ASSIGNMENT-03

Marking Scheme
The d- and f- block elements
Value points/Key points Marks
Multiple Choice Questions
1. (c) 26 1
2. (d) Cu 1
3. (a) Copper liberates hydrogen from acids. 1
4. (a) 𝑉2 𝑂5, 𝐶𝑟2 𝑂3 1
5. (c) Ti < V < Cr < Mn, increasing melting point 1
6. (b) 3.87 B.M. 1
7. (a) 𝐶𝑜2+ and (d) 𝐶𝑟 3+ 1
8. (a) Cu(II) is more stable 1
9. (b) 𝐶𝑢𝐹2 1
10. (c) All ions are coloured. 1
11. (a) 𝑀𝑛2 𝑂7 1
12. (a) 𝐾𝑀𝑛𝑂4 and (b) 𝐶𝑒(𝑆𝑂4 )2 1
13. (d) 𝑀𝑛2+ acts as autocatalyst. 1
14. (a) (i) and (ii) 1
15. (a) 2/5 1
16. (c) 𝐼𝑂3− 1
17. (b) +3 1
18. (a) [𝑋𝑒]4𝑓 7 5𝑑1 6𝑠 2 1
19. (c) As a result of lanthanoid contraction, the properties of 4𝑑 series of the transition 1
elements have no similarities with the 5𝑑 series of elements.
20. (c) lesser energy difference between 5𝑓 and 6𝑑 than between 4𝑓 and 5𝑑 orbitals 1
21. (d) [𝑃𝑡(𝑒𝑛)2 𝐶𝑙2 ]2+ 1
22. (c) 𝑉 3+ , 𝑉 2+ , 𝐹𝑒 3+ 1
23. (b) Completely filled 3d subshell 1
24. (b) 𝑆𝑐 3+ 1
25. (c) Mn (Z = 25) 1
26. (a) They are chemically reactive 1
27. (b) +3 1
28. (d) Variable oxidation states 1
29. (b) 2.82 BM 1
30. (a) Actinides: Radioactive :: Lanthanides: Non-radioactive 1
31. (c) lesser energy difference between 5𝑓 and 6𝑑 than between 4𝑓 and 5𝑑 orbitals 1
32. (d) Sc
Assertion-Reason Questions
33. (a) both A and R are true and R is the correct explanation of A. 1
34. (c) A is true but R is false. 1
35. (d) A is false but R is true. 1
36. (b) both A and R are true and R is not the correct explanation of A. 1
37. (b) both A and R are true and R is not the correct explanation of A. 1
38. (b) both A and R are true and R is not the correct explanation of A. 1

MS/d- and f-block elements/ XII Page 1 of 8

39. (b) both A and R are true and R is not the correct explanation of A. 1
40. (d) A is false but R is true. 1
41. (a) both A and R are true and R is the correct explanation of A. 1
42. (b) both A and R are true and R is not the correct explanation of A. 1
43. (d) A is false but R is true. 1
44. (c) A is true but R is false. 1
45. (b) both A and R are true and R is not the correct explanation of A. 1
46. (d) A is false but R is true. 1
Passage-based/Case-based Questions
47. (i) As zinc atom has completely filled d-orbitals (3𝑑10 ) in its ground state as well as 1 4
in oxidised state, therefore, it is not regarded as a transition element.
(ii) There are five d-orbitals in an energy level and each orbital can contain two
1
electrons. As we move from one element to the next, an electron is added and for
complete filling of the five d-orbitals, 10 electrons are required.
(iii) Vanadium 1+1
Transition elements contain incompletely filled d-subshell, i.e., their electronic
configuration is (𝑛 − 1)𝑑1−10 𝑛𝑠1−2 whereas non-transition elements have no d-
subshell or their subshell is completely filled and have 𝑛𝑠1−2 or 𝑛𝑠 2 𝑛𝑝1−6 in their
outermost shell.
OR
Interstitial compounds are those in which small atoms occupy the interstitial sites in
the crystal lattice.
Interstitial compounds are well known for transition metals because small sized atoms
of H, B, C, N, etc., can easily occupy positions in the voids present in the crystal
lattices of transition metals.
48. (i) 𝑠𝑝3 1 4
(ii) It is used for the estimation of hydrogen peroxide. 1
(iii) 𝐾2 𝑀𝑛𝑂4 , 𝑂2 and 𝑀𝑛𝑂2 will be formed after heating of potassium permanganate.
1+1
OR

