Chapter 7 Step-1

The d- and f-Block Elements

SOLUTIONS
SECTION - A
1. Answer (2)
Their d-shell are completely filled.
2. Answer (2)
Fe+2 (ferrous ion) have 4 unpaired e–.
3. Answer (4)
Phosphorus does not have d e–.
4. Answer (2)
Co is 3d 7, have 3 unpaired e–.
5. Answer (1)
K2Cr2O7 has Cr in +6 oxidation state.
6. Answer (2)
More the unpaired e–, more will be paramagnetism.
7. Answer (2)
2Fe + 3H2O → Fe2O3 + 3H2
8. Answer (1)
Ti3+ have 3d1 configuration.
9. Answer (3)
5PbO2 + 2Mn2+ + 4H+ → 5Pb2+ + 2MnO4– + 2H2O
10. Answer (1)
Left to right, Zeff (increases), basic character decreases.
11. Answer (3)
3Fe + SO2 → 2FeO + FeS
12. Answer (3)
The film is due to formation of Fe3O4.
13. Answer (1)
German silver contains Cu (50%), Zn (30%), Ni (20%) respectively.
14. Answer (4)
Production of steel from haematite ore involve oxidation followed by reduction.

Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005. Phone : 011-47623456
2 The d- and f-Block Elements Solutions of Assignment Step-1

15. Answer (4)

Contain Cr and Ni.
16. Answer (1)
Cuprous ore among the following is cuprite.
17. Answer (4)
Lanthanum are very similar to the elements of 4f-block.
18. Answer (1)
+ + + +
Left to right, size decreases, Yb 3 1 Pm 3 1 Ce 3 1 La 3 .
19. Answer (2)
From a mixed precipitate of AgCl and AgI, ammonia solution only dissolved AgCl.
20. Answer (1)
BaO + ZnO 1100cC
BaZnO 2
21. Answer (4)
Cu+ have zero unpaired e–, Cu+2 have 1 unpaired e–.
22. Answer (1)
In case of iodine, Cu+2 oxidizes I– to I2, hence Cu (II) iodide is not known.
23. Answer (4)
Actinoids form relatively more stable complexes as compared to lanthanoids.
24. Answer (2)
Due to lanthanoid contraction, Zr and Hf have same physical and chemical properties.
25. Answer (1)
Cu has higher SRP, then hydrogen
26. Answer (2)
Highest oxidation state of osmium is +8.

SECTION - B
27. First increase from Sc to V and then decrease.
28. +3, makes it half filled at t2g level.
29. Basic medium.

SECTION - C
30. Fe+3 → 3d 5
 5 (5  2)  35 B.M.
Mn+2 → 3d 5
 35 B.M.

Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005. Phone : 011-47623456
Solutions of Assignment Step-1 The d- and f-Block Elements 3

31. Due to half-filled electronic configuration of Fe+3; Fe+3 is more stable while IE3 of Cu is very high and
hence it is not much stable.
32. Because Mn+2 have E.C. d 5. That is why it is more stable and removal of electron will be difficult, but
Fe+2 have E.C. d 6 and it can easily loose an electron to form more stable E.C.

33. 10I– + 2MnO4– + 16H+ → 2Mn+2 + 8H2O + 5I2

2MnO4– + H2O + I– → 2MnO2 + 2OH– + IO3–

34. I– + Fe+3 → FeI2 + I2

Fe+2 + S2O8–2 → Fe+3 + SO4–2

35.

2773 K H2 O
36. Ln + C Ln2C3 Ln(OH)3 + C2H2
37. As we approach from Ce+3 to Lu+3 size decreases, electronegativity increases. That is why acidic
character increases and basic character decreases.

SECTION - D
38. (i) Transition metal ions can also change their oxidation states and can become more effective so
the catalytic activity of transition metals and their compounds are ascribed mainly to their ability
of adopting variable oxidation states.
(ii) The atomic sizes of transition metals are very similar to each other. Therefore, these attributes
to their nature of forming the alloys. As the atomic sizes are very similar one metal can replace
the other metal from its lattice and form a solid solution which is the alloy.
(iii) [Xe]4f145d36s2
(iv) Manganese exists in 6 different oxidation states, i.e., from +2 to +7. This is the highest number
for any element in the 3d-series. The reason for the existence of such a huge number of oxidation
states in manganese is due to the presence of 5 unpaired electrons in its 3d subshell which can
show easy transitions.

SECTION - E
39. On moving along the lanthanoid series, the atomic number gradually increases by one. With the increase
in atomic number, the number of protons and electrons present in the atom also increases by one.
The effective nuclear charge increases as electrons are being added to the same shell. Owing to the
proton addition being pronounced more above the interelectronic repulsions resulting from electron
addition, nuclear attraction increase happens. Also, with the increase in the atomic number, the number
of electrons in the 4f orbital also increases. The 4f electrons have poor shielding effect. Therefore, the
effective nuclear charge experienced by the outer electrons increases. Consequently, the attraction
of the nucleus for the outermost electrons increases. This results in a steady decrease in the size of
lanthanoids with an increase in the atomic number. This is termed as lanthanoid contraction.

Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005. Phone : 011-47623456
4 The d- and f-Block Elements Solutions of Assignment Step-1

Consequences of lanthanoid contraction :

(a) It is due to lanthanide contraction that there is variation in the basic strength of lanthanide
hydroxides. (Basic strength decreases from La(OH3 to Lu(OH)3).
(b) There is a similarity in the properties of second and third transition series.
(c) Separation of lanthanoids is possible due to lanthanide contraction.
40. (i) Transition metals show paramagnetic behaviour. Paramagnetic arises due to the presence of
unpaired electrons with each electron having a magnetic moment associated with its spin angular
momentum and orbital angular momentum. However, in the first transition series, the orbital
angular momentum is quenched. Therefore, the resulting paramagnetism is only because of the
unpaired electron.
(ii) Transition elements have high effective nuclear charge and a large number of valence electrons.
Therefore, they form very strong metallic bonds. As a result, the enthalpy of atomisation of
transition metals is high.
(iii) Most of the complexes of transition metals are coloured. This is because of the absorption of
radiation from visible light region to promote an electron from one of the d-orbitals to another. In
the presence of ligands, the d-orbitals split up into two sets of orbitals having different energies.
Therefore, the transition of electrons can take place from one set to another. The energy required
for these transitions is quite small and falls in the visible region of radiation. The ions of transition
metals absorb the radiation of a particular wavelength and the rest is reflected, imparting colour
to the solution.
(iv) The catalytic activity of the transition elements can be explained by two basic facts :
(a) Transition metals provide a suitable surface for the reactions to occur.
(b) Owing to their ability to show variable oxidation states and form complexes, transition metals
form unstable intermediate compounds. Thus, they provide a new path with lower activation
energy, Ea, for the reaction.

  

Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005. Phone : 011-47623456
Chapter 7 Step-2

The d- and f-Block Elements

SOLUTIONS
1. Answer (1)
The most abundant transition metal belongs to 3d series.
2. Answer (3)
Ag generally show the oxidation state of +1.
Mn can exhibit oxidation state of 7.
3. Answer (3)
Coinage metal has 3s2 3p6 3d10
So, 18 electron in penultimate shell.
4. Answer (2)
Cr+2 – blue
Mn+3 – violet
5. Answer (3)
Mn+2 and Fe+3 both have five unpaired e–.
6. Answer (1)
Correct order is
Sc > Ti > V > Cr > Fe
7. Answer (4)
Group-12 element are not transition metals.
8. Answer (1)
As charge on central metal increases, basic nature decreases.
9. Answer (1)
Increase left to right with some exception.
10. Answer (4)
In interstitial void, only small atoms such as C, N, H, B etc. These smalls atoms are not uniformly
distributed, so these are nonstoichiometric.
Due to these interstitial voids, some changes occur in physical properties.

Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005. Phone : 011-47623456
6 The d- and f-Block Elements Solutions of Assignment Step-2

11. Answer (4)

Interstitial compounds are soft in nature.

12. Answer (4)

E°(Co+3/Co+2) = +1.97 V

E°(Cr+3/Cr+2) = –0.41 V

13. Answer (4)

Similar atomic radii.

14. Answer (1)

In amalgam, mercury has 0 oxidation state

Calomel → Hg2Cl2 : +1

Corrosive sublimate (HgCl2) : +2

15. Answer (2)

KMnO 4 + KI acidic
I 2 and KIO3

KMnO 4 + KI acidic
medium
KIO3
16. Answer (2)

Ag2S → Black

Ag2CrO4 → Red

AgI → Yellow.

17. Answer (3)

K 4 [Fe (CN) 6] + FeCl3 Fe 4 [Fe (CN) 6] 3 .

18. Answer (3)
 
KMnO 4 Mn 2  5e
Cr has 5 electron in d orbital.

19. Answer (3)



Na 2 CrO 4 H
Cr2 O 72
20. Answer (2)

21. Answer (3)

HCN −3
CuSO 4 5H 2 O (Cu (CN) 4)

CuSO 4 + KI Cu 2 I 2

Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005. Phone : 011-47623456
Solutions of Assignment Step-2 The d- and f-Block Elements 7

22. Answer (1)

White vitriol → ZnSO4.7H2O
Blue vitriol → CuSO4.5H2O
23. Answer (4)
Oxygen has a greater ability to stabilise higher oxidation state which is evident from Mn2O7 and MnF4.
This ability is due to formation of double bonds by oxygen.
24. Answer (1)

2 H 2
CrO 4 Cr2 O 7
(yellow) (orange)

25. Answer (2)

KMnO 4 
K 2 MnO 4  MnO 2  O 2
26. Answer (2)
Cr2O3 is amphoteric.
27. Answer (1)
MnO42– and MnO4– both are tetrahedral with respect to Mn.
28. Answer (4)
FeSO 4 " Fe 2 O3 + SO 2 + SO3
29. Answer (1)
2KMnO4 + 5H2C2O4 + 3H2SO4 → K2SO4 + 2MnSO4 + 10CO2 + 8H2O
30. Answer (3)
 
MnO 2  OH  O 2 MnO 24  H 2 O
(A) (B)
  
MnO 24  H MnO 4  MnO 2  H 2 O
(C) (D) (B)

31. Answer (3)

+
Zn 2 + NaOH Na 2 ZnO 2
32. Answer (4)
Lanthanum has an abnormally low value of the 3rd ionisation enthalpy.
33. Answer (1)
+3 is most stable oxidation state of lanthanoids.
34. Answer (1)
Due to lanthanide contraction.
35. Answer (3)
Other than La3+ and Lu3+ all other lanthanides are paramagnetic in +3 state.
36. Answer (1)
37. Answer (4)
In lanthanoids as atomic number increase size decrease.
38. Answer (1)
Size of Hf > Size of Zr
39. Answer (1)
f-block element are metal so reducing in nature.

Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005. Phone : 011-47623456
8 The d- and f-Block Elements Solutions of Assignment Step-2

40. Answer (05)

The atomic number of Mn is 25. The number of electrons associated with Mn2+ = 23

The electronic configuration of Mn2+ is : 2, 8, 8,

41. Answer (04)

100
% Gold = # 23 = 96
24
Impurities percentage (100 – 96) = 4
42. Answer (08)

The structure of dichromate ion is

43. Answer (05)

   
MnO 4  8H  5e Mn 2  4H 2 O
44. Answer (03)
 
Cr2 O 72 2Cr 3
−
Oxidation number of Cr in Cr2 O 72 is +6, change (6 – 3) = 3

PREVIOUS YEARS QUESTIONS

[Electronic Configuration of the d-Block Elements]

45. Answer (4)

. Mn(25) = [Ar]3d54s2

Mn+3 = [Ar]3d44s0

Ru-belongs to 4d transition series

Co (27) = [Ar]3d74s2

Co+3 = [Ar]3d64s0

Fe(26) = [Ar]3d64s2

Fe+3 = [Ar]3d54s0

46. Answer (1)

The element having atomic number 25 is manganese. The electronic configuration of Mn2+ is

Mn2+ : 3d5

In aqueous solution it exists as [Mn(H2O)6]2+. Since H2O is a weak field ligand, it does not cause pairing
of unpaired electrons. So, its spin only magnetic moment is  5 # 7  5.92 BM .

Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005. Phone : 011-47623456
Solutions of Assignment Step-2 The d- and f-Block Elements 9

47. Answer (1)

To show colour and paramagnetic behaviour, the ion must have unpaired electron(s)
Cu2+ - 3d9 (one unpaired e–)
Cr3+ - 3d3 (three unpaired e–)
Sc+ - 3d2 (two unpaired e–)
48. Answer (3)

have some electronic configuration
Cr  4s 0 3d 5
 3
Mn 2  4s 0 3d 5 in the outer most shell
49. Answer (2)
Valence shell Unpaired
Configuration electrons
V2+ → 3d34s0 n=3
Ni2+ → 3d84s0 n=2
Cr2+ → 3d44s0 n=4
Fe2+ → 3d64s0 n=4
Since Ni has least number of unpaired electrons.
2+

Hence, Ni2+ will have lowest spin only magnetic moment Value.
50. Answer (1)
Pt = [Xe] 4f14 5d9 6s1
51. Answer (1)
O2, Cu2+ and Fe3+ have 2, 1 and 5 unpaired electrons respectively, so these are the paramagnetic
species. Hence, they are attracted by magnetic field.
NaCl and H2O are the diamagnetic species so they are repelled by the magnetic field.

[General Properties of the Transition Elements (d-Block)]

52. Answer (4)

Sc shows fixed oxidation state of +3.

53. Answer (1)

Interstitial compounds are inert.

54. Answer (1)
Electronic configuration of the given transition metal ions are
Sc3+ (Z = 21) 1s22s22p63s23p6
Ti2+ (Z = 22) 1s22s22p63s23p63d2
Ti3+ (Z = 22) 1s22s22p63s23p63d1
V2+ (Z = 23) 1s22s22p63s23p63d3

Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005. Phone : 011-47623456
10 The d- and f-Block Elements Solutions of Assignment Step-2

Magnetic moment is directly proportional to the number of unpaired electrons. So, the correct increasing
order of magnetic moment is
Sc3+ < Ti3+ < Ti2+ < V2+
0 1 2 3 unpaired electrons
55. Answer (1)
Mo and W belong to group-6 and period 5 (4d series) and 6 (5d series) respectively.
Due to lanthanoid contraction, radius of Mo and W are almost same.
56. Answer (4)

Cu Co Fe Cr Zn density in g/cm 3
8.9 8.7 7.8 7.19 7.1

57. Answer (2)

Melting points of the given metals

Hg : –38.83° C

Ag : 961.8° C

Ga : 29.76° C

Cs : 28.44° C

∴ Metal having highest melting point is Ag.

58. Answer (1)

EFe
%
3
| Fe 2
   0.77V

Ec Ti 3
| Ti 2
  –0.37 V

EcMn 3
| Mn
2   1.57 V EcCr 3 
| Cr 2  –0.41 V

Mn+3 is the best oxidising agent among the given series.

59. Answer (3)

Metal E° M2+/M
Cr –0.90 V
Fe –0.44 V
Cu + 0.34 V
Zn (–0.76 V)
The metal having highest E°(M2+/M) standard reduction potential is Cu.
60. Answer (1)
Sc+3 and Zn+2 are colourless as they contain no unpaired electron. Whereas the transition metal ions
Cu+2, Ti+3, V+2 and Mn+2 are coloured as they contain unpaired electrons.
The unpaired electron from lower energy d orbital gets excited to a higher energy d orbital on absorbing
light of frequency which lies in visible region. The colour complementary to light absorbed is observed.

Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005. Phone : 011-47623456
Solutions of Assignment Step-2 The d- and f-Block Elements 11

61. Answer (2)

∆hyd H (M+2)
Cr –1925
Mn –1862
Fe –1560
Co – 1640
Mn+2 has lowest ∆hydH.
62. Answer (4)
m = 3.87
n=3
V23 = 4s23d3

V2+ = 4s03d3 (n = 3)
63. Answer (1)
CrO5 is blue in colour in amyl alcohol.
64. Answer (2)
(i) Mn2O7 → Mn in (+7) oxidation state.
(ii) It is also correct.
(iii) Sc only shows +3 oxidation state.
(iv) Cr+6 is oxidising in nature.
65. Answer (2)
The first ionization energy of 3d series elements is more than that of group 2 metals because in 3d
series of elements successive filling of d-orbitals takes place.
66. Answer (3)
Cu2+ in water is more stable than Cu+ due to much higher hydration enthalpy of Cu2+ ion.
Hence, correct answer is option (3).

[Preparation and Properties of the Compounds of d-Block Elements]

67. Answer (3)

2MnO 2 + 4KOH + O 2 2K 2 MnO 4 + 2H 2 O

(A) (Green)
(B)

K 2 MnO 4 + 4HCl 2KMnO 4 + MnO 2 + 2H 2 O

(Purple)
(C )

2KMnO 4 + H 2 O + KI 2MnO 2 + 2KOH + KIO3

(D)

A – MnO2
D – KIO3

Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005. Phone : 011-47623456
12 The d- and f-Block Elements Solutions of Assignment Step-2

68. Answer (1)

69. Answer (2)

V2O3 (X) is basic and CrO (Y) is also basic. The transition metal oxides in lower oxidation states are
basic.

70. Answer (4)

KMnO4 on heating dissociates as

7 6
2KMnO 4 
K 2 MnO 4  MnO 2  O 2
Permanganate Manganate
Both permanganate and manganate are tetrahedral but only manganate is paramagnetic.

+ 7 Diamagnetic
Mn : 3d 0 4s 0

+ 6 Paramagnetic
Mn : 3d1 4s 0
∴ Statement I is true but statement II is false.

71. Answer (3)

Red colour of the ruby is due to the presence of Cr3+.

RuO4 is an oxidizing agent.

VOSO4 ⇒ VO2+ ⇒ V4+ (it can oxidized)

So, it is a reducing agent.

Cr2O3 is amphoteric oxide.

72. Answer (2)

−
Manganate ion MnO 24 has tetrahedral structure

has only dπ - pπ π-bonds.

+
Fe 3 is not used as a catalyst in the conversion of I– to I2 by K2Cr2O7. K2Cr2O7 oxidise I– in acidic medium
easily.

Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005. Phone : 011-47623456
Solutions of Assignment Step-2 The d- and f-Block Elements 13

73. Answer (3)

Structure of Mn2O7 is as :

∴ There are total 6 M = O bonds are present in Mn2O7 compound.

74. Answer (4)
H2O + 8MnO4– + 3S 2 O 32– → 8MnO2 + 6SO 24– + 2OH–
75. Answer (3)

(NH4)2Cr2O7 N2 + 4H2O + Cr2O3
KMnO4 + HCl → KCl + MnCl2 + Cl2 + H2O
Al + NaOH + H2O → Na(Al(OH)4) + H2

2NaNO3(s) 2NaNO2(s) + O2
76. Answer (3)
SO2 gets oxidised in presence of K2Cr2O7 and it converts to Cr+3 in presence of dil. H2SO4.
Similarly, H2S can also get oxidized to sulphur.
However, most appropriate is (3).
77. Answer (1)

Mn is surrounded tetrahedrally by O-atoms.

Mn2O7, contains Mn-O-Mn Bridge.
78. Answer (1)
The reduction electrode potential of Mn3+/Mn2+ is +1.57 V while that of Fe3+/Fe2+ is +0.77 V, hence A is
wrong. Higher oxidation state of smaller d-block elements is stabilized (or say form compounds) with
smaller anion oxide that can be explained by stearic reason hence B is correct.
The oxidation electrode potential of Cr2+/Cr3+ is +0.41 V hence it can reduce H+ and so liberate H2.
The unpaired electrons in V2+ are 3 hence the magnetic moment of V2+ will be lesser than 4.4 BM.
Hence, only B and C are correct.

[The Lanthanoids]
79. Answer (3)
Due to lanthanoid contraction, size of atom as well as ion of lanthanoid decrease.
80. Answer (4)
Sm+3 = Partially filled f orbital = 4f5
Sm = 4f66s2
Sm+3 = Yellow.
Lu+3 = 4f14 colourless.

Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005. Phone : 011-47623456
14 The d- and f-Block Elements Solutions of Assignment Step-2

81. Answer (4)

 W(VI) is more stable than Cr(VI)
 Permanganate titrations in presence of HCl are unsatisfactory as HCl is oxidised to Cl2
 Lanthanoid oxides are used as phosphors.
82. Answer (4)
Europium (Eu)
Atomic No → 63
Electronic configuration → [Xe]4f76s2
Can show only + 2 and + 3 oxidation state.
83. Answer (2)
Yb (70) = 4f14 6s2
Yb+2 = 4f14 6s0
 All the electrons are paired hence Yb+2 is diamagnetic
84. Answer (2)
Outermost electronic configuration of Eu
Eu (63) = 4f76s2
Eu2+ = 4f7
85. Answer (2)

4 e 3
Ce Ce E° = +1.74 V
Positive SRP and higher SRP means greater oxidising power. So, Ce4+ wants to reduce to Ce3+.
Indicates Ce4+ is less stable than Ce3+.
86. Answer (4)
Nd (60) = 4f4 6s2
Pr (59) = 4f3 6s2
Dy (66) = 4f10 6s2
Yb (70) = 4f14 6s2
Yb+2 has fully-filled 4f orbital, it will require very large amount of energy to reach +4 oxidation state.
87. Answer (2)
E° value of Ce+4|Ce+3 is 1.74 V, which suggests that it is a very good oxidising agent.
88. Answer (1)
Ce → [Xe]4f1 5d1 6s2
Ce+4 → [xe] 4f0 5d0 6s0
Cerium in +4 oxidation state acquires inert gas configuration.

Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005. Phone : 011-47623456
Solutions of Assignment Step-2 The d- and f-Block Elements 15

89. Answer (3)

+2 +3 +4
Eu 4f7
4f6

Tm 4f 13
4f12
Sm 4f6 4f5
Tb 4f9 4f8 4f7
Yb 4f14 4f13
Dy 4f10 4f9
Hence, the pair Tb+4 Yb+2 have half filled and completely filled f subshells respectively.
90. Answer (3)
Eu+2 is 4f7
Yb+2 is 4f14
o o
But Eu+2 is more stable than Yb+2 because EEu | Eu 2 E Yb | Yb .
+2 +2

91. Answer (1)

Species having same number of electrons are isoelectronic
+
Sm 2
+
60 electrons
3 not isoelectronic
Er 3 65 electrons
92. Answer (4)
Ce+4 and Tb+4 are strong oxidising agents as the common oxidation state of Lanthanides is (+3).
93. Answer (3)
Eu has a configuration of 4f76s2 and Yb has a configuration of 4f146s2
Hence, both have high 3rd ionisation energy due to half filled and fully filled configuration respectively.

[The Actinoids]
94. Answer (2)
Actinoids Oxidation state shown
Th +4
Ac +3
Pu +3, +4, +5, +6, +7
Np +3, +4, +5, +6, +7
Bk +3, +4
Cm +3, +4
Lr +3
∴ Maximum oxidation state is shown by (Np and Pu).
95. Answer (1)
Maximum oxidation state shown by
Uranium = + 6
Plutonium = + 7

Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005. Phone : 011-47623456
16 The d- and f-Block Elements Solutions of Assignment Step-2

96. Answer (2)

5f electron can participate in bonding to a far greater extent than 4f electron because 5f orbitals are
more exposed than 4f orbitals.
So, Assertions (A) is true.
5f orbitals are not as buried as 4f orbitals.
So, reason (R) is also true and (R) is the correct explanation of (A),

[Some Applications of d and f-Block Elements]

97. Answer (2)

+4
Ce and Eu have stable oxidation state of +3. So, CeO 2 acts as oxidizing agent to get reduced to +3
+2
and EuSO 4 acts as reducing agent to get oxidized to +3.
98. Answer (3)
Here, we have to match the reactions with their correct catalyst :
Fe x O y + K 2 O + Al 2 O3
(A) N 2 (g) + 3H 2 (g) 2NH3 (g)

(B) CO (g) + 3H 2 (g) Ni

CH 4 (g) + H 2 O (g)

(C) CO (g) + H 2 (g) Cu

HCHO (g)
Cu/ZnO  Cr2 O3
(D) CO (g)  2H 2 (g) CH3  OH (g)

∴ Option (3) is correct option.

99. Answer (2)
V2 O5
(A) 2SO2(g) + O2(g) 2SO3
Pt (s) − Rh (s)
(B) 4NH3(g) + 5O2(g) 4NO(g) + 6H2O(g)
Fe (s)
(C) N2(g) + 3H2(g) 2NH3(g)
Ni (s)
(D) Vegetable oil(l) + H2 Vegetable ghee(s)

100. Answer (3)

Pt (s)
(A) 4NH3(g) + 5O2(g) 4NO(g) + 6H2O(g)
Fe (s)
(B) N2(g) + 3H2(g) 2NH3(g)
H 2 SO 4 (l)
(C) C12H22O11(aq) + H2O(l) C6 H12 O6 + C6 H12 O6
Glu cos e Fructose
NO (g)
(D) 2SO2(g) + O2(g) 2SO3

[Miscellaneous]
101. Answer (2)
In (a), ZnO acts as acidic oxide as Na2O is basic oxide.
In (b), ZnO acts as basic oxide as CO2 is acidic oxide.

Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005. Phone : 011-47623456
Solutions of Assignment Step-2 The d- and f-Block Elements 17

102. Answer (1)

The transition metal atom/ion in a complex may have unpaired electrons ranging from zero to 5. So,
maximum number of unpaired electrons that may be present in a complex is 5. Magnetic moment is
given as
 n ^n  2h BM [no. of unpaired electrons = n)

Maximum value of magnetic moment  5 ^5  2h  35  5.92 BM
103. Answer (3)
Order for I.E. is Ti < Mn < Ni < Zn
104. Answer (3)
Atomic radii follows the order
Eu > Ce > Ho > N
199 pm 183 pm 176 pm 70 pm
105. Answer (2)
Ag and Au have similar atomic radius.
106. Answer (2)
The electronic configurations of the given metals and in their +3 state are :
Mn : 3d 5 4s 2 Mn3+ : 3d 4
Fe : 3d6 4s 2 Fe3+ : 3d 5
Co : 3d 7 4s2 Co3+ : 3d 6
Ni : 3d 8 4s 2 Ni3+ : 3d 7
Since Fe3+ has stable configuration of 3d5, the third ionization energy of Fe is minimum.
107. Answer (2)
Gd3+ (Z = 64) = [Xe] 4f7
 n (n  2)  7 (7  2)  7.9 B.M.
108. Answer (4)
Prolonged heating may oxidise ferrous ions to ferric ions.

[General Properties of the Transition Elements (d-Block)]

109. Answer (5)
Co3+ will not liberate H2 gas an reaction with dilute acid
o
E Co 3 
/Co 2   1.97
And Co3+ has electronic configuration = [Ar] 3d6
∴ 4 unpaired e– are present in it.
∴ Spin-only magnetic moment = 4 ^4 + 2h

= 4·92

≈5

Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005. Phone : 011-47623456
18 The d- and f-Block Elements Solutions of Assignment Step-2

110. Answer (4)

Among the pairs given, Cr3+/Cr2+ has negative reduction potential which is –0.41 V.
Cr (III) ⇒ d3
Number of unpaired electrons = 3
 3 (3  2)  15 - 4 B.M.
111. Answer (02)
Ion Spin only magnetic moment
V 3+ 8
Cr3+ 15
Fe 2+ 24
Ni3+ 15

[Preparation and Properties of the Compounds of d-Block Elements]

112. Answer (18)
K 2 Cr2 O7 NaOH
NaCl conc.H 2 SO 4 CrO 2 Cl 2 Na 2 CrO 4
(A) (B)
dilH 2 SO 4
Na 2 CrO 4 H2 O2 CrO5
(B) (C )

Total number of atoms in A, B and C are 18.

113. Answer (18)

6Cr – O bonds

12Cr – O bonds

114. Answer (0)

−
Chromate ion → CrO 24 , oxidation state of Cr = +6
−
Dichromate ion → CrO 24 , oxidation state of Cr = +6
∴ Difference in oxidation state = zero
115. Answer (3)
Manganese (VI) disproportionates in acidic medium as
 
3MnO 24  4H 2MnO 4–  MnO 2  2H 2 O
Difference in oxidation states of Mn in the products formed = 7 – 4 = 3
116. Answer (3)
The most basic oxide among V2O3, V2O4 and V2O5 is V2O3
V2O3 = V+3(d2)
Magnetic moment = 2 (2 + 2) = 2.83

= 8

= 2.83

Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005. Phone : 011-47623456
Solutions of Assignment Step-2 The d- and f-Block Elements 19

117. Answer (6)

+2
KMnO 4 (acidic medium) + H 2 C 2 O 4 " CO 2 + Mn
Mn+2 has 5 unpaired electrons

∴ Spin only magnetic moment = 5 (5 + 2)

= 5#7

= 35

= 5.92 B.M.

= 6 B.M.

118. Answer (00.00)


 
MnO 42 H
MnO 2  MnO 4  H 2 O

Mn+7 = d0
Hence, magnetic moment = zero

119. Answer (05.00)

MnF3 has the strongest oxidising ability
o
EMn /Mn - 1.57 V
= o G
+3 +2

& EMn /Mn - 1.2 V

+4 +2

So, spin only magnetic moment  4 (4  2)  24 B.M.

- 5

120. Answer (4)

6 4 7
  
3MnO 42  4H " MnO 2  MnO 4
Mn → 4s23d5

Mn+4 → 3d3

n=3
µ = n (n + 2)

= 3 (5)

= 15

= 3.87 ≈ 4 B.M.

121. Answer (6)

FeCr2 O 4 + Na 2 CO3 + O 2 Fe 2 O3 + CO 2 + Na 2 CrO 4

(A)

 2
Na 2 CrO 4  H Cr2 O  H 2 O  Na
7

Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005. Phone : 011-47623456
20 The d- and f-Block Elements Solutions of Assignment Step-2

122. Answer (5)

KMnO 4 + KI + H+ Mn+2 + I 2 + H 2 O
Hence the change in O.S. of Mn is (5).

[Miscellaneous]

123. Answer (10)

Electronic configurations of Ho and Ho3+ are

Ho : 4f11 6s2

Ho3+ : 4f10

∴ Number of electrons present in 4f orbital of Ho3+ is 10.

  

Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005. Phone : 011-47623456
Chapter 7 Step-3

The d- and f-Block Elements

SOLUTIONS
SECTION - A
Objective Type Questions (One option is correct)

1. Answer (4)
It depends on reduction potential.
2. Answer (2)
Stability increases down the group.
3. Answer (3)
Both statements are correct.
4. Answer (3)
AgI and Ag3PO4 are coloured due to polarisation whereas CrO42– is coloured due to Ligand to metal
charge transfer.
5. Answer (3)
Its aqueous solution is acidic due to cationic hydrolysis.
6. Answer (3)
  
2 
I  MnO 4 H
Mn  I 2
  2
OH  MnO 4 Boil
MnO 4  O 2
7. Answer (2)

H 2 SO 4 + 2KMnO 4 " K 2 SO 4 + Mn 2 O7 + H 2 O
8. Answer (3)

Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005. Phone : 011-47623456
22 The d- and f-Block Elements Solutions of Assignment Step-3

9. Answer (2)

It contains 3c–2e– bond.

