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NCERT Textual Exercise (Solved)

1. Write down the electronic configuration of (a) Cr3+ (b) Cu+ (c) Co2+ (d) Mn2+
(e) Pm3+ (f) Ce4+ (g) Lu2+ (h) Th4+.
Sol. (a) Cr3+ = [Ar]18 3d3 (b) Cu+ = [Ar]18 3d10
(c) Co2+ = [Ar]18 3d7 (d) Mn2+ = [Ar]18 3d5
(e) Pm3+ = [Xe]54 4f 4 6s° (f) Ce4+ = [Xe]54
(g) Lu2+ = [Xe]54 4f 14 5d1 (h) Th4+ = [Rn]86
2. Why are Mn compounds more stable than Fe2+ compounds towards
2+

oxidation to their +3 state?

Sol. Electronic configuration of Mn2+ is 3d5. This is a half-filled configuration
and hence stable. Therefore, third ionisation enthalpy is very high (i.e. third
electron cannot be lost easily).
Electronic configuration of Fe2+ is 3d6. It can lose one electron easily to give
a stable configuration 3d5.
3. Explain briefly how +2 state becomes more and more stable in the first half
of the first row transition elements with increasing atomic number.
Sol. This is because the sum of first and second ionisation energy increases. As
a result, the standard electrode potential (E°) become less and less negative.
Hence, the tendency to form M2+ ion decreases.
4. To what extent do the electronic configurations decide the stability of
oxidation states in the first series of transition elements. Illustrate your answer
with example.
Sol. In the first series of transition elements, the oxidation states which lead
to exactly half-filled or completely filled d-orbitals are more stable. For
example, Mn (Z = 25) has electronic configuration [Ar] 3d5 4s2. It shows
oxidation states + 2 to + 7 but Mn (II) is most stable because of half-filled
configuration [Ar] 3d5.
5. What may be the stable oxidation state of the transition element with the
following d-electron configuration in the ground state of their atoms? 3d3,
3d5, 3d8 and 3d4.
Sol. (a) 3d5 4s2 = +5. (b) 3d5 4s2 = +2, +7, 3d5 4s1 = +6.
(c) 3d8 4s2 = +2. (d) 3d4 4s2 = 3d5 4s1 = +6 (and +3).
6. Name the oxo-metal anions of the first series of the transition metals in which
the metal exhibits the oxidation state equal to its group number.
Sol. Cr2O72– and CrO42– (Group number = Oxidation state of Cr = 6).
MnO4– (Group number = Oxidation state of Mn = 7).

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7. In what way is the electronic configuration of transition elements different
from that of the non-transition elements?
Sol. Transition elements contain partially filled d-orbitals, whereas non-transition
elements have no d-orbitals or have completely filled s or p-orbitals.
8. What are different oxidation states exhibited by lanthanides?
Sol. Lanthanides exhibits +2, +3 and +4 oxidation states.
9. For M2+/M and M3+/M2+ systems, E° values for some metals are as follows:
Cr2+/Cr = – 0⋅9 V Mn2+/Mn = – 1⋅2 V Fe2+/Fe = – 0⋅4 V
Cr3+/Cr2+ = – 0⋅4 V Mn3+/Mn2+ = + 1⋅5 V Fe3+/Fe2+ = 0⋅8V
Use this data to comment upon
(a) the stability of Fe3+ in acid solution as compared to that of Cr3+ and
Mn3+.
(b) the ease with which iron can be oxidised as compared to the similar
process for either Cr or Mn metals.
Sol. (a) Cr3+/Cr2+ has negative reduction potential. Hence, Cr3+ cannot be
reduced to Cr2+.
Mn3+/Mn2+ has a large positive reduction potential. Hence, Mn3+ can be easily
reduced to Mn2+.
Fe3+/Fe2+ has small positive reduction potential.
Hence, Fe3+ is more stable than Mn3+ but less stable than Cr3+.
10. Predict which of the following will be coloured in aqueous solution? Ti3+,
V3+, Sc3+, Mn2+, Fe3+ , Co2+ and MnO4–.
Sol. Ions having incompletely filled orbitals will be coloured in aqueous solution.
Among the above mentioned ions, Ti3+, V3+, Mn2+ , Fe3+ and Co2+ are coloured.
MnO4– is also coloured due to charge transfer.
11. Compare the chemistry of actinides with that of lanthanoids with special
reference to
(a) electronic configuration, (b) oxidation state,
(d) atomic and ionic sizes, and (d) chemical reactivity.
Sol. (a) Electronic configuration: The general electronic configuration of
lanthanides is [Xe]54 4f 1 – 14 5d0 – 1 6s2 and that of actinides is [Rn]86
5f 1 – 14 6d0 – 1 7s2. Lanthanides belong to 4f series, whereas actinides
belong to 5f-series.
(b) Oxidation states: Lanthanides show limited oxidation states
(+2, +3, +4) out of which +3 is most common. This is because of
large energy gap between 4f, 5d and 6s orbitals. However, actinides

