Class XII – NCERT – Chemistry Chapter 8

The d and f Block Elements

Question 1:
Write down the electronic configuration of:
(i)Cr 3  (iii)Cu  (v)Co2  (vii) Mn2 (ii) Pm3 (iv)Ce4 (vi) Lu 2 (viii)Th 4

Solution 1:
Cr 3 :1s 2 2s 2 2 p 6 3s 2 3 p 6 3d 3
(i)

Pm3 :1s 2 2s 2 2 p 6 3s 2 3P 6 3d 10 4s 2 4 P 6 4d 10 5s 2 5 p 6 4 f 4
(ii)

Cu  :1s 2 2s 2 2 p 6 3s 2 3P 6 3d 10
(iii)

Ce4 :1s 2 2s 2 2 p 6 3s 2 3 p 6 3d 10 4s 2 4 p 6 4d 10 5s 2 5 p 6
(iv)

Co 2 :1s 2 2 s 2 2 p 6 3s 2 3 p 6 3d 7
(v)
Or ,  Ar  3d 7
18

(vi) Lu 2 :1s 2 2s 2 2 p 6 3s 2 3 p 6 3d 10 4s 2 4 p 6 4d 10 5s 2 5 p 6 4 f 14 5d 1

Mn 2 :1s 2 2s 2 2 p 6 3s 2 3 p 6 3d 5
(vii)

(viii) Th4 :1s 2 2s 2 2 p 6 3s 2 3 p 6 3d 10 4s 2 4 p 6 4 p10 4 f 14 5s 2 5 p 6 5d 10 6s 2 6 p 6

Question 2:
Why are Mn2+compounds more stable than Fe2+ towards oxidation to their +3 state?

Solution 2:
Electronic configuration of Mn2is  Ar  3d 6
Electronic configuration of Fe2is  Ar  3d 6
It is known that half-filled and fully-filled orbitals are more stable. Therefore, Mn in (+2) state
has a stable d5 configuration. This is the reason Mn2+ shows resistance to oxidation to Mn3+.
Also, Fe2+ has 3d6 configuration and by losing one electron, its configuration changes to a more
stable 3d5 configuration. Therefore, Fe2+ easily gets oxidized to Fe2+ oxidation state.

Question 3:

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Class XII – NCERT – Chemistry Chapter 8
The d and f Block Elements

Explain briefly how +2 state becomes more and more stable in the first half of the first row
transition elements with increasing atomic number?

Solution 3:
The oxidation states displayed by the first half of the first row of transition metals are given in
the table below.

It can be easily observed that except Sc, all others metals display +2 oxidation state. Also, on
moving from Sc to Mn, the atomic number increases from 21 to 25. This means the number of
electrons in the 3d-orbital also increases from 1 to 5.
Sc(2)  3d 1
Ti(2)  3d 2
V (2)  3d 3
Cr (2)  3d 4
Mn(2)  3d 5
+2 oxidation state is attained by the loss of the two 4s electrons by these metals. Since the
number of d electrons in (+2) state also increases from Ti(+2) to Mn(+ 2), the stability of +2 state
increases (as d-orbital is becoming more and more half-filled). Mn (+2) has 3d5electrons (that is
half-filled d shell, which is highly stable).

Question 4:
To what extent do the electronic configurations decide the stability of oxidation states in the first
series of the transition elements? Illustrate your answer with examples.

Solution 4:
The elements in the first-half of the transition series exhibit many oxidation states with Mn
exhibiting maximum number of oxidation states (+2 to +7). The stability of +2 oxidation state

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Class XII – NCERT – Chemistry Chapter 8
The d and f Block Elements

increases with the increase in atomic number. This happens as more electrons are getting filled in
the d-orbital. However, Sc does not show +2 oxidation state. Its electronic configuration is 4s2
3d1 . It loses all the three electrons to form Sc3+. +3 oxidation state of Sc is very stable as by
losing all three electrons, it attains stable noble gas configuration, [Ar]. Ti (+ 4) and V(+5) are
very stable for the same reason. For Mn, +2 oxidation state is very stable as after losing two
electrons, its d-orbital is exactly half-filled, [Ar] 3d6

Question 5:
What may be the stable oxidation state of the transition element with the following d electron
configurations in the ground state of their atoms: and 3d 3 , 3d 5 ,3d 8 and 3d 4 ?

Solution 5:

Question 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.

Solution 6:
(i) Vanadate, VO3
Oxidation state of V is +5.
(ii) Chromate, CrO42 
Oxidation state of Cr is +6.
(iii) Permanganate, MnO4
Oxidation state of Mn is +7

Question 7:

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Class XII – NCERT – Chemistry Chapter 8
The d and f Block Elements

What is lanthanoid contraction? What are the consequences of lanthanoid contraction?

Solution 7:
As we move along the lanthanoid series, the atomic number increases gradually by one. This
means that the number of electrons and protons present in an atom also increases by one. As
electrons are being added to the same shell, the effective nuclear charge increases. This happens
because the increase in nuclear attraction due to the addition of proton is more pronounced than
the increase in the interelectronic repulsions due to the addition of electron. Also, with the
increase in 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 the increase in the
atomic number. This is termed as lanthanoid contraction
Consequences of lanthanoid contraction
(i) There is similarity in the properties of second and third transition series.

