2PBCBDC-The d- and f-Block Elements(S)

8. The d- and f- Block Elements

Exercise

Unit I
Very Short Answer questions (VSA)
1. Name the lightest transition metal.
Solution
Scandium
2. Write the electronic configuration of
(i) Cr3+ (ii) Cu+ (iii) Mn 2
(iv) Co2+ (v) Fe 3 (vi) Zn 2
[Given: Z of Cr = 24, Mn = 25, Fe = 26, Co = 27, Cu = 29, Zn = 30]
Solution
(i) Cr3+ : [Ar]18 4s0 3d3 (ii) Cu+ : [Ar]18 4s0 3d10 (iii) Mn 2 : [Ar]18 3d54s0
(iv) Co2+ : [Ar]18 4s0 3d7 (v) Fe 3 : [Ar]18 3d54s0 (vi) Zn 2 :[Ar]18 3d104s0
3. Chromium has the electron configuration [Ar]3d54s1 although its expected configuration is [Ar]3d44s2.
Why?
Solution
3d54s1 (half filled ‘d’ orbital) is more stable than 3d44s2
4. Why zinc is not considered a transition metal?
Solution
Since zinc has completely filled d-orbitals in its ground state as well as in its oxidized state.
5. 3d-series elements exhibit variable oxidation states. Why? [July 2015]
Solution
Due to comparable energy of 3d- and 4s-orbitals.
6. Name the element which exhibits highest oxidation state. [July 2014, March 2017]
Solution
Manganese or Mn
7. Name one 3d series element that do not show variable oxidation state . [March 2020]
Solution
Scandium (Sc3+) or zinc (Zn2+)
8. The transition element in a given compound exists in its highest oxidation state. Does the compound
behave as an oxidizing agent or a reducing agent?
Solution
Behaves as an oxidizing agent
9. Name the transition metal in the 3d series which contains maximum number of unpaired electrons in the
elemental form. [July 2020]
Solution
Cr (Z = 24) : [Ar] 3d5 4s1

1
2PBCBDC-The d- and f-Block Elements(S)

10. Write the formula to calculate spin only magnetic moment. [July 2017, July 2018]
Solution
  n(n  2) B.M where n is the number of unpaired electrons

11. A transition element has three unpaired electrons. What type of magnetic property could be associated
with this element?
Solution
Paramagnetic
12. Why transition metals and their ions are paramagnetic?
Solution
Due to the presence of unpaired electrons.
13. Why are the compounds containing Ti4+colourless?
Solution
Due to 3d0 configuration in Ti4+, There is no d-d transition.
14. Name a transition metal compound which is used as a catalyst.
Solution
Vanadium pentoxide
15. Transition metals are good catalytic agents. Give reason. [March 2019]
Solution
Since they exhibit variable oxidation state and provide large surface area.
16. What are alloys?
Solution
Alloys are a homogeneous solid solution in which atoms of one metal are distributed randomly among
the atoms of the other.
17. Why is Fe3+ more stable than Fe2+?
Solution
Fe2+ : [Ar] 3d6 4s0
Fe3+ : [Ar] 3d5 4s0
Fe3+ has an exactly half-filled 3d-orbital. Hence, it is more stable.
18. How many d-electrons are retained when Fe becomes Fe2+?
Solution
All the six d-electrons are retained.

Short Answer questions (SA)

19. On what ground can you say that scandium (Z = 21) is a transition element but Zinc (Z = 30) is not?
[July 2020]
Solution
Scandium has partially filled d-orbital having [Ar]3d14s2 configuration whereas zinc has completely
filled d-orbital with [Ar]3d10 4s2 configuration.

2
 2PBCBDC-The d- and f-Block Elements(S)

20. Write the outer electronic configuration of iron (Z = 26). Predict the magnetic behaviour of iron.
Solution
Fe (Z = 26): [Ar] 3d64s2
Paramagnetic in nature due to the presence of four unpaired electrons.
21. Copper (I) compounds are diamagnetic whereas copper (II) compounds are paramagnetic. Explain.
Solution
Cu+ : [Ar]18 3d104s0 ; no unpaired electrons
Cu2+ : [Ar]18 3d94s0 ; one unpaired electrons
Since Cu+ ion has no unpaired electrons, it is diamagnetic whereas Cu2+ has one unpaired electron, it is
paramagnetic in nature.
22. Fe 2 , Co3 and Mn 3 ions have equal magnetic moment. Give reason.
Solution
Fe2+ : [Ar]18 3d64s0
Co3+ : [Ar]18 3d64s0
Mn3+ : [Ar]18 3d44s0
Fe 2 , Co3 and Mn 3 have equal magnetic moment since they have the same number (four) of unpaired
electrons.
23. A transition metal ion with 3d 9 configuration has the least magnetic moment. Explain.
Solution
3d9