It is diamagnetic.
49. (i) +3 1 4
3+ 1
(ii) 𝐹𝑒
(iii) The maximum oxidation state of chromium in its compounds is +6 because it has
1+1
only 6 electrons in 𝑛𝑠 and (𝑛 − 𝑙)𝑑-orbitals.
OR
Because the standard potential of vanadium is rather small, making a switch between
oxidation states relatively easy.
50. (i) Due to their ability to show multiple oxidation states and to form complexes / 1 4
provide large surface area.
(ii) Due to poor shielding effect of 4𝑓 orbital. 1

MS/d- and f-block elements/ XII Page 2 of 8

 (iii) The overall decrease in atomic and ionic radii from 𝐿𝑎 to 𝐿𝑢 is known as
lanthanoid contraction. Atomic radii of second and third transition series are very 1+1
similar.
OR
(iii) 𝐶𝑟 is stronger reducing agent than 𝐹𝑒 2+ .
2+

Reason: 𝑑 4 → 𝑑 3 , occurs in case of 𝐶𝑟 2+ to 𝐶𝑟 3+ . But 𝑑 6 → 𝑑 5 occurs in case of

𝐹𝑒 2+ to 𝐹𝑒 3+ . In a medium (like water) 𝑑 3 (𝑡2𝑔 half-filled level) is more stable than
𝑑5.
Very Short Answer Questions [1 Mark]
51. Copper exhibits +2 oxidation state wherein it has incompletely filled d orbitals 1
(3𝑑9 4𝑠 0 ) hence, a transition element.
52. Cr (3𝑑 5 4𝑠1 ) has five unpaired electrons in its d-orbitals whereas Zn (3𝑑10 4𝑠 2 ) has 1
no unpaired electrons in its d-orbitals. As a result of this weak metallic bonds exist in
Zn whereas strong metallic bonds exist in Cr. Hence, Zn is soft whereas Cr is hard.
53. It is due to regular increase in ionisation enthalpy. 1
54. 𝐶𝑟𝑂 < 𝐶𝑟2 𝑂3 < 𝐶𝑟𝑂3 1
Higher the oxidation state, more will be acidic character.
55. Cu shows 𝐸 0 positive value. 1
56. 𝑀𝑛2+ has the maximum paramagnetic character because of the maximum number of 1
unpaired electrons, i.e., 5.
57. Due to symmetrical electronic configuration, there is no orbital contribution in 𝐶𝑟 3+ 1
ion. However, appreciable orbital contribution takes place in 𝐶𝑜2+ .
58. 𝐶𝑢𝐶𝑙2 is more stable than 𝐶𝑢2 𝐶𝑙2 . The stability of 𝐶𝑢2+ (𝑎𝑞) is more than 𝐶𝑢+ (𝑎𝑞) 1
due to the much more negative ∆ℎ𝑦𝑑 𝐻 0 of 𝐶𝑢2+ (𝑎𝑞) than 𝐶𝑢+ (𝑎𝑞).
59. 𝐶𝑢2+ (3𝑑9 4𝑠 0 ) has one unpaired electron in d-subshell which absorbs radiation in 1
visible region resulting in d-d transition and hence 𝐶𝑢2+ salts are coloured.
𝑍𝑛2+ (3𝑑10 4𝑠 0 ) has completely filled d-orbitals. No radiation is absorbed for d-d
transition and hence 𝑍𝑛2+ salts are colourless.
[CBSE Marking Scheme Patna 2015]
60. Pyrophoric alloys emit sparks when struck. Hence, they are used in making flints for 1
lighters.
Short Answer Questions–I [2 marks]
61. (i) This is due to small energy gap between 5f, 6d and 7s subshells in actinoids. 1 2
(ii) This is because with increase in atomic number in a series, the increased nuclear
1
charge is partly cancelled by the increased shielding effect of electrons in the d-
orbitals of penultimate shell.
62. (i) Mn3+ (d4) is less stable than Mn2+ (d5, half filled) while Fe3+ (d5, half filled) is 1 2
more stable than Fe2+ (𝑑4 ). That is why Mn2+ is more resistance than Fe2+ towards
oxidation. 1
(ii) Lanthanoid metals show +2 and +4 oxidation states to attain extra stable 𝑓 0 and
𝑓 7 configurations.
63. (i) 𝐶𝑟 2+ , due to lower standard reduction potential / Higher standard oxidation 1 2
potential.
(ii) 𝑀𝑛2+ , due to highest negative standard reduction potential. 1
64. (i) 𝐶𝑟 3+ because of half filled 𝑡2𝑔 level. ½ 2
(ii) 𝑀𝑛3+ , as the change from 𝑀𝑛3+ to 𝑀𝑛2+ results in stable half filled (𝑑 5 ) ½
configuration.

