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The D-And-f-Block Elements

Question
CBSEENCH12007201

Give reasons:
(i) The d-orbital of Cu is completely filled (3d104s1) still it is considered as transition metal but Zn (3d104s2) is not.

(ii) Zinc salts are colourless at room temperature but nickel salts are coloured.

(iii) The atomic radii of europium and ytterbium do not fit into the concept of lanthanide contraction but ionic radii fit in.

(iv) The atomic radius of Cu is greater than that of Cr but ionic radius of Cr2+ is greater than that of Cu2+.

(v) Cu2+ is colourless while Cu2+ is blue in aqueous solution.

 

Solution

(i) The quantum mechanical definition of a transition element demands that there should be incomplete d-orbital either in the atom or ion of that element. In Cu atom (3d104s1) the 3d10 1s completely filled but in its Cu2+ ion (3d94s0) one of the 3d-orbitals is only half filled. Therefore, copper is a transition elements. On the other hand, in Zn (3d104s2) or Zn2+ (3d104s0) the 3d-orbital is completely filled. Therefore, zinc is not considered as a true transition element, but its electronic configuration does not fit in the quantum mechanical definition.


(ii) Zinc salts are colourless because in Zn2+ ion (3d04s0) there is no unpaired electron in its d-orbital rather 3d orbital is completely filled. Therefore, the visible light is not absorbed but it is transmitted through zinc salts. On the other hand, nickel salts are coloured because in Ni2+ ion (3d84s0) there are 2 unpaired electrons in 3d orbital
( ).
Therefore, some light is absorbed for d-d transition and the complementary part is transmitted. The colour of nickel salt is because of the partly transmitted radiation.


(iii)    Ca. In europium (Eu = 4f75d6s2) the f-orbital is half filled. There are only 2 electrons in 6s-orbitals available for the formation of metallic bond in the crystal lattice of Europium. So, the crystal lattice is less compact. The atomic separation in Eu is large as compared to other metals in which 3 or more electrons can take part in the formation of metallic bonds.
In Ytterbium (Yb = 4f145d06s2) the f-orbitals is completely filled. Therefore, the crystal lattice is less compact and the atomic separation is large. Therefore, the metallic radius of Yb is larger than other members of lanthanide series.
The lanthanide contraction in ionic radii r(M3+) of tri-positive cations is quite smooth because three electrons are removed from the valence orbitals.


(iv)    The atomic radius of Cu is greater than that of Cr because in Cu atom (3d104s1) the d-d electron repulsion is large due to pairing of electrons (       ).
But in Cr atom (3d34s1) the d-d electron repulsion is minimum as the 3d orbitals are singly occupied ().
The ionic radius of Cu2+ is less that of Cr+. Because in Cu2+ ion (3d9) the d-d electron repulsion is reduced due to unpairing of electron spins (   ) and the other electrons are attracted by 29 protons of the nucleus.
Therefore, the attraction of nucleus on the outer electron has become strong and d-electrons are pulled inward.

In Cr2+ the 3d4 electrons are still unpaired (), and there are attracted by only 24 protons of nucleus.


(v) The ion which has unpaired electron is coloured in aqueous solution. Thus Cu+(ion) [s22s22p63s23p63d104s0] does not have any unpaired electron, hence its aqueous solution is colourless.
Cu2+ (ion) [1s22s22p63s23p63d94s0] has a unpaired electron in one of the 3d orbitals, therefore its aqueous solution is coloured (blue).