Important questions based on NCERT syllabus for Chapter 8 - The d and f Block Elements:
Question-1: How would you account for the irregular variation of ionisation enthalpies (first and second) in the first series of the transition elements?
Solution: 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)
Question-2: To what extent do the electronic configurations decide the stability of oxidation states in the first series of the transition elements? Illustrate your answer with examples.
Solution: In the first series of transition elements, the oxidation states which lead to exactly half-filled or completely filled d-orbitals are more stable. For example, Mn (Z = 25) has electronic configuration [Ar] 3d5 4 s2. It shows oxidation states + 2 to + 7 but Mn (II) is most stable because of half-filled configuration [Ar] 3d5. Similarly Sc3+ is more stable then Sc+ and Fe3+ is more stable than Fe2+ due to half filled it f-orbitals.
Question-3: How is the variability in oxidation states of transition metals different from that of the non transition metals? Illustrate with examples.
Solution: The variability of oxidation states, a characteristic of transition elements, arises due to incomplete filling of d-orbitals in such a way that their oxidation states differ from each other by unity, e.g., Fe2+, Fe3+, Cr2+, Cr3+. This is in contrast with the variability of oxidation states of non-transition elements where oxidation states normally differ by a unit of two. i.e., Sn2+, Sn4+, P3+ and P5+, etc.
In the p-block the lower oxidation states are favoured by the heavier members (due to inert pair effect), the opposite is true in the groups of J-block.For example, in group 6, Mo (VI) and W (VI) are found to be more stable than Cr (VI). Thus Cr (VI) in the form of dichromate in acidic medium is a strong oxidising agent, whereas MOO3 and WO3 are not.