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Q.(i) Which ion amongst the following is colourless and why ? Ti4+Ti^{4+}, Cr3+Cr^{3+}, V3+V^{3+} (Atomic number of Ti = 22, Cr = 24, V = 23)

(ii) Why is Mn2+Mn^{2+} much more resistant than Fe2+Fe^{2+} towards oxidation ?
(iii) Highest oxidation state of a metal is shown in its oxide or fluoride only. Justify the statement.
CBSECBSE Class XII Board 2022Subjective· 3mImportance★★★★★
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Colour in transition metal ions arises from d–d transitions, which require unpaired d-electrons. Ti4+Ti^{4+} has a 3d03d^0 configuration (no d-electrons), so it cannot undergo d–d transitions and is colourless. Mn2+Mn^{2+} is more resistant to oxidation than Fe2+Fe^{2+} because its half-filled 3d53d^5 subshell gives exceptional stability. The highest oxidation state of a metal is achieved with oxygen or fluorine because these are the most electronegative elements, capable of stabilising high positive charges.


(i) Colourless ion: Ti4+Ti^{4+}

Why colour appears in transition metal ions

Colour in transition metal ions is primarily due to d–d transitions. When light falls on a transition metal ion, electrons in the lower-energy d-orbitals can absorb energy and jump to higher-energy d-orbitals. The energy gap between these orbitals depends on the metal, its oxidation state, and the surrounding ligands. The absorbed wavelength corresponds to a specific colour; the complementary colour is what we see.

For a d–d transition to occur, the ion must have at least one electron in the d-subshell — that is, the d-orbital must be partially filled. If the d-subshell is completely empty (d0d^0) or completely filled (d10d^{10}), no d–d transition is possible, and the ion appears colourless (or white).

Electronic configurations of the given ions

  1. Ti4+Ti^{4+}: Atomic number of Ti = 22. Ground state: [Ar] 3d2 4s2[Ar]\,3d^2\,4s^2. Removing four electrons (two from 4s and two from 3d) gives Ti4+Ti^{4+}: [Ar] 3d0[Ar]\,3d^0.

    → No d-electrons. No d–d transition. Colourless.

  2. Cr3+Cr^{3+}: Atomic number of Cr = 24. Ground state: [Ar] 3d5 4s1[Ar]\,3d^5\,4s^1 (exception due to half-filled stability). Removing three electrons (one from 4s and two from 3d) gives Cr3+Cr^{3+}: [Ar] 3d3[Ar]\,3d^3.

    → Unpaired d-electrons present. d–d transitions occur. Coloured (typically violet/green).

  3. V3+V^{3+}: Atomic number of V = 23. Ground state: [Ar] 3d3 4s2[Ar]\,3d^3\,4s^2. Removing three electrons (two from 4s and one from 3d) gives V3+V^{3+}: [Ar] 3d2[Ar]\,3d^2.

    → Unpaired d-electrons present. d–d transitions occur. Coloured (typically green).

Watch out

A common mistake is to think that any transition metal ion is coloured. Remember: d0d^0 and d10d^{10} configurations are colourless because no d-electrons are available to jump between d-orbitals. Sc3+Sc^{3+} (d0d^0) and Zn2+Zn^{2+} (d10d^{10}) are also colourless for the same reason.


(ii) Why Mn2+Mn^{2+} is more resistant to oxidation than Fe2+Fe^{2+}

The concept: half-filled subshell stability

A half-filled d-subshell (d5d^5) has all five d-orbitals singly occupied. This arrangement has extra stability due to:

  • Exchange energy: Electrons with parallel spins in different orbitals can exchange positions, lowering the total energy. The maximum number of such exchanges occurs in a half-filled set.
  • Symmetry: The spherical symmetry of a half-filled subshell distributes electron density evenly, reducing electron–electron repulsion.

Comparing Mn2+Mn^{2+} and Fe2+Fe^{2+}

IonElectronic configurationd-electron countStability
Mn2+Mn^{2+}[Ar] 3d5[Ar]\,3d^5d5d^5 (half-filled)Very stable
Fe2+Fe^{2+}[Ar] 3d6[Ar]\,3d^6d6d^6Less stable
  • Mn2+Mn^{2+} has a half-filled 3d53d^5 configuration. To oxidise it to Mn3+Mn^{3+}, you would have to remove an electron from this stable arrangement, breaking the half-filled stability. This requires a lot of energy, so Mn2+Mn^{2+} resists oxidation.
  • Fe2+Fe^{2+} has a 3d63d^6 configuration. Oxidising it to Fe3+Fe^{3+} gives 3d53d^5 — a half-filled, more stable configuration. So oxidation is actually favourable for Fe2+Fe^{2+}.
Tip

Think of it this way: Mn2+Mn^{2+} is already at a "peak" of stability (half-filled). Any change makes it less stable. Fe2+Fe^{2+} is one electron short of that peak — losing one electron gets it there. So Fe2+Fe^{2+} oxidises easily, while Mn2+Mn^{2+} does not.

Standard reduction potentials confirm this:

  • E∘(Mn3+/Mn2+)=+1.51 VE^\circ(Mn^{3+}/Mn^{2+}) = +1.51\ \text{V} (high positive value means Mn2+Mn^{2+} is hard to oxidise)
  • E∘(Fe3+/Fe2+)=+0.77 VE^\circ(Fe^{3+}/Fe^{2+}) = +0.77\ \text{V} (much lower, so Fe2+Fe^{2+} oxidises more readily)

(iii) Highest oxidation state of a metal is shown in its oxide or fluoride only

Why oxygen and fluorine are special

The highest oxidation state of a transition metal represents the maximum number of electrons it can lose (or share) in bonding. To achieve this, the bonding partner must be:

  • Highly electronegative — to pull electron density away from the metal.
  • Small in size — to form strong, short bonds that stabilise the high charge. …

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