10. Answer (1)

La3+ and Lu3+ are colourless.

11. Answer (2)

LnC2 upon hydrolysis liberate acetylene.

12. Answer (3)

Actinoid contraction is greater than Lanthanoid contraction.

13. Answer (1)

Actinoids are highly reactive but slightly affected by HNO3.

14. Answer (4)

Ce+4 is an oxidising agent

Eo Ce+4 | Ce3+ = 1.74 V

15. Answer (3)

Due to small size.

16. Answer (3)

MnO2 is used as a catalyst in decomposition of KClO3 to form O2.

SECTION - B
Objective Type Questions (One or more than one option(s) is/are correct)
1. Answer (3, 4)

Highest oxidation state of any element is stable with O and F.

2. Answer (1, 3)

Cu2+ and Ti+3 have one unpaired e– so magnetic moment of these is 1.73 B.M.
3. Answer (1, 2)

K2Cr2O7 → Colour due to charge transfer (CTLM)

KMnO4 → Colour due to charge transfer (CTLM)

4. Answer (2, 3)

Ni2+ and Ti3+ both have unpaired electrons.

5. Answer (1, 2)

Cr and Cu have both valence shell and penultimate shell partially filled.

Cr → 3d5 4s1

Cu → 3d10 4s1

Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005. Phone : 011-47623456
Solutions of Assignment Step-3 The d- and f-Block Elements 23

6. Answer (1, 2)

Oxidation of manganate ion to permanganate ion can be done by Cl2 and O3.

7. Answer (2, 4)

CuSO 4 
CuO  SO3

1
SO3 " SO 2 + O2 .
2
1
AgNO3 " Ag + NO 2 + O2
2
O2 and NO2 are paramagnetic.

KMnO4 and K2Cr2O7 are coloured due to C.T. spectra.

8. Answer (1, 2, 4)
 
Cl  Cr2 O 22 H 2 SO 4
CrO Cl 2 2
deep red vapours

CrO 2 Cl 2 + NaOH Na 2 CrO 4 + NaCl

9. Answer (1, 2, 3)

Cu (OH) 2 and [Cu (NH3) 4] SO 4 both have 3d0 E.C. so both are pale blue coloured due d-d transition.
10. Answer (1, 2, 3)

It is non-stoichiometric due to pressure of Fe+3. It is a basic oxide.

11. Answer (1, 2, 3)

12. Answer (1, 3)

+
H +2
KMnO 4 Mn
M
Eq. wt. :
5
In acidic medium KMnO4 does not show disproportional reaction because it cannot show the oxidation
number higher than 7.

13. Answer (1, 3)

Prussian blue is Fe4[Fe(CN)6]3 and K[Fe′′′Fe(CN)6]

14. Answer (1, 2, 3, 4)

 
Hg 2 Cl 2 Hg 22  2Cl
(Calomel)

Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005. Phone : 011-47623456
24 The d- and f-Block Elements Solutions of Assignment Step-3

+
Due to metal-metal bonding Hg 22 is diamagnetic

15. Answer (3)

Only K2Cr2O7 is used as primary standard.

SECTION - C
Linked Comprehension Type Questions

Comprehension-I

1. Answer (3)

Mn show the maximum oxidation state of +7.

2. Answer (2)

Due to half-filled E.C. Mn+2 is more stable.

3. Answer (4)

Fact.

Comprehension-II

1. Answer (4)

Due to crystal field splitting.

2. Answer (3)

If unpaired elusion are same, then colour will same.

3. Answer (3)

Due to charge transfer

4. Answer (2)

More polarizability of I–.

Comprehension-III

1. Answer (4)

Enthalpy of formation of all halides is negative.

2. Answer (3)
− − −
Cr2 O 72 Basic
CrO 42 acidic
Cr2 O 72
3. Answer (4)
TiCl 4 + H 2 O Ti (OH) 4 + HCl
TiCl3 + H 2 O Fe (OH) 3 + HCl
CuSO 4 + H 2 O Cu (OH) 2 + H 2 SO 4

Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005. Phone : 011-47623456
Solutions of Assignment Step-3 The d- and f-Block Elements 25

SECTION - D
Matrix-Match Type Questions

1. Answer A(q, r, s), B(q, r), C(p), D(q, r, s)

Mn+2 → 5 # 7 = 35 B.M. paramagnetic and colourless

V+3 → Paramagnetic coloured

Zn+2 → Diamagnetic colourless

Fe+3 → 35 B.M. paramagnetic coloured

2. Answer A(p), B(r), C(q), D(s)

(A) Fe[Fe(CN)6]– → (p) (3)

(B) Ag(CN2)– → (r) (1)

(C) Ni(CO)4 → (q) (0)

(D) CrO5 → (s) (6)

3. Answer A(r, s), B(q, s), C(p), D(p, t)

(A) CrO5

(B) CrO2Cl2

(C) K3CrO8

(D) Cr2(SO4)3

4. Answer A(p, q), B(p, q), C(p, q, t), D(p, q, r, s, t)

CuF2 is coloured due to d-d transition CuSO4 . 5H2O is blue coloured due to d-d transition. All of these
are paramagnetic.