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show a large number of oxidation states because of small energy
gap between 5f, 6d and 7s orbitals.
(c) Atomic and ionic sizes: Both lanthanides and actinides show
decrease in size of their atoms or ions in +3 oxidation state. In
lanthanoids, the decrease is called lanthanoid contraction, whereas in
actinides, it is called actinoid contraction. The contraction is greater
from element to element in actinides due to poorer shielding by 5f
electrons.
(d) Chemical reactivity: The earlier members of the lanthanides series
are quite reactive similar to calcium but, with increasing atomic
number, they behave more like aluminium. The metals combine
with hydrogen when gently heated in the gas. Carbides, Ln3C, Ln2C3
and LnC2, are formed when the metals are heated with carbon. They
liberate hydrogen from dilute acid and burn in halogens to form
halides. They form oxides M2O3 and hydroxides M (OH)3.
Actinoids are highly reactive metals, especially when finely divided. The
action of boiling water on them gives a mixture of oxide and hydride and
combination with most non-metals take place at moderate temperatures. HCl
attacks all metals but most are slightly affected by nitric acid owing to the
formation of protective oxide layers, alkalis have no action.
12. How would you account for the following:
(a) Of the d4 species, Cr2+ is strongly reducing while manganese (III) is
strongly oxidising.
(b) Cobalt (III) is stable in aqueous solution but in the presence of
complexing reagents, it is easily oxidised.
(c) The d1 configuration is very unstable in ions.
Sol. (a) E° value for Cr3+/Cr2+ is negative (– 0⋅41 V), whereas E° values for Mn3+/
Mn2+ is positive (+ 1.57 V). Hence, Cr2+ ions can easily undergo
oxidation to give Cr3+ ions and, therefore, act as strong reducing
agent, whereas Mn2+ can easily undergo reduction to give Mn2+ and
hence act as oxidising agent.
(b) Co (III) has greater tendency to form coordination complexes than
Co (II). Hence, in the presence of ligands, Co (II) changes to Co
(III) (i.e. is easily oxidised).
(c) The ions with d1 configuration have the tendency to lose the only
electron present in d-subshell to acquire stable d0 configuration.
Hence, they are unstable and undergo oxidation or disproportionation.

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13. What are disproportionation reactions? Give two examples.
Sol. Disproportionation reactions are those in which the same substance undergoes
oxidation as well as reduction (i.e. oxidation number of an element increases
as well as decreases to form two different products).
VI VII IV
3 M nO24− + 4H+ →  2 M nO4− + M nO2 + 2H2 O
14. Which metal in the first transition series exhibits +1 oxidation state most
frequently and why?
Sol. Cu has electronic configuration 3d10 4s1. It can easily lose 4s1 electron to
give the stable 3d10 configuration. Hence, it shows +1 oxidation state.
15. Calculate the number of unpaired electrons in the following gaseous ions:
Mn3+, Cr3+, V3+ and Ti3+.
Which one of these is most stable in aqueous solution?
Sol. Mn3+ = 3d4 = 4 unpaired electrons, Cr3+ = 3d3 = 3 electrons,
V3+ = 3d2 = 2 electrons, Ti3+ = 3d1 = 1 electron.
Out of these, Cr3+ is most stable in aqueous solution because of half-filled
t2g level.
16. Give examples and suggest reasons for the following features of the transition
metal chemistry:
(a) The lowest oxide of transition metal is basic the highest is acidic.
(b) A transition metal exhibits higher oxidation states in oxides and
fluorides.
(c) The highest oxidation state is exhibited in oxo-anions of a metal.
Sol. (a) The lower oxide of transition metal is basic because the metal atom
has low oxidation state, whereas highest is acidic due to highest
oxidation state. For example, MnO (II) is basic, whereas Mn2O7 is
acidic.
(b) A transition metal exhibits higher oxidation states in oxides and
fluorides because oxygen and fluorine are highly electronegative
elements, small in size and strongest oxidising agents. For example,
osmium shows an oxidation states of +6 in OsF6 and vanadium shows
an oxidation states of +5 in V2O5.
(c) Oxo-metal anions have highest oxidation state. For example Cr in
Cr2O72– has an oxidation state of +6), whereas Mn is MnO4– has an
oxidation state of +7. This is again due to the combination of the
metal with oxygen, which is highly electronegative and oxidising
agent.

