5.

d & f BLOCK ELEMENTS

1. INTRODUCTION 1.2 Electronic configuration

(1) In d-block elements with increase in atomic number, the d-
1.1 Definition orbitals of penultimate shell i.e. (n-1) d are gradually
filled by electrons. The general electronic configuration
“The elements in which the last differentiating electron
of d- block element is,
enters into the d-orbitals of the penultimate shell
(n-11) d1-10, ns0-2.
i.e. (n–1) d where n is the last shell are called d-block
elements”. A transition element may also be defined as (2) Depending upon the d-orbitals of which penultimate shell
i.e. n = 4, 5, 6, 7 are filled, four rows (called series) os
the element
ten elements each obtained. They correspond to 3d, 4d,
which partially filled d-orbital in their ground state or most
5d and 6d subshells.
stable oxidation state.
Cu (Z = 29) = 1s2 2s2 2p6 3s2 3p6 3d10 4s1 (3) Energy of ‘(n–1)d’ subshell is slightly greater than ‘ns’
subshell, hence orbital is filled first then (n – 1) d orbitals.
Cu2+ = 1s2 2s2 2p6 3s2 3p6 3d9
(4) The general electronic configuration of d-block/d-series
(Cupric ion)
elements be shown as follows :
The properties of these elements are intermediate
1. First (3d) Transition Series (Sc–Zn)
between the properties of s-block and p-block elements.
These elements represent a change or transition in
properties from more electropositive elements (s-block)
to less electropositive elements (p-block). Therefore
these elements are called transition elements. 2. Second (4d) Transition Series (Y-Cd)
Position in the periodic table
The position of d-block element has been shown in
periodic table as follows :
3. Third (5d) Transition Series (La–Hg)

4. Fourth (6d) Transition Series

Exceptional configuration of Cr and Cu. The exceptions

observed in the first series are in case of electronic
configurations of chromium (Z = 24) and copper (Z = 29).
(1) d-block elements lie in between ‘s’ and ‘p’ block It may be noted that unlike other elements, chromium
elements, and copper have a single electron in the 4s-orbital. This
i.e. these elements are located in the middle of the is due to the gain of additonal stability by the atom by
periodic table. either having
(2) d-block elements are present in,
4th period ( Sc to Zn, 10 elements) → 1st Transition series. half-filled configuration (i.e., containing 5 electrons in the
21 30
5th period ( Y to Cd, 10 elements) → 2nd Transition d-sublevel) or completely filled configuration, (i.e.,
series.
39 48

6th period ( 51La, 72Hf to 80 Hg, 10 elements) → 3rd Transition containing 10 electrons in the d-sublevel). The 3d-level
series. in case of chromium gets excatly half-filled with
7th period ( Ac, Rf to Uub, 10 elements) → 4th configuration 3d5 4s1 and that in case of copper, it gets
Transition
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 completely filled
89 104 112
series. with configuration 3d10 4s1. This can be explained on the
basis of exchange energy

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 140 d AND f BLOCK ELEMENTS
Thus, the electronic configuration of chromium (Z = 24) period.
and copper (Z = 29) are 1s2 2s2 2p6 3s2 3p6 3d5 4s1 and 1s2
2s2 2p6 3s6 3p6 3d10 4s1 respectively.

1.3 Properties

1. Atomic Raddii
(i) The atomic radii of the transition metals lie in-between
those of s- and p-block elements.
(ii) Generally the atomic radii of d-block elements in a series
decreas with increase in atomic number but the decrease
in atomic size is small after midway.
Explanation
The atomic radius decreases with the increase in atomic
number as the nuclear charge increases whereas the
shielding effect of d-electron is small. After midway, as
the electrons enter the last but one (penultimate) shell, the
added d-electron shields (screens) the outermost electron.
Hence, with the increase in the d-electrons, screening
effect increases. This counterbalances the increased
nuclear charge due to increase in atomic number. As a
result, the atomic radii remain practically same after
chromium. For example in Fe, the two opposing
tendencies almost counterbalance and there is no change
in the size from Mn to Fe.
(iii) At the end of the period, there is a slight increase in the
atomic radii.
Explanation
Near the end of series, the increased electron-electron
repulsions between added electrons in the same orbitals
are greater than the attractive forces due to the increased
nuclear charge. This results in the expansion of the
electron cloud and thus the atomic radius increases.
(iv) The atomic radii increase down the group. This means
that the atomic radii of second series are larger than those
of first transition series. But the atomic radii of the
second and third transition series are almost the same.
The atomic radii of the elements of the second and third
transition metals are nearly same due to lanthanide
contraction (or also called lanthanoid contraction)
discussed later.

