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The d & f – block elements

Give reasons for the following:
(1). Transition elements generally form coloured compounds.
Ans : The unpaired electrons of transition metals undergo d-d transition by absorbing light from
visible region and radiate complementary colour.

(2). In the series Sc (Z = 21) to Zn (Z = 30), the enthalpy of atomization of zinc is the lowest.
Ans : Due to the absence of unpaired electrons, the inter metallic bonding (M-M bonding) is
weakest in Zn and as a result, it has the least enthalpy of atomization.

3. The enthalpies of atomisation of transition elements are high

Ans : Transition elements have high effective nuclear charge and a large number of unpaired
electrons. Therefore, they form very strong metallic bonds. As a result, the enthalpy of
atomization of transition metals is high.

4.Transition elements are known to form many interstitial compounds.

Ans : It is because they have voids in crystal lattice in which small atoms like ‘C’ , ‘N’ , ‘H’
can fit into forming interstitial compounds .

5.The transition metals and many of their compounds act as good catalyst.
Ans : Because they have large surface area and and free valencies . So they can form unstable
intermediate compounds with reactants which readily changed into products.
6.The highest oxidation state of a metal is exhibited in its oxide or fluoride.
Ans : It is because , Oxygen and fluorine have high electronegativitity, small in size and strong
oxidising agents.

7.Transition metals exhibit variable oxidation states

Ans : It is because electrons from ns – orbitals as well as (n −1)d – orbitals take part in bond
formation .

8. In a transition series of metals , the metal which exhibits the greatest number of oxidation
states occurs in the middle of the series.
Ans : It is because the middle element Mn has electronic configuration 4s²3𝑑5 with 5 unpaired
electrons . Therefore it shows largest number of oxidation states

9.The atomic radii of the metals of the third (5d) series of transition elements are virtually
the same as those of the corresponding members of the second (4d) series.

Ans : Due to lanthanide contraction , effective nuclear charge remains almost same therefore
metallic redii are nearly same.

10. There is hardly any increase in atomic size with increasing atomic number in a series of
transition metals .
Ans : It is because effective nuclear charge does not increase appreciably as pairing of electrons
in d – orbitals take place which cause repulsion after Mn (Z = 25)
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11.The metal – metal bonding is more frequently found with the heavy transition metals
Ans : In the same group of d-block elements, the 4d and 5d transition elements are larger in size
than those of 3d elements. Hence, the valence electrons are less tightly held and form metal–
metal bond more frequently.

12.Scandium (Z = 21) does not exhibit variable oxidation states and yet it is regarded as a
transition element.
Ans : An element is called a transition element if it contains incomplete d orbital. Scandium
(Z = 21) is a transition metal as it has an incompletely-filled 3d orbital in the ground state (3d¹).

13.Zinc is not regarded as a transition element.

Ans : Because Zn has completely filled d – orbital (𝑑10) in its ground state and its oxidation state

13.Zn, Cd and Hg are volatile metals.

Ans: Since these elements has no any unpaired electrons , so they have weak metallic bond and
hence easily volatile.

14. Transition metals form a large number of complexes.

Ans: The transition metals form a large number of complex compounds due to
a) the comparatively smaller sizes of the metal ions
b) their high ionic charges
c) the availability of d orbitals for bond formation.

15.The transition metals (with the exception of Zn, Cd and Hg) are hard and have high melting and
boiling points.

Answer: Because of stronger metallic bonding and high enthalpies of atomization.

16. The ionization enthalpies (first and second) in the first series of the transition elements are
found to vary irregularly.

Ans: Due to irregularities in the electronic configuration there is irregularities in the enthalpies of
atomisation. Hence there is irregular variation in I.E.

17.There is a general increase in density from titanium (Z = 22) to copper (Z = 29).

