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How would you account for the irregular variation of ionization enthalpies (first and second) in the first series of the transition elements? - CBSE (Science) Class 12 - Chemistry

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Question

How would you account for the irregular variation of ionization enthalpies (first and second) in the first series of the transition elements?

Solution 1

Ionization enthalpies are found to increase in the given series due to a continuous filling of the inner d-orbitals. The irregular variations of ionization enthalpies can be attributed to the extra stability of configurations such as d0d5d10. Since these states are exceptionally stable, their ionization enthalpies are very high.

In case of first ionization energy, Cr has low ionization energy. This is because after losing one electron, it attains the stable configuration (3d5). On the other hand, Zn has exceptionally high first ionization energy as an electron has to be removed from stable and fully-filled orbitals (3d10 4s2).

Second ionization energies are higher than the first since it becomes difficult to remove an electron when an electron has already been taken out. Also, elements like Cr and Cu have exceptionally high second ionization energies as after losing the first electron, they have attained the stable configuration (Cr+: 3d5and Cu+: 3d10). Hence, taking out one electron more from this stable configuration will require a lot of energy.

Solution 2

There is a irregularity in the IE’s of 3d-series due to alternation of energies of 4s and 3d orbitals when an e-1 is removed. Thus, there is a reorganisation energy accompanying ionization. This results into release of exchange energy which increases as the number of e-1 s increases in the dn configuration. Cr has low 1st IE because loss of 1 e- gives stable EC (3d6). Zn has very high IE because e~ has to be removed from 4s orbital of the stable configuration (3d10 4s2) After the loss of one e, removal of 2nd e, becomes difficult. Hence, 2nd IE’s are higher and in general, increase from left to right. However, Cr and Cu show much higher values because 2nd e– has to be removed from stable configuration of Cr+ (3d5) and Cu+ (3d10)

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 NCERT Solution for Chemistry Textbook for Class 12 (2018 to Current)
Chapter 8: The d-block and f-block Elements
Q: 5 | Page no. 219

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Solution How would you account for the irregular variation of ionization enthalpies (first and second) in the first series of the transition elements? Concept: General Properties of the Transition Elements (D-block).
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