1.4 Ionic radii

(i) The trend followed by the ionic radii is the same as that
followed by atomic radii.
(ii) Ionic radii of transition metals are different in different
oxidation states.
(iii) The ionic radii of the transition metals are smaller than
those of the representative elements belonging to the same
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d AND f BLOCK ELEMENTS 141
increase for the successive elements is much higher.
1.5 Metallic character
Except for mercury which is a liquid, all the transition
elements have typical metallic structure. They exhibit
all the characteristics of metals. ductile, have high
melting and boiling points, high thermal and electrical
conductivity and high tensile strength.
Transition elements have relatively low ionization
energies and have one or two electrons in their outermost
energy level (ns1 or ns2). As a result, metallic bonds are
formed. Hence, they behave as metals. Greater the
number of unpaired d electrons, stronger is the bonding
due to the overlapping of unpaired electrons between
different metal atoms.
1.6 Melting Point

Transition metals have high melting points which is due

to their strong metallic bond. The metallic bond. The
metalic bonding depends upon the number of unpaired
e–. The melting point first increases (Sc-Cr), reaches a
maximum value (Cr) and then decreases (Fe-Zn)
* Tungsten (W) has the highest melting point.
* Mercury (Hg) has the lowest melting point.
* Mn has the lowest melting point in 3d series typicl
transition elements.
1.7 Ionisation energies or Ionisation enthalpies
(i) The first ionisation enthalpies of d-block elements lie
between s-block and p-block elements. They are higher
than those of s- block elements and are lesser than those
of p-block elements. The ionisation enthalpy gradually
increases with increase in atomic number along a given
transition series though some irregularities are observed
Explanation
(i) The increasing ionization enthalpies are due to
increased nuclear charge with increase in atomic number
which reduces the size of the atom making the removal
of outer electron difficult.
(ii) In a given series, the difference in the ionisation enthalpies
between any two successive d-block elements is very
much less than the difference in case of successive s-
block or p- block elements.
Explanation
The addition of d electrons in last but one [(n — 1) or
penultimate] shell with increase in atomic number
provides a screening effect and thus shields the outer s
electrons from inward nuclear pull. Thus, the effects of
increased nuclear charge and addition of d electrons
tend to oppose each other.
(iii) The first ionization enthalpy of Zn, Cd and Hg are,
however, very high because of the fully filled (n-1) d10
ns2 configuration.
(iv) Although second and third ionization enthalpies also, in
general, increase along a period, but the magnitude of