MS/d- and f-block elements/ XII Page 3 of 8

 (iii) 𝑇𝑖 4+ , as 𝑇𝑖 4+ has empty d-orbitals therefore d-d transition cannot occur in 𝑇𝑖 4+ . ½
(iv) 𝑀𝑛3+ (3𝑑4 4𝑠 0 ). It has 4 unpaired electrons. ½
65. (i) Negative 𝐸 0 values for 𝑀𝑛2+ and 𝑍𝑛2+ are related to stabilities of half-filled and 1 2
fully filled configurations, respectively. But for 𝑁𝑖 2+ , 𝐸 0 value is related to the
highest negative enthalpy of hydration.
(ii) This is due to d-d transition of electron in [𝑇𝑖(𝐻2 𝑂)6 ]3+ complex. 𝑇𝑖 3+ has one 1
electron in d-orbital (3𝑑1 ) which absorbs energy corresponding to blue-green region
1 0 0 1
and jumps from 𝑡2𝑔 to 𝑒𝑔 set of d-orbitals (𝑡2𝑔 𝑒𝑔 → 𝑡2𝑔 𝑒𝑔 ). But 𝑆𝑐 3+ has no
electron in the d-orbital.
66. (i) 𝑀𝑛3+ is less stable and changes to 𝑀𝑛2+ which is more stable due to half-filled 1 2
d-
orbital configuration. That is why, 𝑀𝑛3+ undergoes disproportionation reaction. 1
(ii) Co (II) has electronic configuration [𝐴𝑟]3𝑑 7 4𝑠 0 , i.e., it has three unpaired
electrons. In the presence of strong ligands, two unpaired electrons in 3d-subshell
pair-up and third unpaired electron shifts to higher energy subshell from where it
can be easily lost and hence oxidised to Co (III).
67. 𝐴 = 𝑁𝑎2 𝐶𝑟𝑂4 (Sodium chromate), ½ 2
𝐵 = 𝑁𝑎2 𝐶𝑟2 𝑂7 (Sodium dichromate), ½
𝐶 = 𝐾2 𝐶𝑟2 𝑂7 (Potassium dichromate), ½
½
𝐷 = 𝑁𝑎2 𝑆𝑂4 (Sodium sulphate).
68. (i) 𝑀𝑛𝑂4− + 5𝐶2 𝑂42− + 16𝐻 + → 2𝑀𝑛2+ + 10𝐶𝑂2 + 8𝐻2 𝑂 1 2
(ii) 𝐶𝑟2 𝑂72− + 6𝐹𝑒 2+ + 14𝐻 + → 2𝐶𝑟 3+ + 3𝐹𝑒 3+ + 7𝐻2 𝑂 1
69. (i) 8𝑀𝑛𝑂4− + 3𝑆2 𝑂32− + 𝐻2 𝑂 → 8𝑀𝑛𝑂2 + 6𝑆𝑂42− + 2𝑂𝐻 − 1 2
(ii) 𝐶𝑟2 𝑂72− + 3𝑆𝑛2+ + 14𝐻 + → 2𝐶𝑟 3+ + 3𝑆𝑛4+ + 7𝐻2 𝑂 1
70. (i) 2𝑀𝑛𝑂4− + 10𝐼 − + 16𝐻 + → 2𝑀𝑛2+ + 8𝐻2 𝑂 + 5𝐼2 1 2
(ii) 𝑁𝑎2 𝐶𝑟2 𝑂7 + 2𝐾𝐶𝑙 → 𝐾2 𝐶𝑟2 𝑂7 + 2𝑁𝑎𝐶𝑙 1
71. Reaction between iodide and persulphate ions is: 2
𝐹𝑒 (𝐼𝐼𝐼) 1
2𝐼 − + 𝑆2 𝑂82− → 𝐼2 +2𝑆𝑂42−
Role of Fe (III) ions:
2𝐹𝑒 3+ + 2𝐼 − → 2𝐹𝑒 2+ + 𝐼2 ½
2𝐹𝑒 2+ + 𝑆2 𝑂82− → 2𝐹𝑒 3+ + 2𝑆𝑂42− ½
72. (i) Electronic configuration of 𝑀𝑛2+ is 3𝑑 5 which is half-filled and hence stable. 1 2
Therefore 𝐼𝐸3 is very high i.e., 3rd electron cannot be lost easily. In case of 𝐹𝑒 2+ ,
electronic configuration is 3𝑑 6 . Hence, it can lose one electron easily to give the
stable configuration 3𝑑5 .
(ii) 𝑉(𝑍 = 23): 3𝑑3 4𝑠 2 , 𝑉 3+ = 3𝑑2 (𝑛 = 2) 1
𝜇 = √𝑛(𝑛 + 2) 𝐵. 𝑀. = √2(2 + 2) = √8 = 2.73 𝐵. 𝑀.
73. (i) It is due to completely filled stable configuration, 1 2
10 2
i.e., (𝑛 − 1)𝑑 𝑛𝑠 configuration.
(ii) This is because they involve gradual filling up of inner d-orbitals due to which 1
increase in nuclear charge is partly cancelled by shielding effect provided by inner
d-electrons.
74. 1 2
(i) 𝑆𝑐 3+ has 3𝑑0 outer electronic configuration, therefore it is diamagnetic nature
whereas 𝐶𝑟 3+ has 3𝑑 3 outer electronic configuration. So, it is paramagnetic due to
presence of unpaired electrons.