  1(1  2)
= 3
= 1.73 B.M.
Since it has only one unpaired electron
24. Calculate the magnetic moment of Mn2+ ion [atomic number of Mn = 25]. [July 2015]
Solution
Mn2+ ion has d5 configuration with five unpaired electrons (n = 5).
  n(n  2) B.M
  5(5  2)
= 35
= 5.91 B.M.
25. Calculate the magnetic moment of Ti3+ ion. [July 2019]
Solution
Ti3+ ion has d1configuration with one unpaired electron (n = 1).
  n(n  2) B.M
 1(1  2)
 3  1.73 B.M

3
2PBCBDC-The d- and f-Block Elements(S)

26. Calculate the spin only magnetic moment of Fe2+. [March 2016]
Solution
Fe2+ has d6 configuration with four unpaired electrons (n = 4).
  n(n  2) B.M.
  4(4  2)
= 24
= 4.89 B.M.
27. Give reason: Ti4+ salts are colourless whereas Cr3+ salts are coloured. [March 2018]
Solution
Ti4+ has d0 configuration so does not undergo d-d transition whereas Cr3+has d3 configuration and exhibit
colour due to d-d transition
28. Why Sc3+ salts are colourless whereas Cr3+ salts are coloured? [March 2016]
Solution
Sc3+ has d0 configuration so does not undergo d-d transition whereas Cr3+has d3 configuration and exhibit
colour due to d-d transition
29. Indicate which of following ions are coloured: Cu  , Ni 2 , Cr 2 ? Give reason.
Solution
Cu+ : [Ar]18 3d104s0 ; no ‘d’ electrons
Ni2+: [Ar]18 3d84s0 ; two ‘d’ electrons
Cr2+ :[Ar]18 3d44s0 ; four ‘d’ electrons
Ni2+ and Cr2+ are coloured due to the presence of unpaired electrons in their d-orbital.
30. Compounds of zinc are colourless. Explain.
Solution
In the compounds of zinc, zinc exists in the +2 state which contains all d-electrons are paired. So, the
compounds of zinc are colourless.
31. Ti 4 ion is colourless while V 4 ion is blue. Why?
Solution
Ti 4 :[Ar]18 3d04s0 ; No unpaired electrons
V 4 :[Ar]18 3d14s0 ; one unpaired electrons
V 4 is coloured due to the presence of unpaired electrons in the d-orbital. These electrons absorb certain
part of incident light and the remaining part of light is emitted which gives a definite colour.
32. Give reason for the following:
(a) Second ionisation enthalpy of copper is very high
(b) Spin only magnetic moment of Sc3+ is zero (Z = 21) [March 2015]
Solution
(a) Due to the removal of the second electron from completely filled d10 configuration
(b) Due to d0 configurationof Sc3+, no unpaired electrons
33. Why do transition elements form complex compounds?
Solution
(i) Due to the availability of large number of vacant d-orbitals,
(ii) Due to high polarising power as a result of higher nuclear charge and the small atomic and ionic size.

4
 2PBCBDC-The d- and f-Block Elements(S)

34. Between Fe2+ and Fe3+, which one has higher tendency to form complexes and why?
Solution
Fe3+ has a smaller size and higher charge. So, it has a higher tendency to form complexes.
35. What is the effect of increasing pH above 7 on a solution of potassium dichromate?
Solution
7  2OH  2CrO 4  2H 2O
In aqueous solution: Cr2O   

In basic medium (i.e., increasing pH), equilibrium shifts in the forward direction and the solution turns
yellow.
36. How does acidified permanganate solution react with oxalic acid?
Solution
The ionic equation for the reduction of MnO 4 to Mn 2  in acidic medium is represented as
C 2 O 24  2CO 2  2e  5
   2
MnO  8H  5e  Mn
4  4H 2 O 2
2MnO 4  5C 2 O 24   16H   2Mn 2   10CO 2  8H 2 O

37. Describe oxidizing action of potassium dichromate and write the ionic equations for its reaction with
(a) iodide
(b) iron(II) solution
(c) H2S
Solution
Potassium dichromate is a powerful oxidising agent in the acid medium.
The ionic equation for the reduction of dichromate in the acidic medium is
Cr2 O72   14H   6e   2Cr 3  7H 2 O …(1)
It oxidises
(a) I to I2
2I  I 2  2e  …(2)
2   3
(2)  3 + (1) Cr2 O 7  6I  14H  2Cr  3I 2  7H 2 O
(b) Fe2+ to Fe3+
Fe2+  Fe3+ + e …(2)
Cr2 O 27   14H   6e   2Cr 3  7H 2 O
(2)  6 + (1) Cr2 O 27   6Fe 2  14H   2Cr 3  6Fe3  7H 2 O
(c) S2 to S
S2  S + 2e …(2)
2
Cr2 O 7  14H  6e  2Cr 3  7H 2 O


(2)  3 + (1) Cr2 O72   3S2   14H   2Cr 3  3S  7H 2 O

Long Answer questions (LA)

38. Explain the variation of atomic radii in the transition metals of 3d-series.
Solution
The atomic radii decreases initially (Sc to Cr), remains nearly constant (Cr to Cu) and increases towards
the end (Cu to Zn).

