CHAPTER 4 - d AND f BLOCK ELEMENTS

1. What are transition elements?

Transition elements are those elements which have incompletely filled d orbitals in their
ground state or in any one of its stable oxidation states.

2. Zn, Cd and Hg are not considered as transition elements. Why?

The d orbitals in these elements are completely filled in the ground state as well as in their
stable oxidation state (2+).

3. Copper, silver and gold have completely filled d-orbital but they are known as transition
elements. Why?
Because they have incompletely filled d orbitals in one of their oxidation stable states.
Eg:- Cu2+ - [Ar] 4s03d9

4. Why do transition elements show similarities along the period?

Because in transition metals, electrons enter in d-orbital of second last shell but outer shell
electronic configuration remains the same.

5. With the increase in atomic number the atomic radius does not change very much in the
transition series. Why?
As atomic number increases, the nuclear charge increases, but the addition of electrons in d-
subshell increases the screening effect, which counterbalances the effect of increased nuclear
charge.

6. Towards the end of transition series, atomic radii of elements increase. Why?
Towards the end of transition series, electron-electron repulsion exceeds attractive force due to
increase in nuclear charge. Therefore, electron cloud expands and the size increases.

7. Transition elements show variable oxidation states. Why?

This is due to the participation of inner (n-1) d electrons in addition to outer ns electrons as the
energies of the ns and (n-1) d subshells are almost equal.

8. Transition elements have high enthalpy of atomization. Give reason.

This is due to greater number of unpaired electrons. They have very strong interatomic metallic
bonding and as a result high enthalpy of atomization and high boiling point.
Enthalpy of atomization is maximum at the middle of each transition series due to maximum
number of unpaired electrons.

9. In the series Sc to Zn the enthalpy of atomization of zinc is lowest. Why?

Outer electronic configuration of Zn is 3d104s2.This shows that there are no unpaired electrons.
Thus, the inter atomic metallic bonding in zinc is weakest. So, enthalpy of atomization is
lowest.

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10. Transition elements have high melting point. Give reason.
This is due to the involvement of greater number of electrons from (n-1)d in addition to the ns
electrons in the interatomic metallic bonding.

11. Why do transition metals form coloured compounds?

They form coloured compounds due to the presence of unpaired d electrons. An electron from
a lower energy d orbital is excited to a higher energy d orbital by absorbing certain frequency
of light. This is known as d-d transition. The colour observed corresponds to the
complementary colour of the light absorbed.

12. Why do transition metals form complexes?

i) Comparatively smaller size of metal ions
ii) High ionic charge
iii) Availability of d orbitals for bond formation.

13. Transition metals and their many compounds act as good catalyst. Explain.
It is due to the following reasons: -
i) Ability to show variable oxidation states
ii) Ability to form complexes / provide large surface area.

14. Why do transition metals form interstitial compounds?

Transition metals form interstitial compounds due to their ability to trap small atoms like H, C
or N inside the crystal lattices.
Eg:- Fe3H, VH0.56

15. Why do transition metals form alloys?

Alloys are formed by atoms with metallic radii that are within about 15 percent of each other.
Due to similar radii, transition metals form alloys
Eg:- Brass (copper-zinc) and bronze (copper-tin)

16. Even though Mn has the maximum number of unpaired electrons (5) in the 3d series, its
melting point is less. Why?
Mn has a stable electronic configuration (half filled-3d5) and as a result 3d electrons are more
tightly held by the Mn atomic nucleus and this reduces delocalization of electrons resulting
weaker metallic bonding than previous element (Cr).

17. Among the first transition metals, which divalent metal ion has maximum paramagnetic
character and why?
Mn2+, because of maximum number (5) of unpaired electrons. (3d5)

18. Name the metal in 3d series which exhibits +1 oxidation state most frequently.

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 Copper
19. What is lanthanoid contraction? What are the consequences of lanthanoid contraction?
The overall decrease in the atomic and ionic radii from La to Lu due to the poor shielding
effect of 4f orbitals is called lanthanoid contraction.

Consequences
i) Resemblances of 2nd and 3rd transition series.
Eg:- Atomic radii of 2nd and 3rd transition series elements remain almost the same.
Atomic radius of Zr is 160 pm and that of Hf is 159 pm.

ii) Similarity among lanthanoids

It is very difficult to separate the lanthanoids in their pure state.
.
iii) Basicity differences
As a result of decrease in size, covalent character between lanthanide ion and OH-
increases from La3+ to Lu3+. Therefore, basic strength of hydrides decreases with increase
in atomic number.
Eg:- La(OH)3 is most basic while Lu(OH)3 is least basic.

20. Copper (I) compounds are white and diamagnetic but copper (II) compounds are
coloured and paramagnetic. Why?
In copper (I) ion all orbitals are completely filled so its compounds are white and diamagnetic.
The electronic configuration of copper (II) ion is 1s22s22p63s23p63d9. it has one unpaired
electron so it is paramagnetic and forms blue coloured compounds.