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 142 d AND f BLOCK ELEMENTS
(v) The high values of 3rd ionization enthalpies for Cu, Ni
In ‘3d' series all element contain 2 electrons in ‘4s' and
and Zn explain why they show a maximum oxidation state
hence they all give a common minimum oxidation state
of +2.
of +2. (Except ‘Cr' and ‘Cu' where minimum oxidation
(vi) The first ionisation enthalpies of 5d elements are higher state is +1.] The maximum oxidation state is given by
as compared to those of 3d and 4d elements. This is Mn i.e. Mn+7 in which two electrons are removed from 4s
because the weak shielding of nucleus by 4f electrons in and five unpaired electrons are removed from 3d orbitals.
5d elements results in greater effective nuclear charge (4) The highest oxidation state is shown by Ruthenium (Ru)
acting on the outer valence electrons. and Osmium (Os) i.e. +8.
1.8. Oxidation state (5) Across the period oxidation state increases and it is
maximum at the centre and than decreases even if atomic
“The net numerical charge assigned to an atom of an number increases. The element which shows highest
element in its combined state is known as its Oxidation oxidation state occur in the middle or near the middle of
state or Oxidation number”. the series and than decreases.
(1) With the exception of few elements, most of the d-block (6) Transition metals also show zero oxidation states in
elements show more than one oxidation state i.e. they metal carbonyl complex. (Nickel tetracarbonyl).
show variable oxidation states. The elements show Example : Ni in Ni (CO)4 has zero oxidation state.
variable oxidation state because of following reasons: (7) The bonding in the compounds of lower oxidation state
(i) ‘(n-1) d’ and ‘ns’ orbitals in the atoms of d-block (+2, +3) is mostly ionic and the bonding in the
elements have almost same energies and therefore compounds of higher oxidation state is mostly covalent.
electron can be removed from ‘(n-1)d’ orbitals as easily (8) The relative stabilities of some oxidation states can be
as ‘s’ orbitals electrons. explained on the basis of rule extra stability, according to
(ii) After removing ‘s’ electrons, the remainder is called which d0, d5 and d10 are stable configurations.
Kernel of the metal cations. In d-block elements, the For example, the stability order of some ions is as follows:
kernel is unstable and therefore it loses one or more Ti4+ (3d0, 4s0) > Ti3 (3d1, 4s0)
electrons from (n – 1)d electrons. This results in Mn2+ (3d5, 4s0) > Mn3+ (3d4,
formation of cations with different oxidation states.
4s0) Fe3+, (3d5, 4s0) > Fe2+ (3d6,
(2) All transition elements show variable oxidation state except 4s0)
last element in each series.
(9) Cu+2 is more stable than Cu+1 even when Cu+1 is 3d10
(3) Minimum oxidation state = Total number of electrons in while Cu+2 is 3d due to high heat of hydration.
4s lost. Maximum oxidation state = (Total number of
Variable oxidation states shown by 3d-series of d-block elements.
electrons in 4s + number of unpaired electrons in 3d
lost).
Oxidation States

ELECTRONIC Sc Ti V Cr Mn Fe Co Ni Cu Zn

CONFIGURATION d1s2 d2s2 d3s2 d4s2 d5s2 d6s2 d7s2 d8s2 d9s2 d10s2

d5s1 d10s1
+1 +1

+2 +2 +2 +2 +2 +2 +2 +2 +2 +2

+3 +3 +3 +3 +3 +3 +3 +3 +3

+4 +4 +4 +4 +4 +4 +4

+5 +5 +5 +5 +5

+6 +6 +6
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d AND f BLOCK ELEMENTS 143
+7

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 144 d AND f BLOCK ELEMENTS
(iv) The values of Eo for Mn, Ni and Zn are more negative than
1.9 Standard electrode potentials (Eo) and chemical
expected from the generall trend. This is due to greater
reactivity
stability of half-filled d-subshell (d5) in Mn2+, and
Thermodynamic stability of the compounds of transition completely filled d-subshell (d10) in Zn2+. The exceptional
elements can be evaluated in terms of the magnitude of behaviour of Ni towards Eo value from the regular trend is
ionisation enthalpies of the metals — smaller the due to its high negative enthalpy of hydration.
ionisation enthalpy of the metal, stabler is its compound. Trends in the M3+/M2+ Standard Electrode Potentials
In solution, the stability of the compounds depends upon
(i) A very low value for Eo (Sc3+/Sc2+) reflects the stability
electrode potentials rather than ionization enthalpies.
of Sc3+ ion which has a noble gas configuration.
Electrode potential values depend upon factors such as
enthalpy of sublimation (or atomisation) of the metal, the (ii) The highest value for Zn is on account of very high
ionisation enthalpy and the hydration enthalpy, i.e., stability of Zn2+ ion with d10 configuration. It is difficult to
remove an electron from it to change it into +3 state.
M s —∆—sub—H → M sub
g , (∆ H is enthalpy of
(iii) The comparatively high value of E o (Mn3+/Mn2+) shows
sublimation/ atomisation)
that Mn2+ is very stable which is on account of stable d5
H configuration of Mn2+.
M s —∆—i —→ M + g i+ e– , (∆ H is ionisation
enthalpy) (iv) The comparatively low value of Eo (Fe3+/Fe2+) is on account
M+ g of extra stability of Fe3+ (d5), i.e., low third ionization
+ aq —∆—hyd— aq , (∆ hyd H is enthalpy of
H
→ M+ enthalpy of Fe.
hydration)
(v) The comparatively low value for V is on account of the
The total energy, ∆ H,T for the process involving
sublimation, ionisation and hydration simultaneously, stability of V2+ ion due to its half-filled t3 configuration
i.e., 2g

