® The d- and f-Block Elements



In the transition elements, the d-orbitals are successively filled. The general electronic configuration for the
atoms of d-block is :  n  1 d110 ns1 2 where (n — 1) stands for inner shell (or penultimate shell) and
d-orbitals may have one to ten electrons and the s-orbital of the outermost shell (n) may have one or two
electrons.
The general electronic configuration of d-block elements is :  n  1 d110 ns0 2 .
1.1 Transition series
The transition elements consist of four rows of ten elements. These rows are called first, second, third and
fourth transition series which involve the filling of 3d, 4d, 5d and 6d-orbitals respectively.
First transition series : Scandium (Z = 21) to Zinc (Z = 30)
3d-orbitals are gradually filled.
Second transition series : Yttrium (Z = 39) to Cadmium (Z = 48)
4d-orbitals are gradually filled.
Third transition series : Lanthanum (Z = 57), Hafnium (Z = 72) to Mercury (Z = 80)
5d-orbitals are gradually filled.
Fourth transition series : Actinium (Z = 89), Rutherfordium (Z = 104) to
Copernicium (Z = 112)
6d-orbitals are gradually filled.
Let us discuss the electronic configurations of individual members of these series.
However , it may be noted that the above definition does not include elements of group 12 (previously called
II B) i.e., Zn, Cd and Hg.

2.1 Atomic Radii

The atomic radii of elements of a particular series decrease with increase in atomic number but this decrease
in atomic radii becomes small after midway. For example, for the elements of first transition series, the
atomic radii decrease gradually from scandium to chromium but from chromium to copper, it remains practicall
y constant.
Atomic radii of d-block elements (in pm).

Sc Ti V Cr Mn Fe Co Ni Cu Zn
164 147 135 129 127 126 125 125 128 137
Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
180 160 146 139 136 134 134 137 144 154
La Hf Ta W Re Os Ir Pt Au Hg
187 158 146 139 137 135 136 138 144 157

The atomic radii increase while going down the group. Therefore , the atomic radii of transition metals of
second series have large values than those of the first transition series . However , the transition metals of
third transition series have nearly the same radii as metals of second transition series above them.
With the increase in number of outermost shell, size increases. The similar atomic radii of elements of second
and third transition series are due to a special phenomenon known as lanthanoid contraction. This is associated
with the intervention of the 4f-orbitals which are filled before the 5d series of elements starts. The filling of
4f-orbitals before 5d orbitals results in regular decrease in atomic radii which compensates the expected
increase in atomic size with increasing atomic number. As a result of this lanthanoid contraction, the elements
of second and third transition series have almost similar atomic radii (e.g., Zr 160 pm, Hf 159 pm). Because
of this, these elements of two series also have very similar physical and chemical properties.

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2.2 Metallic Character and Enthalpy of Atomization

All the transition elements are metals. They exhibit all the characteristic of metals . They all have high
density, hardness, high melting and boiling points, high tensile strength, ductility, malleability, high thermal and
electrical conductivities and lustre. With the exception of zinc, cadmium and mercury the transition elements
are much harder , less volatile and brittle than s-block outermost shell. The hardness of these metals suggests
the presence of strong bonding due to overlap of unpaired electrons between different metal atoms. Therefore,
these elements exhibit high enthalpies of atomization . In general, the greater number of unpaired d-electrons,
greater is the number of bonds and therefore, greater is strength of these bonds.
Element Sc Ti V Cr Mn Fe Co Ni Cu Zn
Electronic 3d1 4s 2 3d 2 4s 2 3d 3 4s 2 3d 5 4s1 3d 5 4s 2 3d 6 4s 2 3d 7 4s 2 3d 8 4s 2 3d10 4s1 3d10 4s 2
configuration
No. of 1 2 3 6 5 4 3 2 1 0
unpaired
electrons

The metals of second (4d series) and third (5d series) have greater enthalpies of atomization of their
corresponding elements of first transition series. This is an important factor indicating more frequent metal-
metal bonding in the compounds.
2.3 Density
All these metals have high density. Within a period, the densities vary inversely with the atomic radii. As we
move in a period, the densities increase.
Variation of density  g cm  in first transition series.
3

Element Sc Ti V Cr Mn Fe Co Ni Cu Zn
Density 3.43 4.1 6.07 7.19 7.21 7.8 8.7 8.9 8.9 7.1
densities of third transition series are still higher. Osmium  22.57 g cm  and Iridium  22.61 g cm  have
3 3

very high density among these elements.

2.4 Melting and Boiling Points
The transition metals have very high melting and boiling points. The melting points of the three transition
series are shown in below. It is clear from the figure that the melting points of these metals rise to a maximum
value and then decrease with increase in atomic number. However, Manganese and Technetium metals have
abnormally low melting points.
Therefore , as we move along a particular series , the metallic strength increases upto the middle with
increasing availability of unpaired electrons upto d5 configuration (e.g., Sc has 1, Ti has 2, V has 3, Cr has 5
unipaired electrons) and then decreases with decreasing availability of unpaired d-electrons.
4
W Third series
Re
Ta
3 Os
Nb Mo Ru
mp/10 K

Ir
3

Hf Second series
Cr Tc Rb
2 Zr V First series Pt
Fe Pd
Ti
Co Ni
Cu
Mn
Au
1 Ag
Transition metals
Melting points of transition metals.
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 ® The d- and f-Block Elements
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Note :
Tungsten(W) has the highest melting point among the d-block elements.
2.5 Ionisation Enthalpies
Screening effect of the nucleus and consequently , ionisation enthalpy increases from left to right but quite
5
 
slowly among d-block elements. 3d configuration. On the other hand, zinc has high ionisation enthalpy

10 2
because electron has to be removed from 4s orbital of stable 3d 4s .  

Third series
1000 Second series
First seriesAu Hg
900 Ir Pt
Os Zn
Hf Ta W Re Pd
800 Fe Co Cu
I.E.1 (kJ mol )

Mn Cd
-1

700 Zr Nb Mo
Ni
Tc Ru Rh Ag
600 Ti V Cr
500

Atomic number
Ionisation enthalpies of transition metals

2.6 Oxidation States

This is one of the notable features of the transition elements. With the exception of a few elements, most of
these show variable oxidation states.
Different oxidation states of first transition series.
Element Outer electronic Oxidation states
configuration
Sc 3d1 4s 2 +3
Ti 3d 2 4s 2 +2, +3, +4
V 3d3 4s2 +2, +3, +4, +5
Cr 3d 5 4s1 +2, +3, (+4), (+5), +6
Mn 3d5 4s 2 +2, +3, (+4), (+5), +6, +7
Fe 3d6 4s2 +2, +3, (+4), (+5), (+6)
Co 3d 7 4s 2 +2, +3, (+4)
Ni 3d8 4s2 +2, +3, +4
Cu 3d10 4s1 +1, +2
Zn 3d10 4s 2 +2

* Oxidation states within brackets are unstable.

** Most common oxidation states are in bold type.
(i) Nature of the elements with which the metal is combined. The highest oxidation states are found in compounds
of fluorides and oxides because fluorine and oxygen are most electronegative elements.
(ii) Except scandium, the most common oxidation state of the first row transition elements is +2 which arises due
to loss of two 4s-electrons.
The oxides of manganese have the following behaviour :

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Oxide MnO Mn 3O 4 Mn 2 O3 MnO2 Mn 2O 7

Oxidation state +2 8 +3 +4 +7

3
Ionic/covalent
Ionic character decreases/covalent character increases
character
Acidic/basic Acidic character increases/basic character decreases
character
MnO Mn3 O 4 Mn 2 O3 MnO2 Mn 2 O7

Amphoteric Acidic
Basic
(iii) In the +2 and +3 oxidation states, the bonds formed are mostly ionic. In the compounds of higher oxidation
states (generally formed with oxygen and fluorine), the bonds are essentially covalent. Thus , the bonds in +2
and +3 oxidation states are generally formed by the loss of two or three electrons respectively while the
bonds in higher oxidation states are formed by sharing of d-electrons. For example, in MnO 4 (Mn in +7)
state all the bonds are covalent.
(iv) Within a group, the maximum oxidation state increases with atomic number. For example, Iron (group 8)
shows common oxidation states of +2 and +3 but Ruthenium and Osmium in the same group form compounds
in the +4, +6 and +8 oxidation states.
(v) Transition metals also form compounds in low oxidation states such as +1 and 0 or negative. The common
examples are  Ni  CO 4  ,  Fe  CO 5  in which Nickel and iron are in zero oxidation state.
2.7 Standard Electrode Potentials
Electrode potentials
In addition to ionisation enthalpy, the other factors such as enthalpy of sublimation, hydration enthalpy, etc.
determine the stability of a particular oxidation state in solution. This can be explained in terms of their
electrode potential values. The oxidation potential of a metal involves the following process:
M  s   M   aq   e 
This process actually takes place in the following three steps :
(i) In the first step, the atoms get isolated from one another and become independent in the gaseous state. This
converts solid metal to the gaseous state. The energy needed for this step is known as enthalpy of sublimation.
M s  M g  Enthalpy of sublimation,  sub H
(ii) In the second step, the outer electron is removed from the isolated atom. The energy required for this change
is ionisation enthalpy.
M  g   M   g   e Ionisation enthalpy, IE
(iii) In the third step, the gaseous ion gets hydrated. In this process, energy known as hydration enthalpy, is
liberated.
M   g   nH 2 O  M   aq  Enthalpy of hydration,  hyd H
The above steps may be represented by a cyclic process (called Born Haber cycle) as shown.

