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D and F Block Element

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D and F Block Element

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D AND F BLOCK ELEMENT

1. What is meant by ‘lanthanoid contraction?


Answer:
Lanthanoid contraction: The overall decrease in atomic and ionic radii with
increasing atomic number is known as lanthanoid contraction. In going from La+3 to
Lu+3 in lanthanoid series, the size of ion decreases. This decrease in size in the
lanthanoid series is known as lanthanoid contraction. The lanthanoid contraction
arises due to imperfect shielding of one 4f electron by another present in the same
subshell.

2. Explain the following observations :


(i) Transition elements generally form coloured compounds.
(ii) Zinc is not regarded as a transition element.
Answer:
(i) Because of presence of unpaired d electrons, which undergoes d-d transition by
absorption of energy from visible region and then the emitted light shows complementary
colours. This is how transition elements form coloured compounds.
(ii) Zinc in its common oxidation state of +2 has completely filled d-orbitals. Hence
considered as non-transition element.

3. Assign reasons for each of the following :


(i) Transition metals generally form coloured compounds.
(ii) Manganese exhibits the highest oxidation state of +7 among the 3d series of transition
elements.
Answer:
(i) Because presence of unpaired d electrons, which undergoes d-d transition by absorption
of energy from visible region and then the emitted light shows complementary colours.
(ii) Manganese exhibits highest oxidation of +7 among 3d series of transition elements
because all the oxidation states are exhibited from +2 to +7 by Mn and no other element of
this series shows this highest state of oxidation.

4. Complete the following chemical equations :


(i) MnO4 (aq) + S2O32- (aq) + H2O (1) →
(ii) Cr2O72- (aq) + Fe2+ (aq) + H+ (aq) →
Answer:

5. Assign a reason for each of the following observations:


(i) The transition metals (with the exception of Zn, Cd and Hg) are hard and have high
melting and boiling points.
(ii) The ionization enthalpies (first and second) in the first series of the transition elements
are found to vary irregularly.
Answer:
(i) Because of stronger metallic bonding and high enthalpies of atomization.
(ii) Due to irregulaties in the electronic configuration there is irregularities in the enthalpies of
atomisation. Hence there is irregular variation in I.E.

6. Explain the following observations :


(a) Silver atom has completely filled d-orbitals (4d10) in its ground state, yet it is regarded as
a transition element.
(b) E0 value for Mn3+ /Mn2+ couple is much more positive than Cr3+/Cr2+.
Answer:
(a) Because silver has incomplete d-orbital (4d9) in its +2 oxidation state, hence it is a
transition element.
(b) The large positive E° value for Mn3+/Mn2+ shows that Mn2+ is much more stable than
Mn+3 due to stable half filled configuration (3d5). Therefore the 3rd ionisation energy of Mn will
be very high and Mn3+ is unstable and can be easily reduced to Mn2+. E° value for Cr3+ | Cr2+ is
positive but small i.e. Cr3+ can also be reduced to Cr2+ but less easily. Thus Cr3+ is more
stable than Mn3+.

7. Explain the following observations giving an appropriate reason for each.


(i) The enthalpies of atomization of transition elements are quite high.
(ii) There occurs much more frequent metal- metal bonding in compounds of heavy transition
metals (i.e. 3rd series).
(iii) Mn2+ is much more resistant than Fe2+ towards oxidation.
Answer:
(i) In transition elements, there are large number of unpaired electrons in their atoms, thus
they have a stronger inter atomic interaction and thereby stronger bonding between the
atoms. Due to this they have high enthalpies of atomization.
(ii) Because of high enthalpy of atomisation of 3rd series, there occurs much more frequent
metal-metal bonding in compounds of heavy transition metals.
(iii) The 3d orbital in Mn2+ is half-filled and is more stable compared to Fe2+ has 6 electrons in
the 3d orbital. Mn2+ prefer to lose an electron or get oxidised whereas Fe2+ will readily loose
one electron or get oxidised. Therefore, Mn2+ is much more resistant than Fe2+ towards
oxidation.

8. Why are E- values for Mn, Ni and Zn more negative than expected?

Answer:

The metals will quickly lose their electrons and get oxidised. A negative E value
means that the oxidised species is more stable than the reduced species. Here,
Mn2+ (3d5) and Zn2+ (3d10) have half-filled and fully filled d orbitals, giving them
stability and, therefore, prefer to stay that way and not get reduced. Ni2+ (3d8) has
very high negative hydration enthalpy, balanced by first and second ionisation
enthalpy.
9. Although Zr belongs to 4d and Hf belongs to 5d transition series but it is quite
difficult to

separate them. Why?

Answer:

Separation of Zr and Hf is pretty tricky because of lanthanoid contraction. Due to


lanthanoid contraction, they have almost identical sizes (Zr = 160 pm and Hf =159
pm) and, thus, similar chemical properties. That’s why it is tough to separate them by
chemical methods.

10. E0 of Cu is + 0.34V while that of Zn is – 0.76V. Explain.

Answer:

High ionisation enthalpy to transform Cu(s) to Cu2+ (aq) is not balanced by its
hydration enthalpy. However, in case of Zn, after removing electrons from 4s-orbital,
a stable 3d10 configuration is acquired. Thus, value of E0 of Cu is + 0.34V while that of
Zn is – 0.76V.

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