5
2PBCBDC-The d- and f-Block Elements(S)

This variation of atomic radii is explained on the basis of

(i) nuclear charge
(ii) screening effect
(iii) electron-electron repulsion.
With increase in atomic number, the nuclear charge increases and the screening effect of the added
electron into the d-orbitals is low. Hence, the 4s electrons are drawn closer to the nucleus and the atomic
radius decreases initially.
As the number of d-electrons increases, the screening effect also increases. The screening effect
compensates for the increase in effective nuclear charge. Hence, the atomic radius remains almost
constant.
Towards the end, the increase in the interelectronic repulsion due to pairing of electrons in zinc
(3d10 4s2) increases the radius.
39. With reference to the first row transition series:
(i) Name the metal in 3d series which possesses maximum number of oxidation states.
(ii) Among Zn2+ and Cu2+, which is colourless?
(iii) Between Ti2+ and V2+, which ion contains more number of unpaired electrons? [March 2014]
Solution
(i) Manganese
(ii) Zn2+ is colourless
(iii) V2+ ion contains three unpaired electrons whereas Ti2+ has two unpaired electrons
40. What are interstitial compounds? Why are such compounds known for transition metals? [March 2019]
Solution
Small atoms like H, C, N occupy interstitial space in transition metal crystals which have larger voids.
This results in the formation of non-stoichiometric compounds like VH0.56, TiH1.7 and they are called
interstitial compounds.
41. Describe the manufacture of potassium dichromate from chromite ore. [July 2014, July 2015, March
2014, 2015, 2016 July 2017, March 2019, July 2019, March 2020, July 2020]
Solution
(i) The concentrated chromite ore is roasted with sodium or potassium carbonate in excess free of air.
Sodium chromate, Fe2O3 and CO2 are formed. Quick lime keeps the mass porous.
4FeCr2O4 + 8Na2CO3 + 7O2  8Na2CrO4 + 2Fe2O3 + 8CO2
The roasted mass is leached with water. Sodium chromate dissolves in water. The undissolved
Fe2O3 is removed by filtration.
(ii) The yellow solution of sodium chromate is filtered and acidified with sulphuric acid to give a
solution from which orange sodium dichromate, Na2Cr2O7.2 H2O is crystallized.
2Na2CrO4 + 2H+  Na2Cr2O7 + 2Na+ + H2O
(iii) Sodium dichromate is more soluble than potassium dichromate. Potassium dichromate is prepared
by treating the solution of sodium dichromate with potassium chloride.
Na2Cr2O7 + 2KCl  K2Cr2O7 + 2NaCl

6
 2PBCBDC-The d- and f-Block Elements(S)

42. How is potassium permanganate (KMnO4) prepared from MnO2? Write equations.
[March 2017, March 2018]
Solution
Powdered pyrolusite is fused with KOH in the presence of oxidising agent, KNO3.
2MnO 2  4KOH  O2  KNO3
 2K 2 MnO 4  2H 2O


The fused mass is treated with water. K2MnO4 dissolves in water forming green coloured solution.
K2MnO4 undergoes disproportionation in a neutral / acidic solution to give permanganate.
3MnO 24   4H   2MnO4  MnO 2  2H 2O

Unit II
Very Short Answer questions (VSA)
1. Write the electronic configuration of
(i) Ce4+ (ii) Lu2+ (iii) Th4+
Solution
(i) Ce4+: [Xe]54 4f0 (ii) Lu2+: [Xe]54 4f14 5d1 6s0 (iii) Th4+:[Rn]86 6d0 7s0
2. Mention the cause of Lanthanoid contraction. [Mach 2017]
Solution
In Lanthanoids, the electrons are added to the prepenultimate 4f-orbital. With increase in atomic number,
the nuclear charge gradually increases. This increased nuclear charge pulls the outer electrons inwards,
decreasing the size of the atom. The steady decrease in atomic size leads to lanthanoid contraction.
3. Zr and Hf have almost identical atomic radii. Give reason. [March 2015, July 2014, July 2019]
Solution
Due to lanthanoid contraction
4. Atomic radii of second and third transition series elements are almost identical. Give reason.
[March 2019]
Solution
Due to lanthanoid contraction
5. Why is the separation of lanthanoid elements difficult?
Solution
Due to lanthanoid contraction, the change in the atomic or ionic radii of these elements is very small.
Their chemical properties are similar. This makes their separation difficult.
6. Write the general oxidation state shown by actinoids. [July 2018]
Solution
+3
7. Name a member of Lanthanoid series which is well known to exhibit +4 oxidation state. [July 2020]
Solution
Cerium
8. Why are lanthanoids paramagnetic in nature?
Solution
All lanthanoids except La3+ and Lu3+ contain unpaired electrons. [July 2018]