H
M s M aq

1
Hsub. 3
Hhyd.

IE
M g M g
2
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 ® The d- and f-Block Elements
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The oxidation potential which gives the tendency of the overall change to occur, depends upon the net effect
of these three steps. The overall energy change is
H   sub H  IE   hyd H
REMEMBER
Standard electrode potential stability of the ions in solution
o 2
 
The electrode potential E M | M represents electrode potential for the reaction:

M 2  aq   2e   M  s 
 If E° value is high (more positive or less negative), it means M 2  ions can be readily reduced to metal.
 M 2  ions are less stable than M(s).
 Metal cannot readily lose electrons (i.e., gets oxidised) to form M 2  ions.
 If E° value is small (less positive or more negative), it means M 2  ions cannot be readily reduced to metal.
 M 2  ions are more stable than M(s).
 Metal can readily lose electrons (i.e., gets oxidised) to form M 2  ions.
The smaller the value of total energy change for a particular oxidation state in aqueous solution, greater will
be the stability of that oxidation state. The electrode potentials are a measure of total energy change.
Qualitatively, the stability of the transition metal ions in different oxidation states can be determined on the
basis of electrode potential data. The lower the electrode potential i.e., more negative the standard reduction
potential of the electrode, the more stable is the oxidation state of the transition metal in the aqueous solution.
Trends in the M3 | M 2 Standard Electrode Potentials

Except copper and zinc, all other elements of first transition series show +3 oxidation states also to form M3
ions in aqueous solutions.
(i) The tendency of fluorine to stablise the highest oxidation state is due to either higher lattice enthalpy as in
case of CoF3 or higher bond enthalpy due to higher covalent bonds e.g., VF5 and CrF6 .
It has been observed that many copper (I) compounds are unstable in aqueous solution and they undergo
disproportionation to Cu (II) and Cu (0) as :
2Cu   Cu 2  Cu
2.8 Formation of Coloured Ions
The colour of the compounds of transition metals may be attributed to the presence of incomplete (n - 1)
d-subshell . In the case of compounds of transition metals , the energies of the five d-orbitals in the same
subshell do not remain equal . Under the influence of approaching ions towards the central metal ion , the
d-orbitals of the central metal split into different energy levels . This phenomenon is called crystal field
splitting. For example , when the six ions or molecules approach the metal ion (called octahedral field), the

 
five d-orbitals split up into two sets : one set consisting of two d-orbitals d x 2  y2 ,d z2 of higher energy and

 
the other set consisting of three d-orbitals d xy ,d yz ,d zx of lower energy . This has been discussed in the
next chapter.
NOTE :
Colour of compounds containing completely filled or empty d-orbitals.
It may be noted that transition metal ions containing completely filled d-orbitals (i.e., d10 configuration) such
as Zn 2  ,Cd 2 , Hg 2 ,Cu  , Ag  , etc . are generally white . For example, ZnCl2 , is white. Similarly,,

Sc3 and Ti 4  are white because they have completely empty d-orbitals.

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Colour of different transition metal ions.

Ion Outer configuration Colour of the ion
Sc (III), Ti (IV) 3d 0 Colourless
Ti(III) 3d1 Purple
V(IV) 3d1 Blue
V(III) 3d 2 Green
V(II), Cr(III) 3d 3 Violet
Mn (III) 3d 4 Violet
Cr(II) 3d 4 Blue
Mn(II) 3d 5 Pink
Fe (III) 3d 5 Yellow
Fe (II) 3d 6 Green
Co (III) 3d 6 Blue
Co (II) 3d 7 Pink
Ni (II) 3d8 Green
Cu (II) 3d 9 Blue
Cu(I) 3d10 Colourless
Zn (II) 3d10 Colourless

KMnO 4 and K 2 Cr2 O 7 exhibit colour due to charge transfer spectrum.

COLOUR WHEEL
A colour wheel to determine the complementary colour of a substance from the colour of light absorbed.
Complementary colours are shown on the opposite sides of the colour wheel.
absorbs
650 nm
red
colour Orange

Red Yellow
800 nm
560 nm
400 nm Green
Violet
appears
Blue green
430 nm 490 nm
If a substance absorbs red colour
(720 nm), it appears green.
3 4  2
As it is clear from above table, Sc ,Ti ,Cu and Zn have completely empty or completely filled
d-orbitals and are colourless.
2.9 Magnetic Properties
Types of substances :
(i) Paramagnetic substances.
The substances which are attracted by magnetic field are called paramagnetic substances and this character
arises due to the presence of unpaired electrons in the atomic orbitals.
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 ® The d- and f-Block Elements
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(ii) Diamagnetic substances.
The substances which are repelled by magnetic filed are called diamagnetic substances and this character
arises due to the presence of paired electrons in the atomic orbitals.
Calculated and observed magnetic moments of ions of first transition series.
Ion Outer No. of Magnetic Observed
configuration unpaired moment (B.M.)
electrons Calculated
Sc3 3d 0 0 0 0
Ti3 3d1 1 1.73 1.75
Ti 2 3d 2 2 2.84 2.76
V 2 3d3 3 3.87 3.86
Cr 2 3d 4 4 4.90 4.80
Mn 2 3d5 5 5.92 5.96
Fe2 3d 6 4 4.90 5.3-5.5
Co 2 3d 7 3 3.87 4.4-5.2
Ni 2 3d8 2 2.84 2.9-3.4
Cu 2 3d9 1 1.73 1.8-2.2
Zn 2 3d10 0 0 0

Paramagnetism arises from the presence of unpaired electrons. Each unpaired electron have magnetic
moment associated with its spin angular momentum and orbital angular momentum. In the compounds of first
transition series, the orbital angular momentum does not contribute and hence has no significance. Therefore,
for the first transition series elements, the magnetic moments arise only from the spin of the electrons. This
can be calculated from the relation :
  n  n  2 B.M.
2.10 Tendency to form Complexes
In contrast to representative elements, the transition elements form a large number of coordination complexes.
The transition metal ions bind to a number of anions or neutral molecules in these complexes. The common
examples are
2 3 3 4 2
 Ni  NH 3   , Co  NH3   ,  Fe  CN   ,  Fe  CN   , Cu  NH3   , etc.
 6  6  6  6  4

Explanation.
The high tendency of transition metal ions to form complexes is due to
(i) Small size of the atoms and ions of transition metals
(ii) High nuclear charge
(iii) Availability of vacant d-orbitals of suitable energy to accept lone pairs of electrons donated by other groups
(called ligands).
2.11 Catalytic Properties
Many transition metals and their compounds act as good catalysts for various reactions.
Of these, the use of Fe, Co, Ni, V, Cr, Mn, Pt, etc. are very common.
For example ,
(i) Iron-molybdenum is used as catalyst in the synthesis of ammonia by Haber's process.
(ii) Nickel is used in hydrogenation reactions in organic chemistry.
(iii) Vanadium pentoxide, V2 O5 is used for the oxidation of SO 2 to SO3 in the Contact process for the manufacture
of H 2SO 4 .

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(iv) Manganese dioxide, MnO 2 , is used to catalyse the decomposition of H 2 O 2 solution,

(v) Cobalt salts catalyse the decomposition of bleaching powder .
(vi) Platinum , Pt is used as a catalyst in many processes such as Contact process for making H 2SO 4 , in three
stage converters for cleaning car exhausts.
(vii) Pt/Rh is used in Ostwald process during manufacture of HNO3 .
(viii) Pd is used in hydrogenation reactions in organic chemistry.
Illustration 1 :
Calculate the magnetic moment of a divalent and a trivalent ion in aqueous solution if its atomic
number is 25.
Solution :
Divalent ion having atomic number 25 will have d5 electronic configuration.
No. of unpaired electrons = 5
  n  n  2

 5  5  2   5.92 B.M.

Trivalent ion having atomic number 25 will have d 4 electronic configuration.

No. of unpaired electrons = 4
  4  4  2   4.90 B.M.
Illustration 2 :
Explain as to why the E value for the Mn 3+ / Mn 2+ couple is much more positive than that for
Cr 3+ / Cr 2+ or Fe3+ / Fe 2+ .
Solution :
Mn 2 has 3d electronic configuration. It is stable because of half filled configuration of d-subshell. Therefore,
5

Mn has very high third ionization enthalpy for the change from d 5 to d 4 and it is responsible for much more
positive E  valu e for Mn 3 / Mn 2 couple in comparison to Cr 3 / Cr 2  and Fe3 / Fe 2  couples.
Illustration 3 :
Though both Cr 2+ and Mn 3 have d 4 configuration, yet Cr 2 is reducing while Mn 3 is oxidising.
Explain why?
Solution :
E o value for Cr 3 / Cr 2 is negative (-0.41 V), this means that Cr 3 ions are more stable than Cr 2 .
Therefore, Cr 2 can readily lose electrons to undergo oxidation to form Cr 3 ion and hence Cr (II) is
strongly reducing. On the other hand the E o value for Mn 3 / Mn 2 is positive (+1.57 V), this means that
Mn 3 ions can be readily reduced to Mn 2 and hence Mn (III) is strongly oxidising.
Illustration 4 :
Scandium (Z = 21) is a transition element but zinc (Z = 30) is not. Explain.
Solution :
According to definition, transition elements are those which have partially filled d-subshells in their elementary
state or in their commonly occurring oxidation states. Scandium (Z = 21) has partially filled d-subshell 3d 
1

and is therefore, a transition element. On the other hand, zinc (Z = 30) has the configuration 3d10 4s 2 . It does
 2 10
not have partially filled d-subshell in its elementary form or in commonly occurring oxidation state Zn : 3d . 
Therefore, it is not regarded as transition element.

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 ® The d- and f-Block Elements
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Illustration 5 :
For the first row transition metals, the E  values are :

E V Cr Mn Fe Co Ni Cu
M 2 M  -1.18 -0.91 -1.18 -0.44 -0.28 -0.25 +0.34

Explain tlie irregularity in the above values.