MS/d- and f-block elements/ XII Page 4 of 8

 (ii) Cr has higher melting and boiling points. In a particular series, the metallic 1
strength increases up to middle with increasing number of unpaired electrons, i.e., up
to 𝑑5 configuration. After Cr, the number of unpaired electrons goes on decreasing.
Accordingly, the m.p. and b.p. decrease after middle because of increasing pairing of
electrons.
75. (i) 2𝑀𝑛𝑂4− + 5𝑆𝑂32− + 6𝐻 + → 2𝑀𝑛2+ + 5𝑆𝑂42− +3𝐻2 𝑂 1 2
(ii) 𝐶𝑟2 𝑂72− + 6𝐹𝑒 2+ + 14𝐻 + → 2𝐶𝑟 3+ + 3𝐹𝑒 3+ + 7𝐻2 𝑂 1
Short Answer Questions–II [3 marks]
76. (i) This is because transition metals have strong metallic bonds as they have large 1 3
number of unpaired electrons.
(ii) This is because 5d and 4d-series elements have virtually the same atomic and 1
ionic radii due to lanthanoid contraction.
1
(iii) The members in the actinoid series exhibit larger number of oxidation states
than the corresponding members in the lanthanoid series due to the fact that
the 5f, 6d and 7s levels are of comparable energies.
77. (i) Mn has + 7 oxidation state in Mn2O7 and + 2 in MnO. In low oxidation state of 1 3
the metal, some of the valence electrons of the metal atom are not involved in
bonding. Hence, it can donate electrons and behave as a base. On the other hand,
in higher oxidation state of the metal, valence electrons are involved in bonding
and are not available. Instead, effective nuclear charge is high and hence it can
accept electrons and behave as an acid.
1
(ii) Copper exhibits +2 oxidation state wherein it will have incompletely filled d
orbitals (3d9), hence a transition metal.
1
(iii) Cu shows E0 positive value.
78. (i) (a) As oxygen stabilises manganese more than fluorine by forming multiple 1 3
bonds.
(b) Due to their tendency to show variable oxidation states 1
(ii) 3𝑀𝑛𝑂42− + 4𝐻 + → 2𝑀𝑛𝑂4− + 𝑀𝑛𝑂2 + 4𝐻2 𝑂 1
Manganate Permanganate
79. The oxidising behaviour of KMnO4 depends on pH of the solution. 3
In acidic medium (pH < 7), 𝑀𝑛𝑂4− + 8𝐻 + + 5 𝑒 − → 𝑀𝑛2+ + 4𝐻2 𝑂 1
In alkaline medium (pH > 7), 𝑀𝑛𝑂4− + 𝑒 − → 𝑀𝑛𝑂42− 1
1
In neutral medium (pH = 7), 𝑀𝑛𝑂4− + 2𝐻2 𝑂 + 3𝑒 − → 𝑀𝑛𝑂2 + 2𝑂𝐻 −
80. 𝐴 = 𝑀𝑛𝑂2 (𝑀𝑎𝑛𝑔𝑎𝑛𝑒𝑠𝑒 (𝐼𝑉) 𝑜𝑥𝑖𝑑𝑒] 1 3
𝐵 = 𝐶𝑙2 (𝐶ℎ𝑙𝑜𝑟𝑖𝑛𝑒) 1
𝐶 = 𝑁𝐶𝑙3 (𝑁𝑖𝑡𝑟𝑜𝑔𝑒𝑛 𝑡𝑟𝑖𝑐ℎ𝑙𝑜𝑟𝑖𝑑𝑒) 1
𝑀𝑛𝑂2 + 4 𝐻𝐶𝑙 → 𝑀𝑛𝐶𝑙2 + 𝐶𝑙2 + 2𝐻2 𝑂
A B
𝑁𝐻3 + 3𝐶𝑙2 → 𝑁𝐶𝑙3 + 3𝐻𝐶𝑙
C
81. (i) 2𝑀𝑛𝑂2 + 4𝐾𝑂𝐻 + 𝑂2 → 𝐾2 𝑀𝑛𝑂4 + 2𝐻2 𝑂 1 3
− − +
(ii) 10𝐼 + 2𝑀𝑛𝑂4 + 16𝐻 → 2𝑀𝑛2+ + 8𝐻2 𝑂 + 5𝐼2 1
(iii) 𝐶𝑟2 𝑂72− + 3𝑆𝑛2+ + 14𝐻 + → 2𝐶𝑟 3+ + 3𝑆𝑛4+ + 7𝐻2 𝑂 1
82. (i) This is because 𝐸𝑢2+ tends to change to 𝐸𝑢3+ as +3 is the common oxidation state 1 3
of lanthanoids.
(ii) In alkaline medium, the orange colour of the solution changes to yellow due to
1
conversion of dichromate (𝐶𝑟2 𝑂72− )ion to chromate ion (𝐶𝑟𝑂42− ) ion.