7
2PBCBDC-The d- and f-Block Elements(S)

9. Name the gas liberated when lanthanoids react with acids. [July 2019]
Solution
Hydrogen gas
10. Actinoid contraction is greater from element to element than lanthanoid contraction. Give reason.
[March 2018, July 2020]
Solution
In actinoids, 5f orbitals are filled which offer poor shielding effect than 4f orbitals (in lanthanoids). Thus,
the effective nuclear charge experienced by valence electrons in case of actinoids is much more than that
experienced by lanthanoids. Hence, the size contraction in actinoids is greater as compared to that in
lanthanoids

Short Answer questions (SA)

11. What is Lanthanoid contraction? Mention one of its consequences. [March 2014, March 2017]
Solution
The net decrease in atomic and ionic radii from La to Lu (0.22 Å) is called Lanthanoid contraction.
In Lanthanoids, the electrons are added to the prepenultimate 4f-orbital. With increase in atomic number,
the nuclear charge gradually increases. This increased nuclear charge pulls the outer electrons inwards,
decreasing the size of the atom. The steady decrease in atomic size leads to lanthanoid contraction.
12. Out of La(OH)3 and Lu(OH)3, which is more basic and why?
Solution
La(OH)3 is more basic than Lu(OH)3. As the size of the lanthanoid ions decreases from La3+ to Lu3+, the
covalent character of the hydroxides increases. Hence, the basic strength decreases from La(OH)3 to
Lu(OH)3.
13. Give reasons:
(i) Actinoids show variable oxidation state. [July 2015, 2014, March 2019]
(ii) Cerium (Ce) exhibits +4 oxidation state. [July 2015, March 2018]
Solution
(i) Actinoids show a large number of oxidation states (+3, +4, +5, +6 and +7) out of which +3 is most
common. This is due to the small energy difference between 5f, 6d and 7s subshells.
(ii) Ce(III) having the configuration 4f1 5d06s0 can easily lose an electron to acquire the configuration of
4f0 and form Ce(IV) in aqueous solution.
14. Write two differences between lanthanoids and actinoids. [March 2015]
Solution
Lanthanoids Actinoids
In addition to common oxidation state of +3, they In addition to +3 state, actinoids also show
also show +2 and +4 oxidation states. +4, +5, +6
Have lesser tendency of complex formation Have stronger tendency of complex formation
Except promethium, they are non-radioactive All actinoids are radioactive
Magnetic properties can be easily explained Magnetic properties of actinoids cannot be
explained easily
Do not form oxocations Form oxocations like UO22  , PuO2 , etc.,
Oxides and hydroxides of lanthanoids are less Oxides and hydroxides of actinoids are more basic
basic

8
 2PBCBDC-The d- and f-Block Elements(S)

15. Study of actinoid elements is difficult. Give two reasons. [July 2017, July 2018, March 2020]
Solution
(i) Actinoids are radioactive
(ii) Can be prepared only in small amounts

Long Answer questions (LA)

16. Use Hund’s rule to write the electronic configuration of Ce3+ and calculate its magnetic moment on the
basis of spin only formula.
Solution
54
58 Ce : [Xe] 4f1 5d1 6s2
58 Ce3 : [Xe]54 4f1 ; Has only one unpaired electron, i.e., n = 1
  n(n  2) = 1(1  2) = 1.73 BM

17. Compare the chemistry of actinoids with lanthanoids with respect to

(i) electronic configuration (ii) atomic and ionic size (iii) oxidation state
Solution
(i) General electronic configuration of lanthanoids: [Xe]54 4f 1–14 5d0–1 6s2
General electronic configuration of actinoids: [Rn]5f 1-14 6d0–2 7s2
(ii) Both show decrease in their atomic and ionic (+3 oxidation state) radii.
(iii) Lanthanoids show limited oxidation states (+2, +3, +4), of which +3 is most common.
Actinoids show a large number of oxidation states (+3, +4, +5, +6 and +7), of which +3 is
most common.
18. Which is the last element in the series of actinoids? Write the electronic configuration of this element.
What is the possible oxidation state of this element?
Solution
Last element: Lawrencium
Electronic configuration: [Rn]86 5f14 6d1 7s2
Possible oxidation state: +3
19. Write four similarities in properties of lanthanoids and actinoids.
Solution
Both show mainly an oxidation state of +3.
Both are electropositive and are very reactive.
Both exhibit magnetic and spectral properties.
Actinoids exhibit actinoid contraction like lanthanoid contraction shown by lanthanoids.

***