+Cr3++12H2\mathrm{Cr}^{2+} + \mathrm{H}^+ \rightarrow \mathrm{Cr}^{3+} + \frac{1}{2}\mathrm{H}_2

Also,

ECr3+/Cr2+=0.26VE^\circ_{\mathrm{Cr}^{3+}/\mathrm{Cr}^{2+}} = -0.26 \, \text{V}

This confirms that aqueous Cr2+\mathrm{Cr}^{2+} can liberate hydrogen from dilute acid. So statement (C) is correct.

For statement (D), V2+\mathrm{V}^{2+} has three unpaired electrons, so its magnetic moment is approximately 3.87BM3.87\,\mathrm{BM}, which does not lie in the range 4.4-5.2BM4.4\text{-}5.2\,\mathrm{BM}. Therefore statement (D) is incorrect.

Thus, only statements (B) and (C) are correct. Therefore, the correct option is B.

Statement-wise Evaluation

(A) The claim says iron has greater M3+/M2+\mathrm{M}^{3+}/\mathrm{M}^{2+} reduction potential than manganese. But

EMn3+/Mn2+=+1.57VE^\circ_{\mathrm{Mn}^{3+}/\mathrm{Mn}^{2+}} = +1.57 \, \text{V}

and

EFe3+/Fe2+=+0.77VE^\circ_{\mathrm{Fe}^{3+}/\mathrm{Fe}^{2+}} = +0.77 \, \text{V}

Hence the claim is false.

(B) Oxide ion stabilizes higher oxidation states of transition metals by strong bonding, so this statement is true.

(C) Because Cr2+\mathrm{Cr}^{2+} is readily oxidized to Cr3+\mathrm{Cr}^{3+}, it can reduce acid to hydrogen gas. Thus this statement is true.

(D) For V2+\mathrm{V}^{2+}, the number of unpaired electrons is 33, giving spin-only magnetic moment near 3.87BM3.87\,\mathrm{BM}, not 4.4-5.2BM4.4\text{-}5.2\,\mathrm{BM}. So this statement is false.

Therefore the correct set is (B), (C) only.

Common mistakes

  • Comparing the reduction potentials in statement (A) in the wrong order. The given values show manganese has the higher M3+/M2+\mathrm{M}^{3+}/\mathrm{M}^{2+} reduction potential, not iron. Always compare the actual numerical EE^\circ values before deciding.

  • Assuming statement (B) is false by thinking higher oxidation states are always unstable. In first-row d-block elements, higher oxidation states are often stabilized by oxide ion because strong metal-oxygen bonds are formed. Focus on the ligand effect here.

  • Missing the reducing nature of Cr2+\mathrm{Cr}^{2+} in aqueous solution. Since Cr2+\mathrm{Cr}^{2+} is readily oxidized to Cr3+\mathrm{Cr}^{3+}, it can reduce H+\mathrm{H}^+ to H2\mathrm{H}_2. Check the sign and meaning of the electrode potential carefully.

  • Using the wrong number of unpaired electrons for V2+\mathrm{V}^{2+} in statement (D). V2+\mathrm{V}^{2+} is 3d33d^3 with three unpaired electrons, giving magnetic moment near 3.87BM3.87\,\mathrm{BM}. Do not assign a value corresponding to four unpaired electrons.

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