(ii) Separation of lanthanoids is possible due to lanthanide contraction.

(iii) It is due to lanthanide contraction that there is variation in the basic strength of lanthanide
hydroxides. (Basic strength decreases from La OH 3 to Lu OH 3 )

Question 8:
What are the characteristics of the transition elements and why are they called transition
elements? Which of the d-block elements may not be regarded as the transition elements?

Solution 8:
Transition elements are those elements in which the atoms or ions (in stable oxidation State )
contain partially filled d-orbital. These elements lie in the d-block and show a transition of
properties between s-block and p-block. Therefore, these are called transition elements. Elements
such as Zn, Cd, and Hg cannot be classified as transition elements because these have completely
filled d-subshell.

Question 9:
In what way is the electronic configuration of the transition elements different from that of the
non-transition elements?

Solution 9:
Transition metals have a partially filled d−orbital. Therefore, the electronic configuration of
transition elements is  n 1 d 110 ns02 .
The non-transition elements either do not have a d−orbital or have a fully filled d−orbital.

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Class XII – NCERT – Chemistry Chapter 8
The d and f Block Elements

Therefore, the electronic configuration of non-transition elements is ns12 or ns 2 ns16.

Question 10:
What are the different oxidation states exhibited by the lanthanoids?

Solution 10:
In the lanthanide series, +3 oxidation state is most common i.e., Ln(III) compounds are
Predominant. However, +2 and +4 oxidation states can also be found in the solution or in solid
compounds.

Question 11:
Explain giving reasons:
(i) Transition metals and many of their compounds show paramagnetic behaviour.
(ii) The enthalpies of atomisation of the transition metals are high.
(iii) The transition metals generally form coloured compounds.
(iv) Transition metals and their many compounds act as good catalyst.

Solution 11:
(i) Transition metals show paramagnetic behaviour. Paramagnetism 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
atomization 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) 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.
(b) Transition metals also provide a suitable surface for the reactions to occur.

Question 12:

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Class XII – NCERT – Chemistry Chapter 8
The d and f Block Elements

What are interstitial compounds? Why are such compounds well known for transition metals?

Solution 12:
Transition metals are large in size and contain lots of interstitial sites. Transition elements can
trap atoms of other elements (that have small atomic size), such as H, C, N, in the interstitial sites
of their crystal lattices. The resulting compounds are called interstitial compounds.

Question 13:
How is the variability in oxidation states of transition metals different from that of the non-
transition metals? Illustrate with examples.

Solution 13:
In transition elements, the oxidation state can vary from +1 to the highest oxidation state by
removing all its valence electrons. Also, in transition elements, the oxidation states differ by 1
 Fe 2
and Fe3 ; Cu  and Cu 2   . In non-transition elements, the oxidation states differ by 2, for
example, +2 and +4 or +3 and +5, etc.

Question 14:
Describe the preparation of potassium dichromate from iron chromite ore. What is the effect of
increasing pH on a solution of potassium dichromate?

Solution 14:
Potassium dichromate is prepared from chromite ore  FeCr2O4  in the following steps.
Step (1): Preparation of sodium chromate
4 FeCr2O4  16 NaOH  7O2   8 Na2CrO4  2 Fe2O3  8H 2O
Step (2): Conversion of sodium chromate into sodium dichromate
2 Na2CrO4  conc.H 2 SO4   Na2Cr2O7  Na2 SO4  H 2O
Step(3): Conversion of sodium dichromate to potassium dichromate
Na2Cr2O7  2 KCl   K 2Cr2O7  2 NaCl
Potassium chloride being less soluble than sodium chloride is obtained in the form of orange
coloured crystals and can be removed by filtration. The dichromate ion Cr2O72 exists in
equilibrium with chromate CrO42  ion at pH 4. However, by changing the pH, they can be
interconverted.
2CrO42 
acid
alkali
 2 HCrO4 
acid
alkali
 Cr2 O72
Chromate Hydrogen Dichromate
( yellow) Chromate ( Orange )

Question 15:

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Class XII – NCERT – Chemistry Chapter 8
The d and f Block Elements

Describe the oxidizing action of potassium dichromate and write the ionic equations for its
reaction with:
(i) iodide (ii) iron(II) solution and (iii) H2 S

Solution 15:
K 2Cr2O7 acts as a very strong oxidizing agent in the acidic medium.
K 2Cr2O7  4 H 2 SO4 
 K 2 SO4  Cr2 ( SO4 )3  4 H 2O  3[O]
K 2Cr2O7 takes up electrons to get reduced and acts as an oxidizing agent. The reaction K 2Cr2O7
with other iodide, iron (II) solution, and H2S are given below.
(i) K 2Cr2O7 oxidizes iodide to iodine.
Cr2O72   14H   6e 
 2Cr 3  7 H 2O
2 I    I 2  2e ]  3
-----------------------------------------------------
Cr2O72   6 I   14 H    2Cr 3  3I 2  7 H 2O
-------------------------------------------------------------
(ii) K 2Cr2O7 oxidizes iron (II) solution to iron (III) Solution i.e., ferrous ions to ferric ions.