MS/d- and f-block elements/ XII Page 5 of 8

 𝐶𝑟2 𝑂72− + 2𝑂𝐻 − ⇌ 2𝐶𝑟𝑂42− + 𝐻2 𝑂
(iii) The irregularity is due to the irregular variation of ionisation enthalpies 1
(Δ𝑖 𝐻1 + Δ𝑖 𝐻2 ) and sublimation enthalpies.
83. (i) (a) Higher the reduction potential of a species, greater is the ease with which it 1 3
undergoes reduction. Among these pairs, 𝑀𝑛3+ /𝑀𝑛2+ has largest positive
reduction potential. Hence 𝑀𝑛3+ can be easily reduced to 𝑀𝑛2+ i.e., 𝑀𝑛3+ is
least stable. 𝐶𝑟 3+ /𝐶𝑟 2+ has a negative 𝐸 0 value, therefore, 𝐶𝑟 3+ is most
stable. 𝐹𝑒 3+ /𝐹𝑒 2+ has a positive value but small. Hence, 𝐹𝑒 3+ is more stable
than 𝑀𝑛3+ but less stable than 𝐶𝑟 3+ .
(b) Lower the reduction potential or higher the oxidation potential of a species, 1
greater is the ease with which it undergoes oxidation. Among these pairs,
𝑀𝑛2+ /𝑀𝑛 has the most negative reduction potential or most positive oxidation
potential. Therefore, it will be most easily oxidised. Thus, the decreasing order
of their ease of oxidation is Mn > Cr > Fe.
(ii) In the complex 𝐾4 [𝑀𝑛(𝐶𝑁)6 ] , Mn is in +2 oxidation state. Magnetic moment
2.2BM indicates that it has only one unpaired electron and hence forms inner 1
orbital or low spin octahedral complex. In presence of 𝐶𝑁 − , a strong ligand the
hybridisation involved is 𝑑 2 𝑠𝑝3 .
84. (i) Because the sum of sublimation enthalpy and hydration enthalpy to convert Cu(s) 1 3
to 𝐶𝑢2+ (aq) is so high that it is not balanced by its hydration enthalpy.
(ii) Cr is strongest reducing agent in +2 oxidation state. 𝐶𝑟 2+ has configuration 3𝑑 4 . 1
After losing one electron it forms 𝐶𝑟 3+ which has stable half filled 𝑡2𝑔 level.
(iii) 𝑍𝑛2+ (3𝑑2 ) has completely filled d-orbitals. As a result of this, d-d transition 1
cannot occur and hence, 𝑍𝑛2+ salts are colourless.
85. (i) Copper has high enthalpy of atomisation and low enthalpy of hydration. Since the 1 3
high energy to transform Cu(s) to Cu2+ (aq) is not balanced by hydration enthalpy,
0
therefore, 𝐸𝐶𝑢 2+ ⁄𝐶𝑢 value is exceptionally positive.

(ii) This is due to extra stability of half-filled 3d-orbitals of Mn2+ (d5). 1

(iii) Cr2+ is strongest reducing agent in +2 oxidation state. 𝐶𝑟 2+ has configuration 3𝑑 4 . 1
After losing one electron it forms 𝐶𝑟 3+ which has stable half filled 𝑡2𝑔 level.
Long Answer Questions [5 marks]
86. (i) (a) Oxidation states of transition elements differ from each other by unity. In non- 1 5
transition elements oxidation states normally differ by a unit of two.
(b) In transition elements higher oxidation states are favoured by heavier elements 1
whereas in non-transition elements lower oxidation state is favoured by heavier
elements.
(ii) (a) 𝑀𝑛𝑂4− + 2𝐻2 𝑂 + 3𝑒 − → 𝑀𝑛𝑂2 + 4𝑂𝐻 − ] × 2 1
𝐼 − + 6𝑂𝐻 − → 𝐼𝑂3− + 3𝐻2 𝑂 + 6𝑒 −
2𝑀𝑛𝑂4− + 𝐼 − + 𝐻2 𝑂 → 𝐼𝑂3− + 2𝑀𝑛𝑂2 + 2𝑂𝐻 −
2− +
1
(b) 2CrO4 + 2 H Cr2O72− + H 2O
Acid ( pH less than 7)
Alkali ( pH more than 7)

(c) 2 KMnO4 ⎯⎯⎯

→ K 2 MnO4 + MnO2 + O2
513 K 1

87. (i) (a) Cr, the highest melting point of Cr is attributed to the involvement of greater number 1 5
of electrons (5) from 3d in addition to 4s electrons in interatomic metallic bonding.
(b) Mn, because the change from 𝑀𝑛3+ (3𝑑4 ) to 𝑀𝑛2+ (3𝑑5 ) results in the half-filled 1
configuration which has extra stability.
(c) Zn, in Zn (3𝑑10 4𝑠 2 ) all the electrons present in d-orbitals are paired and hence 1
metallic bonds present in it are weak. That is why, it is soft.

