Maharashtra-HSC-d & F Paper-2 Target

Written according to the New Text book (2012-2013)
published by the Maharashtra State Board of

Secondary and Higher Secondary Education, Pune.

STD.XIISci.
Per f ec t Chemi st r y - I I

Prof. Santosh B. Yadav
(M. Sc., SET, NET)
Department of Chemistry
R. J hunjunwala College, Ghatkopar

Prof. Anil Thomas
(M.Sc., Chemistry)

Salient Features:
Exhaustive coverage of syllabus in Question Answer Format.
Covers answers to all Textual Questions and numericals.
Textual Questions are represented by * mark.
Intext Questions are represented by #mark.
Charts for quick reference.
Simple and Lucid language
Includes Board Question Paper of March 2013.

TargetPublications PVT. LTD.
Mumbai, Maharashtra
Tel: 022 6551 6551
Website : www.targetpublications.org | email : mail@targetpublications.org
Edition: August 2013

Std. XII Sci.
Perfect Chemistry - II

Target Publications PVT. LTD.

Sixth Edition : August 2013

Price : ` 240/-

Printed at:
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email : mail@targetpublications.org
Preface

In the case of good books, the point is not how many of them you can get
through, but rather how many can get through to you.

Organic chemistry as a branch of science represents one of many pillars
that give Chemistry its stand in the world. Without organic chemistry,
learning such a subject is like supporting a dome of steel with pillars of
straw. Organic chemistry deals with the scientific study of structure,
properties, composition, reactions and preparation of chemical
compounds. They form the basis of all earthly life processes. A science
that calls for such deep knowledge of concepts and an intrinsic study of
all aspects must obviously, not be easy to conquer.

Hence to ease this task we bring to you Std. XII Sci. : PERFECT
CHEMISTRY-II a complete and thorough guide critically analysed
and extensively drafted to boost the students confidence. Topic wise
classified question and answer format of this book helps the student to
understand each and every concept thoroughly. The book provides
answers to all textual questions marked with * and intext questions
marked with #. Important definitions, statements and laws are specified
with Italic representation. Charts are given for quick reference.

And lastly, I would like to thank all those people who have helped me in
preparing exclusive guide to all students. There is always room for
improvement and hence we welcome all suggestions and regret any
errors that may have occurred in the making of this book.

A book affects eternity; one can never tell where its influence stops.

Best of luck to all the aspirants!

Yours faithfully
Publisher
PAPER PATTERN

There will be one written paper of 70 Marks in Chemistry.
Duration of the paper will be 3 hours.
Chemistry paper will have two parts viz: Part I of 35 marks and Part II of 35 marks
Same Answer Sheet will be used for both the parts.
In the question paper, for each part there will be 4 Questions.
Students have freedom to decide the sequence of answers.
The paper pattern as per the marking scheme for Part I and Part II will be as follows:

Question 1: (7 Marks)
There will be 7 multiple choice Questions (MCQs), each carrying 1 mark.
Total marks =7

There will be 8 Questions out of which 6 Questions are to be answered, each carrying 2 marks.
Total marks =12

There will be 4 Questions out of which 3 Questions are to be answered, each carrying 3 marks.
Total marks =9
(There will be 3 Questions based on numericals from part I)

There will be 2 Question out of which 1 Question has to be answered.
It will carry 7 marks.
Total Marks =7
(There will be 2/3 marks Questions based on numericals from Part I)

Distribution of Marks According to Type of Questions

Type of Questions Marks Marks with option Percentage (%)
Objectives 14 14 20
Short Answers 42 56 60
Brief Answers 14 28 20
Total 70 98 100

C o ntents

No. Topic Name
Page
No.
Marks
Without
Option
Marks
With
Option
8 d and fBlock Elements 1 05 06
9 Coordination Compounds 35 03 04
10 Halogen Derivatives of Alkanes and Arenes 87 04 06
11 Alcohols, Phenols and Ethers 155 04 06
12 Aldehydes, Ketones and Carboxylic Acids 233 05 07
13 Compounds Containing Nitrogen 312 04 06
14 Biomolecules 371 04 06
15 Polymers 413 03 04
16 Chemistry in Everyday Life 439 03 04
Board Question Paper March 2013 465 - -

Note: All the Textual questions are represented by * mark
All the Intext questions are represented by # mark

1 1

Syllabus

8.0 Prominent Scientists

8.1 General Introduction and Electronic configuration

8.2 Occurrence and characteristics of transition elements

8.3 General trends in properties of the first row transition metals

8.4 Preparation and properties of K
2
Cr
2
O
7
and KMnO
4

8.5 General Introduction and Electronic Configuration

8.6 Lanthanoids

8.7 Actinoids

08
d and f block Elements

TARGET Publications
Std. XII Sci.: Perfect Chemistry - II
1
d and f Block Elements
08
d and f-Block Elements

8.0 Prominent Scientists

Scientists Contribution
Friedrich Wilhelm Ostwald (1853-1932)
(German Chemist)
i. Discovered the law of dilution,
ii. Gave the first modern definition of catalyst.
iii. Devised a method in 1900 to manufacture nitric acid
by oxidizing ammonia.
iv. Got the Nobel prize in 1909 in recognition of his
work on catalysis.
Glenn Theodore Seaborg (1912-1999)
(American Chemist)
i.

Discovered and isolated ten transuranic elements
which includes Plutonium, Americium, Curium,
Berkelium, Californium, Einsteinium, Fermium,
Mendelevium, Nobelium and Seaborgium.
ii. Shared the Nobel prize with McMillon in 1951 for
significant contributions in the field of transuranic
elements.
d-Block Elements

8.1 General Introduction Electronic configuration

*Q.1. What are d-block elements?
Ans: The elements in which the last electron enters the d-orbital of the penultimate shell i.e.(n1)d orbital where
n is the outermost shell, are called d-block elements.
Their general electronic configuration is (n 1)d
1 10
ns
1 2
.

*Q.2. Explain the position of d-block elements in the periodic table.
Ans: Position of d-block elements:
i. The d-block elements lie in between s- and p-block elements, i.e. these elements are located in the
middle part of the periodic table.
ii. The d-block elements are present in
4
th
period (Sc to Zn 10 elements),
5
th
period (Y to Cd 10 elements),
6
th
period (La,

Hf to Hg 10 elements),
7
th

period (Ac, Rf to Uub 10 elements)
iii. d-block elements are present in the groups 3 to 12.
Each series starts with elements of Group 3 and ends with elements of Group 12.
Position of d-block elements in the periodic table

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
s-block d-block p-block
4 19 20 21
Sc
22
Ti
23
V
24
Cr
25
Mn
26
Fe
27
Co
28
Ni
29
Cu
30
Zn
31 32 33 34 35 36
5 37 38 39
Y
40
Zr
41
Nb
42
Mo
43
Tc
44
Ru
45
Rh
46
Pd
47
Ag
48
Cd
49 50 51 52 53 54
6 55 56 57
La
72
Hf
73
Ta
74
W
75
Re
76
Os
77
Ir
78
Pt
79
Au
80
Hg
81 82 83 84 85 86
7 87 88 89
Ac
104
Rf
105
Db
106
Sg
107
Bh
108
Hs
109
Mt
110
Ds
111
Rg
112
Uub
113 114 115 116 117 118

TARGET Publications Std. XII Sci.: Perfect Chemistry - II
2
*Q.3. Explain the meaning of transition series.
Ans: i. d-block elements are also known as transition elements. There are four series of transition elements in
the long form of periodic table. These are known as transition series.
ii. Four transition series are 3d, 4d, 5d and 6d series wherein orbitals of (n 1)
th
main shell gets filled
respectively.
iii. The 3d series includes all the elements from Sc (Z =21) to Zn (Z =30) belonging to the 4
th
period.
iv. The 4d series includes all the elements from Y (Z =39) to Cd (Z =48) belonging to the 5
th
period.
v. The 5d series begins with element La (Z =57) and includes all the elements from Hf (Z =72) to
Hg (Z =80) belonging to the 6
th
period.
vi. The 6d series begins with element Ac (Z =89) and includes all the elements from Rf (Z =104) to
Uub (Z =112) belonging to the 7
th
period.

Q.4. Why are d-block elements called transition elements?
Ans: i. Transition elements are defined as those elements which have partly or incompletely filled (n1)d
orbitals in their elementary state or in any of their common oxidation states.
ii. The 3d, 4d, 5d and 6d subshells of the d-block elements are incomplete and the last electron enters the
(n1)d-orbital.
iii. d-block elements are called transition elements as they shows transition in the properties from the most
electropositive s-block elements to the less electropositive p-block elements.

Q.5. Give the general electronic configuration of four series of d-block elements.
Ans: The general electronic configuration of d-block elements is (n1)d
110
ns
12
.
The general electronic configuration of the four series of d-block elements are as mentioned below:
i. 3d series: [Ar] 3d
110
4s
12

ii. 4d series: [Kr] 4d
110
5s
02

iii. 5d series: [Xe] 5d
110
6s
2

iv. 6d series: [Rn] 6d
110
7s
2

Q.6. Give the electronic configuration of all the elements belonging to the 3d series of d-block elements.
Ans: 3d series or first row transition series (Sc to Zn) belonging to the fourth period has the general electronic
configuration [Ar] 3d
110
4s
12
.
3d series or First Row Transition Series (Sc to Zn)
Elements Symbols Atomic
number
Expected Electronic
configuration
Observed Electronic Configuration
Scandium Sc 21 [Ar] 3d
1
4s
2
[Ar] 3d
1
4s
2
Titanium Ti 22 [Ar] 3d
2
4s
2
[Ar] 3d
2
4s
2

Vanadium V 23 [Ar] 3d
3
4s
2
[Ar] 3d
3
4s
2

Chromium Cr 24 [Ar] 3d
4
4s
2
[Ar] 3d
5
4s
1

Manganese Mn 25 [Ar] 3d
5
4s
2
[Ar] 3d
5
4s
2

Iron Fe 26 [Ar] 3d
6
4s
2
[Ar] 3d
6
4s
2

Cobalt Co 27 [Ar] 3d
7
4s
2
[Ar] 3d
7
4s
2

Nickel Ni 28 [Ar] 3d
8
4s
2
[Ar] 3d
8
4s
2

Copper Cu 29 [Ar] 3d
9
4s
2
[Ar] 3d
10
4s
1

Zinc Zn 30 [Ar] 3d
10
4s
2
[Ar] 3d
10
4s
2

#Q.7. In which period of the periodic table, will an element, be found whose differentiating electron is a 4d
electron?
Ans: Fifth period of the periodic table consist of elements in which the differentiating electron is a 4d electron.

Q.8. Silver atom has completely filled d-orbitals (4d
10
) in its ground state. How can you say that it is a
transition element? (NCERT)
Ans: The outer electronic configuration of Ag (Z =47) is 4d
10
5s
1
. In addition to +1, it shows an oxidation state
of +2 (Eg. AgO and AgF
2
exist). In +2 oxidation state, the configuration is d
9
, i.e. the d subshell is
incompletely filled hence it is a transition element.
Ag
2+
: [Kr]
36
4d
9
. Therefore, Ag is a transition element.

TARGET Publications
3
Q.9. In what way is the electronic configuration of transition elements different from that of the non-
transition elements? (NCERT)
Ans: Transition elements contain incompletely filled d subshell, i.e. their electronic configuration is (n1) d
110

ns
12
whereas non-transition elements have no d subshell or their d subshell is completely filled and they
have the outer electronic configuration of ns
12
or ns
2
np
16
.

Q.10. Write down the electronic configuration of: (NCERT)
i. Cr
3+
ii. Cu
+
iii. Co
2+
iv. Mn
2+
Ans: i. Cr
3+
=1s
2
2s
2
2p
6
3s
2
3p
6
3d
3
ii. Cu
+
=1s
2
2s
2
2p
6
3s
2
3p
6
3d
10
iii. Co
2+
=1s
2
2s
2
2p
6
3s
2
3p
6
3d
7
iv. Mn
2+
=1s
2
2s
2
2p
6
3s
2
3p
6
3d
5

*Q.11. Why does copper show abnormal electronic configuration?
Ans: Copper has atomic number 29. Its expected and actual electronic configurations are:

29
Cu (Expected): 1s
2
2s
2
2p
6
3s
2
3p
6
3d
9
4s
2

(Actual): 1s
2
2s
2
2p
6
3s
2
3p
6
3d
10
4s
1

Explanation:
i. The energy difference between the 3d and 4s orbitals is very low.
ii. The d-orbital being degenerate, acquires more stability when it is half-filled (3d
5
) or completely filled
(3d
10
).
iii. Due to the interelectronic repulsion forces one 4s electron from the 4s orbital is transferred to the 3d
orbital in Cu so that Cu has completely filled 3d
10
orbital, thus acquiring more stability.

*Q.12. Why chromium has electronic configuration 3d
5
4s
1
and not 3d
4
4s
2
?
Ans: Chromium has atomic number 24. Its expected and actual electronic configurations are:

24
Cr (Expected): 1s
2
2s
2
2p
6
3s
2
3p
6
3d
4
4s
2

(Actual): 1s
2
2s
2
2p
6
3s
2
3p
6
3d
5
4s
1

Explanation:
i. The energy difference between the 3d and 4s orbitals is very low.
ii. The d-orbital being degenerate, acquires more stability when it is half-filled (3d
5
) or completely filled
(3d
10
).
iii. Due to inter electronic repulsion forces, one 4s electron gets transferred to 3d orbital in Cr in order to
acquire the half-filled orbital configuration i.e. 1s
2
2s
2
2p
6
3s
2
3p
6
3d
5
4s
1
in which the 3d and 4s subshells
have extra stability, thus resulting in the greater stability of the Cr atom.

