To determine the order of second ionization enthalpies, we must look at the electronic configurations of the unipositive ions (M+) from which the second electron is removed:
- Ti (Z=22): Ground state [Ar]3d24s2. Ti+ is [Ar]3d24s1. Electron removed from 4s.
- V (Z=23): Ground state [Ar]3d34s2. V+ is [Ar]3d34s1. Electron removed from 4s.
- Cr (Z=24): Ground state [Ar]3d54s1 (exceptionally stable half-filled d-shell). Cr+ is [Ar]3d5. The second electron must be removed from the stable half-filled 3d orbital, requiring a very high amount of energy.
- Mn (Z=25): Ground state [Ar]3d54s2. Mn+ is [Ar]3d54s1. Electron removed from 4s.
Trends:
- Cr vs others: The second ionization enthalpy of Cr is exceptionally high because it involves breaking the stable half-filled d5 configuration (1592 kJ mol−1).
- Mn, V, Ti: For these elements, the second electron is removed from the 4s 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) in kJ/mol .
Combining these, the correct order is Cr>Mn>V>Ti.