Cr2O72   14H   6e 

 2Cr 3  7 H 2O
Fe2    Fe3  e ]  6
------------------------------------------------------
Cr2O72   14 H   6 Fe 2    2Cr 3  6 Fe3  7 H 2O
----------------------------------------------------------------
(iii) K 2Cr2O7 Oxidizes H2S to sulphur.
Cr2O72   14H   6e 
 2Cr 3  7 H 2O
H 2 S   S  2 H   2e ]  3
--------------------------------------------------
Cr2O72   3H 2 S  8H    2Cr 3  3S  7 H 2O
-----------------------------------------------------------

Question 16:
Describe the preparation of potassium permanganate. How does the acidified Permanganate
solution react with (i) iron (II) ions (ii) SO2 and (iii) oxalic acid? Write the ionic equations for
the reactions.

Solution 16:
Potassium permanganate can be prepared from pyrolusite (MnO2). The ore is fused with KOH in
the presence of either atmospheric oxygen or an oxidizing agent, such as KNO3

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Class XII – NCERT – Chemistry Chapter 8
The d and f Block Elements

or KClO4, to give K2MnO4.

2MnO2  4KOH  O2  Heat
 2K 2 MnO4  2H 2O
( Green )

The green mass can be extracted with water and then oxidized either electrolytically or by
Passing chlorine/ozone into the solution. Electrolytic oxidation.
 2 K   MnO42 
K 2 MnO4 
 H   OH 
H 2O 
At anode, manganate ions are oxidized to permanganate ions.
MnO42   MnO4  e
Green Purple

Oxidation by chlorine
2 K 2 MnO4  Cl2  2 KMnO4  2 KCl
2 MnO42   Cl2 
 2MnO4  2Cl 
Oxidation by ozone
2 K 2 MnO4  O3  H 2O 
 2 KMnO4  2 KOH  O2
2MnO42   O3  H 2O 
 2MnO42   2OH   O 2
(i) Acidified KMnO4 solution oxidizes Fe (II) ions to Fe (III) ions i.e., ferrous ions to ferric ions.
MnO4  8H   5e 
 Mn2   4H 2O
Fe2    Fe3  e ]  5
-------------------------------------------------
MnO4  5Fe 2   8H    Mn 2   5Fe3  4 H 2O
---------------------------------------------------------------
(ii) Acidified potassium permanganate oxidizes SO2 to sulphuric acid.
MnO4  6H   5e   Mn2   3H 2O]  2
2 H 2O  2SO2  O2   4 H   2SO42   2e ]  5
-----------------------------------------------------------
2MnO4  5C2O42   16 H    2Mn 2   10SO42   8H 
-------------------------------------------------------------------
(iii) Acidified potassium permanganate oxidizes oxalic acid to carbon dioxide.
MnO4  8H   5e   Mn2   4 H 2O]  2
C2O42    2CO2  2e ]  5
-----------------------------------------------------
2MnO4  5C2O42   16 H    2Mn 2   10CO2  8H 2O
--------------------------------------------------------------------

Question 17:
For M 2 / M and M 3 / M 2  systems, the E  values for some metals are as follows:

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Class XII – NCERT – Chemistry Chapter 8
The d and f Block Elements

Cr 2  / Cr  0.9V
Cr 3 / Cr 2   0.4V
Mn2  / Mn  1.2V
Mn3 / Mn 2   1.5V
Fe2  / Fe  0.4V
Fe3 / Fe2   0.8V
Use this data to comment upon:
(i) The stability of Fe3+ in acid solution as compared to that of Cr3+or Mn3+ and
(ii)The ease with which iron can be oxidized as compared to a similar process for either
chromium or manganese metal.

Solution 17:
(i) The E  value for Fe3+ / Fe2+ is higher than that for Cr3+ / Cr2+ and lower than that for Mn3+ /
Mn2+. So, the reduction of Fe3+ to Fe2+ is easier than the reduction of Mn3+ to Mn2+, but not as
easy as the reduction of Cr3+ to Cr2+ Hence, Fe3+ is more stable than Mn3+, but less stable than
Cr3+. These metal ions can be arranged in the increasing order of their stability as: Mn3+ < Fe3+ <
Cr3+
(ii) The reduction potentials for the given pairs increase in the following order.
Mn2 / Mn  Cr 2 / Cr  Fe2 / Fe. So, the oxidation of Fe to Fe2+ is not as easy as the oxidation
of Cr to Cr2+ and the oxidation of Mn to Mn2+. Thus, these metals can be arranged in the
increasing order of their ability to get oxidized as: Fe < Cr < Mn

Question 18:
Predict which of the following will be coloured in aqueous solution?
Ti 3 , V 3 , Cu  , Sc3 , Mn2  , Fe3 and CO 2  . Give reasons for each.

Solution 18:
Only the ions that have electrons in d-orbital will be coloured. The ions in which d-orbital is
empty will be colourless.
Element Atomic Number Ionic State Electronic configuration in ionic
State
Ti 22 Tl3+ [Ar]3d1
V 23 V3+ [Ar]3d2
+
Cu 29 Cu [Ar]3d10
Sc 21 Sc3+ [Ar]
Mn 25 Mn2+ [Ar]3d5
Fe 26 Fe3+ [Ar]3d5
2+
Co 27 Co [Ar]3d7

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Class XII – NCERT – Chemistry Chapter 8
The d and f Block Elements

From the above table, it can be easily observed that only Sc3+ has an empty d-orbital. All other
ions, except , Sc3+, will be coloured in aqueous solution because of d−d transitions.