for the process, M s ——→ –

aq + e , will be the (discussed in unit 9).
M+ sum
of the three types of enthalpies, i.e., the oxidizing acids (HNO3 and H2SO4) which are reduced.
The reason for positive Eo value for copper is that the sum
∆TH = ∆subH + ∆iH + ∆hydH. of enthalpies of sublimation and ionization is not balanced
by hydration enthalpy.
Thus, ∆T H, is the total enthalpy change when solid meal,
M is brought in the aqueous medium in the form of
monovalent ion, M+ (aq).

Trends in the M2+/M Standard Electrode Potentials

(i) There is no regular trend in the Eo (M2+/M) values. This
is because their ionization enthalpies (I1 + IE2) and
sublimation enthalpies do not show any regular trend.
(ii) The general trend towards less negative E o values along
the series is due to the general increase in the sum of first
and second ionization enthalpies.
(iii) Copper shows a unique behaviour in the series as it is the
only metal having positive value for Eo. This explains
why is does not liberate H2 gas from acids. It reacts only
with
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 d AND f BLOCK ELEMENTS 145
Chemical Reactivity and Eo Values. The transition
metals vary very widely in their chemical reactivity.
Some of them are highly electropositive and dissolve in
mineral acids whereas a few of them are ‘noble’, i.e., they
do not react with simple acids. Some results of chemical
reactivity of transition metals as related to their Eo values
are given below :
(i) The metals of the first transition series (except copper)
are relatively more reactive than the othr series. Thus,
they are oxidized by H+ ions though the actual rate is
slow, e.g., Ti and V are passive to dilute non-oxidizing
acids at room temperature.
(ii) As already explained, less negative Eo values for M2+/M
along the series indicate a decreasing tendency to form
divalent cations.
(iii) More negative Eo values than expected for Mn, Ni and
Zn show greater stability for Mn2+, Ni2+ and Zn2+.
(iv) Eo values for the redox couple M3+/M2+ indicate that
Mn3+ and Co3+ ions ar the strongest oxidizing agents in
aqueous solution whereas Ti2+, V2+ and Cr2+ are
strongest reducing agents and can liberate hydrogen
from a dilute acid, e.g., 2 Cr2+ (aq) + 2 H+ (aq) ——→ 2
2 Cr3+ (aq) + H (g)

1.10 Catalytic Property

Most transition elements and their compounds have
good catalytic properties because
(a) They possess variable oxidation state.

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 146 d AND f BLOCK ELEMENTS
(b) They provide a large surface area for the reactant to
be absorbed. 2. COMPLEX FORMATION
Catalysts Uses Transition metal ions form a large number of complex
compounds. Complex compounds are those which have
TiCl4 + Al (C2H5)3 a metal ion linked to a number of negative ions (anions)
Ziegler-Natta catalyst, used in or neutral molecules having lone pairs of electrons.
V2O5 polymerisation of ethylene These ions or molecules are called ligands. They
donate lone pairs of electrons to the central transition
Fe Contact process SO2 → SO3 metal ion forming coordinate bonds
Haber Bosch process A few examples are given below :
PdCl2 [Fe(CN) ]3–, [Fe(CN) ]4–, [Cu(NH ) ]2+, [Zn(NH ) ]2+,
Wacker’s process for CH3CHO 6 6 3 4 3 4
[Ni(CN) ]2– and [Ptcl ]2–
4 4
manufacturing
Pd Such complex compounds are not formed by s - and p -
Hydrogenation of alkene, block elements.