8.2 Occurrence and characteristics of transition elements

Q.13. Explain the occurrence of d-block elements.
Ans: i. d-block elements occur in free state as well as in combined states.
ii Among the d-block elements, soft elements occur as sulphide minerals and more electropositive hard
metals occur as oxides.
iii. Occurrence of some d-block elements:
a. Titanium occurs in the combined state. It is found in small quantities of coal, clay, rocks, sand
etc.
Eg. Rutile (TiO
2
), Ilmenite (FeTiO
3
).
b. Vanadium occurs in the ores vanadinite and carnotite.
c. Chromium occurs in the ores as Chromite (FeO, Cr
2
O
3
), Chrom ochre (Cr
2
O
3
), Crocoisite
(PbCrO
4
).
d. Manganese does not occur in the free state but mainly occurs in pyrolusite ore (MnO
2
) and
other minerals.
e. Iron occurs in free as well as combined states.
f. Nickel is found in cobalt ores.
g. Copper is found in rocks, soil, sea, mineral waters and in ores like cuprite (Cu
2
O), malachite
[CuCO
3
, Cu(OH)
2
], azurite [2CuCO
3
, Cu(OH)
2
] etc.
h. Zinc is found in the ores of silver, copper, lead and platinum.

4
Q.14. State the general characteristics of transition elements or d-block elements.
Ans: Characteristics of transition elements:
i. Most of the transition elements are metals and thereby they show metallic properties such as ductility,
malleability, electrical conductivity, high tensile strength and metallic lustre.
ii. Except mercury which is liquid at room temperature, other transition elements have typical metallic
structures.
iii. Their compounds generally contain unpaired electrons, hence they are paramagnetic in nature and
form coloured compounds.
iv. They exhibit variable oxidation states.
v. They have tendency to form large number of complexes.
vi. They have higher densities as compared to the metals of IA and IIA group (s-block).
vii. They are heavy metals with higher melting and boiling point as well as higher heats of vaporisation.
viii. Transition elements are less reactive than s-block elements due to their higher ionisation energy.
ix. Most of the transition metals such as Mn, Ni, Co, Cr, V, Pt, etc. and their compounds are used as
catalysts.
x. They are good conductors of heat and electricity.
xi. They form alloys with different metals.
xii. They form interstitial compounds with elements such as hydrogen, boron, carbon, nitrogen etc.
xiii. They form organometallic compounds.

Q.15. Why do transition metals possess high density and high melting and boiling points?
Ans: i. The densities of d-block elements are relatively higher as compared to the s-block elements due to the
decrease in the size of the atoms and the consequent increase in the nuclear charge, which results in
the compact structure of the elements.
ii. The density of the atoms increases with the decrease in the size of the atom. Therefore the density of
the elements goes on increasing from left to right across a period.
iii. Transition elements form strong metallic bond in which both (n1) and ns electrons take part. Due to
the notable covalent character of the strong metallic bond, considerable amount of energy is required
to break the metallic bond in order to melt the metal. Hence these metals possess high melting and
boiling points.
Note:
Atomic properties of 3d series:

Element Density
(g cm
3
)
Radii/pm Ionization enthalpy
kJmol
1
M
+
M
2+
M
3+

Sc 21 2.99 164 73 631
Ti 22 4.50 147 67 656
V 23 5.96 135 79 64 650
Cr 24 7.20 129 82 65 653
Mn 25 7.21 137 82 65 717
Fe 26 7.86 126 77 65 762
Co 27 8.90 125 74 61 758
Ni 28 8.90 125 70 60 736
Cu 29 8.92 128 73 745
Zn 30 7.14 137 75 906

TARGET Publications
5
Q.16. All d-block elements are not transition elements. Explain.
Ans: i. The d-block elements are those in which the last electron enters the d orbital.
ii. The transition elements are those elements which have incompletely filled (partly filled) d-subshells
in their elementary state or in any one of their oxidation states.
iii. Hence, only those d-block elements which have completely filled d orbitals, (n1)d
10
are not
transition elements.
iv. Eg. Zn, Cd and Hg atoms have completely filled d-orbitals (3d
10
) in their ground state as well as in
their oxidised states, hence they are d-block elements but not transition elements.

8.3 General trends in properties of the first row transition metals

Q.17. Explain the metallic characters of the d-block elements.
Ans: i. Except mercury which is a liquid, all the transition elements are metallic in nature.
ii. They are hard, lustrous, malleable and ductile with high melting and boiling points, and having good
thermal and electrical conductivities.
iii. The metallic character of transition elements may be attributed to their low ionization enthalpies and
the presence of several vacant orbitals in their outermost shell, which favours the formation of
metallic bonds in them.
iv. In addition to the electrons from outermost energy level, the unpaired d-electrons also contribute for
the formation of metallic bond.
v. So, greater the number of unpaired d-electrons, stronger is the bonding due to the overlapping of the
d-orbitals containing unpaired electrons.

Q.18. Why are Cr, Mo and W hard metals while Zn, Cd and Hg are not very hard metals?
Ans: i. The hardness of the metals indicates the presence of covalent bonds in them.
ii. The d-orbitals containing unpaired electrons may overlap to form covalent bonds.
iii. Greater the number of unpaired d-electrons present in a transition metal atom, more is the number of
covalent bonds formed by it and thus greater is the strength and hardness of the metal.
iv. Cr, Mo and W have maximum number of unpaired d-electrons and are, therefore, hard metals
whereas Zn, Cd and Hg are not very hard metals due to the absence of unpaired electrons.

Q.19. Explain the trends in melting and boiling points of first row transition metals.
Ans: i. The high melting and boiling points of transition metals are due to their close-packed structures, in
which the transition metals are held together by strong metallic bonds which have significant covalent
character.
ii. Considerable amount of energy is required to break the metallic bonds in order to melt the metal,
therefore, these metals have very high melting points and boiling points.
iii. The strength of metallic bonds depends upon the number of unpaired electrons. Greater the number of
valence electrons, stronger is the metallic bonding, and consequently, melting points are higher.
iv. Therefore, as we move along a particular series, the metallic strength increases upto the middle with
increasing availability of unpaired electrons upto d
5
configuration (Eg. Sc has 1, Ti has 2, V has 3, Cr
has 5 unpaired electrons) and then decreases with decreasing availability of unpaired d-electrons
(Eg. Fe has 4, Co has 3 unpaired electrons and so on).
v. Thus the melting and boiling points increase from Sc to Cr. Chromium has the maximum melting
point in the first transition series. After Cr, the melting and boiling points decrease from Cr to Cu.
vi. Zn, Cd, Hg have no unpaired electrons. Thus these metals have low melting and boiling points.
Mercury (Hg) is liquid at room temperature and has melting point of 234 K. The unexpectedly lower
melting point of Mn and Tc are probably due to their complicated lattice structure. These metals have
low values for enthalpies of atomization.

Q.20. Define Ionisation enthalpy.
Ans: It is the amount of energy required to remove the outermost electron completely from a gaseous atom in its
ground state.

6
Q.21. Explain the trends observed in the ionisation enthalpies of the d-block elements.
Ans: i. The ionization enthalpies of transition metals are quite
high and lie between those of s-block and p-block
elements.
ii. The first ionization enthalpy increases irregularly with
increase in atomic number across a given transition
series. The added electron enters into (n1) d-subshell
and shields the valence electrons from the nucleus.
Thus, the effect of increased nuclear charge is opposed
by the screening effect of (n1) d-electrons. Therefore,
the increase in ionization enthalpy with the increase in
atomic number is rather small and not very regular.
iii. The first ionization enthalpies of elements of third transition series are higher than those of the
elements of first and second transition series, due to the poor shielding effect of the electrons present
in the filled 4-f orbitals.

Note:
The energy required to remove first electron from gaseous atom in its ground state is called first ionisation
enthalpy, to remove second electron, it is called second ionisation enthalpy and for removal of third
electron it is called third ionisation enthalpy.

Q.22. Explain thermodynamic stability of transition metal compound on the basis of ionization enthalpy.
Ans: The smaller the sum of ionization enthalpies needed for transition metals to attain a particular oxidation
state, greater is the stability of the compounds of that metal in that particular oxidation state.
Eg. Nickel (II) compounds, are thermodynamically more stable than platinum (II) compounds, whereas
platinum (IV) compounds are more stable than nickel (IV) compounds.
Explanation:
i. Sum of first and second ionization enthalpies (IE
1
+IE
2
) for nickel is lesser as compared to that of
platinum (Pt). This implies that ionization of Ni to Ni
2+
ion requires lesser energy (enthalpy) than the
energy required by Pt to form Pt
2+
ion. Therefore Ni(II) compounds are thermodynamically more
stable than Pt (II) compounds.
ii. On the other hand, the sum of first four ionization enthalpies (IE
1
+ IE
2
+ IE
3
+ IE
4
) for
Pt(9.36 10
3
kJ mol
1
) is lesser than that required by Ni to form Ni
4+
. Therefore, smaller amount of
energy is required to ionize Pt to Pt
4+
ion.
iii. Thus Pt(IV) compounds are thermodynamically more stable than Ni(IV) compounds.

*Q.23. Explain the oxidation states of first row elements of transition series.
Ans: i. The oxidation states of transition elements are related to the electronic configuration.
Transition elements have last two orbitals incompletely filled i.e. They contain ns and (n1)d orbitals.
ii. Thus these elements possess +2 and +3 common oxidation states.
iii. Since (n1)d-electrons and ns-electrons have nearly equal energies, both are available for chemical
bonding.
iv. Hence, the transition metals form compounds showing more than one (variable) oxidation states.
v. Since the transition metals of the first series have two electrons in their outermost shell with the
exception of Cr and Cu (4s
1
), the lowest oxidation states of these elements are +1 or +2, which is due
to their 4s electrons.
vi. As the 3d electrons take part in the chemical bonding one after another, in addition to the +2
oxidation state, there are number of other oxidation states as illustrated below.
900
800
700
600
Ti
V
Cr
Zr Nb
Mo
Mn
Tc
Rh
Ru
Ni Ag
Cu
Hf
Ta
W
Re
Fe
Co
Pd
Os
Ir
Pt
Au
F
i
r
s
t

i
o
n
i
s
a
t
i
o
n
a
l
(
k
J

m
o
l
-
1
)

e
n
t
h
a
l
p
y

Transition Elements
The first ionization enthalpies
of Transition elements

TARGET Publications
7
Oxidation states of first transition (3d) series elements:
Sc Ti V Cr Mn Fe Co Ni Cu Zn
+2 +2 +2 +1 +2 +2 +2 +2 +1 +2
+3 +3 +3 +2 +3 +3 +3 +3 +2
+4 +4 +3 +4 +4 +4 +4
+5 +4 +5 +5 +5
+5 +6 +6
+6 +7

vii. As the number of unpaired electrons in the 3d orbitals increases, the number of oxidation state also
increases.

Q.24. Compare the stability of +2 oxidation state for the elements of the first transition series. (NCERT)
Ans: i. In the beginning of 3d transition series, Sc
2+
is virtually not known or in other words it is not stable in
comparison to Sc
3+
. Ti
2+
, V
2+
, Cr
2+
are known but less stable in comparison to their most common
oxidation state of +3.
ii. In the middle of the 3d transition series, Mn
2+
, Fe
2+
,

Co
2+
are known and quite common. Mn
2+
and
Mn
7+
are most stable in Mn. Fe
2+
is less stable in comparison to Fe
3+
due to fact that Fe
3+
tends to
lose one electron to acquire d
5
structure, which has extra stability. Co
2+
is less stable as compared to
Co
3+
. Ni
2+
is most common and most stable among its +2, +3, +4 states. Cu
2+
is more stable and is
most common species as compared to Cu
1+
.
iii. At the end of the 3d transition series, Zn forms only Zn
2+
which is highly stable as it has 3d
10

configuration.

Q.25. Write the different oxidation states of manganese. Why +2 oxidation state of manganese is more
stable? [March 2013]
Ans: Oxidation states of Mn:
+2, +3, +4, +5, +6 and +7.
Electronic configuration of Mn:
1s
2
2s
2
2p
6
3s
2
3d
5
4s
2

Due to the presence of half filled d orbital, the +2 oxidation state of Manganese is more stable

Q.26. To what extent do the electronic configurations decide the stability of oxidation states in the first
series of transition elements? Illustrate with example. (NCERT)
Ans: In a transition series, the oxidation states which lead to noble gas or exactly half-filled or completely filled
d-orbitals are more stable.
Eg. In the first transition series, electronic configuration of Mn (Z =25) is [Ar] 3d
5
4s
2
. It shows oxidation
states +2 to +7 but Mn (II) is most stable because it has the half-filled configuration [Ar] 3d
5
.
Similarly, Sc
3+
and Zn
2+
are more stable as illustrated below:
Sc =[Ar] 3d
1
4s
2
, Sc
3+
=[Ar] i.e. noble gas configuration.
Zn =[Ar] 3d
10
4s
2
, Zn
2+
=[Ar] 3d
10
i.e. completely filled configuration.

Q.27. What may be the stable oxidation state of the transition element with the following d-electron
configurations in the ground state of their atoms: 3d
3
, 3d
5
, 3d
8
and 3d
4
? (NCERT)
Ans: The stable oxidation state of transition elements with the d-electron configuration 3d
3
, 3d
5
, 3d
8
and 3d
4
in
ground state of atoms is as follows:

Sr.
No.
d-electron
configuration
Symbol of
Element
Stable oxidation
States
1. 3d
3
V (3d
3
4s
2
) +2, +3, +5
2. 3d
4
Cr (3d
5
4s
1
) +2, +3, +6
3. 3d
5
Mn (3d
5
4s
2
) +2 , +7
4. 3d
8
Ni (3d
8
4s
2
) +2, +4

8
Q.28. How is the variability of oxidation states of the transition elements different from that of the non-
transition elements? Illustrate with examples. (NCERT)
Ans: i. The variability in oxidation states of transition metals is due to the incomplete filling of d-orbitals in
such a way that their oxidation states differ from each other by unity.
Eg. Fe
2+
and Fe
3+
, Cu
+
and Cu
2+
etc.
In case of non-transition elements, the oxidation states differ by units of two.
Eg. Pb
2+
and Pb
4+
, Sn
2+
and Sn
4+
etc.
ii. In transition elements, the higher oxidation states are more stable for heavier elements in a group.
Eg. In group 6, Mo (VI) and W (VI) are more stable than Cr (VI).
In p-block elements, the lower oxidation states are more stable for heavier members due to inert pair
effect,
Eg. In group 16, Pb (II) is more stable than Pb (IV).