Question 19:
Compare the stability of +2 oxidation state for the elements of the first transition series.

Solution 19:

From the above table, it is evident that the maximum number of oxidation states is shown by Mn,
varying from +2 to +7. The number of oxidation states increases on moving from Sc to Mn. On
moving from Mn to Zn, the number of oxidation states decreases due to a decrease in the number
of available unpaired electrons. The relative stability of the +2 oxidation state increases on
moving from top to bottom. This is because on moving from top to bottom, it becomes more and
more difficult to remove the third electron from the d-orbital.

Question 20:
Compare the chemistry of actinoids with that of the lanthanoids with special reference to:
(i) electronic configuration (iii) oxidation state
(ii) atomic and ionic sizes and (iv) chemical reactivity.

Solution 20:
(i) Electronic configuration
The general electronic configuration for lanthanoids is [ Xe] 54 4 f 014 5d 01 6 s 2 and that for
actinoids is [ Rn]86 5 f 114 6d 01 7 s 2 . Unlike 4f orbitals, 5f orbitals are not deeply buried and
Participate in bonding to a greater extent.
(ii) Oxidation states
The principal oxidation state of lanthanoids is (+3). However, sometimes we also encounter
oxidation states of + 2 and + 4. This is because of extra stability of fully-filled and half-filled
orbitals. Actinoids exhibit a greater range of oxidation states. This is because the 5f, 6d, and 7s

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Class XII – NCERT – Chemistry Chapter 8
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levels are of comparable energies. Again, (+3) is the principal oxidation state for actinoids.
Actinoids such as lanthanoids have more compounds in +3 state than in +4 state.
(iii) Atomic and lonic sizes
Similar to lanthanoids, actinoids also exhibit actinoid contraction (overall decrease in atomic and
ionic radii). The contraction is greater due to the poor shielding effect of 5orbitals.
(iv). Chemical reactivity
In the lanthanide series, the earlier members of the series are more reactive. They have reactivity
that is comparable to Ca. With an increase in the atomic number, the lanthanides start behaving
similar to Al. Actinoids, on the other hand, are highly reactive metals, especially when they are
finely divided. When they are added to boiling water, they give a mixture of oxide and hydride.
Actinoids combine with most of the non-metals at moderate temperatures. Alkalies have no
action on these actinoids. In case of acids, they are slightly affected by nitric acid (because of the
formation of a protective oxide layer).

Question 21:
How would you account for the following:
(i) Of the d4 species, Cr2+ is strongly reducing while manganese (III) is strongly oxidizing.
(ii) Cobalt(II) is stable in aqueous solution but in the presence of complexing reagents it is easily
oxidized.
(iii) The d1configuration is very unstable in ions.

Solution 21:
(i) Cr2+ is strongly reducing in nature. It has a d4 configuration. While acting as a reducing agent,
it gets oxidized to Cr3+ (electronic configuration, d3 ). This d3 configuration can be written as t2l g
configuration, which is a more stable configuration. In the case of Mn3+ (d14) it acts as an
oxidizing agent and gets reduced toMn2+ (d5). This has an exactly half-filled d-orbital and is
highly stable.
(ii) Co (II) is stable in aqueous solutions. However, in the presence of strong field complexing
reagents, it is oxidized to Co (III). Although the 3rd ionization energy for Co is high, but the
higher amount of crystal field stabilization energy (CFSE) released in the presence of strong field
ligands overcomes this ionization energy.
(iii) The ions in d1configuration tend to lose one more electron to get into stable d0 configuration.
Also, the hydration or lattice energy is more than sufficient to remove the only electron present
in the d-orbital of these ions. Therefore, they act as reducing agents.

Question 22:
What is meant by ‘disproportionation’? Give two examples of disproportionation reaction
in aqueous solution.

Solution 22:

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Class XII – NCERT – Chemistry Chapter 8
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It is found that sometimes a relatively less stable oxidation state undergoes an oxidation-
reduction reaction in which it is simultaneously oxidized and reduced. This is called
disproportionation.
For example,
(i) 3CrO43  8H   2CrO42   Cr 3  4H 2O
Cr (V ) Cr (VI ) Cr ( III )

Cr (V) is oxidized to Cr (VI) and reduced to Cr (III).

(ii) 3MnO42   4H   2MnO4  MnO2  2H 2O
Mn (VI ) Mn (VII ) Mn (VI )

Mn (VI) is oxidized to Mn (VII) and reduced to Mn (VI).

Question 23:
Which metal in the first series of transition metals exhibits +1 oxidation state most frequently
and why?

Solution 23:
In the first transition series, Cu exhibits +1 oxidation state very frequently. It is because Cu (+1)
has an electronic configuration of [Ar] 3d10. The completely filled d-orbital makes it highly
stable.

Question 24:
Calculate the number of unpaired electrons in the following gaseous ions: Mn3+, Cr3+, V3+ and
Ti3+. Which one of these is the most stable in aqueous solution?

