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Q.Give reasons for the following:

(a) Transition metals form complex compounds.
(b) E∘E^\circ values for (Zn2+/Zn)(Zn^{2+}/Zn) and (Mn2+/Mn)(Mn^{2+}/Mn) are more negative than expected.
(c) Actinoids show wide range of oxidation states.
CBSECBSE Class XII Board 2019Subjective· 3mImportance★★★★★
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The answer explains three distinct properties of d- and f-block elements: (a) transition metals form complexes due to small size, high charge, and vacant d-orbitals;

(b) Zn and Mn have anomalously negative E∘E^\circ values because of stable electronic configurations (filled d¹⁰ and half-filled d⁵);

(c) actinoids show many oxidation states because 5f, 6d, and 7s orbitals are close in energy, allowing variable electron loss.


(a) Transition metals form complex compounds.

Concept and intuition:

A complex compound (or coordination compound) forms when a central metal ion is surrounded by molecules or ions (ligands) that donate electron pairs. For this to happen, the metal must have two things: the ability to accept electrons (vacant orbitals) and a strong enough positive field to attract the ligands. Transition metals are uniquely suited for this.

Step-by-step reasoning:

  1. Small size and high charge density — Transition metal ions are relatively small and carry a positive charge (often +2 or +3). This creates a strong electrostatic field that attracts electron-rich ligands (like NH3\text{NH}_3, H2O\text{H}_2\text{O}, Cl−\text{Cl}^-). The higher the charge on the ion, the stronger the attraction.

  2. Availability of vacant d-orbitals — In transition metals, the (n−1)d(n-1)d orbitals are incompletely filled. These orbitals are of suitable energy and symmetry to accept lone pairs from ligands, forming coordinate bonds. The d-orbitals also participate in π\pi-back bonding in many cases, further stabilising the complex.

  3. Variable oxidation states — Because transition metals can exist in multiple oxidation states, they can form complexes with different ligands and geometries. This flexibility is rare in main-group elements.

  4. Small size favours high coordination numbers — The compact nature of transition metal ions allows several ligands to pack around them without excessive steric hindrance.

Tip

A quick way to remember: transition metals are like "electron-pair magnets" — they have the space (vacant d-orbitals) and the pull (high charge) to grab ligands.


(b) E∘E^\circ values for (Zn2+/Zn)(Zn^{2+}/Zn) and (Mn2+/Mn)(Mn^{2+}/Mn) are more negative than expected.

Concept and intuition:

Standard electrode potential E∘E^\circ measures the tendency of a metal to lose electrons and go into solution as its ion. A more negative E∘E^\circ means the metal is less easily reduced (or more easily oxidised). For Zn and Mn, the values are unusually negative compared to their neighbours in the 3d series. The reason lies in the stability of the electronic configurations of the ions formed.

Step-by-step reasoning:

  1. General trend in 3d series — For most 3d metals, E∘E^\circ values become less negative as we move from left to right, because nuclear charge increases and atomic size decreases, making it harder to remove electrons. But Zn and Mn break this pattern.

  2. Zinc (Zn2+\text{Zn}^{2+}) — Zinc loses two 4s electrons to form Zn2+\text{Zn}^{2+}, which has a completely filled d¹⁰ configuration (3d103d^{10}). This is an exceptionally stable arrangement. The stability of Zn2+\text{Zn}^{2+} means that the reverse reaction (reduction of Zn2+\text{Zn}^{2+} to Zn) is energetically unfavourable, so E∘E^\circ is very negative (−0.76-0.76 V).

  3. Manganese (Mn2+\text{Mn}^{2+}) — Manganese loses two 4s electrons to form Mn2+\text{Mn}^{2+}, which has a half-filled d⁵ configuration (3d53d^5). Half-filled shells have extra stability due to exchange energy and symmetry. Again, this makes Mn2+\text{Mn}^{2+} very stable, so reduction to Mn metal is difficult, giving a more negative E∘E^\circ (−1.18-1.18 V) than expected from the trend.

Watch out

A common mistake is to think that a more negative E∘E^\circ means the metal is more stable. Actually, it means the ion is more stable relative to the metal. The metal itself is more reactive (easily oxidised).

For a half-cell reaction Mn++ne−→M\text{M}^{n+} + n e^- \rightarrow \text{M}, a more negative E∘E^\circ implies the equilibrium lies to the left — the metal is a stronger reducing agent.


(c) Actinoids show a wide range of oxidation states.

Concept and intuition:

Actinoids are the 5f series (elements 90–103). Unlike lanthanoids (4f), where the 4f orbitals are deeply buried and shielded, the 5f orbitals in actinoids are more diffuse and closer in energy to the 6d and 7s orbitals. This allows electrons to be removed from multiple orbitals with relatively small energy differences. …

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