MS/d- and f-block elements/ XII Page 6 of 8

 (ii) Sodium chromate is acidified with sulphuric acid to give a solution from which orange
sodium dichromate, 𝑁𝑎2 𝐶𝑟2 𝑂7 . 2𝐻2 𝑂 can be crystallised. 1
2𝑁𝑎2 𝐶𝑟𝑂4 + 2𝐻 + → 𝑁𝑎2 𝐶𝑟2 𝑂7 + 2𝑁𝑎+ + 𝐻2 𝑂
Sodium dichromate is more soluble than potassium dichromate. The latter is therefore,
prepared by treating the solution of sodium dichromate with potassium chloride. 1
𝑁𝑎2 𝐶𝑟2 𝑂7 + 2𝐾𝐶𝑙 → 𝐾2 𝐶𝑟2 𝑂7 + 2𝑁𝑎𝐶𝑙
88. (i) Conversion of pyrolusite (𝑀𝑛𝑂2 ) into potassium manganate (𝐾2 𝑀𝑛𝑂4 )
2𝑀𝑛𝑂2 + 4𝐾𝑂𝐻 + 𝑂2 → 2𝐾2 𝑀𝑛𝑂4 + 2𝐻2 𝑂
Electrolytic oxidation:
𝐾2 𝑀𝑛𝑂4 ⇌ 2𝐾 + + 𝑀𝑛𝑂42−
At anode: 𝑀𝑛𝑂42− → 𝑀𝑛𝑂4− + 𝑒 −
At cathode: 𝐻 + + 𝑒 − → 𝐻, 2𝐻 → 𝐻2
It oxidises oxalate (𝐶2 𝑂42− ) to carbon dioxide (𝐶𝑂2 ) in acidic medium.
𝑀𝑛𝑂4− + 8𝐻 + + 5𝑒 − → 𝑀𝑛2+ + 4𝐻2 𝑂] × 2
𝐶2 𝑂42− → 2𝐶𝑂2 + 2𝑒 − ] × 5
2𝑀𝑛𝑂4− + 5𝐶2 𝑂42− + 16𝐻 + → 2𝑀𝑛2+ + 10𝐶𝑂2 + 8𝐻2 𝑂
(ii)

89. (i) dil. 𝐻2 𝑆𝑂4 is an oxidising agent and oxidises 𝐹𝑒𝑆𝑂4 to 𝐹𝑒2 (𝑆𝑂4 )3 . Dil. HCl is a 1+1 5
reducing agent and liberates chlorine on reacting with 𝐾𝑀𝑛𝑂4 solution.
(ii) (a) In these oxoanions the oxygen atoms are directly bonded to the transition