Solution 24:
Gaseous ions Number of unpaired electrons
3+ 4
(i) Mn , [Ar]3d 4
(ii) Cr3+, [Ar]3d3 3
3+ 2
(iii) V , [Ar]3d 2
2+ 1
(iv) Ti , [Ar]3d 1
Cr is the most stable in aqueous solutions owing to a half filled t23g configuration.
3+

Question 25:
Give examples and suggest reasons for the following features of the transition metal chemistry:
(i) The lowest oxide of transition metal is basic, the highest is amphoteric/acidic.
(ii) A transition metal exhibits highest oxidation state in oxides and fluorides.
(iii) The highest oxidation state is exhibited in oxoanions of a metal.

Solution 25:

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(i) In the case of a lower oxide of a transition metal, the metal atom has a low oxidation state.
This means that some of the valence electrons of the metal atom are not involved in bonding. As
a result, it can donate electrons and behave as a base. On the other hand, in the case of a higher
oxide of a transition metal, the metal atom has a high oxidation state. This means that the valence
electrons are involved in bonding and so, they are unavailable. There is also a high effective
nuclear charge. As a result, it can accept electrons and behave as an acid. For example, is basic
and is acidic.
For example, MnII O is basic and Mn2VII O7 is acidic.
(ii) Oxygen and fluorine act as strong oxidizing agents because of their high electro negativities
and small sizes. Hence, they bring out the highest oxidation states from the transition metals. In
other words, a transition metal exhibits higher oxidation states in oxides and fluorides. For
example, in OsF6 and V2O5, the oxidation states of Os and V are +6 and +5 respectively.
(iii) Oxygen is a strong oxidizing agent due to its high electronegativity and small size. So, oxo-
anions of a metal have the highest oxidation state. For example in MnO4 , the oxidation state of
Mn is +7.

Question 26:
Indicate the steps in the preparation of:
(i) K2Cr2O7 from chromite ore.
(ii) KMnO4 from pyrolusite ore.

Solution 26:
Potassium dichromate K2Cr2O7 is prepared from chromite ore (FeCr2O4) in the following steps.
Step (1): Preparation of sodium chromate
4 FeCr2O4  16 NaOH  7O2   8 Na2CrO4  2 Fe2O3  8H 2O
Step (2): Conversion of sodium chromate into sodium dichromate
2 Na2CrO4  conc.H 2 SO4   Na2Cr2O7  Na2 SO4  H 2O
Step(3): Conversion of sodium dichromate to potassium dichromate
Na2CrO7  2 KCl   K 2Cr2O7  2 NaCl
Potassium chloride being less soluble than sodium chloride is obtained in the form of orange
coloured crystals and can be removed by filtration. The dichromate ion  Cr2O72   exists in
equilibrium with chromate  Cr2O42   ion at pH 4. However, by changing the pH, they can be inter
converted.
2CrO42  
acid
alkali
 2 HCrO4 
acid
alkali
 Cr2O72 
Chromate Hydrogen Dichromate
( yellow ) Chromate ( Orange )

(ii) Potassium permanganate (KMnO4) can be prepared from pyrolusite (MnO2).The ore is fused
with KOH in the presence of either atmospheric oxygen or an oxidizing agent, such as

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KNO3 or KClO4 , to give K 2 MnO4 .

2MnO2  4KOH  O2  
heat
 2K 2 MnO4  2H 2O
( Green )

The green mass can be extracted with water and then oxidized either electrolytically or by
passing chlorine/ozone into the solution. Electrolytic oxidation.
K 2 MnO4   2 K   MnO42 
 H   OH 
H 2O 
At anode, manganate ions are oxidized to permanganate ions.
MnO42   MnO4  e
Green Purple

Oxidation by chlorine
2 K 2 MnO4  Cl2  2 KMnO4  2KCl
2MnO42   Cl2 
 2MnO4  2Cl
Oxidation by ozone
2 K 2 MnO4  O3  H 2O 
 2KMnO4  2KOH  O2
2MnO42   O3  H 2O 
 2MnO42   2OH   O2

Question 27:
What are alloys? Name an important alloy which contains some of the lanthanoid metals.
Mention its uses.

Solution 27:
An alloy is a solid solution of two or more elements in a metallic matrix. It can either be a
partial solid solution or a complete solid solution. Alloys are usually found to possess different
physical properties than those of the component elements. An important alloy of lanthanoids is
Mischmetal. It contains lanthanoids (94−95%), iron (5%), and traces of S, C, Si, Ca, and Al.
Uses
(1) Mischmetal is used in cigarettes and gas lighters.
(2) It is used in flame throwing tanks.
(3) It is used in tracer bullets and shells.

Question 28:
What are inner transition elements? Decide which of the following atomic numbers are the
atomic numbers of the inner transition elements: 29, 59, 74, 95, 102, 104.

Solution 28:
Inner transition metals are those elements in which the last electron enters the f-orbital. The
elements in which the 4f and the 5f orbital’s are progressively filled are called f-block elements.

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Among the given atomic numbers, the atomic numbers of the inner transition elements are 59,
95, and 102.

Question 29:
The chemistry of the actinoid elements is not so smooth as that of the Lanthanoids. Justify this
statement by giving some examples from the oxidation state of these elements.