Q.29. Why does scandium show only +2 and +3 oxidation states?
Ans: Scandium (Sc) has electronic configuration,
Sc: 1s
2
2s
2
2p
6
3s
2
3p
6
3d
1
4s
2

Due to the loss of two electrons from the 4s-orbital, Sc acquires +2 oxidation state.
Sc
2+
: 1s
2
2s
2
2p
6
3s
2
3p
6
3d
1

By the loss of one more electron from the 3d-orbital, it acquires +3 oxidation state.
Sc
3+
: 1s
2
2s
2
2p
6
3s
2
3p
6

Since Sc
3+
acquires extra stability of inert element [Ar], it does not form higher oxidation state.

#Q.30.Why is manganese more stable in the +2 state than in the +3 state and the reverse is true for iron?
OR
Why Mn
2+
compounds are more stable than Fe
2+
towards oxidation to their +3 state? (NCERT)
Ans: Electronic configuration of Mn
2+
is [Ar] 3d
5
which is half filled and hence it is stable. So third ionisation
enthalpy is very high i.e third electron cannot be easily removed. Whereas in case of Fe
2+
, the electronic
configuration is 3d
6
. Therefore, Fe
2+
can easily lose one electron to acquire 3d
5
stable electronic
configuration.

Q.31. Why Zn does not exists in variable oxidation states?
Ans: The oxidation state of an element depends on its electronic configuration.
Zn: 1s
2
2s
2
2p
6
3s
2
3p
6
3d
10
4s
2

When Zn loses two electrons from 4s-orbital, it gets a very stable electronic configuration wherein all the
electrons are paired in d-orbital, giving a +2 oxidation state.
Zn
2+
: 1s
2
2s
2
2p
6
3s
2
3p
6
3d
10

Since all the orbitals are completely filled with paired electrons, it has a very stable electronic
configuration.
Therefore, Zn shows only one oxidation state of +2.

#Q.32.Which element of 3d series of the transition metals exhibits the largest number of oxidation states
and Why?
Ans: i. Among transition metals, Manganese exhibits the largest number of oxidation states ranging from +2
to +7.
ii. The electronic configuration of Mn is:
Mn: 1s
2
2s
2
2p
6
3s
2
3p
6
3d
5
4s
2
iii. Different oxidation states shown by Mn are:

2
2
MnCl
+
,
+3
2 3
Mn O ,
2
4
O Mn
+
,
5
5
F Mn
+
,
4
6
2
O Mn K
+
,
4
7
O Mn K
+
.
iv. Mn
2+
state is very stable due to extra stability of half filled 3d
5
subshell.
v. Mn
7+
is a good oxidising agent since it can be easily reduced to Mn
4+
and Mn
2+
.
vi. As the number of unpaired electrons in 3d subshell increases, the number of oxidation state increases.

TARGET Publications
9
#Q.33. Explain why iron, cobalt and nickel do not show the expected highest oxidation states of +8, +9 and
+10 respectively.
Ans: i. The oxidation states of an element depends on its electronic configuration and the number of unpaired
electrons.
ii. The electronic configuration of Fe, Co and Ni are as follows:

Available electrons for excitation
Fe: [Ar] 3d
6
4s
2
6 +2 =8
Co: [Ar] 3d
7
4s
2
7 +2 =9
Ni: [Ar] 3d
8
4s
2
8 +2 =10

iii. Hence the expected oxidation states of Fe, Co and Ni shall be +8, +9 and +10 respectively.
iv. Fe by the loss of two electrons from 4s subshell forms Fe
2+
and further loss of one more electron from
3d-orbital forms Fe
3+
, which is very stable due to half filled orbital, 3d
5
. Hence, there is no further
loss of electrons from the 3d subshell and thus Fe does not show +8 oxidation.
v. Co forms Co
2+
due to the loss of two electrons from 4s subshell and further loss of one more electron
from 3d-orbital forms Co
3+
. In cobalt +2 and +3 oxidation states are more stable and it does not lose
electrons further. Hence Co does not show +9 oxidation state.
vi. Ni forms Ni
2+
by the loss of two electrons from 4s-orbital and by the loss of one more electron from 3d-
orbital, it forms Ni
3+
. Now there are 7 electrons in 3d-orbital which give extra stability. Hence, there is
no further loss of electrons and therefore Ni does not show +10 oxidation state.
Q.34.Which metal in the first transition series exhibits +1 oxidation state most frequently and why?
(NCERT)
Ans: Copper has electronic configuration [Ar] 3d
10
4s
1
. It can easily lose one (4s
1
) electron to give stable 3d
10
configuration.

Q.35. Why is the highest oxidation state of a metal exhibited in its oxide or fluoride only? (NCERT)
Ans: Oxygen and fluorine have small size and high electronegativity so they can easily oxidise the metal to its
highest oxidation state.

Q.36. Name the oxometal anions of the first series of the transition metals in which the metal exhibits the
oxidation state equal to its group number.
Ans: MnO
4
: Oxidation state of Mn =+7 (Group No =7)

CrO
4
2
: Oxidation state of Cr =+6 (Group No =6)

Q.37. Comment on the statement that the elements of the first transition series possess many
properties different from those of heavier transition elements. (NCERT)
Ans: The given statement is true because:
i. Atomic radii of the heavier transition elements (4d and 5d series) are larger than the corresponding
elements of the first transition series though those of 4d and 5d series are very close to each other.
ii. For first transition series, +2 and +3 oxidation states are more common whereas for heavier
transition elements, higher oxidation states are more common.
iii. Melting and boiling points of heavier transition elements are greater than those of the first
transition series due to stronger intermetallic bonding (MM bonding).
iv. Ionisation enthalpies of 5d series are higher than the corresponding elements of 3d and 4d series.
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 low spin complexes
irrespective of the strength of the ligand field.

*Q.38. Explain the trend of atomic radii in transition elements.
Ans: i. The atomic radii for transition metals are smaller than their corresponding s-block elements.

Transition metals
Sc Cu
s-block elements
K Ca
4
th
period
At. Radius (pm) 203 174 144 117

10
The atomic radii of the elements of a given series decrease with the increase in atomic number but
this decrease becomes small after midway.

Element Sc Ti V Cr Mn Fe Co Ni Cu Zn
Atomic radii (pm) 144 132 122 118 117 117 116 115 117 125

ii. In the first transition series, the atomic radius gradually decreases from scandium to chromium but
from chromium to copper, it is nearly the same. Similar behaviour has been observed in the second
and third transition series.
iii. The decrease in atomic radii in each series, in the beginning, is due to an increase in nuclear charge
across the period, which tends to pull the ns electrons inward, i.e. it tends to reduce the size.
iv. The addition of extra electrons to (n1) d-orbitals also provides the screening effect. As the number
of d-electrons increases, the screening effect increases. Thus, there are two operating effects namely
screening effect and nuclear charge effect which oppose each other.
v. In the midway onwards of the series, both these effects become nearly equal and thus, there is no
change in atomic radii inspite of the fact that atomic number increases gradually.
vi. The values of atomic radii at the end of each series are slightly higher which is due to electron-
electron repulsions among (n1) d-electrons. These repulsions become predominant at the end of
each series and thus resulting in the increase in size.
vii. In a vertical row, the atomic radii is expected to increase from top to bottom. Therefore, the atomic
radii of transition metals of second series have larger values than those of the first transition series.
However, the transition metals of third series except the first member, lanthanum, have nearly the
same radii as metals of second transition series above them which is due to the Lanthanoid
contraction.

*Q.39. Explain the trend of the ionic radii in transition elements?
Ans: i. In the table given below ionic radii of the oxidation states of +2 and +3 are given. In general ionic
radii decreases with increase in the oxidation state. For the same oxidation state, the ionic radii
generally decrease with increase in the nuclear charge in a given transition series. This trend is more
pronounced for the divalent ions of the elements belonging to the first transition series. The gradual
decrease in ionic radii in going from Ti
2+
ion to Cu
2+
ion is due to an increase in the effective nuclear
charge.

Element Sc Ti V Cr Mn Fe Co Ni Cu Zn
Ionic radii in pm M
2+
90 88 84 80 76 76 72 72 74
M
3+
81 76 74 69 66 64 63
ii. The ionic radii decreases with the increase in the oxidation state. This is due to the increase in the
effective nuclear charge. Ionic radii of the transition elements are smaller than those of the
representative elements of the same period.

Q.40. Explain the splitting of d-orbitals in transition elements.
Ans: i. In a free metal ion, all the orbitals at the same
energy level are called degenerate orbitals.
ii. However, when they are in the form of
compounds, the five d-orbitals split into two
groups.
iii. One group consist of three orbitals namely d
xy
, d
yz
,
d
xz
and they are of lower energy level.
iv. The second group consists of two orbitals
2 2
d
x y
and
2
z
d and are of slightly higher energy
level.
v. The splitting of d-orbitals is caused by the groups
linked to the metal ions.
vi. The difference in energy (E) between the two
sets of d-orbitals is small.
E
E
n
e
r
g
y
d-orbitals
d
xy
d
yz
d
xz
2 2
x -y
d
2
z
d
Splitting of d-orbitals

TARGET Publications
11
*Q.41. Explain, most of the transition metal compounds are remarkably coloured.
OR
Explain, most of the transition elements form coloured compounds.
Ans: i The colour of a substance depends upon the absorption of light of a particular wavelength of visible
lights.
ii. The colour of the compounds of the transition metals may be attributed to the presence of incomplete
(n1) d subshell. In these compounds, the energies of the five d-orbitals in the same sub-shell do not
remain same.
iii. The amount of energy required to excite some of the electrons to the higher energy states within the
same d-subshell, is quite small.
iv. In case of transition metal ions, the electrons can be easily promoted from one energy level to other
within the same d-subshell. This transition is called the d-d transition.
v. The energy corresponding to such small transitions is available within the visible range.
vi. Therefore, the transition metal ions absorb certain radiations from visible region and appear coloured.

Q.42. What are the factors responsible for colour of a transition metal ions?
Ans: Factors responsible for colour of a transition metal ions:
i. The presence of incompletely filled d-orbitals in metal ions.
ii. The presence of unpaired electrons in d-orbitals.
iii. d-d transitions of electrons due to absorption of radiation in the visible region.
iv. Nature of groups (anions or ligands) linked to the metal ion in the compound or a complex.
v. Type of hybridisation in metal ion in the complex.
vi. Geometry of the complex formed by the metal ion.

Note:
Colour of 3d transition metal ions:

Ion Outer
electronic
configuration
Number of
unpaired
electrons
Colour Ion Outer
electronic
configuration
Number of
unpaired
electrons
Colour
Sc
3+
3d
0
0 Colourless Fe
2+
3d
6
4 Pale green
Ti
3+
3d
1
1 Purple Fe
3+
3d
5
5 Yellow
Ti
4+
3d
0
0 Colourless Co
2+
3d
3
3 Pink
V
3+
3d
2
2 Green Ni
2+
3d
8
2 Green
Cr
3+
3d
3
3 Violet Cu
2+
3d
9
1 Blue
Mn
2+
3d
5
5 Light Pink Cu
1+
3d
10
0 Colourless
Mn
3+
3d
4
4 Violet Zn
2+
3d
10
0 Colourless

Q.43. Why some of the transition metal ions are colourless?
Ans: i. Transition metal ions exhibit colour due to the presence of unpaired electrons in (n1)d-orbitals
which undergo d-d transition.
ii. The metal ions which does not have unpaired electrons (n1)d
0
or which have completely filled
d-orbital (n1)d
10
do not absorb radiations in visible region, since d-d transitions are not possible.
Hence, they are colourless ions.
Eg. Cu
+
(3d
10
), Ag
+
(4d
10
), Zn
2+
(3d
10
), Cd
2+
(4d
10
), Hg
2+
(5d
10
), etc.

#Q.44. Why salts of Sc
3+
, Ti
4+
, V
5+
are colourless?
Ans: i. Electronic configurations of Sc
3+
, Ti
4+
, V
5+
are:
Sc
3+
: [Ar] 3d
0

Ti
4+
: [Ar] 3d
0

V
5+
: [Ar] 3d
0

ii. Since the ions Sc
3+
, Ti
4+
and V
5+
have completely empty d orbitals i.e. no unpaired electron, their salts
are colourless.

12
*Q.45. Explain why the compounds of copper (II) are coloured but those of zinc are colourless.
Ans: i. The electronic configuration of
Cu: [Ar] 3d
10
4s
1
and Cu
2+
: [Ar] 3d
9

ii. In copper compounds, Cu
2+
ions have incompletely filled 3d-orbital (3d
9
).
iii. Due to the presence of one unpaired electron in 3d-orbital, Cu
2+
ions absorb red light from visible
spectrum and emit blue radiation due to d-d transition. Therefore copper compounds are coloured.
iv. In case of zinc, the configuration is
Zn: [Ar] 3d
10
4s
2
and Zn
2+
: [Ar] 3d
10

v. Since 3d subshell is completely filled and there are no unpaired electrons, d-d transition is not possible
and hence Zn
2+
ions do not absorb radiation in visible region. Therefore the compounds of Zn are
colourless.

Q.46. Explain why the solution of Ti
3+
salt is purple in colour?
Ans: i. In [Ti(H
2
O)
6
]
3+
, Ti
3+
has 3d
1
configuration.
ii. This one electron will occupy one of the orbital of lower energy and the complex (ion) will absorb
suitable wavelength of white light and promote the electron from lower energy level to higher energy
level.
iii. Since the complex absorbs light around 500 nm region, yellow and green lights are absorbed to excite
the electron and the transmitted light is of the complementary colour i.e. red blue (purple).
iv. Hence solution containing hydrated Ti
3+
ion is purple in colour.