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17. What are alloys? Name an important alloy which contains some of the
lanthanoid metals. Mention its uses.
Sol. An alloy is a homogeneous mixture of two or more metals and non-metals. An
important alloy containing lanthanoid metals is misch metal which contains
95% lanthanoid metal and 5% iron along with traces of S, C, Ca and Al. It is
used in magnesium based alloy to produce bullets, shells and lighter flints.
18. What are inner-transition elements? Decide which of the following atomic
numbers are the numbers of the inner-transition elements: 29, 59, 74, 95,
102, 104.
Sol. The f-block elements in which the last electron enters into f-subshell are
called inner-transition elements. These include lanthanoids (Z = 58–71) and
actinoids (Z = 90–103). Thus, the elements with atomic numbers 59, 95 and
102 are the inner transition elements.
19. The chemistry of the actinoid elements is not so smooth as that of the
lanthanides. Justify this statement by giving some examples from the
oxidation state of these elements.
Sol. Lanthanoids show limited number of oxidation state, viz, +2, +3 and +4 (out
of which +3 is most common). This is because of large energy gap between
4f, 5d and 6s subshells. The dominant oxidation state of actinoids is also +3
but they show a number of other oxidation states also. For example, uranium
(Z = 92) and plutonium (Z = 94), show +3, +4, +5 and +6, neptunium
(Z = 94) shows +3, +4, +5 and +7, etc. This is because of the small energy
difference between 5f, 6d and 7s orbitals of the actinoids.
20. Which is the last element in the series of the actinides? Write the electronic
configuration of this element. Comment on the possible oxidation state of
this element.
Sol. Last actinoid = Lawrencium (Z = 103)
Electronic configuration = [Rn]86 5f14 d1 7s2
Possible oxidation state = +3.
21. Use Hund’s rule to derive the electronic configuration of Ce3+ ion and
calculate its magnetic moment on the basis of spin only formula.
Sol. Ce (Z = 58) = [Xe]58 4f 1 5d1 6s2
∴ Ce3+ = [Xe]58 4f 1
∴ µ = n ( n + 2)
n = only one unpaired electron.

∴ µ = 1 (1 + 2) = 3 = 1 ⋅ 73 BM.

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22. Name the members of the lanthanoid series which exhibit +4 oxidation
states and those which exhibit +2 oxidation states. Try to correlate this type
of behaviour with the electronic configuration of these elements.
Sol. +4 oxidation state in Ce (Z = 58) , Nd (Z = 60) , Tb (Z = 65) , Dy (Z = 66).
+2 oxidation state in Nd (Z = 60), Eu (Z = 63), Tm (Z = 69), Yb (Z = 70).
+2 oxidation state is exhibited when the lanthanoid has the configuration
5d0 6s2 so that two electrons are easily lost.
+4 oxidation state is exhibited when the configuration is left close to 4f0
(e.g. 4f 0, 4f 1, 4f 2) or close to 4f 7 (e.g. 4f 7 or 4f 8).
23. Write the electronic configuration of the elements with atomic numbers 61,
91, 101 and 109.
Sol. Z = 61 (Promethium, Pm) ⇒ [Xe]54 4f 5 5d° 6s2

Z = 91 (Protactium, Pa) ⇒ [Xe]86 4f 2 5d1 7s2

Z = 101 (Mendelevium, Md) ⇒ [Xe]86 4f 13 5d° 7s2

Z = 109 (Meitnerium, Mt) ⇒ [Xe]86 4f 14 5d7 7s2
24. Compare the general characteristics of the first series of transition metals
with those of the second and third series metals in the respective vertical
columns. Give special emphasis on the following points:
(a) Electronic configuration (b) Oxidation states
(c) Ionisation enthalpies (d) Atomic sizes
(e) Enthalpies of atomisation
Sol. (a) Electronic configuration: The elements in the same vertical column
generally have similar electronic configuration. First transition series
shows only two exceptions (i.e. Cr = 3d5 4s1 and Cu = 3d10 4s1). But
second transition series shows more exceptions (i.e. Mo = 4d5 5s1
Tc = 4d6 5s1, Ru = 4d7 5s1, Rh = 4d8 5s1, Pd = 4d10 5s0, Ag = 4d10
5s1). In third transition, there are many exceptions (i.e. W = 5d4 6s2,
Pt = 5d9 6s1 and Au = 5d10 6s1).
Thus in the same vertical column, in a number of cases, the electronic
configuration of the three series are not similar.
(b) Oxidation states: The elements in the same vertical column generally
show similar oxidation states. The number of oxidation states
shown by the elements in the middle of each series is maximum
and minimum at the extreme ends.
(c) Ionisation enthalpies: The first ionisation enthalpies in each series
generally increases gradually as we move from left to right though
some exceptions are observed in each series. The first ionisation