Solution 29:
Lanthanoids primarily show three oxidation states (+2, +3, +4). Among these oxidation states, +3
state is the most common. Lanthanoids display a limited number of oxidation states because the
energy difference between 4f, 5d, and 6s orbitals is quite large. On the other hand, the energy
difference between 5f, 6d, and 7s orbitals is very less. Hence, actinoids display a large number of
oxidation states. For example, uranium and plutonium display +3, +4, +5, and +6 oxidation
states while neptunium displays +3, +4, +5, and +7. The most common oxidation state in case of
actinoids is also +3.

Question 30:
Which is the last element in the series of the actinoids? Write the electronic configuration of this
element. Comment on the possible oxidation state of this element.

Solution 30:
The last element in the actinoid series is lawrencium, Lr. Its atomic number is 103 and its
electronic configuration is [Rn]5f146d17s2 The most common oxidation state displayed by it is
+3; because after losing 3 electrons it attains stable f14 configuration.

Question 31:
Use Hund’s rule to derive the electronic configuration of Ce3+ ion and calculate its magnetic
moment on the basis of ‘spin-only’ formula.

Solution 31:
Ce :1s 2 2s 2 2 p 6 3s 2 3 p 6 3d 10 4s 2 4 p 6 4d 10 5s 2 5 p 6 4 f 1 5d 1 6s 2
Magnetic moment can be calculated as:   n(n  2)
Where,
n = number of unpaired electrons
In Ce, n = 2
Therefore,   2(2  1)

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 2 4
 8
2 2
= 2.828BM

Question 32:
Name the members of the lanthanoid series which exhibit +4 oxidation state and those which
exhibit +2 oxidation state. Try to correlate this type of behavior with the electronic
configurations of these elements.

Solution 32:
The lanthanides that exhibit +2 and +4 states are shown in the given table. The atomic numbers
of the elements are given in the parenthesis.
+2 +4
Nd(60) Ce(58)
Sm(62) Pr(59)
Eu(63) Nd(60)
Tm(69) Tb(65)
Yb(70) Dy(66)
Ce after forming Ce4+ attains a stable electronic configuration of [Xe].
Tb after forming Tb4+ attains a stable electronic configuration of [Xe]4f7
Eu after forming Eu2+ attains a stable electronic configuration of [Xe]4f7.
Yb after forming Yb2+ attains a stable electronic configuration of [Xe]4f14

Question 33:
Compare the chemistry of the actinoids with that of lanthanoids with reference to:
(i) electronic configuration
(ii) oxidation states and
(iii) chemical reactivity.

Solution 33:
Electronic configuration
The general electronic configuration for lanthanoids is [ Xe]54 4 f 0 14 5d 0 1 6s 2 and that for
actinoids is [ Rn]86 5 f 114 6d 0 1 7 s 2 Unlike 4f orbitals, 5f orbitals are not deeply buried and
participate in bonding to a greater extent.
Oxidation states
The principal oxidation state of lanthanoids is (+3). However, sometimes we also encounter
oxidation states of + 2 and + 4. This is because of extra stability of fully-filled and half-filled
orbitals. Actinoids exhibit a greater range of oxidation states. This is because the 5f, 6d, and 7s

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levels are of comparable energies. Again, (+3) is the principal oxidation state for actinoids.
Actinoids such as lanthanoids have more compounds in +3 state than in +4 state.
Chemical reactivity
In the lanthanide series, the earlier members of the series are more reactive. They have reactivity
that is comparable to Ca. With an increase in the atomic number, the lanthanides start behaving
similar to Al. Actinoids, on the other hand, are highly reactive metals, especially when they are
finely divided. When they are added to boiling water, they give a mixture of oxide and hydride.
Actinoids combine with most of the non-metals at moderate temperatures. Alkalies have no
action on these actinoids. In case of acids, they are slightly affected by nitric acid (because of the
formation of a protective oxide layer).

Question 34:
Write the electronic configurations of the elements with the atomic numbers 61, 91, 101, and
109.

Solution 34:
Atomic number Electronic
configuration
61 [ Xe]54 4 f 5 5d 0 6s 2
91 [ Rn]86 5 f 2 6d 1 7 s 2
101 [ Rn]86 5 f 13 5d 0 7 s 2
109 [ Rn]86 5 f 14 6d 7 7 s 2

Question 35:
Compare the general characteristics of the first series of the transition metals with those of the
second and third series metals in the respective vertical columns. Give special
emphasis on the following points:
(i) electronic configurations,
(ii) oxidation states,
(iii) ionisation enthalpies, and
(iv) atomic sizes.

Solution 35:
(i) In the 1st, 2nd and 3rd transition series, the 3d, 4d and 5d orbitals are respectively filled. We
know that elements in the same vertical column generally have similar electronic configurations.
In the first transition series, two elements show unusual electronic configurations:
Cr (24)  3d 5 4s1
Cr (29)  3d 10 4s1