Pt/ alkyne etc Explanation. The transition elements form complexes

PtO because of the following reasons :
Adam’s catalyst for selective
(i) Comparatively smaller size of their metal ions.
reduction
Pt (ii) Their high ionic charges.
Catalytic convertor, for
(Because of (i) and (ii), they have large charge/size ratio)
cleaning
(iii) Availability of vacant d-orbitals so that these orbitals
car exhaust fumes Ostwald’s can accept lone pairs of electrons donated by the
Pt/Rh
process : NH3 → NO ligands.
Oxidation of alcohols
Cu 2.1 Interstitital Compounds

The transition metals form a large number of interstitial

compounds in which small atoms such as hydrogen,
1.11 Magnetic Behaviour carbon, boron and nitrogen occupy the empty spaces
(interstitial sites) in their lattices (Fig.).
When a substance is placed in a magnetic field of They are represented by formulae like TiC, TiH , Mn N,
strength
2 4
H, the intensity of the magnetic field in the substance Fe3H, Fe3C etc. However, actually they are non-
may be greater than or less than H. If the field in the stoichiometric materials, e.g., TiH1.7, VH0.56 etc. and the
substance is greater than H, the substance is a bonds present in them are neither typically ionic nor
paramagnetic material and attracts line of force. If the covalent. Some of their important characteristics are as
field in the substance is less than H, the substance is follows:
diamagnetic. Diamagnetic materials tend to repel lines of (i) They are very hard and rigid, e.g., steel which is an
force. The magnetic moment of a substance depends on interstitial compound of Fe and Cis quite hard.
the strength of magnetic field generated due to electronic Similarly, some borides are as hard as diamond.
spin, there is a change in electric flux which leads to (ii) They have high melting points which are higher than those
induction of magnetic field. The electron is also under of the pure metals.
orbital angular momentum or orbital spin. It leads to
(iii) They show conductivity like that of the pure metal.
generation of magnetic moment.
(iv) They acquire chemical inertness.
In first transition elements series the orbital angular
magnetic moment is insignificant the orbital contribution 2.2 Alloy formation
is quenched by the electric fields of the surrounding
atoms so magnetic moment is equal to the spin magnetic Alloys are homogeneous solid solutions of two or more
moment only.
µeff = n(n + 2)BM metals obtained by melting the components and then
cooling the melt. These are formed by metals whose
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d AND f BLOCK ELEMENTS 147
atomi c
n → no. of unpaired electron. radii differ by not more than 15% so that the atoms of one
Maximum transition elements and compounds are metal can easily take up the positions in the crystal
paramagnetic due to presence of unpaired electrons. lattice of the other (Fig.)

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 148 d AND f BLOCK ELEMENTS
Now, as transition metals have similar atomic radii and (v) In general, the oxides in the lower oxidation states of
other characteristics, hence they form alloys very
the metals are basic and in their higher oxidation states,
readily. Alloys are generally harder, have higher
melting points and more resistant to corrosion than the they are acidic whereas in the intermediate oxidation
individiual metals. state, the oxides are amphoteric.

The most commonly used are the ferrous alloys the For example, the behaviour of the oxides of manganese
metals chromium, vanadium, molybdenum, tungsten may be represented as follows :
and manganese are used in the formation of alloy steels
+2 +8 /3 +3 +4 +7
and stainless steels. Some alloys of transition metals with
MnO Mn3O4 Mn2O3 MnO2 Mn2O7
non- transition metals are also very common. e.g.,
brass
(Cu + Zn) and bronze (Cu + Sn) Basic Amphoteric Amphoteric Amphoteric Acidic

Thus, Mn2O7 dissolves in water to give the acid HMnO4.

3.2 KMnO4 Potassium permanganate

It is prepared from the ore called chromite or

ferrochrome or chrome iron, FeO.Cr2O3. The various
steps involved are as follows :
(i) Preparation of sodium chromate. The ore is finely
powdered, mixed with sodium carbonate and quick
lime and then roasted, i.e., heated to redness in a
reverberatory furnace with free exposure to air when
sodium chromate (yellow in colour) is formed and
carbon dioxide is evolved. Quick lime keeps the mass
porous and thus facilitates oxidation.

