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The correct order of decreasing second ionization enthalpy of Ti(22), V(23), Cr(24) and Mn(25) is:

A

Cr > Mn > V > Ti

B

V > Mn > Cr > Ti

C

Mn > Cr > Ti > V

D

Ti > V > Cr > Mn

Step-by-Step Solution

To determine the order of second ionization enthalpies, we must look at the electronic configurations of the unipositive ions (M+M^+) from which the second electron is removed:

  • Ti (Z=22): Ground state [Ar]3d24s2[Ar]3d^2 4s^2. Ti+Ti^+ is [Ar]3d24s1[Ar]3d^2 4s^1. Electron removed from 4s4s.
  • V (Z=23): Ground state [Ar]3d34s2[Ar]3d^3 4s^2. V+V^+ is [Ar]3d34s1[Ar]3d^3 4s^1. Electron removed from 4s4s.
  • Cr (Z=24): Ground state [Ar]3d54s1[Ar]3d^5 4s^1 (exceptionally stable half-filled dd-shell). Cr+Cr^+ is [Ar]3d5[Ar]3d^5. The second electron must be removed from the stable half-filled 3d3d orbital, requiring a very high amount of energy.
  • Mn (Z=25): Ground state [Ar]3d54s2[Ar]3d^5 4s^2. Mn+Mn^+ is [Ar]3d54s1[Ar]3d^5 4s^1. Electron removed from 4s4s.

Trends:

  1. Cr vs others: The second ionization enthalpy of Cr is exceptionally high because it involves breaking the stable half-filled d5d^5 configuration (1592 kJ mol11592 \text{ kJ mol}^{-1}).
  2. Mn, V, Ti: For these elements, the second electron is removed from the 4s4s orbital (or destabilizes the shell less than breaking a half-filled shell). The energy required generally follows the trend of increasing effective nuclear charge across the period. Thus, Mn(1509)>V(1414)>Ti(1309)Mn (1509) > V (1414) > Ti (1309) in kJ/mol .

Combining these, the correct order is Cr>Mn>V>TiCr > Mn > V > Ti.

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