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Similarly, there are exceptions in the second transition series. These are:
Mo(42)  4d 5 5s1
Tc(43)  4d 6 5s1
Ru (44)  4d 7 5s1
Rh(45)  4d 8 5s1
Pd (46)  4d 10 5s 0
Ag (47)  4d 10 5s1
There are some exceptions in the third transition series as well. These are:
W (74)  5d 4 6 s 2
Pt (78)  5d 9 6 s1
Au (79)  5d 10 6 s1
As a result of these exceptions, it happens many times that the electronic configurations of the
elements present in the same group are dissimilar.
(ii) In each of the three transition series the number of oxidation states shown by the elements is
the maximum in the middle and the minimum at the extreme ends. However, +2 and +3
oxidation states are quite stable for all elements present in the first transition series. All metals
present in the first transition series form stable compounds in the +2 and +3 oxidation states. The
stability of the +2 and +3 oxidation states decreases in the second and the third transition series,
wherein higher oxidation states are more important.
4 3
 II   III 
For example  Fe(Cn)6  , Co( NH 3 )6  , Ti ( H 2O)6  are stable complexes, but no such
3

   
complexes are known for the second and third transition series such as Mo, W, Rh,
In. They form complexes in which their oxidation states are high. For example: WCl6 . ReF7,
RuO4 etc.
(iii) In each of the three transition series, the first ionization enthalpy increases from left to right.
However, there are some exceptions. The first ionization enthalpies of the third transition series
are higher than those of the first and second transition series. This occurs due to the poor
shielding effect of 4f electrons in the third transition series. Certain elements in the second
transition series have higher first ionization enthalpies than elements corresponding to the same
vertical column in the first transition series. There are also elements in the 2nd transition series
whose first ionization enthalpies are lower than those of the elements corresponding to the same
vertical column in the 1st transition series.
(iv) Atomic size generally decreases from left to right across a period. Now, among the three
transition series, atomic sizes of the elements in the second transition series are greater than those
of the elements corresponding to the same vertical column in the first transition series. However,
the atomic sizes of the elements in the third transition series are virtually the same as those of the
corresponding members in the second transition series. This is due to lanthanoid contraction.

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Question 36:
Write down the number of 3d electrons in each of the following ions:
Ti 2  , V 2  , Cr 3 , Mn2  , Fe2  , Fe3 , CO 2  , Ni 2  and Cu 2 
Indicate how would you expect the five 3d orbitals to be occupied for these hydrated ions
(octahedral).

Solution 36:
Metal ion Number of d-electrons Filling of d-orbitals
Ti2+ 2 t22g
V2+ 3 t23g
Cr3+ 3 t23g
Mn2+ 5 3 2
t2g eg
Fe2+ 6 4 2
t2g eg
Fe3+ 5 3 2
t2g eg
CO2+ 7 5 2
t2g eg
Ni2+ 8 6 2
t2g eg
Cu2+ 9 6 3
t2g eg

Question 37:
Comment on the statement that elements of the first transition series possess many properties
different from those of heavier transition elements.

Solution 37:
The properties of the elements of the first transition series differ from those of the heavier
transition elements in many ways.
(i) The atomic sizes of the elements of the first transition series are smaller than those of the
heavier elements (elements of 2nd and 3rd transition series). However, the atomic sizes of the
elements in the third transition series are virtually the same as those of the corresponding
members in the second transition series. This is due to lanthanoid contraction.
(ii) +2 and +3 oxidation states are more common for elements in the first transition series, while
higher oxidation states are more common for the heavier elements.
(iii) The enthalpies of atomization of the elements in the first transition series are lower than
those of the corresponding elements in the second and third transition series.

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(iv) The melting and boiling points of the first transition series are lower than those of the
heavier transition elements. This is because of the occurrence of stronger metallic bonding (m−M
bonding).
(v) The elements of the first transition series form low-spin or high-spin complexes depending
upon the strength of the ligand field. However, the heavier transition elements form only low-
spin complexes, irrespective of the strength of the ligand field.

Question 38:
What can be inferred from the magnetic moment values of the following complex species?
Example Magnetic Moment (BM)
K 4  Mn(CN )6  2.2
 Fe( H 2O)6 
2
5.3
K 2 [ MnCl4 ]5.9

Solution 38:
(Magnetic moment (  ) =   n(n  2)
For value n = 1,   1(1  2)  3  1.732BM
For value n = 2,   2(2  2)  8  2.83BM
For value n = 3,   3(3  2)  15  3.87BM
For value n = 4,   4(4  2)  24  4.899BM
For value n = 5,   5(5  2)  35  5.92BM
(i) K4  Mn(CN )6 
For in transition metals, the magnetic moment is calculated from the spin-only formula.
Therefore,
n(n  2)  2.2BM
We can see from the above calculation that the given value is closest to n=1. Also, in this
complex, Mn is in the +2 oxidation state. This means that Mn has 5 electrons in the d orbital.
Hence, we can say that CN− is a strong field ligand that causes the pairing of electrons.
(ii)  Fe( H 2O)6 
2

n(n  2)  5.3BM
We can see from the above calculation that the given value is closest to n=4 Also, in this
complex, Fe is in the +2 oxidation state. This means that Fe has 6 electrons in the d orbital.
Hence, we can say that H2O is a weak field ligand and does not cause the pairing of electrons.
(iii) K2  MnCl4 

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n(n  2)  5.9BM
We can see from the above calculation that the given value is closest to n=5. Also, in this
complex, Mn is in the +2 oxidation state. This means that Mn has 5 electrons in the d orbital.
Hence, we can Cl- say that is a weak field ligand and does not cause the pairing of electrons.

Intext Questions
Question 1:
Silver atom has completely filled d orbitals (4d10) in its ground state. How can you say that it is a
transition element?