21. Why do Eθ(M2+/M) values show irregular trend from Vanadium to Zinc?
Because of irregular values of (∆iH1+∆iH2) and sublimation enthalpies.

22. Why is the highest oxidation state of a metal exhibited in its oxide or fluoride only?
Oxygen and fluorine can oxidise the metal to its highest oxidation states due to small size
and high electronegativity.
23. Which is more stable in aqueous solution, Cu+ or Cu2+? Give reason.
In aqueous solution, Cu2+ is more stable than Cu+.
In aqueous solution, Cu+ undergoes disproportionation.
2Cu+(aq) → Cu2+(aq) + Cu(s).

24. The ability of oxygen to stabilize the high oxidation states exceeds that of fluorine. Why?
This is due to the ability of oxygen to form multiple bonds to metals.
Eg:- Highest Mn fluoride is MnF4 whereas the highest oxide is Mn2O7.

25. KMnO4 is a stronger oxidizing agent than K2Cr2O7. Give reason.

When acts as an oxidizing agent, MnO4- is converted to highly stable Mn2+(half filled d
configuration) and Cr2O72- is converted to lesser stable Cr3+.
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26. Which is stronger reducing agent, Cr2+ or Fe2+? Explain your answer.
Cr2+ is stronger reducing agent.
When acts as a reducing agent, Cr2+ → Cr3+ (d3) and Fe2+ → Fe3+ (d5). Cr3+ is more stable than
Fe3+ due to half-filled t2g configuration.

27. Why is Eθ value for Mn3+/Mn2+ couple much more positive than that for Cr3+/Cr2+ and
Fe3+/Fe2+? Explain.
Reduction from Mn3+ to Mn2+ is highly favorable because Mn2+ is very highly stable due to
half-filled state (d5). Therefore, 3rd ionization enthalpy of Mn is very high.

28. Calculate the magnetic moment of a trivalent ion if its atomic number is 27.
E3+ - 4s03d6. It contains 4 unpaired electrons.
Therefore, μ = √n(n+2)
=√4 x (4+2)
= √24 BM
29. How would you account for the following?

a) Of the d4 species Cr2+ is strongly reducing agent while manganese (III) is strongly
oxidizing agent.
b) Cobalt (II) is stable in aqueous solution but in the presence of complexing reagents it is
easily oxidized.
c) The d1 configuration is very unstable in ions.

a) Cr2+ is reducing, as its configuration changes from d4 to d3, the latter having a half filled
t2g level. On the other hand, the change from Mn3+ to Mn2+ results in the half filled (d5)
configuration which has extra stability.

b) Cobalt gets oxidized from +2 to +3 because Co(III) in octahedral field has extremely stable
t2g6 eg0 configuration, after pairing of 6 electrons.

c) The ions with d1 configuration have the tendency to lose the only electron present in d-sub
shell to acquire stable d0configuration and thus, has a very low ionization enthalpy.

30. Explain the characteristics of interstitial compounds.

i) High melting point
ii) Very hard
iii) Good conductivity
iv) Chemically inert.

31. Why are the ionization energies of 5d series elements greater than 3d series elements?
The atomic size of 5d series element is small and its nuclear charge is more due to lanthanoid
contraction. That is why ionization energies of 5d series element is greater than that of 3d
elements.

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32. Which of the following ions would be coloured?
Cu+, V2+, Sc3+, Ni2+
Cu+ 3d10 colourless.
2+ 3
V 3d coloured.
3+ 0
Sc 3d colourless
2+ 8
Ni 3d coloured.

33. Which one, Fe2+ & Fe3+, is more paramagnetic and why?
Fe - 3d6 4s2
Fe2+ 3d6 4 unpaired electrons.
Fe3+ 3d5 5 unpaired electrons.
More number of unpaired electrons, more paramagnetic. Thus, Fe3+ is more paramagnetic.

34. Zinc, cadmium and mercury are found to have low melting and boiling points. Explain.
The electronic configuration Zn, Cd and Hg is as follows
Zn - 3d10 4s2 Cd - 4d10 5s2 Hg - 5d10 6s2
Since all the electrons are paired so they have weak metallic bond and hence low melting and
boiling points.
35. Among the lanthanoides, Ce(III) can be easily oxidized to Ce (IV). Why?
Ce3+ (4f1 5do 6so) loses an electron to form Ce4+(4fo 5do 6so) which has all outer orbitals empty
and so has extra stability.

36. Why is the separation of lanthanoide elements difficult?

Due to lanthanoide contraction, all lanthanides have similar size and hence similar chemical
properties.

37. Name members of the lanthanoid series which are known to exhibit +4 oxidation state.
Cerium and Terbium.
Ce - [Xe] 4f0
4+
Tb4+ - [Xe] 4f7

38. Name members of the lanthanoid series which are known to exhibit +2 oxidation state.
Europium and Ytterbium
Eu2+ - [Xe] 4f7 Yb2+ - [Xe] 4f14

39. Cu(II) iodide is not known. Why?

Cu2+ has strong tendency to oxidise I – to iodine.