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enthalpies of some elements in the second (4d) series are higher
while some of them have lower value than the elements of 3d series
in the same vertical column. However, the first ionisation enthalpies
of third (5d) series are higher than those of 3d and 4d series. This
is because of weak shielding of nucleus by 4f-electrons in the 5d
series.
(d) Atomic sizes: In general, ions of the same charge or atoms in a
given series show progressively decrease in radius with increasing
atomic number though the decrease is quite small. But the size of
the atoms of the 4d series is larger than the corresponding elements
of the 3d series, whereas those of corresponding elements of the
5d-series nearly the same as those of 4d series because of lanthanoid
contraction.
(e) Enthalpies of atomisation: The metals of the second and third
series have greater enthalpies of atomisation than the corresponding
elements of the first series. This is due to much more frequent metal-
metal bonding in compounds of heavy transition metals.
25. Write down the number of 3d electrons in each of the following ions:
Ti2+, V2+, Cr3+, Mn2+, Fe2+, Fe3+, Co2+, Ni2+ and Cu2+.
Indicate how would you expect the five 3d orbitals to be occupied for these
hydrated ions (octahedral).
 Sol.

Ion Configuration No. of 3d Occupancy of 3d

Electrons Orbitals
eg
Ti2+ 3d2 2
t 2
2g
t2g

eg
V2+ 3d2 3
t
2
3g t2g
eg
Cr3+ 3d3 3 t3g2 t2g
eg
Mn2+ 3d5 5 5
t2g t2g

eg
Fe2+ 3d6 6
t2g6 t2g

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(continued)
eg
Fe3+ 3d5 5 5
t 2g t2g

eg
CO2+ 3d7 7 5
t2g t2g
eg
Ni2+ 3d8 8
te 6 2
2 t2g
eg
Cu2+ 3d9 6
te 6 3
t2g
26. Comment on the statement that the elements of the first transition series
possess many properties different from those of heavier transition elements.
Sol. The above mentioned statement is true, because
(a) Atomic radii of the heavier transition elements (4d and 5d series) are
larger than those of the corresponding elements of the first transition
series though those of 4d and 5d series are very close to each other.
(b) Melting and boiling points of heavier transition elements are greater
than those of the first transition series due to stronger intermetallic
bonding.
(c) Enthalpies of atomisation of 4d and 5d series are higher than the
corresponding elements of the first series.
(d) Ionisation enthalpies of 5d series are higher than the corresponding
elements of 3d and 4d series.
27. What can be inferred from the magnetic moment of the following complex
species:
Example Magnetic moment (BM)
K4 [Mn (CN)6] 2×2
[Fe (H2O)]2+ 5×3
K2 [MnCl4] 5×9
Sol. Magnetic moment, µ = n (n + 2) BM
For n = 1, µ = 1 (1 + 2) = 3 = 1 ⋅ 73
n = 1, µ = 2 (2 + 2) = 8 = 2 ⋅ 83

n = 3, µ = 3 (3 + 2) = 15 = 3 ⋅ 87

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n = 4, µ = 4 (4 + 2) = 32 = 5 ⋅ 66

n = 5, µ = 5 (5 + 2) = 35 = 5 ⋅ 92

K4 [Mn (CN)6]: In this complex, Mn is in +2 oxidation state and
(i)
µ = 2⋅2 BM.
It means that it has only one unpaired electron. When CN– ligands
approach Mn2+ ion, the electrons in 3d pair up.

Thus CN– is a strong ligand.
The hybridisation is d2 sp3 forming inner-orbital octahedral complex.
(ii) [Fe (H2O)6]2+: In this complex, Fe is in +2 oxidation state and
m = 5×3. It means that there are four unpaired electrons in 3d. Also,
the 3d electrons do not pair up when the H2O molecules approach.
Thus, H2O is a weak ligand.

The hybridisation involved is sp3d2, forming an outer-orbital
octahedral complex.
(iii) K2[MnCl4]: In this complex, Mn is in +2 oxidation state and
m = 5 × 92. It means that there are five unpaired electrons. The
hybridisation involved is sp3, forming a tetrahedral complex. Cl– is
a weak ligand.

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