Solution :

 
The E  M 2 M values are not regular. This can be explained due to irregular variation of ionization enthalpies
 IE1  IE 2  and also the sublimation enthalpies which are relatively much less for Mn and V
 Mn  240 kJ mol 1

and V  470 kJ mol 1 .
Illustration 6 :
Why do transition elements exhibit higher enthalpies of atomization ?
Solution :
The high enthalpies of atomization are due to large number of unpaired electrons in their atoms. Therefore,
they have stronger interatomic interactions and hence, stronger bonding between atoms. Thus, they have
high enthalpies of atomization.
Illustration 7 :
What is meant by disproportionation of an oxidation state ? Give one example.
Solution :
When a particular oxidation state becomes less stable relative to other oxidation states, one lower and one
higher, it is said to undergo disproportionation. For example, manganese (VI) becomes unstable relative to
manganese (VII) and manganese (IV) in acidic solution
VI VII IV
3MnO 24  4H   2MnO 4  MnO 2  2H 2 O
Illustration 8 :
Following are the transition metal ions of 3d series.
Ti 4 , V 2 , Mn 3 ,Cr 3
(Atomic numbers: Ti = 22,V = 23, Mn = 25, Cr = 24)
Answer the following:
(i) Which ion is most stable in an aqueous solution and why?
(ii) Which ion is a strong oxidising agent and why?
(iii) Which ion is colourless and why?
Solution :
3
(i) Cr 3 because of half filled t 2g configuration.
(ii) Mn 3 due to stable d5 configuration of Mn 2
(iiii) Ti 4  because it has no unpaired electrons.
Illustration 9 :
Why are Mn 2 compounds more stable than Fe 2  towards oxidation to their +3 state ?
Solution :
Electronic configuration of Mn 2 is [Ar] 3d 5 which is half filled and hence it is stable. Therefore, third
ionisation enthalpy is very high i.e., third electron cannot be easily removed. 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.
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Illustration 10 :
The E o 2  for copper is positive (0.34 V). Copper is the only metal in the first series of transition
M |M
elements showing this behaviour. Why ?
Solution :
The E o 2  value for copper is positive and this shows that it is least reactive metal among the elements of
M |M
first transition series. This is because copper has high enthalpy of atomisation and enthalpy of ionization.
Therefore, the high energy required to convert Cu  s  to Cu 2   aq  is not balanced by its hydration enthalpy..
2.12 Formation of Interstitial Compounds
Transition metals form interstitial compounds wit h elements such as hydrogen, boron, carbon and nitrogen.
The small atoms of these non-metallic elements (H, B, C, N, etc.) get trapped in vacant spaces of the lattices
of the transition metal atoms.
They are generally non-stoichiometric and are neither typically ionic nor covalent. The common examples of
interstitial compounds of transition metals are TiC, Mn 4 N, Fe3 H, Fe3C,TiH 2 , etc. It may be noted that these
formula do not correspond to any normal oxidation state of the metal. Generally, the non stoichiometric
material s areobtained having the composition as TiH1.7 , VH 0.56 , etc. Because of the nature of their composition,
these compounds are referred to as interstitial compounds.
Explanation.
The transition metals can easily accommodate the small non-metallic atoms because of spaces between the
metal atoms. These spaces are present because of defects in their structures and existence of variable
oxidation states.
The general characteristic physical and chemical properties of these compounds are :
(i) They have high melting points which are higher than those of pure metals.
(ii) They retain metallic conductivity.
(iii) They are very hard. Some borides have hardness as that of diamond.
(iv) They are chemically inert.

1. How is the variability in oxidation states of transition metals different from that of the non transition metals ?
Illustrate with examples.
2. For M 2 / M and M 3 / M 2 system the E o values for some metals are as folows :

Cr 2  / Cr 0.9V Cr 3 / Cr 2 0.4V
Mn 2  / Mn 1.2V Mn 3 / Mn 2  1.5V
Fe 2 / Fe 0.4V Fe3 / Fe2  0.8V
Use this data to comment upon :
(a) The stability of Fe3 in acid solution as compared to that Cr 3 or Mn 3 , and
(b) The ease with which iron can be oxidised as compared to the similar process for either chromium or
manganese metal.
3. Which metal in the first series of transition metals exhibits +1 oxidation state most frequently and why ?
4. Calculate the number of unpaired electrons in the following gaseous ions : Mn 3+, Cr3+, V3+ and Ti3+. Which
one of these is most stable in aqueous solution?
5. Give example and suggest reasons for the following features of the transition metal chemistry :
(a) The lowest oxide of transition metal is basic, the highest is amphoteric/acidic .
(b) A transition metal exhibit s highest oxidation state i n oxides and fluorides.
(c) The highest oxidation state is exhibited in oxoanions of a metal.

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

1. Maximum oxidation number of manganese is in

(A) K 2 MnO 4 (B) MnO 2 (C) KMnO 4 (D) Mn 2 O 4
2. Electronic configuration of Fe2 ion is
(A)  Ar  4s 2 3d 4 (B)  Ar  4s1 3d 5 (C)  Ar  3d 6 (D)  Ar  3d 8
3. Electronic configuration of Cr (Z = 24) is
(A) 3d 4 4s 2 (B) 3d 6 4s 0 (C) 3d 5 4s1 (D) None of these
4. Increasing order of paramagnetism is
(A) Cu 2  ,Co 2  , Mn 2  , Ni 2  (B) Co 2  ,Cu 2  , Mn 2  , Ni 2 
(C) Cu 2  , Ni 2  , Co 2  , Mn 2  (D) Mn 2  ,Co 2  , Ni 2  ,Cu 2 
5. Which is colourless in H 2 O ?
(A) Ti3 (B) V3 (C) Cr 3 (D) Sc3
6. Which one is coloured ?
3 2 3
(A) Cu 2 Cl 2 (B) Sc  H 2 O 6  (C)  Zn  H 2 O 6  (D) Ti  H 2 O 6 
7. Which of the following titanium compounds cannot be prepared ? (Atomic No. of T i = 22)
(A) TiO (B) TiO 2 (C) K 2 TiO 4 (D) TiCl2
8. The transition element that has lowest enthalpy of atomisation, is :
(A) Zn (B) Cu (C) V (D) Fe
9. The element that usually does not show variable oxidation states is :
(A) V (B) Ti (C) Sc (D) Cu
10. The pair that has similar atomic radii is :
(A) Sc and Ni (B) Ti and Hf (C) Mo and W (D) Mn and Re
11. The atomic radius of Ag is closest to :
(A) Cu (B) Hg (C) Au (D) Ni
12. What is the correct order of the following elements with respect to their density?
(A) Cr  Zn  Co  Cu  Fe (B) Zn  Cu  Co  Fe  Cr
(C) Zn  Cr  Fe  Co  Cu (D) Cr  Fe  Co  Cu  Zn
13. The common positive oxidation states for an element with atomic number 24, are :
(A) +2 to +6 (B) +1 and +3 to +6 (C) +1 and +3 (D) +1 to +6

 
3.1 Preparation
It is prepared from Chromite ore for Chrome iron.  FeO,Cr2 O3 or FeCr2O 4  . The various steps involved
ore.
(a) Preparation of sodium chromate (Na2CrO4) :
The powdered chromite ore in fused with sodium hydroxide or sodium carbonate in the presence of air in a
reverbesatory furnace.
4FeCr2 O 4  16NaOH  7O 2  8Na 2 CrO 4  2Fe 2 O3  8H 2 O
4FeCr2 O 4  8Na 2CO3  7O 2  8Na 2 CrO 4  2Fe 2 O3  8CO 2
After the reaction the roasted mass is extracted with water. So sodium chromate is completely dissolved
while ferric oxide is left behind.
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(b) Preparation of sodium dichromate  Na 2 Cr2 O 7  from sodium chromate  Na 2 CrO 4  :

The solution of sodium chromate is filtered and acidified with dil/con. H 2SO 4 acid giving its dichromate.
2Na 2 CrO 4  H 2SO 4  Na 2 Cr2 O 7  Na 2SO 4  H 2 O
On cooling, sodium sulphate being less soluble crystalline out as Na 2SO 4 .10H 2 O and is removed. The
resulting solution contains sodium dichromate  Na 2 Cr2 O 7  .
(c) Formation of potassium dichromate from sodium dichromate :
The hot concentrate solution of sodium dichromate is heated with calculated amount of KCl.
Na 2 Cr2 O 7  2KCl  K 2 Cr2 O 7  2NaCl
Sodium chloride, being the least soluble precipitates out from the hot solution and is removed by filtration.
Change red crystals of potassium dichromate separate out from mother liquid on cooling.

3.2 Properties
(a) Colour and Melting Point : -
Orange red crystals. 670 K
(b) Solubility : -
Moderately soluble is cold water but readily soluble in hot water.
(c) Action of Heat : -
It decompose on heating to give potassium chromate. chromic code and oxygen.
Heat
4K 2 Cr2 O7   4K 2 CrO 4  2Cr2O3  3O 2
Potassium Chromic
chromate oxide
(d) Action of Alkalies : -
On heating with aliconlies the orange colour of dichromate solution changed to yellow due to the formation of
chromate ions.
K 2 Cr2 O 7  2KOH  2K 2 CrO 4  H 2 O

Cr2 O72  2OH   2CrO 24  H 2 O

This chromate on acidifying reconverts into dichromate.
2K 2 CrO 4  H 2SO 4  K 2 Cr2 O 7  K 2SO 4  H 2 O

CrO24   2H   Cr2 O72  H 2 O

The interconversion is explained by the fact that dichromate ion and chromate ion exist in equilibrium at a pH
of about 4.

HCrO 4
Cr2 O72  H 2 O   2
 2CrO 4  2H


When alkali added, H  consumed so forward direction. When acid added, H  increases so backward
direction.
(e) Chromyl chloride Test : -
When potassium dichromate is heated with conc. H 2SO 4 acid and a soluble metal chloride (ex. NaCl)
orange red vapours of chromyl chloride  CrO 2 Cl2  are formed.
K 2 Cr2 O 7  4NaCl  6H 2SO 4  2KHSO 4  4NaHSO 4  2CrO 2 Cl 2  3H 2 O
(f) Reaction with H2O2 : -
Acidified solution of dichromate can give deep blue colour solution with H 2 O 2 . The blue colour sides away
gradually due to the disproportions of CrO5 with Cr2+ .
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Cr2 O72  4H 2 O 2  2H   2CrO5  5H 2O Cr (Butterfly structure)

(g) Action with HCl : -

Potassium dichromium recats with hydrochloric acid and evolves chlorine.
K 2 Cr2 O 7  14HCl  2KCl  2CrCl3  7H 2 O  3Cl 2
(h) Action of con. H2SO4
(i) In cold, and crystals of chromic anhydride are formed.
K 2 Cr2 O7  2H 2SO 4  2CrO3  2KHSO 4  H 2 O
(ii) On heating the structure oxygen in evolved.
2K 2 Cr2 O 7  8H 2SO 4  2K 2SO 4  2Cr2  SO 4 3  8H 2 O  3O 2
(i) Oxidising properties :
The dichromates act as powerful oxidising agent in acidic medium. In presence of dil H 2SO 4 .K 2 Cr2 O 7
liberates Naicent oxygen and therefore acts as an oxidising agent.
K 2 Cr2 O 7  4H 2SO 4  K 2SO 4  Cr2  SO 4 3  4H 2 O  3  O 