4FeO.Cr2O3 + 8Na2CO3+ 7O2 ——→ 8Na

2
CrO
4
+ 2Fe
2 3
O + 8CO
2

Chromite ore Sod. chromate Ferric oxide

After the reaction, the roasted mass is extracted with

water when sodium chromate is completely dissolved
3. COMPOUNDS OF TRANSITION ELEMENTS while ferric oxide is left behind. Ferric oxide is
separated out by filtration.
3.1 Oxides
(ii) Conversion of sodium chromate into sodium
(i) The metals of the first transition series form oxides dichromate. The filtrate containing sodium chromate
with oxygen at high temperature. solution is treated with concentrated sulphuric acid
when sodium chromate is converted into sodium
(ii) The oxides are formed in the oxidation, states +1 to +7 (as dichromate.
given in Table 8.10, page 8/14).
2Na 2 CrO 4 + H 2SO 4 ——→ Na 2 Cr2 O7 + Na 2SO 4 + H 2 O
(iii) The highest oxidation state in the oxides of any Sod.chromate Conc. Sod. dichromate

transition Sodium sulphate being less soluble crystallizes out as

metal is equal to its group number, e.g., 7 in Mn2O7. decahydrate, Na2SO4. 10H2O and is removed. The clear
Beyond group 7, no higher oxides of iron abov Fe O are
known.
2
Some metals in higher oxidation state stabilize by decreases, e.g., Mn2O7 is a covalent green oil.
Even CrO3 and V2O5
forming oxocations, e.g., VV
2 as VO+ , VIV as VO2+ and
have low melting points.
TiIV as TiO2+.
+2 +8 / 3 +3 +4 +7

(iv) All the metals except scandium form the oxides with the MnO Mn3O4 Mn2O3 MnO2 Mn2O7
formula MO which are ionic in nature. As the oxidation
number of the metal increases, ionic character
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 d AND f BLOCK ELEMENTS 149
solution is then evaporated in iron pans to a specific
gravity of 1.7 when a further crop of sodium sulphate is
formed. It is removed and the solution is cooled when orange
crystals of sodium dichromate, Na2Cr2O7. 2H2O
separate on standing.
(iii) Conversion sodium dichromate into potassium
dichromate. Hot concentrated solution of sodium dichromate
is treated with calculated amount of potassium chloride when
potassium dichromate, being much less soluble than sodium
salt, crystallizes out on cooling as orange crystals.

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(b) On heating the mixture, oxygen is evolved.
Na 2 Cr2 O7 + 2KCl ——→ + 2NaCl
K 2 Cr2 O7
Sodium dichromate Potassium dichromate
2K 2 Cr2 O7 + 8H 2SO 4 ——→ 2K 2SO 4 + 2Cr2 SO 4 3 + 8H2O +
3O2

6. Oxidising properties. It is a powerful oxidising agent. In

3.3 Properties
the presence of dilute sulphuric acid, one molecule of
1. Colour and Melting point. It forms orange crystals potassium dichromate furnishes 3 atoms of available
which melt at 669 K. oxygen as indicated by the equation :

2. Solubility. It is moderately soluble in cold water but

K 2 Cr2 O 7 + 4H 2SO 4 ——→ K 2SO 4 + SO4 3 + 4H2O + 3O
freely soluble in hot water. Cr2
or Cr2 O72– +14H + + 6e– ——→ 2Cr 3+ + 7H O
3. Action of heat. When heated to a white heat, it 2

decomposes with the evolution of oxygen.

Eq. wt. of K2Cr2O7 = Mol. wt. = 294 = 49
4K Cr O ——→ 4K CrO + 2Cr O + 6 6
3O
2 2 7 2 4 2 3 2

4. Action of alkalies. When an alkali is added to an (i) It liberates I2 from KI

orange red solution of dichromate, a yellow solution
K 2 Cr2 O 7 + 7H 2SO 4 + 6KI ——→ 4K 2SO 4 + Cr2 SO 4
results due to the formation of chromate. 3