40. Write the general electronic configuration of f-block elements.

(n2)f 114 (n  1) d 0 – 1 ns 2
41. How is the variability in oxidation states of transition metals different from that of the
non-transition elements?

In transition metals, oxidation states differ by +1 whereas in non-transition, it is by +2.

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. 42. Cr(VI) in the form of dichromate (Cr2O72-) in acidic medium is a strong oxidising agent,
whereas MoO3 and WO3 are not. Why?
On moving down the group in the transition elements, the stability of higher oxidation states
increases. This is due to the similarity of the energy of (n-1) d orbitals with ns orbitals on
moving down the group. Hence the d orbitals are more available towards the bond formation.
43. The lower oxides of transition metals are basic whereas the highest are amphoteric/acidic.
Why?
Lower oxides of transition metals are ionic & ionic character decreases or covalent character
increase with increase in oxidation state.

IONIC EQUATIONS – COVERSIONS

In Acid medium In Alkaline (Basic) medium
i) MnO4- → Mn2+ i) MnO4- → MnO2
ii) Cr2O72- → Cr3+ ii) I- → IO3-
iii) C2O42- → CO2 iii) S2O32- → SO42-
iv) Fe2+ → Fe3+
v) NO2- → NO3-
vi) I- → I2
vii) H 2S → S
viii) SO32- → SO42-
ix) S2O32- → S4O62-
x) Sn2+ → Sn4+

POTASSIUM DICHROMATE, K2Cr2O7

Preparation
Step 1
Iron chromite (FeCr2O4) is first fused with Na2CO3 in presence of free oxygen.

Step 2
The yellow solution of sodium chromate is filtered and acidified with sulphuric acid.

Step 3
Sodium dichromate is then treated with KCl to crystallize out orange K2Cr2O7

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Inter-conversion of chromate and dichromate ions
1. In acid medium

2. In alkaline/basic medium

STRUCTURES

POTASSIUM PERMANGANATE, KMnO4

Preparation of KMnO4
Step I: MnO2 is fused with KOH and an oxidizing agent like KNO3 to give dark green K2MnO4.
2MnO2 + 4KOH + O2 → 2 K2MnO4 + 2H2O

Step II: K2MnO4 disproportionates in a neutral or acidic solution to give dark purple KMnO4
3 MnO42- + 4H+ → 2MnO4- + MnO2 + 2H2O

Commercial preparation
Step I: MnO2 is fused with KOH and an oxidizing agent like KNO3 to give dark green K2MnO4.
Step II: Electrolytic oxidation of K2MnO4 to KMnO4 in alkaline solution.

Laboratory preparation
Oxidation of Mn2+ to permanganate by peroxodisulphate (S2O82-)
2Mn2+ + 5 S2O82- + 8H2O → 2MnO4- + 10SO42- + 16H+

Qn. Which is paramagnetic, KMnO4 or K2MnO4? Why?

K2MnO4, due to the presence of one unpaired electron.
Qn. Hydrochloric acid is not used in the titration with KMnO4. Why?
HCl is oxidized by KMnO4 to Cl2
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STRUCTURES

ACTINOIDS

1. The chemistry of actinoid elements is not so smooth as that of the lanthanoids. Explain.
Lanthanoids show limited number of oxidation states (+2, +3, +4) but +3 oxidation state is
most common. The dominant oxidation state of actinoids is also +3 but actinoids show many
other oxidation states as well. This is due to a small energy difference between 5f, 6d and 7s
subshells of actinoids.

2. Actinoid contraction is greater from element to element than lanthanoid contraction.

Why?
This is due to the poorer shielding effect of 5f electrons in actinoids than to 4f electrons in
lanthanoids.

3. Actinoids show a greater number of oxidation states than lanthanoids. Why?

5f orbitals are not as buried as 4f orbitals. Hence, 5f electrons can participate in bonding to a
greater extent. Only a small energy difference between 5f, 6d and 7s subshells

4. Differentiate between Lanthanoids and Actinoids.

No. Lanthanoids Actinoids

don’t show a wide range of Show a wide range of oxidation
1 oxidation state. Besides the states. Besides the common 3+
common 3+ state, some lanthanoids state, they show +4, +5, +6 and
exhibit 2+ and 4+ states too +7+
2. Lesser tendency to form complexes Greater tendency to form
complexes
3. Do not form oxoanions They form oxoanions.
Eg:- UO2+, UO+, PuO2+ etc.
4. Non-radioactive, except All are radioactive
Promethium
5. Most of their ions are colourless Most of their ions are coloured

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IMPORTANT EQUATIONS

1.

2.

3.

4. 3 MnO4 2– + 4 H+ → 2 MnO4- + MnO2 + 2H2O

Similarities between chemistry of lanthanoids and actinoids

1. Both show variable oxidation states

2. Both show f-f transitions
3. Both show irregularity in electronic configuration.
4. Both have common +3 oxidation state
5. Both show contraction in atomic radii.
6. Ions are coloured.

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