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Q.Which one of the following first row transition elements is expected to have the highest third ionization enthalpy?
(A) Iron (Z = 26)
(B) Manganese (Z = 25)
(C) Chromium (Z = 24)
(D) Vanadium (Z = 23)

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✓ Free question

The third ionization enthalpy is highest for the element whose +2 ion has the most stable electronic configuration (half-filled or fully filled d-subshell). Among Fe, Mn, Cr, and V, the +2 ion of manganese (Mn²⁺) has a half-filled 3d⁵ configuration, making it exceptionally stable and hardest to remove an electron from. Thus, Mn has the highest third ionization enthalpy.

The key to this question lies not in memorizing numbers but in understanding what the third ionization enthalpy actually measures. It is the energy required to remove the third electron from a gaseous atom — that is, to go from the +2 ion to the +3 ion. So we are really comparing the stability of the M²⁺ ions of these elements. The more stable the M²⁺ ion, the harder it is to pull off another electron, and the higher the third ionization enthalpy.

Now, stability in transition metal ions is heavily influenced by the d-electron configuration. A half-filled d⁵ or fully filled d¹⁰ subshell confers exceptional stability. Let us examine each element’s +2 ion.

  1. Vanadium (Z = 23)

    Electronic configuration of V: [Ar] 3d3 4s2[\text{Ar}]\,3d^3\,4s^2

    V²⁺: remove two 4s electrons → [Ar] 3d3[\text{Ar}]\,3d^3

    This is neither half-filled nor fully filled. It is a relatively ordinary configuration.

  2. Chromium (Z = 24)

    Cr has a special ground state: [Ar] 3d5 4s1[\text{Ar}]\,3d^5\,4s^1 (half-filled d gives extra stability).

    Cr²⁺: remove the 4s electron and one 3d electron → [Ar] 3d4[\text{Ar}]\,3d^4

    This is not half-filled. The half-filled stability of Cr atom is lost in Cr²⁺.

  3. Manganese (Z = 25)

    Mn: [Ar] 3d5 4s2[\text{Ar}]\,3d^5\,4s^2

    Mn²⁺: remove two 4s electrons → [Ar] 3d5[\text{Ar}]\,3d^5

    This is exactly half-filled! The d⁵ configuration is exceptionally stable. Removing a third electron would break this stable half-filled shell, requiring a large amount of energy.

  4. Iron (Z = 26)

    Fe: [Ar] 3d6 4s2[\text{Ar}]\,3d^6\,4s^2

    Fe²⁺: remove two 4s electrons → [Ar] 3d6[\text{Ar}]\,3d^6

    This is one electron beyond half-filled. While not as stable as d⁵, it is more stable than d⁴ or d³, but still less stable than the half-filled d⁵ of Mn²⁺.

Watch out

A common mistake is to look at the stability of the neutral atom rather than the +2 ion. For example, Cr has a half-filled d⁵ configuration in its neutral state, but Cr²⁺ is d⁴ — not particularly stable. The third ionization enthalpy depends on the +2 ion, not the atom.

Tip

For first-row transition metals, the third ionization enthalpy often peaks at manganese because Mn²⁺ (d⁵) is the most stable +2 ion. The next highest is usually iron (d⁶), then chromium (d⁴), then vanadium (d³). This pattern is a direct consequence of exchange energy and half-filled shell stability.

Thus, the order of third ionization enthalpy is:

Mn > Fe > Cr > V.

✓Final answer

The element with the highest third ionization enthalpy is manganese (Mn), corresponding to option (B).

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