Q.47. Explain why copper sulphate is blue in colour when dissolved in water but turns yellow when treated
with concentrated HCl.
Ans: i. The electronic configuration of Cu: [Ar] 3d
10
4s
1
and Cu
2+
: [Ar] 3d
9
.
ii. In the aqueous solution of copper sulphate, Cu
2+
forms blue hydrated complex [Cu(H
2
O)
6
]
+2
because
it has one unpaired electron in 3d subshell. The complex has octahedral geometry.
iii. When CuSO
4
solution is treated with concentrated HCl solution, it forms a new complex [CuCl
4
]
2
.
[Cu(H
2
O)
6
]
2+
+4Cl
[CuCl
4
]
2
+6H
2
O
iv. The complex [CuCl
4
]
2
has a tetrahedral geometry with one unpaired 3d
1
electron. Due to a change in
geometry and hybridisation of the complex, the colour of the solution changes from blue to yellow.

*Q.48. Explain why transition elements show tendency to form large number of complexes.
Ans: i. All the transition metals have a tendency to form complexes.
ii. The tendency arises due to the following reasons:
a. They have small ionic radii
b. They have high effective ionic charge.
c. Hence they have high ratio of ionic charge to ionic radius.
d. Transition metals and ions have vacant d-orbitals which can accomodate the lone pairs of
electrons from the ligands to form coordination compounds.
e. Transition metals show variable oxidation states.
f. After accepting the electrons from the ligands, metal ions acquire a stable electronic
configuration of the nearest inert element and form stable complexes.
g. Eg. [Cu(NH
3
)
4
]
2+
, [Co(NH
3
)
6
]
3+
, [Ni(CN)
4
]
2
, etc.
iii. The stability of these complexes depends upon the nature of the metal ion, ligands and their bonding.

*Q.49. Explain, why Pt(IV) complexes are generally octahedral while Pt(II) complexes are square planar.
Ans: i. In case of Pt(II) complexes the central metal atom has d
8
configuration and it shows coordination
number 4. According to valence bond theory, central ion undergoes dsp
2
hybridisation which results
in formation of square planar complexes.
ii. In the Pt (IV) complexes the central metal atom has d
6
configuration and it shows coordination
number 6. According to valence bond theory, central ion undergoes d
2
sp
3
or sp
3
d
2
hybridisation which
results in the formation of octahedral complexes.

TARGET Publications
13
Q.50. Explain catalytic activity of transition metals.
Ans: i. Many transition metals and complexes are used as catalysts which influence the rate of chemical
reaction. The rate of a chemical reaction increases by the decrease in activation energy of the
reactants. This decrease is caused by the catalyst which probably alter the path of the reaction.
ii. Catalysts at solid surface involve the formation of bonds between reactant molecules and atoms on
the surface of the catalyst (first row transition metals utilise 3d and 4s-electrons for bonding). This
results in the formation of reaction intermediates which provides path of lower activation energy and
therefore, increase the rate of the reaction.
A +B + C [ABC] A B + C
Reactants Catalyst Intermediate Product Catalyst
iii. These reaction intermediates readily decompose yielding the products and regenerating the original
substance.
iv. Many transition metals are used as catalysts for reactions. The commonly used transition metals as
catalysts are Fe, Co, Pt, Cr, Mn, etc.
v. Eg.
a. MnO
2
acts as a catalyst for decomposition of KClO
3
to O
2
.
b. Nickel acts as a catalyst in hydrogenation of oils to fats.
c. Vanadium pentoxide is used as catalyst in the manufacture of H
2
SO
4
by contact process.
d. Fe(III) catalyzes the reaction between iodide and persulphate ions.
2I
+
2
2 8
S O

I
2
+2
2
4
SO

e. Titanium tetrachloride (in Ziegler-Natta catalyst) is used in the manufacture of high density
polythene.
nCH
2
=CH
2

Zeigler Nattacatalyst
[CH
2
CH
2
]
n

f. In the manufacture of ammonia, Fe with Mo is used as a catalyst.
g. Co-Th alloy is used in Fischer Tropsch process in the synthesis of gasoline.

Q.51. Explain catalytic property of 3d series elements.
Ans: The catalytic property of 3d series elements can be explained as follows:
i. Because of variable oxidation states, transition metals easily absorb and re-emit wide range of
energies to provide necessary activation energy.
ii. Mechanism of 2I
+
2
2 8
S O

3
Fe
+
I
2
+2
2
4
SO

is explained as
a. 2Fe
3+
+2I
2Fe
2+
+I
2

b. 2Fe
2+
+
2
2 8
S O

2Fe
3+
+2
2
4
SO

iii. Because of the presence of free valencies on the surface, they can absorb the reacting molecules,
thereby increasing the concentration of the reactants on the surface and hence resulting in increase of
the rate of reaction.

Q.52. Transition metals and many of their compounds show paramagnetic behaviour. Explain.
Ans: i. Paramagnetism is a property due to the presence of unpaired electrons.
ii. In case of transition metals, as they contain unpaired electrons in the (n1)d orbitals, most of the
transition metal ions and their compounds are paramagnetic in nature.
iii. As the number of unpaired electrons increases from one to five, paramagnetic character also increases.

Note:
i. Paramagnetism:
The substances which are attracted by the applied magnetic field are called paramagnetic
substances. This property of substances is known as paramagnetism. (They have unpaired electrons)
Eg. Magnesium, Lithium
ii. Diamagnetism:
The substances which are repelled by the applied magnetic field are called diamagnetic substances.
This property of substances is known as diamagnetism. (They have paired electrons)
Eg. Copper, Silver, Gold

14
iii. Ferromagnetism:
The substances which exhibits permanent magnetism even when the magnetic field is removed are
called ferromagnetic substances. This property of substances is known as ferromagnetism.
Eg. Iron, Nickel, Cobalt

Q.53. Explain magnetic moment for transition elements and give formula for its calculation.
Ans: i. The magnetic moment of an electron is partly due to its orbital motion and partly due to its spin motion.
ii. In transition metal ions, the orbital magnetic moment is suppressed by the electrostatic field of other
atoms, ions or molecules surrounding the metal ion. Thus the effective magnetic moment arises
mainly from the spin of electrons.
iii. The expression for the effective magnetic moment is,
= n(n 2) + B.M
where n is number of unpaired electrons. B.M stand for Bohr magneton (unit of magnetic moment)
iv. Magnetic moment of a substance varies only with the number of unpaired electrons present.

Q.54. The d-electron configuration of Co
2+
and Cu
2+
is d
7
and d
9
respectively. Which one of these ions will be
more paramagnetic?
Ans: Co
2+
, (electronic configuration: 3d
7
)

contains three unpaired electrons while Cu
2+
, (electronic configuration:
3d
9
)

contains only one unpaired electron. More the unpaired electrons present, more paramagnetic is the
substance. So, Co
2+
is more paramagnetic.

Q.55. Why does Mn(II) ion show maximum paramagnetic character amongst bivalent ions of first
transition series?
Ans: The electronic configuration of Mn(II) ion (atomic number of Mn =25) is [Ar] 3d
5
4s
0

It has five unpaired electrons in its d-orbitals which is a maximum value among the first transition metal
ions. As the paramagnetic character is due to the presence of unpaired electron, Mn(II) ions shows
maximum paramagnetic character.

#Q.56. Why are zinc metal and Zn
++
ions diamagnetic?
Ans: The atomic number of zinc is 30 and the electronic configuration of Zn is [Ar] 3d
10
4s
2
and Zn
++
is
[Ar] 3d
10
. In zinc metal and Zn
++
all electrons are paired and hence they are diamagnetic.

Q.57. Calculate the magnetic moment of Fe
3+
ion (atomic number of Fe = 26).
Ans: Electronic configuration of Fe
3+
ion is [Ar] 3d
5
4s
0

So d-orbital has following distribution of electrons,

It has 5 unpaired electrons,
Magnetic moment,
= n(n 2) + = 5(5 2) + =5.9 B.M

Q.58. Calculate the magnetic moment of divalent ion in aqueous solution if its atomic number is 24.
Ans: With atomic number 24, the divalent ion in aqueous solution will have d
4
configuration (Four unpaired
electrons). The magnetic moment is
= 4(4 2) + =4.89 B.M

#Q.59. Calculate the Spin only magnetic moment of M
2+
(aq)
ion (Z = 26).
Ans: Atomic number =26
Electronic configuration of M atom =[Ar] 3d
6
4s
2
.
Electronic configuration of M
2+
=[Ar] 3d
6

So d-orbital has following distribution of electrons.

There are 4 unpaired electrons.

TARGET Publications
15
Spin only magnetic moment () = n(n 2) + B.M.
= 4(4 2) + B.M.
= 4.89 B.M.

Q.60.Calculate magnetic moment of Fe
2+
(aq)
ion (Z = 26) [March 2013]
Ans: Refer Q.59

Q.61. Calculate the Spin only magnetic moment of M
2+
(aq)
ion (Z = 27). (NCERT)
Ans: Atomic number =27
Electronic configuration of M atom =[Ar] 3d
7
4s
2
.
Electronic configuration of M
2+
=[Ar] 3d
7

So d-orbital has following distribution of electrons.

There are 3 unpaired electrons.
Spin only magnetic moment () = n(n 2) + B.M.
= 3(3 2) + B.M.
= 3.87 B.M.

Q.62. What are interstitial compounds? Why interstitial compounds are well known for transition metals?
(NCERT)
Ans: i. Interstitial compounds are those which are formed when small atoms like H, C, N, B etc. are trapped
inside the crystal lattice of metals.
They are generally non-stoichiometric and neither typically ionic, nor covalent.
ii. Most of the transition metals form interstitial compounds with small non-metals such as H, C, N, B
etc.
iii. These small atoms enter into the void sites between the packed atoms of crystalline transition metals
and form chemical bonds with transition metals.
Eg. steel and cast iron become hard by forming interstitial compound with carbon.
iv. The presence of vacant (n1) d orbitals in transition elements and their ability to make bonds with
trapped small atoms is the main cause of interstitial compound formation.

Q.63. State the characteristics of interstitial compounds.
Ans: Characteristics of interstitial compounds:
i. Their chemical properties are same as that of parent metal.
ii. These interstitial compounds are hard and show electrical and thermal conductivity and lustre.
iii. They have high melting points, higher than those of pure metals as the metal-nonmetal bonds are
stronger than metal-metal bonds in pure metals.
iv. Their densities are lesser than the parent metal.
v. Hydrides of transition metals are used as powerful reducing agents.
vi. The metallic carbides are chemically inert and extremely hard as diamond.

Q.64. Explain alloy formation in case of transition elements.
Ans: i. Alloys are formed by metals whose atomic radii differ by not more than 15% so that the atoms of one
metal can easily take up the positions in crystal lattice of the other.
ii. The transition metals have similar atomic radii and other characteristics, hence they form alloys very
readily. Alloys are generally harder, have high melting points and more resistant to corrosion than the
individual metals.
iii. The metals chromium, vanadium, molybdenum, tungsten and manganese are used in the formation of
alloy steels and stainless steels. Ferrous alloys are the most common alloys.
iv. Some alloys of transition metals with non-transition metals are also very common.
Eg. Brass (Cu +Zn) and Bronze (Cu +Sn)

16

8.4 Preparation and properties of K
2
Cr
2
O
7
and KMnO
4

Q.65. Indicate the steps involved in the preparation of K
2
Cr
2
O
7
from chromite ore (FeO.Cr
2
O
3
).
OR
How is potassium dichromate prepared from chrome iron?
Ans: Preparation of K
2
Cr
2
O
7
from chrome iron (FeO.Cr
2
O
3
):
Step I: Concentration of ore:
Powdered chromite ore is concentrated by washing with current of water in a hydraulic classifier. Lighter
gangue is carried away by water while the heavier chromite ore settles at the bottom thus resulting in its
separation.

Step II: Conversion of chromite ore into sodium chromate (Roasting):
Concentrated ore is mixed with soda ash (sodium carbonate) and lime stone (calcium carbonate) and
roasted with excess of air in reverberatory furnace. The mass turns yellow because of the formation of
sodium chromate. Lime stone is added to keep the mass porous so that the oxidation by air becomes easy.
4FeO.Cr
2
O
3
+O
2
2Fe
2
O
3
+4Cr
2
O
3

[2Cr
2
O
3
+4Na
2
CO
3
+3O
2
4Na
2
CrO
4
+4CO
2
] 2
______________________________________________
4FeO.Cr
2
O
3
+8Na
2
CO
3
+7O
2
2Fe
2
O
3
+8Na
2
CrO
4
+8CO
2

Roasted mass is extracted with water. Sodium chromate goes into solution and insoluble substances are
separated by filtration.
Step III: Conversion of sodium chromate into sodium dichromate:
The filtrate containing sodium chromate solution is treated with concentrated sulphuric acid during which
sodium chromate is converted into sodium dichromate.
2Na
2
CrO
4
+H
2
SO
4
Na
2
Cr
2
O
7
+Na
2
SO
4
+H
2
O
Sodium (conc.) Sodium
chromate dichromate
Sodium sulphate being less soluble crystallizes out as decahydrate, Na
2
SO
4
.10H
2
O and is removed. The
crystals are separated by filtration and concentrated solution of sodium dichromate is obtained.

Step IV: Conversion of sodium dichromate into potassium dichromate:
Hot concentrated solution of sodium dichromate is treated with calculated amount of potassium chloride.
Double decomposition takes place forming potassium dichromate and sodium chloride.
Na
2
Cr
2
O
7
+2KCl K
2
Cr
2
O
7
+2NaCl
Sodium Potassium
dichromate dichromate

The solution is concentrated and the hot solution is cooled. The less soluble potassium dichromate separates
as orange red crystals which is separated by filtration and purified by recrystallization, while sodium
chloride remains in the solution.