Ans: From titanium to copper the atomic size of elements decreases and mass increases as A
result of which density increases

18.Both O2 and F2 stabilize high oxidation states of transition metals but the ability of oxygen to do
so exceeds that of fluorine.
Answer: The ability of O2 to stabilize higher oxidation states exceeds that of fluorine because
oxygen can form multiple bonds with metals

19. Silver atom has completely filled d-orbitals (4d10) in its ground state, yet it is regarded as a
transition element.
Answer: Because silver has incomplete d-orbital (4d9) in its +2 oxidation state, hence it is a
transition element.
20. Cu+ is not stable in aqueous solution.
Ans; Cu2+(aq) is much more stable than Cu+(aq). This is because hydration enthalpy) for Cu2+(aq)
is much more negative than that for Cu+(aq) and hence it more than compensates for the second
ionization enthalpy of copper. Therefore, Cu+ is unstable in aqueous solution and undergo
disproportionation as follows :
2Cu+ → Cu2+ + Cu
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21.Cr2+ is reducing in nature while with the same d-orbital configuration (d4) Mn3+ is an oxidising
agent.

Cr2+ has the configuration 3d4 which easily changes to d3 due to stable half filled t2g orbitals.
Therefore Cr2+ is reducing agent. While Mn2+ has stable half filled d5 configuration. Hence
Mn3+ easily changes to Mn2+ and acts as oxidising agent.

22.which is a stronger reducing agent Cr2+ or Fe2+ .why?

Ans; Cr2+ is a stronger reducing agent than Fe2+. Cr2+ (d4) is easily oxidised to Cr3+ (d3) which has
half filled t2g3 which is more stable than 3d5 in Fe3+

23. Out of 𝐶𝑟3+ and 𝑀𝑛3+, which is a stronger oxidising agent and why?

Ans: Mn³⁺ is oxidising in nature since Mn³⁺ is reduced into Mn²⁺

Mn³⁺ + e⁻ → Mn²⁺ , outer electronic configuration changes from 3𝑑4 to 3𝑑 5 which has extra
stability while Cr2+ is reducing as its configuration changes from d4 to d3

24. Mn²⁺ is much more resistant(stable) to oxidation than Fe²⁺

Ans- Electronic configuration of Mn²⁺ is [Ar] 3𝑑5 :
Electronic configuration of Fe²⁺ is [Ar] 3𝑑6
As we know 𝑑 5 configuration is more stable than 𝑑 6 configuration. Therefore, Mn²⁺ shows
resistance to oxidation to Mn³⁺.
On the other hand, Fe²⁺ has 3𝑑6 configuration and by losing one electron, its configuration
changes to a more stable 3𝑑5 configuration. Therefore, Fe²⁺ easily gets oxidized to Fe³⁺ state.

25. The E⁰ 𝑀2+/𝑀 value for manganese is much more negative than expected from the trend for
other elements in the series.
Ans : : Because of the stability of 𝑀𝑛2+ due to half filled 𝑑5 configuration

26. i)E°M2+/M values are not regular for first row transition metals (3d series).
ii) Mn (III) undergoes disproportionation reaction easily.
(iii) Co (II) is easily oxidised in the presence of strong ligands.

Ans; i) E°M2+/M values are not regular for first row transition metals due to abnormalities and
irregularities in their ionization enthalpies (IE1 + IE1) and sublimation enthalpies.

ii) Mn3+ is less stable and changes to Mn2+ which is more stable due to half filled d-orbital
configuration. That is why, Mn3+ undergoes disproportionation reaction.

(iii) Co (II) has electric configuration 3d7 4s0, i.e., it has three unpaired electron. In the presence of
strong ligands, two unpaired electrons in 3d subshell pair up and third unpaired electron shift to
higher energy subshell from where it can be easily lost and hence oxidised to Co(III).

27.The E°M2+/M, for copper is positive (+ 0.34 V). It is the only metal in the first series of transition
elements showing this type of behaviour.
Ans: The sum of high enthalpy of atomisation and ionisation is not balanced by the low hydration
enthalpy.

28.E0 value for Mn3+ /Mn2+ couple is much more positive than Cr3+/Cr2+.
Ans: 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+.
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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+.

29.The lowest oxide of transition metal is basic, the highest is amphoteric/acidic.