In terms of electronic concept the Cr2 O 72  ion takes up electrons in the acidic medium and hence acts as an
oxidising agent.
Cr2 O72  14H   6e   2Cr 3  7H 2O
 It oxidises iodides to iodine : -
Cr2 O 72   14H   6e   2Cr 3  7H 2 O
 2I   I 2  2e    3
 
Cr2 O72  14H   6I   2Cr 3  3I2  7H 2 O
K 2 Cr2 O 7  7H 2SO 4  6KI  4K 2SO 4  Cr2  SO 4 3  7H 2 O  3I 2
 Acidified ferrous sulphate to ferric sulphate

Cr2 O 72  14H   6e   2Cr 3  7H 2 O

Fe 2  Fe3  e 1  6

Cr2 O72   14H   6Fe 2  2Cr 3  6Fe 3  7H 2 O

K 2 Cr2 O 7  6FeSO 4  7H 2SO 4  Cr2  SO 4 3  3Fe 2  SO 4 3  7H 2 O  K 2SO 4

 Oxidiese H 2S to sulphur

Cr2 O 72   14H   6e   2Cr 3  7H 2 O

H 2S  S  2H   e 1  3

Cr2 O72   3H 2S  8H   2Cr 3  3S  7H 2O

K 2 Cr2 O 7  3H 2S  4H 2SO 4  Cr2  SO 4 3  3S  7H 2 O  K 2SO 4
Similarly, it oxidises sulphites to sulphates, chloride to chlorine, nitrites to nitrates, thiosulphates to sulphates

and sulphur and stannous Sn

2
 
salts to stannic Sn
4

salts. 
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3SO32  Cr2 O 72  8H   3SO 24  2Cr 3  4H 2O

3NO2  Cr2 O72  8H   3NO3  2Cr 3  4H 2 O

3S2 O32  Cr2 O72  8H   3SO 42  3S  2Cr 3  4H 2O

6Cl   Cr2 O72   14H   3Cl 2  2Cr 3  7H 2 O

3Sn 2  Cr2 O72   14H   3Sn 4  2Cr 3  7H 2 O

It oxidises SO 2 to sulphuric acid,
K 2 Cr2 O 7  4H 2SO 4  K 2SO 4  Cr2  SO 4 3  4H 2 O  3O

SO 2  O  H 2 O  H 2SO 4
3.3 Structure
The chromate ion has tetrahedral structure in which four atoms around chromium atom are oriented in a
tetrahedral arrangement.

O O

Cr Cr
or
O O O O
O O
Chromate ion
The structure of dichromate ion consist of two tetrahedra sharing an oxygen atom at the common corner.

O O O
O m O O
0p
18 Cr Cr
130o Cr 16 or
Cr 0p O
m O
O O
O O
O O
Dichromate ion

 
4.1 Preparation
Potassium permanganate is prepared from mineral pyrolusite  MnO 2  . The preparation involves the following
steps.
(a) Conversion of pyrolusite ore to potassium manganate :
The pyrolusite MnO 2 is fused with caustic potash (KOH) or potassium carbonate in the presence of air or
oxidising agents, such as KNO3 or KClO3 to give a green mass due to the formation of potassium manganate

 K 2 MnO 4  .
2MnO 2  4KOH  O 2  2K 2 MnO 4  2H 2 O
2MnO 2  4K 2 CO 3  O 2  2K 2 MnO 4  2CO 2

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 ® The d- and f-Block Elements
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(b) Oxidation of potassium manganate to potassium permanganate :
The green mass is extracted with water resulting is green solution of potassium manganate. The solution is
then treated with a current of Cl 2 or ozone or CO 2 to oxide K 2 MnO 4 to KMnO 4 . The solution is
concentrated and dark purple crystals of KMnO 4 seperate out.
2K 2 MnO 4  Cl 2  2KCl  2KMnO 4
2K 2 MnO 4  O3  H 2 O  2KMnO 4  2KOH  O 2
3K 2 MnO 4  2CO2  2K 2 CO3  MnO2  2KMnO4
Alternatively, alkali potassium manganate is electrolytically oxidised.
Electrolytic method :
The potassium manganate solution is taken in an electrolytic cell which contains iron cathode and nickel
anode. When current is passed the manganate ion is oxidised to permanganate ion at anode and hydrogen is
liberated at cathode.
K 2 MnO4  2K   MnO 24 
At anode : MnO 24  MnO 4  e 
Green
At cathode : 2H   2e   2H
2H  H 2
Laboratory Method of Preparation :
In Laboratory a Manganese (ii) Salt is oxidised by peroxodisulphate to permanganate
2Mn 2 5 s2 O8 2 8H 2 O 2MnO4 10SO42 16H
4.2 Properties
(a) Colour and M.P. - Does Violet crystalline solid, M.P. 523 K.
(b) Solubility : - Moderately soluble is room temperature, but fairly soluble in hot water giving purple solution
(c) Heating : - When heated stromgly it decomposes at 746 K to give K 2 MnO 4 and O 2 .
513K
2KMnO 4 K 2 MnO 4 MnO 2 O2
Solid KMnO 4 gives KOH, MnO and water vapours, when heated in current of hydrogen.

2KMnO 4  5H 2   2KOH  2MnO  4H 2 O
(d) Action of alkali : -
On heating with alkali, potassium permanganate changes into potassium manganate and oxygen gas is evolved.
4KMnO 4  4KOH  4K 2 MnO 4  2H 2 O  O 2
(e) Oxidising character : -
KMnO 4 acts as powerful oxidising agent in neutral. alkaline or acidic solution because it liberates nascent
oxygen as : -
Acidic solution : - Mn 2 ions are formed
2KMnO 4  3H 2SO 4  K 2SO 4  2MnSO 4  3H 2O  5  O 

 M
MnO4  8H   5e   Mn 2  4H 2O  Equivalent wt.  
 5
Neutral solution : MnO 2 is formed
2KMnO 4  H 2 O  2KOH  2MnO 2  3 O 

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 M
MnO 4  2H 2O  3e  MnO 2  4OH   Equivalent wt.  
 3
During the reaction the alkali produced generates the alkaline medium even if we start from neutral medium
Alkaline medium : Manganate ions are formed.
2KMnO 4  2KOH  2K 2 MnO 4  H 2O  O 
Reactions in Acidic Medium :
In acidic medium KMnO 4 oxidizes : -
(a) Ferrous salts to feric salts
MnO 4 8H 5e Mn 2 4H 2 O
2 3
Fe Fe e 1 5

MnO 4 5Fe 2 8H Mn 2 5Fe 3

4H 2 O
(b) Oxalates to CO 2 :
2
[MnO 4 8H 5e Mn 4H 2 O] 2
[C2O 42 2CO 2 2e ] 5
2MnO 4 5C2 O42 16H 2Mn 2 10CO 2 8H 2O
(c) Iodides to Iodine
2
[MnO 4 8H 5e Mn 4H 2 O] 2
[2I I2 2e ] 5
2
10I 2MnO 4 16H 2Mn 5I 2 8H 2 O
(d) Sulphities to sulphates
2
[MnO 4 8H 5e Mn 4H 2 O] 2
[SO32 H 2O SO24 2H 2e ] 5
5SO32 2MnO4 6H 2Mn 2
5SO 42 3H 2 O

(e) It oxidizes H 2S to S
2
[MnO 4 8H 5e Mn 4H 2 O] 2
[S2 S 2e ] 5
2 2
2MnO 4 16H 5S 2Mn 5S 8H 2 O
(f) It oxidizes SO 2 to sulphuric acid
2KMnO 4 3H 2SO 4 K 2SO 4 2MnSO 4 3H 2O 5 O
[SO 2 H 2O O H 2SO 4 ] 5
2KMnO 4 5SO 2 2H 2O K 2SO 4 2MnSO 4 2H 2SO 4
(g) It oxidizes Nitrites to nitrates
2KMnO 4 3H 2SO 4 K 2SO 4 2MnSO 4 3H 2 O 5 O
[KNO 2 O KNO3 ] 5
2KMnO 4 5KNO2 3H 2SO 4 K 2SO 4 2MnSO 4 5KNO3 3H 2 O
Reactions in Neutral Medium :
(a) It oxidizes H 2S to sulphur :

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 ® The d- and f-Block Elements


2KMnO 4 H2O 2KOH 2MnO 2 3O

H 2S O H 2O S 3
2KMnO 4 3H 2S 2KOH 2MnO 2 2H 2 O 3S

(b) It oxidizes Manganese sulphate  MnSO 4 to MnO 2  manganese dioxide :

2KMnO 4  H 2 O  2KOH  2MnO 2  3 O 

MnSO 4  H 2 O  O  MnO 2  H 2SO 4  3
2KOH  H 2SO 4  K 2SO 4  2H 2 O
2KMnO 4  3MnSO 4  2H 2 O  5MnO 2  K 2SO 4  2H 2SO 4

(c) It oxidizes Sodium thiosulphate to sulphate and sulphur :

2KMnO 4 H 2O 2KOH 2MnO 2 3O

Na 2S2 O3 O Na 2SO 4 S 3
2KMnO 4 3Na 2S2 O 3 H2O 2MnO 2 3Na 2SO 4 2KOH 3S
Reactions in alkaline Medium :
(a) It oxidizes Iodides to Iodates in alkaline medium :

2KMnO 4  H 2 O  2KOH  2MnO 2  3 O 

KI  3O  KIO3
2KMnO 4  KI  H 2 O  2MnO 2  2KOH  KIO 3

(b) Alkaline KMnO 4 (Baeyers reagent) oxidizes ethylene to ethylene glycol.

CH 2 CH 2 OH
H 2O O
CH 2 CH 2 OH

4.3 Structure
MnO4
O

Mn
O O
O

1. Calculate the oxidation state of underlined atom in the molecule. KMnO4 , K 2 Cr 2O7 ,CrO5
2. What is chromyl chloride Test. Write the Balance Reaction.
3. Wite the Balance chemical Reaction using ion - electron method.
(a) K 2 Cr2 O 7  HCl  KCl  CrCl3  Cl 2  H 2 O

(b) K 2 Cr2 O 7  KI  H 2SO 4  K 2SO 4  Cr2  SO 4 3  H 2 O  I 2

(c) K 2 Cr2 O 7  H 2S  H 2SO 4  Cr2  SO 4 3  S  H 2 O  K 2SO 4

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4. Draw the structure of Cr2 O 72 ion & Explain the bond length properties using Ressonance concept.
5. Discuss the preparation method of KMnO 4 from MnO 2 .
6. Describe the preparation of potassium dichromate from iron chromite ore . What is the effect of increasing
pH on a solution of potassium dichromate?
7. Describe the oxidising action of potassium dichromate and write the ionic equations for its reaction with :
(a) Iodide (b) Iron (II) solution and (c) H 2S .
8. Describe the preparation of potassium permanganate. How does the acidified permanganate solution reacts
with
(a) Iron (II) ions (b) SO 2 and (c) Oxalic acid ?
Write the ionic equations for the reactions.