Q.66. State properties of K
2
Cr
2
O
7
.
Ans: Properties of K
2
Cr
2
O
7
:
i. Physical properties:
It is orange colored crystalline solid, soluble in water (readily soluble in hot water) and melts at 669 K.
ii. Action of alkali:
When potassium hydroxide solution is added to orange red coloured solution of potassium
dichromate, a yellow coloured solution of potassium chromate is obtained.
K
2
Cr
2
O
7
+ 2KOH 2K
2
CrO
4
+ H
2
O
Potassium Potassium
dichromate chromate

TARGET Publications
17
iii. Oxidizing properties:
K
2
Cr
2
O
7
is a powerful oxidising agent in acidic medium where dichromate is reduced to chromium
sulphate. Its oxidizing action can be represented as

2
2 7
Cr O

+14 H
+
+6e
2Cr
3+
+7H
2
O
a. Action on ferrous sulphate:
In acidic medium potassium dichromate oxidizes ferrous sulphate to ferric sulphate, potassium
dichromate is reduced to chromic sulphate.
K
2
Cr
2
O
7
+ 4H
2
SO
4
K
2
SO
4
+ Cr
2
(SO
4
)
3
+ 4H
2
O + 3(O)
[2FeSO
4
+(O) +H
2
SO
4
Fe
2
(SO
4
)
3
+H
2
O] 3

K
2
Cr
2
O
7
+6FeSO
4
+7H
2
SO
4
K
2
SO
4
+ Cr
2
(SO
4
)
3
+ 3Fe
2
(SO
4
)
3
+7H
2
O

b. Action on potassium iodide:
Acidified potassium dichromate oxidizes potassium iodide to iodine.
K
2
Cr
2
O
7
+6KI +7H
2
SO
4
4K
2
SO
4
+ Cr
2
(SO
4
)
3
+ 7H
2
O +3I
2

liberated Iodine turns the solution brown.
c. Action on hydrogen sulphide:
It oxidizes H
2
S to a pale yellow precipitate of sulphur. Potassium dichromate is reduced to
chromic sulphate and the orange colour of the solution turns green.
K
2
Cr
2
O
7
+4H
2
SO
4
+3H
2
S K
2
SO
4
+Cr
2
(SO
4
)
3
+7H
2
O +3S
d. Action on sulphur dioxide:
It oxidizes sulphur dioxide to sulphuric acid. Potassium dichromate is reduced to chromic
sulphate and the orange colour of the solution turns green.
K
2
Cr
2
O
7
+3SO
2
+H
2
SO
4
K
2
SO
4
+Cr
2
(SO
4
)
3
+H
2
O
e. Action on alcohols:
Primary and secondary alcohols are oxidized to aldehyde and ketones respectively. Aldehydes
are further oxidized to carboxylic acids.
CH
3
CH
2
OH +(O) CH
3
CHO + H
2
O
Ethyl alcohol Acetaldehyde
CH
3
CHO +(O) CH
3
COOH
Acetaldehyde Acetic acid
CH
3
CHOH CH
3
+(O) CH
3
CO CH
3
+H
2
O
Isopropyl alcohol Acetone

iv. Formation of chromyl chloride (CrO
2
Cl
2
):
When a mixture of potassium dichromate crystals and sodium chloride (or KCl) is heated with
concentrated sulphuric acid, red vapours of chromyl chloride is evolved. On condensing, it gives oily
red liquid.
K
2
Cr
2
O
7
+6H
2
SO
4
+4NaCl 2KHSO
4
+4NaHSO
4
+ 2CrO
2
Cl
2
+3H
2
O

Q.67. Describe the oxidizing action of potassium dichromate and write the ionic equations for its
reaction with: (NCERT)
a. iodide b. iron (II) solution c. H
2
S.
Ans: Potassium dichromate, K
2
Cr
2
O
7
is a strong oxidizing agent and is used as a primary standard in volumetric
analysis involving oxidation of iodides, ferrous ion and S
2-
ions etc.
a. It oxidizes potassium iodide to iodine.
K
2
Cr
2
O
7
+6KI +7H
2
SO
4

4K
2
SO
4
+Cr(SO
4
)
3
+7H
2
O +3I
2
.
b. It oxidizes iron (II) salt to iron (III) salt
K
2
Cr
2
O
7
+6FeSO
4
+7H
2
SO
4
K
2
SO
4
+Cr
2
(SO
4
)
3
+3Fe(SO
4
)
3
+7H
2
O
c. It oxidizes H
2
S to S
K
2
Cr
2
O
7
+4H
2
SO
4
+3H
2
S K
2
SO
4
+Cr(SO
4
)
3
+7H
2
O +3S

18
Q.68. Explain structure of chromate ion and dichromate ion.
Ans: Structure of chromate and dichromate ions

The chromate ion is tetrahedral whereas the dichromate ion consists of two tetrahedral sharing one corner
with the CrOCr bond angle of 126.
Q.69. State the uses of potassium dichromate.
Ans: Uses of K
2
Cr
2
O
7
:
K
2
Cr
2
O
7
is used
i. in volumetric analysis, as a primary standard for the estimation of Fe
2+
(ferrous ions) and I
(iodides)
in redox titrations.
ii. in the manufacture of chromium compounds such as lead chromate and chrome alum.
iii. in calico printing and dyeing.
iv in photography and in hardening gelatine film.
v. as an oxidising agent.
vi. in the detection of chloride ion by chromyl chloride test.
vii. in the manufacture of pigments and in the manufacture of inks.

Q.70. Indicate the steps involved in the preparation of KMnO
4
from pyrolusite ore (MnO
2
) (NCERT)
OR
How is potassium permanganate prepared from pyrolusite ore?
Ans: Preparation of KMnO
4
from pyrolusite ore (MnO
2
):
Step I: Conversion of MnO
2
into potassium manganate.
The finely powdered pyrolusite mineral is fused with potassium hydroxide or potassium carbonate in the
presence of air or oxidising agent such as potassium nitrate or potassium chlorate giving green coloured
potassium manganate.
2MnO
2
+ 4KOH + O
2
2K
2
MnO
4
+ 2H
2
O
Potassium
manganate
2MnO
2
+ 2K
2
CO
3
+ O
2
2K
2
MnO
4
+ 2CO
2
MnO
2
+ 2KOH + KNO
3
K
2
MnO
4
+ KNO
2
+ H
2
O
3MnO
2
+ 6KOH + KClO
3
3K
2
MnO
4
+ KCl + 3H
2
O

The fused mass obtained containing K
2
MnO
4
is treated with water and then converted into KMnO
4
either
by oxidation or by electrolysis.

Step II: Oxidation of potassium manganate to potassium permanganate.
There are two methods for oxidation of potassium manganate,
a. Chemical oxidation:
Oxidation of K
2
MnO
4
to KMnO
4
, disproportionation is carried out by H
2
SO
4
, by passing CO
2
or Cl
2

or O
3
through the solution.
3K
2
MnO
4
+2H
2
SO
4
2K
2
SO
4
+2KMnO
4
+2H
2
O

+MnO
2

3K
2
MnO
4
+4CO
2
+2H
2
O 2KMnO
4
+MnO
2
+4KHCO
3

2K
2
MnO
4
+Cl
2
2KMnO
4
+2KCl
2K
2
MnO
4
+H
2
O +O
3
2KMnO
4
+2KOH +O
2

The carbon dioxide process is uneconomical as one third of the original manganate is reconverted to
manganese dioxide. However, this process has the advantage that the potassium carbonate formed as
a byproduct can be used for the oxidative fusion of manganese dioxide. In the chlorine process,
potassium chloride obtained as a byproduct is lost.
O
Cr
O
O
O
Cr
O
O
O
126
2
O
Cr
O
O
O
2
Chromate ion Dichromate ion

TARGET Publications
19
b. Electrolytic oxidation:
For manufacturing potassium permanganate commercially, the method of electrolytic oxidation is
preferred. The alkaline manganate solution obtained in step (I) is electrolysed between iron electrodes
separated by diaphragm. The reactions taking place are as follows:
K
2
MnO
4

2K
+
+
2
4
MnO

H
2
O
H
+
+OH

At anode:
2
4
MnO

4
MnO
+e

At cathode: 2H
+
+2e
H
2
Thus, manganate ions are oxidized to permanganate at the anode and hydrogen gas is liberated at the
cathode.
2K
2
MnO
4
+H
2
O +O K
2
MnO
4
+2KOH
After the oxidation is complete, the solution is filtered and evaporated under controlled conditions to
obtain the deep purple black crystals of potassium permanganate.
Note:
Laboratory Preparation:
In the laboratory, potassium permanganate is prepared by oxidation of manganese (II) ion salt by
peroxodisulphate.
2Mn
2+
+
2
2 8
5S O

+ 8H
2
O
4
2MnO
+
2
4
10SO

+ 16H
+
Peroxodisulphate Permanganate
ion ion
Q.71. State the properties of KMnO
4
.
Ans: Properties of KMnO
4
:
i. Physical properties:
It is a deep purple crystalline solid, moderately soluble in water at room temperature and it is more
soluble in hot water.
ii. KMnO
4
when heated to 473 K, readily decomposes giving oxygen.
2KMnO
4

heat
K
2
MnO
4
+MnO
2
+O
2

At red heat, potassium permanganate decomposes into potassium manganate (K
2
MnO
3
) and oxygen.
2K
2
MnO
4

Redheat
2K
2
MnO
3
+O
2

iii. With well cooled conc H
2
SO
4
, KMnO
4
gives Mn
2
O
7
, which on warming decomposes to MnO
2
.
2KMnO
4
+2H
2
SO
4

Mn
2
O
7
+2KHSO
4
+H
2
O
2Mn
2
O
7
4MnO
2
+3O
2
With warm conc. H
2
SO
4
, O
2
gas is evolved.
4KMnO
4
+6H
2
SO
4
2K
2
SO
4
+4MnSO
4
+6H
2
O +5O
2
iv. Solid KMnO
4
when heated in current of H
2,
gives KOH, MnO and water vapours.
2KMnO
4
+5H
2

2KOH +2MnO +4H

2
O
v. KMnO
4
is a powerful oxidising agent.
a. In neutral medium:
2KMnO
4
+H
2
O 2KOH +2MnO
2
+3[O]
MnO
4
+2H
2
O +3e
MnO
2
+4OH

Manganous salt is oxidised to MnO
2
;
2KMnO
4
+3MnSO
4
+2H
2
O 5MnO
2
+K
2
SO
4
+2H
2
SO
4

b. In alkaline medium:
2KMnO
4
+2KOH 2K
2
MnO
4
+H
2
O +[O] or
MnO
4
+ e
MnO
4
2

In the presence of a reducing agent, K
2
MnO
4
is further reduced to manganese dioxide.
K
2
MnO
4
+H
2
O MnO
2
+2KOH +O or
MnO
4
2
+ 2H
2
O +2e
MnO
2
+4OH

Hence the complete equation can be written as:
MnO
4
+2H
2
O +3e
MnO
2
+4OH

20
c. In acidic medium:
In the presence of dil. H
2
SO
4
, it acts as oxidizing agent because of the reaction
2KMnO
4
+3H
2
SO
4
K
2
SO
4
+2MnSO
4
+3H
2
O +5[O] or
MnO
4
+8H
+
+5e
Mn
2+
+4H
2
O

Q.72. How does acidified permanganate solution react with
i. iron (II) ions ii. SO
2
iii. oxalic acid? (NCERT)
Ans: i. Acidified permanganate solution oxidizes iron (II) salt to iron (III) salts.
2MnO
4
2
+16H
+
+10Fe
2+
2Mn
2+
+8H
2
O +10Fe
3+

ii. It oxidizes sulphur dioxide to sulphuric acid.
2MnO
4

+5SO
2
+2H
2
O 5SO
4
2
+2Mn
2+
+4H
+

iii. It oxidizes oxalic acid to CO
2
and H
2
O.
2MnO
4
+16H
+
+ 5C
2
O
4
2
2Mn
2+
+8H
2
O +10CO
2

Q.73. Explain the structures of manganate and permanganate ion.
Ans: Structures of manganate and permanganate ion:
The manganate and permanganate ions have tetrahedral structures. The manganate ion is green in colour
and is paramagnetic with one unpaired electron while the permanganate ion is purple in colour and is
diamagnetic.
The -bonding takes place by overlap of p-orbitals of oxygen with d-orbitals of manganese.

Q.74. What is meant by disproportionation? Give two examples of disproportionation reaction in aqueous
solution. (NCERT)
Ans: Sometimes transition metal species in same oxidation state undergo a chemical change in such a way that
some species get oxidized and some other get reduced.
Eg. Cr (V) and Mn (VI) species undergo disproportionation reaction in acidic medium as follows:
3CrO
4
3
+ 8H
+
2CrO
4
2
+ Cr
3+
+ 4H
2
O
(Cr in +5 o.s.) (Cr in +6 o.s.) (Cr in +3 o.s.)
3MnO
4
2
+ 4H
+
2MnO
4
+ MnO
2
+ 2H
2
O
(Mn in +6 o.s.) (Mn in +7 o.s.) (Mn in +4 o.s.)
Cr in +5 oxidation state undergo disproportionation into its +6 and +3 states. Similarly Mn in +6 oxidation
state undergoes disproportionation into +7 and +4 oxidation states.
Q.75. State the uses of potassium permanganate.
Ans: Uses of KMnO
4
: KMnO
4
is used
i. in volumetric analysis for the estimation of ferrous salts, oxalates, iodides and hydrogen peroxide.
ii. as a strong oxidising agent in the laboratory as well as an effective oxidising agent in organic
synthesis. Alkaline potassium permanganate is used for testing unsaturation in organic compounds
and is known as Baeyers reagent.
iii. as a disinfectant and germicide. A very dilute solution of permanganate is used for washing wounds
and gargling for mouth sore. It is also used for purifying water of stinking wells.
iv. for bleaching of wool, cotton, silk and other textile fibres because of its strong oxidizing power and
also for decolourisation of oils.