metal. Since oxygen is highly electronegative, the oxoanions bring out the 1
highest oxidation state of the metal.
(b) 𝐶𝑒 4+ has the tendency to attain +3 oxidation state which is more stable and
1
so, it is used as an oxidising agent in volumetric analysis.
(c) 𝑍𝑛2+ ion has all its orbitals completely filled whereas in 𝐶𝑢2+ ion there is 1
one half-filled 3d-orbital. Therefore, due to d-d transition 𝐶𝑢2+ has a
tendency
to form coloured salts whereas 𝑍𝑛2+ has no such tendency.
90. 𝐴 = 𝐾𝑀𝑛𝑂4 (Potassium permanganate), 𝐵 = 𝐾2 𝑀𝑛𝑂4 (Potassium manganate), ½ 5
𝐶 = 𝑀𝑛𝑂2 (Manganese (IV) oxide), 𝐷 = 𝑀𝑛𝐶𝑙2 (Manganese (II) chloride) ½
∆ ½
2𝐾𝑀𝑛𝑂4 → 𝐾2 𝑀𝑛𝑂4 + 𝑀𝑛𝑂2 + 𝑂2
½
A B C
1
𝑀𝑛𝑂2 + 2𝐾𝑂𝐻 + 𝐾𝑁𝑂3 → 𝐾2 𝑀𝑛𝑂4 + 𝐻2 𝑂 + 𝐾𝑁𝑂2
1
C B
1
𝑀𝑛𝑂2 + 4𝑁𝑎𝐶𝑙 + 4𝐻2 𝑆𝑂4 → 𝑀𝑛𝐶𝑙2 + 4𝑁𝑎𝐻𝑆𝑂4 + 2𝐻2 𝑂 + 𝐶𝑙2
D
91. 𝐴 = 𝑀𝑛𝑂2 (Manganese (IV) oxide), 𝐵 = 𝐾2 𝑀𝑛𝑂4 (Potassium manganate), ½ 5
𝐶 = 𝐾𝑀𝑛𝑂4 (Potassium permanganate), 𝐷 = 𝐾𝐼𝑂3 (Potassium iodate) ½
2𝑀𝑛𝑂2 + 4𝐾𝑂𝐻 + 𝑂2 → 2𝐾2 𝑀𝑛𝑂4 + 2𝐻2 𝑂 ½
A B ½
3𝐾2 𝑀𝑛𝑂4 + 4𝐻 + → 2𝐾𝑀𝑛𝑂4 + 𝑀𝑛𝑂2 + 2𝐻2 𝑂 + 4𝐾 + 1
C 1
−
2𝑀𝑛𝑂4 + 𝐻2 𝑂 + 𝐾𝐼 → 2𝑀𝑛𝑂2 + 2𝑂𝐻 − + 𝐾𝐼𝑂3 1
A D