Compounds of Transition Elements

1. K 2 MnO 4 can be converted into KMnO 4 by :
(A) Passing O3 gas (B) By passing Cl 2 (C) Electrolytic oxidation (D) All of these
2. When MnO 2 is heated with fused KOH in presence of air, then the product formed is :
(A) KMnO 4 , purple (B) MnO 3 , brown (C) K 2 MnO 4 , Green (D) K 2 MnO 4 , Black
3. The product of oxidation of I  with MnO 4 in alkaline medium is :

(A) IO3 (B) I 2 (C) IO  (D) I 4 O 9

4. Which of the following statements is false :-
(A) Cr2 O27  has a Cr  O  Cr bond (B) CrO24 is tetrahedral in shape
(C) Na 2 Cr2 O 7 is a primary standard in volumetry (D) Na 2 Cr2 O 7 is less soluble than K 2 Cr2 O 7
5. The dark purple colour of KMnO4 disappears in the titration with oxalic acid in acidic medium. The overall
change in the oxidation number of manganese in the reaction is :
(A) 5 (B) 1 (C) 7 (D) 2
6. The total types of Cr - O bonds in K 2Cr2O7 is ____.
(A) 4 (B) 5 (C) 2 (D) 3
7. In neutral or alkaline solution, MnO4 oxidises thiosulphate to :
(A) S2 O 72  (B) S2 O82  (C) SO32 (D) SO24
8. Given below are two statements : One is labelled as Assertion A and the other is labelled as Reason R
Assertion A : Permanganate titrations are not performed in presence of hydrochloric acid.
Reason R : Chlorine is formed as a consequence of oxidation of hydrochloric acid.
In the light of the above statements, choose the correct answer from the options given below
(A) Both A and R are true and R is the correct explanation of A
(B) Both A and R are true but R is NOT the correct explanation of A
(C) A is true but R is false
(D) A is false but R is true

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

The elements in which the additional electron enters in  n  2  f orbitals are called inner transition elements
or f-block elements.

 Position in the periodic table

The lanthanides resemble with yttrium in most of their properties. So it became necessary to accomodate all
the fifteen elements together at one place. This has been done by placing the first element, lanthanum below
yttrium and placing the remaining fourteen elements separately in the lower part of the periodic table.
Lanthanide series  Z  58  71  Ce  Lu 
Actinide series  Z  90  103  Th  Lw 
LANTHANIDES (RARE EARTHS OR LANTHANONES)
(i) Lanthanides are reactive elements so do not found in free state in nature.
(ii) Most important minerals for lighter Lanthanides are - Monazite, cerites and for heavier lanthanides - Gadolinite
and Xenotime

 Electronic configuration
(i) The general configuration of lanthanides may be given as 4f 114 5s 2 5p6 5d 01 6s 2 .

Outer
Atomic Configuration
Element Symbol electronic
Number +3 ion
Atomic
58 Cerium Ce 4f 1 5d1 6s 2 4f 1
59 Praseodymium Pr 4f 3 6s 2 4f 2
60 Neodymium Nd 4f 4 6s 2 4f 3
61 Promethium Pm 4f 5 6s 2 4f 4
62 Samarium Sm 4f 6 6s 2 4f 5
63 Europium Eu 4f 7 6s 2 4f 6
64 Gadolinium Gd 4f 7 5d1 6s 2 4f 7
65 Terbium Tb 4f 9 6s 2 4f 8
66 Dysprosium Dy 4f 10 6s 2 4f 9
67 Holmium Ho 4f 11 6s 2 4f 10
68 Erbium Er 4f 12 6s 2 4f 11
69 Thulium Tm 4f 13 6s 2 4f 12
70 Ytterblum Yb 4f 14 6s 2 4f 13
71 Lutecium Lu 4f 14 5d1 6s 2 4f 14
(ii) It is to be noted that filling of 4f orbitals in the atoms is not regular. A 5d electron appears in Gadolinium
 Z  64  with an outer electronic configuration of 4f 7 5d1 6s 2 (and not 4f 8 6s 2 ). This is because the 4f and
5d electrons are at about the same potential energy and that the atoms have a tendency to retain stable half
filled configuration.
(iii) On the other hand, the filling of f-orbitals is regular in tripositive ions.
(iv) After losing outer electrons, the f-orbitals shrink in size and became more stable.
(v) Pm is the only synthetic radioactive lanthanide.

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 Oxidation states
Lanthanides Oxidation
Ce 58 +3, +4
Pr59 +3, (+4)
Nd 60 +3
Pm61 +3
Sm 62 (+2), +3
Eu 63 +2, +3
Gd 64 +3
Tb 65 +3, +4
Dy 66 +3, (+4)
Ho 67 +3
Er68 (+2), +3
Tm 69 (+2), +3
Yb 70 +2, +3
Lu 71 +3

(i) The lanthanides contains two s electrons in the outermost shell, they are therefore expected to exhibit
characteristic oxidation state of +2. But for the lanthanides, the +3 oxidation is common.
This corresponds to the use of two outermost electrons  6s  alongwith one inner electron. The inner electron
2
(ii)
used is a 5d electron (in La, Gd and Lu), or one of the 4f electron if no 5d electrons present.
(iii) All the lanthanides attains +3 oxidation state and only Cerium, Praseodymium, and Terbium exhibits higher
oxidation state (+4). Eu and Yb exhibit +2 oxidation state.
(iv) Oxidation states +2 and +4 occur particularly when they lead to
(a) A noble gas configuration. Ex : Ce  f 
4 0

(b) A half filled 'f' orbital. Ex : Eu ,Tb ,  f 

2 4 1

(c) A completely filled 'f' orbital. Ex : Yb 2 f 14

(v) Therefore, in higher oxidation state, they act as oxidising while in lower state as reducing agents.

 Magnetic properties :
(i) In tripositive lanthanide ions the number of unpaired electrons regularly increases from lanthanum to Gadolinium
(0 to 7) and then continuously decreases upto lutecium (7 to 0).
(ii) Lanthanum and lutecium ions are diamagnetic, while all other tripositive lanthanide ions are paramagnetic
(Exception - Neodyomium is the most paramagnetic lanthanide).
(iii) Ce 4 and Yb 2 are also diamagnetic ions.

 Colour
(i) The lanthanide ions have unpaired electrons in their 4f orbitals. Thus these ions absorbs visible region of light
and undergo f-f transition and hence exhibit colour.
(ii) The colour exhibited depends on the number of unpaired electrons in the 4f orbitals.
(iii) The ions often with 4f 1 configuration have similar colour to those ions having 4f 14  n configuration.
(iv) Lanthanide ions having 4f 0 ,4f 14 are colourless.

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 ® The d- and f-Block Elements

 Other Properties
(i) Highly dense metals with high m.pts. do not show any regular trend.
(ii) Ionisation Energies : Lanthanides have fairly low ionisation energies comparable to alkaline earth metals.
(iii) Electro positive character : High due to low I.P.
(iv) Complex formation : Do not have much tendency to form complexes due to low charge density because of
their large size. Lu 2 is smallest in size can only form complex.
(v) Reducing Agent : They readily lose electrons so are good reducing agent.
(vi) Alloy : Alloys of lanthanides with Fe are called mish metals.
(vii) Basic Nature : La OH 3
is most basic in nature while Lu  OH 3 least basic.
(viii) Carbide : Lanthanides form MC 2 type carbide with carbon, which on hydrolysis gives C 2 H 2 .

 Lanthanide contraction :
(i) In the lanthanide series with increasing atomic number, there is a progressive decrease in the size from
lanthanum to lutecium or from La 2 to Lu 3 . This contraction in size is known as lanthanide contraction.
(ii) The general electronic configuration of these elements is 4f 114 5s 2 5d 01 6s 2 . In these elements the added
electron enters the deep seated f-orbitals and therefore experiences considerable pull by the nucleus.
(iii) Due to very poor shielding effect of  n  2  f electrons, they exert very little screening effect on the outermost
6s 2 electrons. Hence with increasing atomic number, the enhanced nuclear charge leads to contraction in the
size of atoms and ions.
(iv) The atomic volumes of Europian and Ytterbium are unexceptely large. The large atomic size of Eu and Yb
suggest weaker bonding in the solid elements. Both these elements have only two electrons extra than the
stable configurations (half filled, f7, and completely filled, f14), hence they utilise two electrons in metallic
bonding as in the case with barium.