*Q.76. Write the preparation, properties and uses of potassium permanganate.
Ans: Refer Q.70, 71 and 75
O

O
Tetrahedral
permanganate
(purple) ion
O
Mn
O
O
MnO
4
Mn
O
O
O

Tetrahedral
Manganate
(green) ion
MnO
4
2

TARGET Publications
21
f-Block elements

8.5 General Introduction and Electronic Configuration

*Q.77. What are f-block elements?
Ans: i. The elements in which the last electron enters into (n2) f-orbital of the atoms are called f-block
elements.
ii. In these elements, the last electron enters in to the prepenultimate (n2) shell (called
antepenultimate).
iii. The general electronic configuration is:
(n2)f
114
(n1)d
01
ns
2
.

*Q.78. Explain the meaning of inner transition series.
OR
What are inner-transition elements?
Ans: i. The last electron in the f-block elements enters into (n2) f-orbitals, i.e. inner to the penultimate
energy level and they form a transition series within the transition series (d-block elements). Hence
the f-block elements are known as inner transition series.
ii. There are two series of inner transition elements:
a. Lanthanoids (58-71) and
b. Actinoids (90-103).

Q.79. What are rare earth elements?
Ans: Rare earth elements are a collection of seventeen chemical elements in the periodic table, namely scandium,
yttrium and the fifteen lanthanoids (4f-series). They are originally isolated as oxides and are referred as
earths and rare because of their isolation from relatively rare minerals.

Q.80. Write the general electronic configuration of 4f and 5f series elements. [March 2013]
Ans: General electronic configuration
4f series [Xe]4f
1 14
5d
0 1
6s
2

5f series [Rn]5f
1 14
6d
0 1
7s
2

8.6 Lanthanoids

Q.81. Define lanthanoids.
Ans: The series involving the filling of 4f-orbitals following lanthanum La (Z = 57) is called lanthanoid series.
The elements present in this series are called lanthanoids.

*Q.82. Explain the position of lanthanoids in the periodic table.
Ans: Position of lanthanoids in the periodic table:
i. The 14 elements (from 58 to 71) of lanthanoid series have been placed along with lanthanum
(at no. 57) in the IIIB group (3
rd
column) and sixth period of the periodic table.
ii. In the periodic table, as we move from one element to other, either from left to right or from top to
bottom, the properties exhibit a gradual change. But these fifteen are so similar to one another, that
they cannot be placed one after the other or one below the other.
iii. As the fourteen elements i.e. Ce(58) to Lu(71) are closely similar to La(57), the best place for them is
along with Lanthanum (La) i.e. IIIB group (3
rd
column) and sixth period in the periodic table.
iv. In case, these elements are given different position in order of their increasing atomic numbers, the
symmetry of the periodic table would be disrupted.
v. Due to this reason, the lanthanoids are placed at the bottom of the periodic table with a reference to the
IIIB group in the sixth period.

22

IA IIA VIIIA
1 2 IIIA IVA VA VIA VIIA 18
13 14 15 16 17

IIIB IVB VB VIB VIIB VIIIB IB IIB

3 4 5 6 7 8 9 10 11 12

La *
Ac
*
*

*
Lanthanoids
58
Ce
59
Pr
60
Nd
61
Pm
62
Sm

Eu

67
Ho
68
Er
69
Tm
70
Yb
71
Lu
**
Actinoids
90
Th
91
Pa
92
U
93
Np
94
Pu
95
Am
96
Cm
97
Bk
98
Cf
99
Es
100
Fm
101
Md
102
No
103
Lr

Q.83. Briefly explain why electronic configurations of lanthanoids are not known with certainty.
Ans: In the lanthanoids, 4f and 5d subshells are very close in energy. The outermost 6s-orbital remains filled
with two electrons (6s
2
). The electrons can easily jump from 4f to 5d or vice-versa. Further, irregularities in
electronic configurations are also related to the stabilities of f
0
, f
7
and f
14
occupancy of f-orbitals. Hence,
their electronic configurations are not known with certainty.

Q.84. State the general electronic configuration of 4f-series (lanthanoids).
Ans: Electronic configuration of 4f-series:
The elements of 4f-series begin from La to Lu.
The electronic configuration of these elements can be expressed in terms of its nearest inert gas Xe (54).
Electronic configuration of Xe (54) =1s
2
2s
2
2p
6
3s
2
3p
6
3d
10
4s
2
4p
6
4d
10
5s
2
5p
6

Therefore, general electronic configuration of 4f-series is [Xe] 4f
1-14
5d
0-1
6s
2
.

Element Symbol
Atomic
Number
Expected electronic
configuration
Observed electronic
configuration
Lanthanum La 57 [Xe] 4f
0
5d
1
6s
2
[Xe] 4f
0
5d
1
6s
2

Cerium Ce 58 [Xe] 4f
1
5d
1
6s
2
[Xe] 4f
2
5d
0
6s
2

Praseodymium Pr 59 [Xe] 4f
2
5d
1
6s
2
[Xe] 4f
3
5d
0
6s
2

Neodymium Nd 60 [Xe] 4f
3
5d
1
6s
2
[Xe] 4f
4
5d
0
6s
2

Promethium Pm 61 [Xe] 4f
4
5d
1
6s
2
[Xe] 4f
5
5d
0
6s
2

Samarium Sm 62 [Xe] 4f
5
5d
1
6s
2
[Xe] 4f
6
5d
0
6s
2

Europium Eu 63 [Xe] 4f
6
5d
1
6s
2
[Xe] 4f
7
5d
0
6s
2

Gadolinium Gd 64 [Xe] 4f
7
5d
1
6s
2
[Xe] 4f
7
5d
1
6s
2

Terbium Tb 65 [Xe] 4f
8
5d
1
6s
2
[Xe] 4f
9
5d
0
6s
2

Dysprosium Dy 66 [Xe] 4f
9
5d
1
6s
2
[Xe] 4f
10
5d
0
6s
2

Holmium Ho 67 [Xe] 4f
10
5d
1
6s
2
[Xe] 4f
11
5d
0
6s
2

Erbium Er 68 [Xe] 4f
11
5d
1
6s
2
[Xe] 4f
12
5d
0
6s
2

Thulium Tm 69 [Xe] 4f
12
5d
1
6s
2
[Xe] 4f
13
5d
0
6s
2

Ytterbium Yb 70 [Xe] 4f
13
5d
1
6s
2
[Xe] 4f
14
5d
0
6s
2

Lutetium Lu 71 [Xe] 4f
14
5d
1
6s
2
[Xe] 4f
14
5d
1
6s
2

Mnemonic:
Lazy College Professors Never Produce Superior Excellent Graduates To Dramatically Help Executives Trim
Yearly Losses.
Transition Elements
INNER TRANSITION ELEMENTS
s
-
b
l
o
c
k

e
l
e
m
e
n
t
s

d-block elements
p-block elements
63 64
Gd
65
Tb
f-block elements
66
Dy
1
2
3
4
5
6
7
P
E
R
I
O
D
S

TARGET Publications
23
Q.85. Write down the electronic configuration of
i. Pm
3+
ii. Ce
4+
iii. Lu
2+
(NCERT)
Ans: i. Pm
3+
=1s
2
2s
2
2p
6
3s
2
3p
6
3d
10
4s
2
4p
6
4d
10
4f
4
5s
2
5p
6
.

ii. Ce
4+
=1s
2
2s
2
2p
6
3s
2
3p
6
3d
10
4s
2
4p
6
4d
10
5s
2
5p
6
.

iii. Lu
2+
=1s
2
2s
2
2p
6
3s
2
3p
6
3d
10
4s
2
4p
6
4d
10
4f
14
5s
2
5p
6
5d
1
.

Q.86. Why lanthanum, gadolinium and lutetium show different electronic configurations?
Ans: i. It is observed that lanthanum, gadolinium and lutetium show different electronic configuration
because the 5d and 4f-orbitals are nearly of the same energy and the distinction between the two is
difficult.
ii. Due to this, some extra stability is achieved when the 4f is half-filled and completely filled so the
next electron goes in 5d-orbital instead of 4f-orbital.

Q.87. State the features of electronic configuration for lanthanoids.
Ans: Features of electronic configuration of lanthanoids:
i. Electronic configuration of Ba (Z =56) is [Xe] 6s
2
.
ii. Lanthanum has electronic configuration [Xe] 4f
0
5d
1
6s
2
. It does not have any 4f electrons.
iii. The next incoming electron after lanthanum does not enter into 5d-subshell but enters into 4f-
subshell.
iv. As atomic number increases successively by one unit from La to Lu, the fourteen electrons are filled
in the 4f-subshell progressively.
v. Elements La, Gd and Lu possess single electron in 5d-subshell. In case of other lanthanoids 5d-orbital
is empty.
vi. In idealised electronic configuration filling up of 4f-orbitals is regular. In observed electronic
configuration filling of 4f-orbitals is not regular. Observed configuration involves moving of the
single electron from 5d to 4f sub-shell.
vii. f
0
, f
7
, f
14
electronic configurations achieve extra stability due to empty, half filled and completely
filled f-orbitals respectively.
Eg. La(4f
0
), Gd (4f
7
) and Lu (4f
14
).
viii. The 4f electrons in pre-penultimate i.e. (n2) shell are totally shielded by higher outer orbitals.

Q.88. Explain the trends in atomic and ionic sizes of lanthanoids
Ans: Trends in atomic and ionic sizes of lanthanoids:
i. In the lanthanoid series, with increasing atomic number, the atomic and ionic radii decrease from one
element to another but the decrease is very small.
ii. For example, on moving from Ce to Lu, the atomic radius decreases from 183 pm to 173 pm and the
decrease is only 10 pm.
iii. Similarly, the ionic radius decreases from 103 pm to 85 pm on moving from Ce
3+
to Lu
3+
ions and the
decrease is only 18 pm.
iv. Thus, for an increase of atomic number 14, the decrease in atomic radii or ionic radii are very small
i.e., only 10 pm and 18 pm respectively in comparison to elements of other groups and periods,.
v. The steady decrease in atomic and ionic sizes of lanthanoid elements with increasing atomic number
is called lanthanoid contraction.

*Q.89. Explain, the trends in atomic and ionic sizes of lanthanoids.
Ans: Refer Q.88.

*Q.90. Explain the oxidation states of lanthanoids.
Ans: i. All lanthanoids exhibit a common stable oxidation state of +3.
ii. In addition, some lanthanoids show +2 and +4 oxidation states also.
iii. These are shown by those elements which by doing so attain the stable f
0
, f
7
or f
14
configurations i.e.
empty, half-filled and completely filled 4f sub-shells.
Eg. Ce and Tb exhibit +4 oxidation states, Eu and Yb exhibit +2 oxidation states, La, Gd and Lu
exhibit only +3 oxidation states.

24
Oxidation states of Lanthanoids are as shown in following table:

Element Outer electronic
configuration
Oxidation states
M
2+
M
3+
M
4+

Lanthanum 4f
0
5d
1
6s
2
- 3+ -
Cerium 4f
2
5d
0
6s
2
- 3+ 4+
Praseodymium 4f
3
5d
0
6s
2
- 3+ 4+
Neodymium 4f
4
5d
0
6s
2
2+ 3+ 4+
Promethium 4f
5
5d
0
6s
2
- 3+ -
Samarium 4f
6
5d
0
6s
2
2+ 3+ -
Europium 4f
7
5d
0
6s
2
2+ 3+ -
Gadolinium 4f
7
5d
1
6s
2
- 3+ -
Terbium 4f
9
5d
0
6s
2
- 3+ 4+
Dysprosium 4f
10
5d
0
6s
2
- 3+ 4+
Holmium 4f
11
5d
0
6s
2
- 3+ -
Erbium 4f
12
5d
0
6s
2
- 3+ -
Thullium 4f
13
5d
0
6s
2
2+ 3+ -
Ytterbium 4f
14
5d
0
6s
2
2+ 3+ -
Lutetium 4f
14
5d
1
6s
2
- 3+ -

Q.91. Explain why Eu and Yb show oxidation state +2.
Ans: i. In the +2 oxidation state, Eu donates two electrons from its 6s-orbitals making 4f-orbitals half-filled
i.e. 4f
7
which is a more stable state than partially filled.
ii. Similarly in the +2 oxidation state, Yb donates two electrons from its 6s-orbitals making 4f-orbitals
completely filled i.e. 4f
14
which is more stable than partially filled state.
Therefore Eu and Yb show +2 oxidation states.

Q.92. La, Gd and Lu show only +3 oxidation state. Explain.
Ans: i. The electronic configuration of
57
La,
64
Gd and
71
Lu in +3 oxidation state are as follows:
La
+3
: [Xe] 4f
0

Gd
+3
: [Xe] 4f
7

Lu
+3
: [Xe] 4f
14
.
ii. f-orbital acquires extra-stability when it is half filled or completely filled. Hence, La, Gd and Lu
exhibit only +3 oxidation state.

Q.93. 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. (NCERT)
Ans: +4 =Ce, Pr, Nd, Tb, Dy
+2 =Nd, Sm, Eu, Tm,Yb
+2 oxidation state is exhibited when the lanthanoid has the configuration 5d
0
6s
2
so that 2 electrons
are easily lost. +4 oxidation state is exhibited when the configuration left is close to 4f
0
(Eg. 4f
0
, 4f
1
,
4f
2
) or close to 4f
7
(Eg. 4f
7
or 4f
8
)

*Q.94. Why do lanthanoids form coloured compounds?
Ans: Unpaired electrons are present in the outermost 4f subshell of lanthanoid ions. Therefore, they can undergo
f-f transitions and hence form coloured compounds.

TARGET Publications
25
*Q.95. Explain why Gd
3+
is colourless.
Ans: i. Gd
3+
has electronic configuration [Xe] 4f
7
.
ii. Lanthanoids show colour due to partially filled f orbitals which allow f-f transitions.
iii. Gd
3+
ion has exactly half filled electronic electronic configuration. So, electrons for f-f transition are
absent due to which it is colourless.