Solution 1:
Ag has a completely filled 4d orbital in its ground state. Now, silver displays two oxidation states
(+1 and +2). In the +1 oxidation state, an electron is removed from the s-orbital. However, in the
+2 oxidation state, an electron is removed from the d-orbital. Thus, the d-orbital now becomes
incomplete (4d9). Hence, it is a transition element.

Question 2:
In the series Sc (Z = 21) to Zn (Z = 30), the enthalpy of atomization of zinc is the lowest, i.e. . 1
126KJ mol-1 Why?

Solution 2:
The extent of metallic bonding an element undergoes decides the enthalpy of atomization. The
more extensive the metallic bonding of an element, the more will be its enthalpy of atomization.
In all transition metals (except Zn, electronic configuration: 3d104s2), there are some unpaired
electrons that account for their stronger metallic bonding. Due to the absence of these unpaired
electrons, the inter-atomic electronic bonding is the weakest in Zn and as a result, it has the least
enthalpy of atomization.

Question 3:
Which of the 3d series of the transition metals exhibits the largest number of oxidation states and
why?

Solution 3:
Mn( Z  25)  3d 5 4s 2
Mn has the maximum number of unpaired electrons present in the d-subshell (5 electrons).
Hence, Mn exhibits the largest number of oxidation states, ranging from +2 to +7.

Question 4:

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The E   M 2  / M  value for copper is positive (+0.34V). What is possibly the reason for this?
(Hint: consider its high  a H  and low hyd H  )

Solution 4:
The E   M 2 / M  value of a metal depends on the energy changes involved in the following:
1. Sublimation: The energy required for converting one mole of an atom from the solid state to
the gaseous state.
M ( g ) 
 M ( g ) g H (Sublimation energy)
2. Ionization: The energy required to take out electrons from one mole of atoms in the gaseous
state.
 M 2( g ) g H (Ionization energy)
M ( g ) 
3. Hydration: The energy released when one mole of ions are hydrated.
M 2( g ) 
 M 2( aq) hyd H (Hydration energy)
Now, copper has a high energy of atomization and low hydration energy. Hence, the
E   M 2  / M  E   M 2 / M  value for copper is positive.

Question 5:
How would you account for the irregular variation of ionization enthalpies (first and second) in
the first series of the transition elements?

Solution 5:
Ionization enthalpies are found to increase in the given series due to a continuous filling of the
inner d-orbitals. The irregular variations of ionization enthalpies can be attributed to the extra
stability of configurations such as d0, d5, d10. Since these states are exceptionally stable, their
ionization enthalpies are very high.
In case of first ionization energy, Cr has low ionization energy. This is because after losing one
electron, it attains the stable configuration (3d5). On the other hand, Zn has exceptionally high
first ionization energy as an electron has to be removed from stable and fully-filled orbitals (
3d 10 4s 2 ).
Second ionization energies are higher than the first since it becomes difficult to remove an
electron when an electron has already been taken out. Also, elements like Cr and Cu have
exceptionally high second ionization energies as after losing the first electron, they have attained
the stable configuration  Cr  : 3d 5 and Cu  : 3d 10  . Hence, taking out one electron more from
this stable configuration will require a lot of energy.

Question 6:

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Why is the highest oxidation state of a metal exhibited in its oxide or fluoride only?

Solution 6:
Both oxide and fluoride ions are highly electronegative and have a very small size. Due to these
properties, they are able to oxidize the metal to its highest oxidation state.

Question 7:
Which is a stronger reducing agent Cr 2  or Fe 2  and why?

Solution 7:
The following reactions are involved when Cr 2  and Fe2  act as reducing agents.
 CrCr2  3 Fe 2  
  Fe3
E 0Cr3 / Cr 2 The value is -0.41 V and E 0 Fe3 / Fe2 is +0.77 V. This means that Cr 2 can be easily
oxidized to Cr 3 but Fe2 does not get oxidized to Fe3 easily. Therefore, Cr 2 is a better
reducing agent that Fe3 .

Question 8:
Calculate the ‘spin only’ magnetic moment of M2+ (aq) ion (Z = 27)

Solution 8:
Z = 27
 [ Ar ]3d 7 4s 2
 M 2   ( Ar )3d 7 4s 2
3d 7      
i.e., 3 unpaired electrons
n  3
 n(n  2)  
 3(3  2)  
 15  
  4BM

Question 9:
Explain why Cu+ ion is not stable in aqueous solutions?

Solution 9:

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In an aqueous medium, Cu2+ is more stable than Cu+. This is because although energy is
Required to remove one electron from Cu+ to Cu2+, high hydration energy of Cu2+ compensates
for it. Therefore, Cu+ ion in an aqueous solution is unstable. It disproportionates to give Cu2+
and Cu
2Cu(aq) 
Cu(2aq )  Cu( x)

Question 10:
Actinoid contraction is greater from element to element than lanthanoid contraction. Why?

Solution 10:
In actinoids, 5f orbitals are filled. These 5f orbitals have a poorer shielding effect than 4f orbitals
(in lanthanoids). Thus, the effective nuclear charge experienced by electrons in valence shells in
case of actinoids is much more that that experienced by lanthanoids. Hence, the size contraction
in actinoids is greater as compared to that in lanthanoids.

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