 Effects of Lanthanide Contraction

Close resemblance of Lanthanides :
The general decrease in the sizes of the landanides with an increase in their nuclear charges result in a small
increase in their ionisation energies. Hence their basic and ionic nature gradually decreases from La to Lu.
This also explains the variations in properties such as increased tendency for hydrolysis and formation of
complex salts and decreased thermal stability, solubility of their salts.
Similarity of Yttrium with Ianthanides :
The properties of Yttrium are so similar to the lanthanides that it is considered more a member of the
lanthanide series than a congener of scandium.
Anomalous behaviour of post-lanthanides :
The following anomalies may be observed in the behaviour of post-lanthanide elements.
(a) Atomic size :
The ionic radii of Zr 4 is about 9% more than Ti 4 . Similar trend is not maintained on passing from the
second to third transition series. The ionic radius of Hf 4 , instead of increasing (beacuse of inclusion of one
more electronic shell), decreases (or is vitually equal to Zr 4 ) as a consequence of the lanthanide contraction.
This explains the close similarities between the members of the second and third transition series than between
the elements of the first and second series.
(b) Ionisation potential and electronegativity :
The effect of lantahnide contradiction is also seen in the increase in the ionisation potential values and
electronegativities of the elements of the third transition series, contrary to the general trend.
Because of the lanthanide contraction, the post-lanthanide elements have stronger positive field and thus the
electrons are held more tightly.
The greater effective nuclear charge of the former make them more electronegative than the latter.
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(c) High density :

Because of lanthanide contraction, the atomic sizes of the post lanthanide elements become very small.
Consequently, the packing of atoms in their metallic crystals become so much compact that their densities are
very high.
The densities of the third transition series elements are almost double to those of the second series elements.
 Application of lanthanides
Cerium is most useful element in the lanthanides
Misch metal is pyropheric and is used in cigarette and gas lighter.
ACTINIDES (5F-BLOCK ELEMENTS)
(i) The elements in which the extra electron enters 5f-orbitals of  n  2  th main shell are known as actinides.
(ii) The man-made eleven elements Np93  Lw100 are placed beyond uranium in the periodic table and are
collectively called trans-uranium elements.
(iii) Th, Pa and U first three actinides are natural elements.
 Electronic Configuration
The general configuration of actinides may be given as 5f 114 6d 01 ,7s 2 .
Atomic Electronic
Elements Symbol
Number Configuration
90 Thorium Th 5f 0 6d 2 7s 2
91 Proactenium Pa 5f 2 6d1 7s 2
92 Uranium U 5f 3 6d1 7s 2
93 Neptunium Np 5f 4 6d1 7s 2
94 Plutonium Pu 5f 6 6d 0 7s 2
95 Americium Am 5f 7 6d0 7s 2
96 Curium Cm 5f 8 6d1 7s 2
97 Berkellium Bk 5f 9 6d 0 7s 2
98 Californium Cf 5f 10 6d 0 7s 2
99 Einstenium Es 5f 11 6d 0 7s 2
100 Fermium Fm 5f 12 6d 0 7s 2
101 Mendalevium Md 5f 13 6d 0 7s 2
102 Nobellium No 5f 14 6d 0 7s 2
103 Lawerencium Lr 5f 14 6d1 7s 2
 Oxidation states
Actinides Oxidation state Actinides Oxidation state
Th 90 +4 Br97 +3, (+4)
Pa 91 (+4), +5 Cl98 +3
U 92 (+3), (+4), (+5), +6 Es90 +3
Np 90 (+3), (+4),(+5,( +6), (+7) Fm100 +3
Pu 94 (+3), +4, (+5), (+6), (+7) Md101 +3
Am96 +2, (+3), (+4), (+5), (+6) No102 +3
Cm 96 +3, (+4) Lw 103 +3

(i) In lanthanides and actinides +3 oxidation is the most common for both of the series of elements.
(ii) This oxidation state becomes increasingly more stable as the atomic number increases in the actinide series.
(iii) Highest oxidation states in the axtinides is +7 exhibited by Np93 and Pu 94 . It is unstable.
(iv) Highest stable oxidation state is +6 shown by 92 U.
26
 ® The d- and f-Block Elements

 Other Properties :
(i) Physical appearance : Acitinides are silvery white metals. They get tamished when exposed to the attack
of alkalies.
(ii) Density : All the actinides except thorium and americium have high densities.
(iii) Colour : Actinide ions are generally coloured. The colour of actinide ions depends upon the number of 5f
electrons. The ions containing no unpaired 5f-electrons (exactly full filled f-subshell) are colourless, as expected.
(iv) Ionisation energies : Ionisation energies values of actinides are low.
(v) Electropositive character : All the known actinide metals are highly electropositive. They resemble lanthanide
series in this respect.
(vi) Melting Boiling properties : They have high melting and boiling points. They do not follow regular gradation
of melting or boiling points with increase in atomic number.
(vii) Magnetic properties : The actinide elements are paramagnetic due to the presence of unpaired electrons.
(viii) Radioactive nature : All the actinides are radioactive in nature.
(ix) Actinide contraction : The size of atom/cation decrease regularly along the actinides series. The steady
decrease in ionic radii with increase in atomic number is referred to as actinide contraction. This is due to
poor shielding of 5f-electrons.

Illustration 11 :
The correct order of ionic radii of Ce, La, Pm and Yb in +3 oxidation state is :
(A) La 3  Pm 3  Ce3  Yb3 (B) La 3  Ce3  Pm 3  Yb3
(C) Yb3  Ce3  Pm 3  La 3 (D) Yb3  Pm 3  Ce3  La 3
Solution :
Due to Lanthanide contraction decreases atomic sizes from La 3
to Lu 3 . Hence, the correct order will be
(D) for the given lens.

Illustration 12 :
In contact of the lanthanide, which of the following statements is not correct?
(A) Availability of electrons results in the formation of compounds in +4 state for all the members
of the series
(B) There is a gradual decreases in the radii of the members with increasing atomic number in the
series
(C) All the members exhibit +3 oxidation state
(D) Because of similar properties the separation of lanthanoids is not easy.
Solution :
All members of 4f do not show +4 oxidation state.

1. What is Lanthanide contraction?

2. What is called Lanthanide series?
3. Ce 4 is diamagnetic in nature. Explain.
4. What is Misch Metal?
5. What are the trans-uranic elements?
6. Write the name of synthetic radioactive element?
7. Write the general electronic configuration of Lanthanide Series.
8. Write the electronic configuration of Gd.

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f-Block Group
1. Lanthanoid contraction implies :-
(A) Decrease in density (B) Decrease in mass
(C) Decrease in ionic radii (D) Decrease in radioactivity
2. The correct order of ionic radii of
Y3 , La 3 , Eu 3 and Lu 3 is : -
(A) Y 3  La 3  Eu 3 <Lu 3 (B) Y 3  Lu 3  Eu 3 <La 3
(C) Lu 3  Eu 3 <La 3  Y 3 (D) La 3  Eu 3 <Lu 3  Y 3
3. Which of the following is not a consequence of the Lanthanoid contraction ?
(A) 5d series elements have higher IE1 then 3d or 4d series
(B) Zr and Hf have a comparable size
(C) Zr and Hf occurs together in the earth crust in their minerals
(D) High density of the sixth period elements
4. Actinoids show higher property in comparision to lanthanides in :
(A) Radioactivity (B) Possibility of higher oxidation state
(C) Basic nature of hydroxides (D) All of these
5. The common oxidation state of the elements of lanthanide series is :-
(A) + 2 (B) + 3 (C) + 4 (D) + 1
6. Which of the following is not a lanthanoid element?
(A) Cerium (B) Europium (C) Lutetium (D) Thorium
7. Knowing that the chemistry of lanthanoids (Ln) is dominated by its +3 oxidation state, which of the
following statements is incorrect ?
(A) Ln(III) compounds are generally colourless
(B) Ln(III) hydroxides are mainly basic in character
(C) Because of the large size of the Ln(III) ions the bonding in its compounds is predominently ionic in
character
(D) The ionic sizes of Ln(III) decrease in general with increasing atomic number
8. In context of the lanthanoids, which of the following statements is not correct ?
(A) Because of similar properties the separation of lanthanoids is not easy
(B) Availability of 4f electrons results in the formation of compounds in +4 state for all the members of the
series
(C) There is a gradual decrease in the radii of the members with increasing atomic number in the series
(D) All the members exhibit +3 oxidation state
9. The maximum number of possible oxidation states of actinoides are shown by
(A) Berkelium (Bk) and californium (Cf) (B) Nobelium (No) and lawrencium (Lr)
(C) Actinium (Ac) and thorium (Th) (D) Neptunium (Np) and plutonium (Pu)
10. The electronic configurations of bivalent europium and trivalent cerium are
(atomic number : Xe = 54, Ce = 58, Eu = 63)

(A)  Xe 4f and  Xe 

 4f 9
(B)  Xe  4f 7 and  Xe 4f
1

(C)  Xe  4f 7 6s 2 and  Xe 4f (D)  Xe  4f 2 and  Xe 4f

2
6s 2 7

11. Which one of the following lanthanoids does not form MO 2 ? [M is lanthanoid metal]
(A) Pr (B) Dy (C) Nd (D) Yb

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 ® The d- and f-Block Elements

12. Cerium (IV) has a noble gas configuration. Which of the following is correct statement about it?
(A) It will not prefer to undergo redox reactions.
(B) It will prefer to gain electron and act as an oxidizing agent
(C) It will prefer to give away an electron and behave as reducing agent
(D) It acts as both, oxidizing and reducing agent
13. The most common oxidation state of Lanthanoid elements is +3. Which of the following is likely to deviate
easily from +3 oxidation state?
(A) Ce (At. No. 58) (B) La (At. No. 57) (C) Lu (At. No. 71) (D) Gd (At. No. 64)
14. The ‘f’ orbitals are half and completely filled, respectively in lanthanide ions
(Given : Atomic no. Eu, 63; Sm, 62; Tm, 69; Tb, 65; Yb, 70; Dy, 66)
(A) Eu2+ and Tm2+ (B) Sm2+ and Tm2+ (C) Tb4+ and Yb2+ (D) Dy3+ and Yb3+

Que. 1 2 3 4 5 6 7 8 9 10
Ans. C C C C D D C B C C
Que. 11 12 13
Ans. C C A

Que. 1 2 3 4 5 6 7 8
Ans. D C A C A C D A

Que. 1 2 3 4 5 6 7 8 9 10
Ans. C B C D B D A B D B
Que. 11 12 13 14
Ans. D B A C

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 For explaining the irregularities found in the observed electronic configuration, one has to consider the net
effect of so many other factors such as :
(i) Nuclear electronic attraction (ii) Screening effect
(iii) Inter-electronic repulsion (iv) The exchange energy force etc.
 Zn  30    Ar  3d 4s
10 2
Cd  48    Kr  4d10 5s 2 Hg  80    Xe  4f 14 5d10 6s 2
(i) These three elements do not have any unpaired electrons in their 'd' orbitals in atomic as well as in their
common oxidation states. Therefore they are only classified as 'd' block elements and not as transition
elements.
(ii) Copper, Silver and Gold, the elements of IB group i.e., coinage metals, have ns1  n  1 d10 configuration.
They are transition elements as in their higher oxidation state they have an unpaired electron in their 'd'
orbitals.
 Example of Some coloured metal ions :
Ti 3 Purple Cr 3 Green Mn 2 Light pink Fe 2 Green
Fe 3 Yellow Co 3 Pink Ni 2 Green Cu 2 Blue
Sc3 Colourless Ti 4 Colourless Ti3 Purple V 4 Blue
V 3 Green V 2 Violet Cr 2  Blue Cr 3 Green
Mn 3 Violet Mn 2 Pink Fe 2 Green(light) Fe3 Yellow
Co 2  Pink Ni 2  Blue Zn 2 Colourless
 Transition metals and their compounds exhibiting catalytic properties in various processes are -