MS/d- and f-block elements/ XII Page 7 of 8

92. (i) (a) 2𝐶𝑢2+ + 4𝐼 − → 𝐶𝑢2 𝐼2 + 𝐼2 1 5
2−
(b) 𝐶𝑟2 𝑂7 + 14𝐻 + 6𝑒 − →
+
2𝐶𝑟 3+ + 7𝐻2 𝑂 1
𝐹𝑒 2+ → 𝐹𝑒 3+ + 𝑒 − ] × 6
𝐶𝑟2 𝑂72− + 14𝐻 + + 6𝐹𝑒 2+ → 2𝐶𝑟 3+ + 6𝐹𝑒 3+ + 7𝐻2 𝑂
(ii) (a) Third series has the highest first ionization energy due to poorest shielding effect of 1
the fully filled 4f subshell.
(b) Due to lanthanoid contraction, some pair of elements have almost similar size and as 1
a result, such pairs have very similar properties which makes their separation
difficult.
(c) 𝑆𝑚2+ , 𝐸𝑢2+ and 𝑌𝑏 2+ ions are good reducing agents as they tend to acquire 1
common oxidation state of + 3 shown by lanthanoids by the loss of one
electron while 𝐶𝑒 4+ gains one electron to attain + 3. Hence, 𝐶𝑒 4+ is an
oxidising agent.
93. (i) In transition elements, the oxidation states differ from each other by unity, e.g., 1 5
𝐹𝑒 2+ and 𝐹𝑒 3+ etc., while in non-transition elements (p-block elements), the
oxidation states differ by two, e.g., 𝑃𝑏 2+ and 𝑃𝑏 3+ etc.
In transition elements the higher oxidation states are more stable for the heavier 1
elements in a group, e.g., Mo (VI) is more stable than Cr (VI) whereas in non-
transition elements (p-block elements), the lower oxidation states are more stable
for heavier elements due to inert pair effect, e.g., Pb (II) is more stable than Pb
(IV).
(ii) (a) d–block elements exhibit more oxidation states because of less energy gap 1
between d and s subshell whereas f-block elements have large energy gap
between f and d subshell.
(b) On adding NaOH, pH of solution increases and the orange colour of the 1
solution changes to yellow due to conversion of dichromate ion to chromate ion.
𝐶𝑟2 𝑂72− + 2𝑂𝐻 − ⇌ 2𝐶𝑟𝑂42− + 2𝐻2 𝑂
Dichromate ion Chromate ion
(Orange) (Yellow)
(c) This is due to filling of 4f-orbitals which have poor shielding effect (Lanthanoid 1
contraction).

MS/d- and f-block elements/ XII Page 8 of 8