Ans-- Lower the oxidation state ,higher is the ionic character and so higher is the metallic character
and therefore higher is the basic character where as in higher oxidation state, lower is the ionic
character and so lower is the metallic character and therefore higher is the amphoteric/acidic
character . For example, MnO is basic and 𝑀𝑛₂𝑂7 is acidic

ANSWER THE FOLLOWING

30. In the 3d series (Sc = 21 to Zn = 30) :

(i) Which element shows maximum number of oxidation states? Ans; Mn
(ii) Which element shows only +3 oxidation state? Ans: Sc
(iii) Which element has the lowest enthalpy of atomization? Ans: Zn

31.Explain the preparation of potassium dichromate from chromite ore

32. When chromite ore FeCr2O4 is fused with NaOH in presence of air, a yellow coloured
compound (A) is obtained which on acidification with dilute sulphuric acid gives a compound (B).
Compound (B) on reaction with KCl forms an orange coloured crystalline compound (C).
(i) Write the formulae of the compounds (A), (B) and (C).
(ii) Write one use of compound (C)

Ans: A=Na2CrO4 B= Na2Cr2O7 C= K2Cr207 K2Cr207 is used as an oxidising agent

33.Complete the following equations

a) Cr2O72- + Fe2+ + H+ ----------
b) Cr2O72- + I- + H+ ----------
c) Cr2O72- + Sn2+ + H+ ----------
d) Cr2O72- + H2S + H+ ----------
34.Describe the preparation of potassium permanganate. How does the acidified permanganate
solution react with oxalic acid? Write the ionic equations for the reactions.
35. When MnO2 is fused with KOH in the presence of KNO3 as an oxidizing agent, it gives a dark
green compound (A).Compound (A) disproportionates in acidic solution to give purple compound (B).
An alkaline solution of compound (B) oxidises KI to compound (C) whereas an acidified solution of
compound (B) oxidises KI to (D). Identify (A), (B), (C), and (D).

A= K2MnO4 B= KMnO4
in alkaline solution,
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36.The correct order of oxidising power in 3d series of transition elements

Mn04-, Cr2072-, V02+
Ans: V02+ < Cr2072- < Mn04- . This is due to the increasing stability of the lower species to which
they are reduced.
Note:Learn the oxidising action of KMn04 in acidic as well as neutral or alkaline medium
F block elements
Give reason:
36. 𝐶𝑒4+ (or Tb4+) a good oxidising agent where as Sm²⁺ is a good reducing agent.
Ans : Ce & Sm are lanthanoids whose stable oxidation state is (+3). 𝐶𝑒4+ gains one electron to
get stable oxidation state (+3) .Hence, it acts as oxidising agent. 𝐶𝑒4+ + e⁻ → Ce⁺³ on the other
hand, Sm²⁺ lose one electron to get stable oxidation state (+3) . Hence, it acts as reducing agent.
37.La(OH)₃ is stronger base than Lu(OH) ₃ .
Ans : Due to lanthanoid contraction , ionic size of Lu³⁺ is smaller than La³⁺ . Hence Lu−O bond is
stronger than La−O bond , so La(OH)₃ is stronger base.
38.(a) What is meant by the term lanthanoid contraction?
(b)What is it due to and what consequences does it have on the chemistry of elements
following lanthanoids in the periodic table?
Ans : (a) The decrease in atomic and ionic size with increase in atomic number in lanthanoids is
called lanthanoid contraction .
(b) The 4f electrons have poor shielding effect. Therefore, the attraction of the nucleus for the
outermost electrons increases. This results in a steady decrease in the size of lanthanoids with the
increase in the atomic number. Consequences of lanthanoid contraction: (i) Lanthanoids has
similar chemical properties due to similar ionic size. (ii) Basic strength decreases from La(OH)₃ to
Lu(OH)₃)
39. Actinoid contraction is greater than lanthanoid contraction.
Ans: The shielding effect of 5f orbitals is poorer than the shielding effect of 4f orbitals. Due to
this, the valence shell electrons of actinoids experience greater effective nuclear charge than that
experienced by lanthanides. Hence, actinoid contraction is greater than lanthanoid contraction.
40. Actinoids show wide range of oxidation states.
Ans:Actinoids have a greater range of oxidation states due to comparable energies of 5f, 6d and
7s orbitals. Hence, all their electrons can take part in bond formation.
41. write the differences between lanthanoids and actinoids (refer notes)
42.Eu2+ (or Yb2+) is a good reducing agent.
Ans: Eu2+ is esily oxidised to Eu3+ , the common oxidation state of lanthanoids