Catalyst Used
TiCl3 Used as the Ziegler-Natta catalyst in the production of polythene.
V2 O5 Convert SO 2 to SO3 in the contact process for making H 2SO 4
MnO 2 Used as a catalyst to decompose KClO3 to give O 2
Fe Promoted iron is used in the Haber-Bosch process for making NH 3
FeCl3 Used in the production of CCl 4 from CS2 and Cl 2
FeSO 4 and H 2 O 2 Used as Fenton's reagent for oxidizing alcohols to aldehydes.
PdCl2 Wacker process for converting C 2 H 4  H 2 O  PdCl2 to
CH 3CHO  2HCl  Pd .
Pd Used for hydrogenation (e.g. phenol to cyclohexanone).
Pt / PtO Adams catalyst, used for reductions.
Pt Formerly used for SO 2  SO3 in in the contact process for making
H 2SO 4
Pt / Rh Formerly used in the ostwald process for making HNO3 to oxidize
NH 3 to NO .
Cu Is used in the direct process for manufacture of  CH 3 2 SiCl2 used to
make silicones.
Cu/V Oxidation of cyclohexanol/cyclohexanone mixture to adipic acid which
is used to make Nylon-66
CuCl2 Decon process of making Cl 2 from HCl
Ni Raney nickel, numerous reduction processes (e.g. manufacture of
hexamethylenediamine, production of H 2 from NH 3 , reducing
anthraquinone to anthraquinol in the production of H 2 O 2
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 ® The d- and f-Block Elements
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 Comparision of lanthanides and Actinides
Points of Resemblance :
(i) Both lanthanides and actinides show a dominant oxidation state of +3.
(ii) Both are electropositive and act as strong reducing agents.
(iii) Cations with unpaired electrons in both of them are paramagnetic.
(iv) Most of the cations of lanthanides and actinides are coloured.
(v) Both of them show a steady decrease in their ionic radii along the series. Thus, lanthanides show lanthanide
contraction and actinides show actinide contraction.
 Difference between lanthanides & Actinides
Lathanides :
(i) Besides the most common oxidation state of +3 lanthanides show +2 and +4 oxidation states in case of
certain elements.
(ii) Lanthanides have less tendency towards complex formation.
(iii) Except promethium, they are non radioactive.
(iv) Oxides and hydroxide of lanthanides are less basic.
Actinides :
(i) Besides the most common oxidation state of +3, actinides show +4, + 5 and +6 oxidation states in case
of certain elements.
(ii) Actinides have a stronger tendency towards complex formation.
(iii) All the actinides are radioactive.
(iv) Oxides and hydroxides of actinides are more basic.
Chemical behaviour of Lanthanides :
Lanthanides chemical behaviour is similar to calicium but with increase in atomic number, they behave more
like Aluminium.
Ln2O3

Burns in
O2 H2
s
id
ac
th
Heate
d wi
S3 with S
Ln 2
With halogens
Ln LnX3
N Wi
with th H
d 2 O
eate
H With C
2773 K Ln(OH)3 + H2
LnN

LnC2

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1. When Cu 2 ion is treated with KI , a white precipitate is formed. Explain the reaction with the help of
chemical equation.
2. Out of Cu 2 Cl 2 and CuCl 2 , which is more stable and why ?
3. When a brown compound of manganese (A) is treated with HCl it gives a gas (B). The gas taken in excess,
reacts with NH 3 to give an explosive compound (C). Identify compounds A, B and C.
4. Although fluorine is more electronegative than oxygen, but the ability of oxygen to stabilise higher oxidation
states exceeds that of fluorine. Why ?
5. Although Cr 3 and Co 2  ions have same number of unpaired electrons but the magnetic moment of Cr 3 is
3.87 B.M. and that of Co 2 is 4.87 B.M. Why ?
6. 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.
7. Describe the preparation of potassium dichromate from iron chromite ore. What is the effect of increasing
pH on a solution of potassium dichromate ?
8. A solution of KMnO 4 on reduction yields either a colourless solution or a brown precipitate or a green
solution depending on pH of the solution. What different stages of the reduction do these represent and how
are they carried out?
9. The second and third rows of transition elements resemble each other much more than they resemble the
first row. Explain why ?
10. E of Cu is + 0.34 V while that of Zn is -0.76 V. Explain.

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 ® The d- and f-Block Elements


1. Chromium forms most stable compound in the following oxidation state -

(A) Cr(l) (B) Cr(ll) (C) Cr(lll) (D) Cr(v)
2. In which of the following complexes the oxidation number of metal is zero -
(A)  Pt  NH 3  2 Cl 2  (B) Cr  CO 6  (C) Cr  NH 3 3 Cl3  (D) Cr  en 2 Cl 2 
3. Among the following outermost configuration metals, which shows the highest oxidation state :-
3 2 5 2 5 1 6 2
(A) 3d 4s (B) 3d 4s (C) 3d 4s (D) 3d 4s
4. Not more than one oxidation state is shown by-
(A) Mn (B) Cr (C) Fe (D) Sc
5. The metallic bond strength in first transition series increase from -
(A) Sc to Mn (B) Sc to Cr (C) Cr to Zn (D) Sc to Cu
6. The pair in which both the elements generally show only one oxidation state is -
(A) Sc and Zn (B) Zn and Cu (C) Cu and Ag (D) Zn and Au
7. Transition elements show variable oxidation states because they lose electrons from the following orbitals :
(A) ns and np (B) (n - 1) d and ns (C) (n - 1) d (D) ns
8. CrO 3 is a/an
(A) Acidic oxide (B) Basic oxide (C) Neutral oxide (D) Amphoteric
9. 2
Ti and Ni 2  contain -

(A) Equal number of paired electrons (B) Equal number of unpaired electrons
(C) Different number of 2p electrons (D) Different number of 3p electrons
10. Which of the following is not a characteristic property of transition metal -
(A) High enthalpy of atomisation (B) Formation of interstitial compounds
(C) Diamagnetism (D) Variable oxidation state
11. The general electronic configuration of transition element is -
(A)  n  1 d15 (B)  n  1 d110 ns1 (C)  n  1 d110 ns1 2 (D) None of these
12. The highest oxidation state achieved by a transition metal is given by -
(A) ns electrons (B) (n - 1) d electrons (C) (n + 1) d electrons (D) ns + (n - 1) d electrons
13. Which of the following ions in solution undergoes disproportionation -
(A) Fe2 (B) Cr 3 (C) Cu  (D) Zn 2
14. Amongst TiF62 ,CoF63 ,Cu 2 Cl 2 and NiCl 42
(At. No. of Ti = 22, Co = 27, Cu = 29, Ni = 28). The colorless species are :
(A) CoF63 and NiCl24  (B) TiF62 and CoF63 (C) Cu 2 Cl2 and NiCl24 (D) TiF62  and Cu 2 Cl2
2
15. Cu  H 2 O 4  absorbs yellow light and one determine complementary colour will be :-
(A) Green (B) Orange (C) Blue (D) Violet
16. Largest radii of iron is present in -
(A) K 4  Fe  CN 3  (B) FeSO 4 .7H 2 O

(C) FeSO 4 .  NH 4 2 SO 2 .6H 2 O (D) Fe  CO 5

17. Which of the following transition metal ion is diamagnetic :
(A) Co 2 (B) Ni 2 (C) Cu 2 (D) Hg 2
18. Which of the following compounds is paramagnetic and coloured also :
(A) K 2 Cr2 O 7 (B)  NH 4  2 TiCl6  (C) VOSO 4 (D) K 3  Cu  CN  4 

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19. Zero magnetic moment will be shown by the compound :

3 1 3
(A) Cr  NH3 6  (B)  Ag  CN 2  (C)  Fe  CN 6  (D)  CoF6 
3

20. Diamagnetic ion is

(A) Cu 2 (B) Cr 3 (C) Ti 3 (D) None of the above
21. Amongst TiF62 ,CoF63 ,Cu 2 Cl 2 and NiCl 42
(At. No. of Ti = 22, Co = 27, Cu = 29, Ni = 28). The colorless species are :
(A) TiF62  and Cu 2 Cl2 (B) Cu 2 Cl2 and NiCl24 (C) TiF62 and CoF63 (D) CoF63 and NiCl24 
22. Which of the following is diamagnetic : -
(A) Zn 2  (B) Ni 2 (C) Co 2 (D) Cu 2
23. If n is the number of unpaired electron, the magnetic moment (ln B.M.) of transition metal /Ion is given by
(A) n  n  2 (B) 2n  n  1 (C) n  n  2 (D) 2n  n  1
24. Which of the following transition metal ion has definity magnetic moment -
(A) Sc3 (B) Ti3 (C) Cu  (D) Zn 2 
25. Transition metals ions form innerstitial compounds because -
(A) Interstices are available in their crystal lattice (B) The have empty d-orbitals
(C) They have high value of ionic potential (D) They show variable oxidation states
26. Transition elements act as catalyst because -
(A) Their melting points are higher (B) Their I.P. values are higher
(C) They have high density (D) They can show variable oxidation states
27. Titanium shows magnetic moment of 1.73 B.M. in its compounds. What is the oxidation number of Ti is
compound?
(A) +1 (B) +4 (C) +3 (D) +2
28. The magnetic moment for Ti 2 , V 3 and Ni 2  is -
(A) 4.90 (B) 3.87 (C) 2.83 (D) 1.73
29.   15 is true for the pair -
(A) Co 2 , Cr 3 (B) Fe 2 , Cr 3 (C) Fe 3 ,Cr 2 (D) Mn 2 , Fe 2
30. In a transition series as the atomic number increases, paramagnetic : -
(A) Increase gradually
(B) Decrease gradually
(C) First increases to a maximum and then decreases
(D) First decreases to a minimum and then increases
31. The magnetic moment of a transition metal ion is formed to be 3.87 B.M. The number of unpaired electrosis
present in it is : -
(A) 2 (B) 3 (C) 4 (D) 5
32. Which of the following transition metal has the highest melting point : -
(A) Cr (B) Mo (C) W (D) Hg
33. During the course of the reaction :
(A) Catalyst undergoes changes in oxidation satte
(B) Catalyst increases the rate of reaction
(C) Catalyst is regenerated in its original form when the reactants from the products
(D) All are correct
34. Which of the following group of transition metals is called coinage metals :
(A) Cu, Ag, Au (B) Ru, Rh, Pd (C) Fe, Co, Ni (D) Os, lr, Pt
35. Which of the following contains that maximum number of unpaired electrons : -
(A) TiCl2 (B) MnCl2 (C) FeSO 4 (D) CuSO 4
34
 ® The d- and f-Block Elements