Q.96. Explain the chemical reactivity of lanthanoids.
Ans: i. Carbides:
When lanthanoids are heated around 2500 C with carbon, they form carbides having formulae
Ln
3
C, LnC
2
and Ln
2
C
3

Ln +C
2500 C
Lanthanoid carbide

ii. Hydrides:
The metals combine with hydrogen when gently heated in the hydrogen gas.
4Ln +3H
2

2LnH
3

iii. Oxides:
When burnt in oxygen, they forms oxides, with formula Ln
2
O
3
.
2Ln +3O
2

2Ln
2
O
3

The oxide Ln
2
O
3
reacts with water to form insoluble hydroxides.
Ln
2
O
3
+3H
2
O 2Ln(OH)
3
and with CO
2
they form carbonates.
Ln
2
O
3
+3CO
2
Ln
2
(CO
3
)
3

iv. Reaction with nitrogen:
On heating with nitrogen they form nitrides.
2Ln +N
2

2LnN

v. Reaction with mineral acids:
Lanthanoids when treated with mineral acids liberate H
2
gas as they have reduction potential of 2.0
to 2.4V
2Ln +6HCl 2LnCl
3
+3H
2

vi. Reaction with water:
When treated with water they form consequently hydroxides and liberates H
2
gas. The hydroxides are
ionic and basic in nature.
Ln +3H
2
O Ln(OH)
3
+3H
2

vii. Reaction with sulphur:
Heating lanthanoids with sulphur forms corresponding sulphides
2Ln +3S Ln
2
S
3

Q.97. Write a short note on lanthanoid contraction.
Ans: Lanthanoid contraction:
i. The atomic and ionic radii of lanthanoids show gradual decrease with increase in atomic number. It
is known as Lanthanoid contraction.
ii. In Lanthanoids, after Lanthanum (La), the electrons are added to prepenultimate shell i.e. 4f-orbital.
iii. There are 14 Lanthanoids from Ce to Lu.
iv. For each electron, one proton is also added to the nucleus of the atom of the element. Hence from Ce
to Lu as atomic number increases, nuclear charge increases, therefore nuclear attraction increases.
v. As atomic number increases, atomic volume or radius decreases as observed with all the elements
along the period.
vi. But in case of Lanthanoids this decrease in atomic volume or radius is comparatively very small. This
is explained in terms of Lanthanoid contraction.

26
Q.98. Explain the causes of the lanthanoid contraction.
Ans: i. As the atomic number of the members of lanthanoids
series increases, the positive charge on nucleus
increases by +1 unit and one more electron enters in
the same 4f subshell.
ii. There is inadequate shielding of one electron by
another electron in the same 4f subshell.
iii. The extent of shielding for electrons is less in 4f
subshell as compared to electrons in d subshell, 4f
valence shell have diffused shapes. Due to which
with increase of nuclear charge the valence shell is
pulled slightly towards nucleus.
iv. Because of this pull, the size of M
3+
ions goes on
decreasing with increase in atomic number. However
decrease in size is very small.
v. In the complete f series only 10 pm decrease in atomic radii and 18 pm decrease in ionic radii is
observed.
vi. The graph indicates lathanoid contraction of various lanthanoids.
vii. Though the contraction in size from one element to another is very small, the net contraction over the
fourteen elements from Ce to Lu is appreciable.
viii. Atomic radii show some irregularities but ionic radii decrease steadily from La to Lu.

Q.99. Explain the effects of lanthanoid contraction.
Ans: i. Decrease in Basicity:
a. Because of lanthanoid contraction size of lanthanoid ions decreases regularly with increase in
atomic number. As a result of decrease in size, the covalent character between lanthanoids ion
and OH
ions increases from La

3+
to Lu
3+
.
b. The ionic character of MOH bond decreases and covalent character of MOH bond gradually
increases.Therefore, the basic strength of the hydroxides decreases with increase in atomic
number. Thus, Lu(OH)
3
is least basic while La(OH)
3
is most basic.
c. Basicity and Ionic character of hydroxides decreases in the order of
La(OH)
3
>Ce(OH)
3
>.. Lu(OH)
3
.
ii. Ionic radii of post lanthanoids :
The elements which follow the lanthanoids in the third transition series are known as post-
lanthanoids. There is a regular increase in size from Sc to Y to La. Similarly there will be increase in
size in other groups as:
Ti Zr Hf
V Nb Ta
But after the lanthanoids the increase in radii from second to third transition series almost vanishes.
Pairs of elements such as ZrHf (group 4), NbTa (group 5), MoW (group 6) and Tc-Re (group 7)
possess almost same size. These pair of elements are called chemical twins. The properties of these
elements are also similar. So due to lanthanoid contraction elements of second and third series
resemble each other.
iii. Similarity among lanthanoids:
Lanthanoids show very small change in radii so their chemical properties are quite similar. Thus it is
very difficult to separate the elements in pure state.

*Q.100. What are chemical twins elements? Give their examples.
Ans: A pair of elements having similar properties due to similar atomic radii and almost same size are called
chemical twin elements.
This effect arises due to lanthanoid contraction.
Eg: Zr and Hf; Nb and Ta; Mo and W; Tc and Re are a pair of chemical twins elements.
85
90
95
100
105
110
57
59
61 63 65 67 69 71
Lu
3+
Yb
3+
Tm
3+
Er
3+
Ho
3+
Dy
3+
Tb
3+
Gd
3+
Eu
3+
Sm
3+
Pm
3+
Nd
3+
Pr
3+
Ce
+3
La
3+
Atomic number
I
o
n
i
c

r
a
d
i
u
s

(
i
n

p
m
)

TARGET Publications
27
Q.101. Write a short note on uses of lanthanoids.
Ans: Uses of lanthanoids:
i. Lanthanoids do not find any use in the pure state. The most important use of lanthanoids is in the
production of alloy steels to improve the strength and workability of steel.
ii. Their oxides (Eg. La
2
O
3
) are used in glass industry, for polishing glass and for making coloured
glasses for goggles as they give protection against UV light and as phosphor for television screens and
similar fluorescing surfaces. Mixed oxides of lanthanoids are used as catalysts in petroleum cracking.
iii. Because of their paramagnetic and ferromagnetic properties, their compounds are used in making
magnetic and electronic devices.
iv. Ceric sulphate is a well known oxidizing agent in volumetric analysis.

Q.102. What is Misch metal? Give its one use.
Ans: Misch metal is an alloy of a lanthanoid metal and iron and traces of S, Ca, C or Al. It is used in making
bullets and lighter flint.

8.7 Actinoids

*Q.103. What are actinoids?
Ans: The series of elements from Thorium (Z = 90) to Lawrencium (Z = 103) in which 5f orbitals are
progressively filled are called actinoids.
The elements are called actinoid because many physical and chemical properties are similar to actinium.

Note:
Actinium (Z =89) has electronic configuration [Rn] 5f 6d
1
7s
2
. There is no electron in 5f orbital.

*Q.104. What are trans-uranic elements? Write their names. [March 2013 old course]
Ans: The man made elements having atomic number higher than Uranium-92 are collectively called as trans-
uranic elements. Elements from Rf(Z =104) to Uub (Z =112) have been identified. Elements upto atomic
number 118 are also synthesized as shown in the table given below:

Sr.
No
Name Symbol
Atomic
Number
Sr.
No
Name Symbol
Atomic
number
1. Neptunium Np 93 14. Seaborgium Sg 106
2. Plutonium Pu 94 15. Bohrium Bh 107
3. Americium Am 95 16. Hassium Hs 108
4. Curium Cm 96 17. Meitnerium Mt 109
5. Berkelium Bk 97 18. Darmstadtium Ds 110
6. Californium Cf 98 19. Rontgenium/Unununium Rg/Uuu 111
7. Einsteinium Es 99 20. Copernicium/Ununbium Cn/Uub 112
8. Fermium Fm 100 21. Ununtrium Uut 113
9. Mendelevium Md 101 22. Ununquadium Uuq 114
10. Nobelium No 102 23. Ununpentium Uup 115
11. Lawrencium Lr 103 24. Ununhexium Uuh 116
12. Rutherfordium Rf 104 25. Ununseptium Uus 117
13. Dubnium Db 105 26. Ununoctium Uuo 118

*Q.105. Explain the position of actinoids in the periodic table.
Ans: Position of actinoids in the periodic table.
i. Actinoids belongs to the IIIB group of periodic table in the seventh period.
ii. In the periodic table, as we move from one element to another, either from left to right or from top to
bottom, the properties exhibit a gradual change. But these fifteen elements are so similar to one
another, that they cannot be placed one after the other or one below the other.
iii. As the fourteen elements i.e. Th(90) to Lr(103) are closely similar to Ac(89), the best place for them
is along with actinium(89) i.e. IIIB group (3
rd
column) and seventh period in the periodic table.

28
iv. In case these elements are give different positions in order of their increasing atomic numbers, the
symmetry of the periodic table would be disrupted. Due to this reason, the actinoids are placed at the
bottom of the periodic table with a reference to the IIIB group in the seventh period i.e the position of
actinium.
For position refer figure shown in Q. 82

Q.106. Explain the electronic configuration of actinoids.
Ans: Electronic configuration of actinoids:
The elements of 4f-series begin from Ac to Lr.
The electronic configuration of these elements can be expressed in terms of Rn (86).
Electronic configuration of Rn (86) =1s
2
2s
2
2p
6
3s
2
3p
6
3d
10
4s
2
4p
6
4d
10
5s
2
5p
6
5d
10
5f
14
6s
2
6p
6
.

Therefore, General electronic configuration of actinoids : [Rn] 5f
114
6d
0 1
7s
2

Element Symbol Atomic Number
Electronic
configuration Expected
Electronic
configuration Observed
Actinium Ac 89 [Rn] 5f
0
6d
1
7s
2
[Rn] 5f
0
6d
1
7s
2

Thorium Th 90 [Rn] 5f
1
6d
1
7s
2
[Rn] 5f
0
6d
2
7s
2

Protactinium Pa 91 [Rn] 5f
2
6d
1
7s
2
[Rn] 5f
2
6d
1
7s
2

Uranium U 92 [Rn] 5f
3
6d
1
7s
2
[Rn] 5f
3
6d
1
7s
2

Neptunium Np 93 [Rn] 5f
4
6d
1
7s
2
[Rn] 5f
4
6d
1
7s
2

Plutonium Pu 94 [Rn] 5f
5
6d
1
7s
2
[Rn] 5f
6
6d
0
7s
2

Americium Am 95 [Rn] 5f
7
6d
0
7s
2
[Rn] 5f
7
6d
0
7s
2

Curium Cm 96 [Rn] 5f
7
6d
1
7s
2
[Rn] 5f
7
6d
1
7s
2

Berkelium Bk 97 [Rn] 5f
8
6d
1
7s
2
[Rn] 5f
9
6d
0
7s
2

Californium Cf 98 [Rn] 5f
9
6d
1
7s
2
[Rn] 5f
10
6d
0
7s
2

Einsteinium Es 99 [Rn] 5f
10
6d
1
7s
2
[Rn] 5f
11
6d
0
7s
2

Fermium Fm 100 [Rn] 5f
11
6d
1
7s
2
[Rn] 5f
12
6d
0
7s
2

Mendelevium Md 101 [Rn] 5f
12
6d
1
7s
2
[Rn] 5f
13
6d
0
7s
2

Nobelium No 102 [Rn] 5f
14
6d
0
7s
2
[Rn] 5f
14
6d
0
7s
2

Lawrencium Lr 103 [Rn] 5f
14
6d
1
7s
2
[Rn] 5f
15
6d
1
7s
2

Q.107. Write down the electronic configuration of Th
4+
. (NCERT)
Ans: Electronic configuration of Th
4+
=1s
2
2s
2
2p
6
3s
2
3p
6
3d
10
4s
2
4p
6
4d
10
4f
14
5s
2
5p
6
5d
10
5f
1
6s
2
6p
6
6d
1
7s
2
.

Q.108. The electronic configurations of actinoid elements are not known with certainty. Explain.
Ans: In actinoids, 5f and 6d subshells are close in energy. The outermost 7s orbital remains filled with 2
electrons (7s
2
). The electron can easily jump from 5f to 6d or vice versa. Further, irregularities in electronic
configurations are also related to the stabilities of f
0
, f
7
and f
14
occupancy of the 5f-orbitals. Hence, they
show a large number of oxidation states (Moreover, they are radioactive with short half-lives. Hence, their
properties cannot be studied easily).

*Q.109. Explain the oxidation states of actinoids
OR
Write a short note on oxidation states of actinoids.
Ans: i. The dominant oxidation state of actinoid elements is +3. Besides +3, actinoids also exhibit +4
oxidation state.
ii. Some actinoids show still higher oxidation states.
iii. The maximum oxidation state first increases upto middle of the series and then decreases.