SECTION - E
Assertion-Reason Type Questions

1. Answer (3)
Fe can show the oxidation state + 8/3.
2. Answer (4)
In Zinc, outermost shell is not completely filled.
Zn does not show variable oxidation number because it has full filled d-orbital in its atomic or ionic
state.
3. Answer (2)
Group-12 elements are not transition metals.
4. Answer (1)
Ni does not show co-ordination number of six.

Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005. Phone : 011-47623456
26 The d- and f-Block Elements Solutions of Assignment Step-3

5. Answer (2)

−
MnO 4 is pink coloured due to charge transfer.
6. Answer (4)
Two set of Cr–O bond length is present in Cr2O7–2.
7. Answer (2)
Reduction of AgBr may take place in presence of sunlight.
8. Answer (3)
CuO is paramagnetic.
9. Answer (4)
Lu(OH)3 is less basic than Ce(OH)3.
10. Answer (2)
Fact.

SECTION - F
Integer Answer Type Questions
1. Answer (23)
X=7
Y=4
Z=6
W=6
Sum = 23
2. Answer (3)
Sc show only +3 oxidation state.
3. Answer (3)
Fe3+ has five electron.
4. Answer (24)
Ti, V, Cr, Mn, Fe, Co, Ni, Cu
x=8
3x = 24
5. Answer (2)
Four bond length are small and two bond length are large.
6. Answer (4)
KMnO4 is converted into MnO2 in neutral medium.

Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005. Phone : 011-47623456
Solutions of Assignment Step-3 The d- and f-Block Elements 27

7. Answer (2)
Sc 2 O3 + C 1000cC
ScC 2 .

8. Answer (9)
Colour of element having 'n' electron in f-sub-shell is same that having 14-n electron.
9. Answer (3)
CdI2 show hcp packing.
10. Answer (2)
(Fe2+)

SECTION - G
Previous Years Questions

1. Answer (D)
2. Answer (B)
4Ag + 8NaCN + 2H2O + O2
↓
4Na [Ag (CN)2] + 4NaOH
3. Answer (C)
In CuF2, copper is in +2 oxidation state
∴ Coloured. In other options copper is in +1 oxidation state therefore colourless.
4. Answer (A)
Complementary colour of blue is (Orange-red)
5. Answer (B)
Zn + 2NaOH → Na2ZnO2 + H2
Iron becomes passive with conc. HNO3.
Copper liberates NO2 with HNO3.
6. Answer (C)
aq. NaOH
MnCl2 Mn (OH) 2 + NaCl
(P) (Q)

PbO 2
Mn(OH) 2 H 2 SO 4 MnO 4
(P)  (X)

MnO(OH) 2 KI
NaCl Conc. H 2 SO 4 Cl 2 Starch Blue
 (Y)

7. Answer (A, B, C)
Cr2+ is a reducing agent and Mn3+ is an oxidizing agent and both have electronic configuration d4.
o o
E Cr /Cr   0.41 V
3 2 EMn 3 
/Mn 2  1.51 V
Above E° values explains reducing nature of Cr2+ and oxidizing behaviour of Mn3+.

Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005. Phone : 011-47623456
28 The d- and f-Block Elements Solutions of Assignment Step-3

8. Answer (B, D)
(A) Manganese show pale purple colour in flame test.
+2 H2 S
(B) Cu HCl CuS .
Blackppt.

(C) Both Cu+2 and Mn+2 form precipitate with H2S in basic medium.
o
(D) E Cu 2
/Cu   0.34
o
EMn 2
/Mn   1.18V

9. Answer (A, B, D)

2MnO 2 + 4KOH + O 2 Fusion

2K 2 MnO 4 + 2H 2 O
^Wh

Electrolysis of aq K2MnO4 oxidises MnO 24– to MnO 4–

2K 2 MnO 4 + 2H 2 O Electrolysis
2KMnO 4 + 2KOH + H 2
^Wh ^ Xh

K2MnO4 in acidic medium undergoes disproportionation

+
3MnO 24– + 4H 2MnO 4– + MnO 2 + 2H 2 O
^ Yh ^Z h

K2MnO4 is green in colour and KMnO4 is in purple colour. Both are tetrahedral in shape involving
pπ – dπ bond.

10. Answer (6)

−
MnO 2 KOH
fuse MnO 24
Oxidation state = 6.
11. Answer (6)
2AgNO3 ^s h 
2Ag ^s h  2NO 2 ^gh  O 2 ^gh
Both the NO2 and O2 gases are paramagnetic. NO2(g) has 1 unpaired electron and O2(g) has 2 unpaired
electrons.
According to MOT, electronic configuration of O2 is
2 2 2 2 2 2 2 1 1
 1 s  1 s  2s  * 2 s  2 p  2 p    * 2p   * 2p
* 2 x
2p y
x y

Total number of electrons present in antibonding molecular orbitals = 6

  

Corporate Office : Aakash Tower, 8, Pusa Road, New Delhi-110005. Phone : 011-47623456