2
36. The electrode potential of M / M of 3d-series elements shows positive value of :
(A) Zn (B) Fe (C) Co (D) Cu
37. Fex 2 and Fey3 are known when x and y are :
(A) x  F,Cl, Br, I and y  F,Cl, Br (B) x  F,Cl, Br and y  F,Cl,Br, I
(C) x  Cl, Br,I and y  F,Cl, Br, I (D) x  F,Cl,Br, I and y  F,Cl, Br,I
38. The oxide that shows magnetic property is :
(A) SiO 2 (B) Mn 3 O 4 (C) Na 2 O (D) MgO
39. Given below are two statement : one is labelled as Assertion A and the other is labelled as Reason R:
Assertion A : Size of Bk 3 ion is less than Np3 ion.
Reason R : The above is a consequence of the lanthanoid contraction.
In the light of the above statements, choose the correct answer from the options given below :
(A) A is false but R is true
(B) Both A and R are true but R is not the correct explanation of A
(C) Both A and R are and R is the correct explanation of A
(D) A is true but R is false
40. Metals generally melt at very high temperature. Amongst the following, the metal with the highest melting
point will be
(A) Hg (B) Ag (C) Ga (D) Cs
41. The metal ion (in gaseous state) with lowest spin-only magnetic moment value is
(A) V2+ (B) Ni2+ (C) Cr2+ (D) Fe2+
2+
42. In 3d series, the metal having the highest M /M standard electrode potential is
(A) Cr (B) Fe (C) Cu (D) Zn
43. In following pairs, the one in which both transition metal ions are colourless is :
(A) Sc3 , Zn 2  (B) Ti 4  , Cu 2 (C) V 2  , Ti3 (D) Zn 2  , Mn 2 
44. Which of the following 3d-metal ion will give the lowest enthalpy of hydration   hyd H  when dissolved in
water ?
(A) Cr2+ (B) Mn2+ (C) Fe2+ (D) Co2+
45. Which one of the lanthanoids given below is the most stable in divalent form?
(A) Ce (Atomic Number 58) (B) Sm (Atomic Number 62)
(C) Eu (Atomic Number 63) (D) Yb (Atomic Number 70)

35
KCET-Chemistry 
®

1. On the basis of the standard electrode potential values stated for acid solutions, predict whether Ti 4 species
may be used to oxidise Fe II to Fe III .

Reaction E / V
Ti IV  e   Ti3 :  0.01
3  2
Fe  e  Fe :  0.77
2. Chromium is a typical hard metal while mercury is a liquid.
3. Silver is a transition metal but zinc is not.
4. Based on the data, arrange Fe 2  , Mn 2  and Cr 2 in the increasing order of stability of +2 oxidation state :
E 0Cr3 |Cr 2  0.4 V, E 0Mn3 |Mn 2  1.5 V, E 0Fe3 |Fe2  0.8V
5.
(i) Name the element showing maximum number of oxidation states among the first series of transition
metals from Sc (Z = 21) to Zn (Z = 30).
(ii) Name the element which shows only +3 oxidation state.
6. Complete the following reaction equations :
(i) Cr2 O27   Sn 2  H 
(ii) MnO4  Fe 2  H  
7. What happens when potassium dichromate is heated with sodium chloride and conc. H 2SO 4 ?
8. CrO3 is an acid anhydride. Explain.
9. Complete the following chemical equations :
(i) KMnO 4 
513 K

(ii) MnO 2  KOH  O 2 
10. Among the lanthanoids, Ce (III) can be easily oxidized to Ce (IV). (At. No. of Ce = 58)
11. Why do Zr and Hf exhibit similar properties ?
12. What are different oxidation states exhibited by lanthanoids ?
13. What is the basic difference between the electronic configurations of transition and inner transition elements?
14. Which trivalent ion has maximum size in lanthanide series ?
15. Give one example each of lanthanoid ion having +2, +3 and +4 oxidation states.
16. Name an important alloy which contains some of the lanthanoid metals.
17. Identify the lanthanoid element that exhibits +4 oxidation state.

36
 ® The d- and f-Block Elements


1. The spin only magnetic moment of Fe2 ion (in B.M.) is approximately [2011]
(A) 4 (B) 7 (C) 5 (D) 6
2. Which one of the following has a magnetic moment of 1.75 B.M.? [2012]
3 3 3
(A) Ti3 (B) V (C) Cr (D) Fe
3. The "spin only" magnetic moment of Ni 2 in aqueous solution would be [At No. of Ni = 28]

(A) 6B.M (B) 15B.M (C) 2B.M (D) 8B.M

4. Which one of the following shows highest magnetic moment?
(A) Fe2 (B) Co 2 (C) Cr 3 (D) Ni 2
5. In a transition series, with the increase in atomic number, the paramagnetism
(A) Increases gradually
(B) Decreases gradually
(C) First increases to a maximum and then decreases
(D) First decreases to a minimum and then increases
6. Which one of these is not known?
(A) CuCl 2 (B) CuI 2 (C) CuF2 (D) CuBr2
7. The correct statement is
(A) The earlier memebers of lanthanoid series resemble calcium in their chemical properties
(B) The extent of actinoid contraction is almost the same as lanthanoid contraction
(C) In general, lanthanoids and actinoids do not show variable oxidation states
(D) Ce 4 in aqueous solution is not known.
8. The electronic configuration of Gd 2 is [2015]
(at.no. of Gd is 64)
(A)  Xe  4f 7 (B)  Xe  4f 7 5d1 (C)  Xe  4f 8 (D)  Xe  4f 7 5d1 6s 2
9. On heating potassium permanganate, one of the following compound is not obtained [2015]
(A) MnO (B) K 2 MnO 4 (C) O 2 (D) MnO 2
10. The bivalent metal ion having maximum paramagnetic behaviour among the first transition series element is
[2016]
(A) Mn 2  (B) Cu 2 (C) Sc2 (D) Cu 
11. Mn 2  compounds are more stable than Fe compounds towards oxidation to their +3 state, because
2

[2016]
(A) Mn 2  is more stable with high 3rd ionisation energy
(B) Mn 2  is bigger in size
(C) Mn 2  has completely filled d-orbitals
(D) Mn 2  does not exist.
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KCET-Chemistry 
®

12. Which of the following does not represent property stated against it? [2021]
(A) Co 2  Fe2   Mn 2   Ionic size (B) Ti < V < Mn - Number of oxidation states

(C) Cr 2  Mn 2  Fe 2  Paramagnetic behaviour (D) Sc > Cr > Fe - Density

13. What will be the value of x in Fe x  , if the magnetic moment,   24BM ? [2022]
(A) 0 (B) +1 (C) +2 (D) +3
14. The only lathanoid which is radioactive [2022]
(A) Promethium (B) Praseodymium (C) Lanthanum (D) Cerium
15. All Cu(II) halides are known, except iodide, the reason for it is that [2022]
(A) Cu 2 has much more negative hydration enthalpy
(B) Cu 2 ion has smaller size
(C) Iodide is bulky ion
(D) Cu 2 oxidises iodide to iodine.
16. In which one of the following pairs, both the elements does not have  n  1 d10 ns 2 configuration in its
elementary state? [2023]
(A) Zn, Cd (B) Cd, Hg (C) Hg, Cn (D) Cu, Zn
17. Which of the following is correct with respect to melting point of a transition element?
[2023]
(A) V > Cr (B) Cr > Mn (C) Mn > Fe (D) Ti > V
18. aMnO4  bS2 O32  H 2O  xMnO 2  ySO 42  zOH  a and y respectively are [2023]
(A) 8 ; 3 (B) 8 ; 6 (C) 3 ; 6 (D) 8 ; 8
19. Match the following. [2024]
I. Zn 2 i. d 8 configuration
II. Cu 2 ii. Colourless
III. Ni 2
iii.   1.73 B.M.
Codes :
(A) I - i, II - ii, III - iii (B) I - ii, II - iii, III - i (C) I - ii, II - i, III - iii (D) I - i, II - iii, III - ii
20. Which of the following sttements related to lanthanoids incorrect? [2024]
(A) Lanthanoids are silvery white soft metals.
(B) Samarium shows +2 oxidation state.
(C) Ce 4 solutions are widely used as oxidising agents in titrimetric analysis.
(D) Colour of lanthanoid ion in solution is due to d-d transition.
21. The transition element (  5% ) present with lanthanoid metal in Misch metal is [2024]
(A) Mg (B) Fe (C) Zn (D) Co
22. In the reaction between moist SO 2 and acidified permanganate solution [2024]

(A) SO 2 is oxidised to SO24 MnO4 is reduced to Mn 2 

(B) SO 2 is reduced to S MnO4 is oxidised to MnO 4

(C) SO 2 is oxidised to SO32 MnO4 is reduced to MnO 2

(D) SO 2 is reduced to H 2S MnO4 is oxidised to MnO 4

38
 ® The d- and f-Block Elements


Que. 1 2 3 4 5 6 7 8 9 10
Ans. C B B D B A B A B C
Que. 11 12 13 14 15 16 17 18 19 20
Ans. C D C D D D D C B D
Que. 21 22 23 24 25 26 27 28 29 30
Ans. A A A B A D C C A C
Que. 31 32 33 34 35 36 37 38 39 40
Ans. B C D A B D A B D B
Que. 41 42 43 44 45
Ans. B C A B C

Que. 1 2 3 4 5 6 7 8 9 10
Ans. C B D A C B A B A A
Que. 11 12 13 14 15 16 17 18 19 20
Ans. C C C A D D B B B D
Que. 21 22
Ans. B A

39