TARGET Publications
29
Eg. Oxidation state increases from +4 for the Th to +5, +6 and +7 for Pa, U and Np but decreases in the
succeeding elements.
Oxidation states of actinium and actinoids

Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
+2 +2 +3 +3 +3 +3 +2, +3 +3 +3 +3 +3 +3 +3 +3
+3 +3 +3
+4 +4 +4 +4 +4 +4 +4 +4 +4
+5 +5 +5 +5 +5 +5
+6 +6 +6 +6
+7 +7

Q.110. 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. (NCERT)
Ans: 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 and 5d-subshells. The dominant oxidation state
of actinoids is also +3 but they show a number of other oxidation states also. Eg. uranium (Z =92) and
plutonium (Z =94), show +3, +4, +5 and +6, neptunium (Z =93) shows +3, +4, +5 and +7 etc. This is due
to small energy difference between 5f, 6d and 7s-subshells of the actinoids.
Q.111. Which is the last element in the series of the actinoids? Write the electronic configuration of this
elements, comment on the possible oxidation state of this element. (NCERT)
Ans: Last element : Lawrencium (Z =103)
Electronic Configuration : [Rn] 5f
14
6d
1
7s
2

Possible oxidation state : +3
Q.112.Compare the chemistry of actinoids with that of the lanthanoids with special reference to : (NCERT)
i. electronic configuration
ii. oxidation state
iii. atomic size and ionic sizes
iv. chemical reactivity
Ans:
Characteristics Lanthanoids Actinoids
i. Electronic
configuration
It may be represented by [Xe]4f
x
5d
y

6s
2
, where x varies from 0 to 14 and
y =0 or 1.
It may be represented by [Rn]5f
x
6d
y

7s
2
, where x varies from 0 to 14 and
y =0 or 1.
ii. Oxidation state Show +3 oxidation state only, except
in few cases where it is +2 or +4.
They never show more than +4
oxidation state.
Show higher oxidation states such
as +4, +5, +6, +7 also in addition to
+3 oxidation state.
iii. Atomic and ionic sizes The ionic radii of M
3+
ions in
lanthanoids series show a regular
decrease in size of ions with increase
in atomic number. This decrease is
known as lanthanoid contraction.
There is a greater and gradual
decrease in the size of atoms or M
3+

ions across the series. This greater
decrease is known as actinoid
contraction.
iv. Chemical reactivity These are less reactive metals and
form oxides, sulphides, nitrides,
hydroxides and halides etc. These
also form H
2
with acids. They show
a lesser tendency for complex
formation.
These are highly reactive metals
especially in finely divided state.
They form a mixture of oxide and
hydride by action of boiling water.
They combine with non-metals even
at moderate temperature. They
show a greater tendency for
complex formation.

30
*Q.113. Differentiate between lanthanoids and actinoids.
Ans:
No. Lanthanoids Actinoids
i. Differentiating electron enters in 4f orbitals Differentiating electron enters in 5f orbitals
ii. Belong to sixth period and form a part of the
third transition series. They constitute first
inner transition series.
Belong to seventh period and form a part of the
fourth transition series. They constitute second
inner transition series.
iii. Except promethium, all elements occur in
nature.
Except Uranium and Thorium which occur in
nature, all other elements are synthesized in
laboratory.
iv. Binding energy of 4f orbitals are higher Binding energy of 5f orbital are lower.
v. Only promethium is radioactive. All the members of the series are radioactive
vi. Besides +3 oxidation state lanthanoids show
+2 and +4 oxidation states in few cases.
Besides +3 oxidation state, actinoids show higher
oxidation states such as +4, +5, +7 also.
vii. Lanthanoids show less tendency to form
complexes.
Actinoids show greater tendency to form
complexes.
viii. Some of the ions of lanthanoids are fairly
coloured.
Most of the ions of actinoids are deeply coloured
U
3+
(red) , U
4+
(green)
ix. Lanthanoids cannot form oxocations.
Actinoids form oxocations such as
2
2
UO
+
,
PuO
2+
, UO
+
.
x. Lanthanoids hydroxides are less basic in
nature.
Actinoids hydroxides are more basic in nature.
xi. Contraction is relatively less. Contraction is greater in this series due to poor
shielding of 5f electrons.

#Q.114. The extent of actinoid contraction is greater than lanthanoid contraction, Explain why?
OR
Actinoid contraction is greater from element to element than lanthanoid contraction. Why?(NCERT)
Ans: Actinoid contraction is greater than lanthanoid contraction:
i. The size of the atoms or ions of actinoids decrease regularly along the series with the increase in
atomic number from actinium to lawrencium.
ii. This steady decrease in the ionic radii with the increase in atomic number is called actinoid
contraction.
iii. The actinoid contraction is due to the imperfect shielding of 5f-electron.
iv. Despite of the imperfect shielding of 5f-orbitals, the effective nuclear charge increases which results
in contraction of the size.
v. It may be noted that in actinoid contraction, there are bigger jumps in ionic size between the
consecutive members as compared to lanthanoids.
vi. This is due to lesser shielding of 5f-electrons which results in greater increase in the effective nuclear
charge and therefore, larger attraction.

Q.115. Write a short note on uses of actinoids.
Ans: Uses of actinoids:
The three most important actinoids which find uses as such or in the form of their compounds are thorium,
uranium and plutonium.
i. Thorium:
It is used in atomic reactors and in the treatment of cancer. Its salts are used in making incandescent
gas mantles.
ii. Uranium:
It is used as a nuclear fuel. Its salts are used in glass industry (for imparting green colour), textile
industry, ceramic industry and in medicines.
iii. Plutonium:
It is used as a fuel for atomic reactors as well as for making atomic bombs.

TARGET Publications
31
Points to Remember

Transition elements are classified as those whose atoms or ions have partly filled d-orbitals.
General electronic configuration of transition elements is (n-1) d
110
ns
12
.
Transition metals possess high density and high melting and boiling points
Within a group, the atomic sizes of elements first increase from 3d to 4d and then decrease from 4d to 5d.
This is due to lanthanoid contraction in 5d elements.
The ionization enthalpies of transition elements increase across a period, but this increase is not regular.
This is again due to imperfect shielding power of (n1) d electrons.
The atomic radii for transition metals are smaller than their corresponding s-block elements.
An important feature of transition elements is the colour of their compounds. The colour is linked with the
electronic configurations of ions and d-d transitions. Ions with d
0
and d
10
configurations are colourless
while d
5
ions show light colours.
Transitions elements exhibit a variety of oxidation states. The highest oxidation states, for example, +6 for
Cr in CrO
4
2
and +7 for MnO
4
, are attained by highly electronegative elements oxygen and fluorine.

Transition metals and their compounds find applications as catalysts in various industrial chemical
processes.
Many transition metals and their compounds show magnetic behaviour. The number of unpaired electrons
present can be obtained from the measurement of magnetic moments () as = n(n 2) + B.M, where n is
the number of unpaired electrons.
Two series of f-block elements (4f and 5f) are embedded in transition elements. These are called inner
transition elements. Elements in 4f series are known as lanthanoids and those of 5f series as actinoids.
In the lanthanoid series, with increasing atomic number, the atomic and ionic radii decreases from one
element to another but the decrease is very small. This is called Actinoid contraction.
Actinoid contraction is greater from element to element than lanthanoid contraction.
Elements of f-series also behave in a manner similar to transition elements in many respects.

Multiple choice Questions

1. The general outer electronic configuration of
transition elements is
(A) (n1) d
110
ns
1
(B) (n1) d
10
ns
2

(C) (n1) d
110
ns
12

(D) (nl) d
5
ns
1

2. Which of the following is a lanthanoid?
(A) Ta (B) Th
(C) Lu (D) Rh

3. Which of the following belongs to the actinoid
series?
(A) U (B) Yb
(C) Lu (D) Tb

4. Lanthanoid contraction implies
(A) decrease in density
(B) decrease in mass
(C) decrease in ionic radii
(D) decrease in radioactivity
5. Which one of the following does not show
different oxidation states?
(A) Iron (B) Copper
(C) Zinc (D) Manganese
6. Paramagnetism is the property of
(A) filled electronic sub-shells
(B) unpaired electrons
(C) non-transition elements
(D) m.p and b.p of elements.

7. In KMnO
4
oxidation number of Mn is
(A) +2 (B) +4
(C) +6 (D) +7

8. Which of the following would be
diamagnetic?
(A) Cu
2+
(B) Ni
2+

(C) Cd
2+
(D) Ti
3+

9. Which among the following pairs is not a
chemical twin? [March 2013 old course]
(A) Mo W
(B) Nb - Mo
(C) Nb Ta
(D) Zr - Hf

10. Which of the following has the maximum
number of unpaired electrons?
(A) Fe
2+
(B) Cr
3+

(C) Fe
3+
(D) Co
2+

32
11. Which one of the following characteristic of
the metals is associated with their catalytic
activity?
(A) Paramagnetic behaviour
(B) Colour of hydrated ions
(C) Variable oxidation states
(D) High enthalpy of atomisation

12. Which of the following ions has the highest
magnetic moment?
(A) Ti
3+
(B) Sc
3+

(C) Mn
2+
(D) Zn
2+

13. Which lanthanoid has the smallest atomic
radius?
(A) Gadolinium (B) Scandium
(C) Lutetium (D) Cerium

14. The lanthanoid contraction is responsible for
the fact that
(A) Zr and ,Y have about same radius
(B) Zr and Nb have similar oxidation state
(C) Zr and Hf have about same radius
(D) Zr and Zn have same oxidation state

15. The atomic number of an element is 22. The
highest oxidation state exhibited by it in its
compounds is
(A) 1 (B) 2
(C) 3 (D) 4

16. Reduction in atomic size with increase in
atomic number is a characteristic of elements
of
(A) radioactive series
(B) p-Block
(C) d-Block
(D) f-Block

17. The element having general electronic
configuration (n1)d
110
ns
12
is
(A) Noble gas (B) Non-metal
(C) Metalloid (D) Transition metal

18. Variable valency is shown by
(A) Typical elements
(B) Normal elements
(C) Transition elements
(D) None of these

19. Zinc is a member of IIB or 12th group of
periodic table. The other members of this
group are
(A) Boron and aluminium
(B) Cadmium and mercury
(C) Silver and gold
(D) Tin and lead
20. Which one of the following ions is colourless?
(A) Cu
+
(B) Co
2+

(C) Ni
2+
(D) Fe
3+

21. The d-block elements include
(A) metals and non-metals
(B) only non-metals
(C) only metals
(D) metals, non-metals and metalloids
22. The most abundant transition metal is
(A) Zn (B) Fe
(C) Hg (D) Au
23. Which of the following statement is NOT
TRUE?
(A) Colourless compounds of transition
elements are paramagnetic
(B) Coloured compounds of transition
elements are paramagnetic
(C) Colourless compounds of transition
elements are diamagnetic
(D) Transition elements form the complex
compounds
24. The maximum oxidation state shown by
actinoids is
(A) +6 (B) +7
(C) +5 (D) +4
25. The element with the electronic configuration
[Xe]
54
4f
14
5d
1
6s
2
is a
(A) representative element
(B) transition element
(C) lanthanoids
(D) actinoid
26. With increase in atomic number the ionic radii
of actinoids,
(A) contract slightly
(B) increase gradually
(C) show no change
(D) change irregularly
27. The general electronic configuration of
lanthanoids is
(A) [Xe] 4f
114
5d
01
6s
2

(B) [Xe] 4f
014
5d
12
6s
1
(C) [Xe] 4f
014
5d
01
6s
12

(D) None of these
28. The Lanthanoid ions are coloured due to
(A) d-d transition (B) d-f transition
(C) f-f transition (D) All of these
29. Actinoids
(A) are all synthetic elements
(B) include element 104
(C) have only short lived isotopes
(D) have variable valency

TARGET Publications
33
30. The catalytic activity of the transition metals
and their compounds is ascribed to
(A) their chemical reactivity
(B) their unfilled dorbitals
(C) their ability to adopt multiple oxidation
states and their complexing ability
(D) less metallic character

31. Which ion has the highest ionic radii?
(A) Cr
3+
(B) Mn
3+

(C) Fe
3+
(D) Co
3+

32. Actinoid and Lanthanoid are placed
respectively in
(A) III B group and 6th and 7th period of
periodic table
(B) III A group and 7th and 6th period of
periodic table
(C) III B group and 7th and 6th period of
periodic table
(D) Both III A and III B group of the
periodic table

33. _____ is paramagnetic in nature.
(A) La
3+
(B) Lu
3+

(C) Gd
3+
(D) Ce
4+

34. Which of the following factors may be
regarded as the main cause of lanthanoid
contraction?
(A) Poor shielding of one of 4f electron by
another in the subshell
(B) Effective shielding of one of 4f
electrons by another in the subshell
(C) Poorer shielding of 5d electrons by 4f
electrons
(D) Greater shielding of 5d electron by 4f
electrons

35. Cerium can show the oxidation state of +4
because,
(A) it resembles alkali metals
(B) it has very low value of I.E.
(C) of its tendency to attain noble gas
configuration of xenon
(D) of its tendency to attain 4f
7

configuration

36. Which is the strongest base among the
following?
(A) La(OH)
3
(B) Lu(OH)
3

(C) Ce(OH)
3
(D) Yb(OH)
3

37. Contraction in atomic and ionic radii is given
by
(A) lanthanoids but not actinoids
(B) actinoids but not lanthanoids
(C) both lanthanoids and actinoids
(D) neither lanthanoids nor actinoids.

38. Chemical formula of pyrolusite is
(A) Mn
2
O
3
(B) MnO
3

(C) MnO
2
(D) Mn
2
O
7

39. Which one of the following ions is coloured?
(A) Sc
3+
(B) Ti
4+

(C) Zn
2+
(D) V
2+

40. In which of the following pair highest
oxidation states of transition metals are found?
[March 2013]
(A) nitriles and chlorides
(B) fluorides and chlorides
(C) fluorides and oxides
(D) nitriles and oxides

Answers to Multiple Choice Question

1. (C) 2. (C) 3. (A) 4. (C)
5. (C) 6. (B) 7. (D) 8. (C)
9. (B) 10. (C) 11. (C) 12. (C)
13. (C) 14. (C) 15. (D) 16. (D)
17. (D) 18. (C) 19. (B) 20. (A)
21. (C) 22. (B) 23. (A) 24. (B)
25. (C) 26. (A) 27. (A) 28. (C)
29. (D) 30. (C) 31. (A) 32. (C)
33. (C) 34. (A) 35. (C) 36. (A)
37. (C) 38. (C) 39. (D) 40. (C)

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Written according to the New Text book (2012-2013)

published by the Maharashtra State Board of

Target Publications PVT. LTD.

: Oxidation state of Mn =+7 (Group No =7)

2KOH +2MnO +4H

ions increases from La

, are attained by highly electronegative elements oxygen and fluorine.

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