K Cr O + KOH ——→ 2K CrO +

H O +3I2 + 7H2O
2 2 7 2 4 2
Pot. dichromate Pot.chromate (ii) It oxidises ferrous salts to ferric salts

or Cr O 2– + 2 OH – ——→ 2 CrO2– +
H O 2 7 K 2 Cr2 O7 + 7H 2SO 4 + 6FeSO 4 ——→ K 2SO 4 + SO4 3
4 2
Cr2

On acidifying, the colour again changes to orange red

due to the reformation of dichromate. +3Fe SO4 3
+ 2H2O
2

2 K 2 CrO4 + H 2SO4 ——→ K 2 Cr2 O7 + K 2SO4 + (iii) It oxidises H2S to

H2O sulphur

or 2 CrO2– + 2 H + ——→ Cr O2– + H

O K 2 Cr2 O 7 + 4H 2SO 4 + 3H 2S ——→ K 2SO 4 + Cr2
SO 4 3
4 2 7 2
+ 7H2O + 3S
This interconversion is explained by the fact that in (iv) It oxidises sulphites to sulphates and thiosulphates to
dichromate solution, the Cr2O 2–
ions are invariably in sulphates and sulphur
7

equilibrium with CrO2– ions at pH = 4, K 2 Cr2 O 7 + 4H 2SO 4 + 3Na 2SO3 ——→ K 2SO4 + SO4 3
i.e., 4 Cr2
pH = 4
Cr O 2–+ + H O —— — — ~ 2CrO 2–
+ 2H + 4H2O + 3Na2SO4
(v) It oxidises nitrites to
nitrates
2 7 2 v——— 4
Orange red Yellow
dichromate chromate
K 2 Cr2 O7 + 4 H 2SO 4 + 3NaNO2 ——→ K 2 SO 4 + SO4 3
Cr2
On adding an alkali (i.e., increasing the pH of the law of chemical equilibrium, the reaction proceeds in the
solution), the H+ ions are used up and according to the forward direction producing yellow chromate solution. On
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d AND f BLOCK ELEMENTS 151
the other hand, when an when an acid is added (i.e., pH
+ 3 NaNO3 + 4 H2O
of the
(vi) It oxidises halogen acids to halogen

K 2Cr2 O7 +14 HCl ——→ 2KCl + 2CrCl3 + 7H2 O + 3Cl2

solution is decreased), the concentration of H + ions is (vii) It oxidises SO2 to sulphuric acid
increased and the reaction proceeds in the backward
K 2 Cr2 O 7 + H 2 SO 4 + 3SO 2 ——→ K 2 SO 4 SO4 + 3H 2O
direction producing an orange red dichromate solution. 3
+ Cr2
5. Action of concentrated sulphuric acid
(viii) It oxidises stannous salts to stannic salts
(a) In cold, red crystals of chromic anhydride
Cr O2– +14 H+ + 3Sn 2+ ——→ 2 Cr 3+ + 3 Sn 4+ + 3 Sn 4+ + 7 H
(chromium trioxide) are formed. O2 7 2

(ix) It oxidises ethyl alcohol to acetaldehyde and acetic acid.

K 2 Cr2 O7 + 2H2SO 4 ——→ 2CrO3 + 2KHSO4 +
K Cr O + 4H SO ——→ K SO + Cr SO + 4H
H2O O + 3O
2 2 7 2 4 2 4 2 4 3 2

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(iii) In organic chemistry, it is used as an oxidising
CH 2 CH 2OH+ O ——→ CH3CHO + agent.
H2 O Structures of chromate and dichromate ions.
Ethyl alcohol

CH 3 CHO+ O ——→ CH 3COOH

Acetaldehyde Acetic acid

or
Test for a drunken driver. The above reaction helps to
test whether a driver has consumed alcohol or not. he is
asked to breathe into the acidified K2Cr2O7 solution taken
in a test tube. If the orange colour of the solution changes
into green colour (due to Cr2(SO4)3 formed in the
reaction), the driver is drunk, otherwise not.
7. Chromyl chloride test (Reaction with a chloride and conc. or
sulphuric acid). When heated with concentrated
hydrochloric acid or with a chloride and strong sulphuric
acid, reddish brown vapours of chromyl chloride are
obtained. 3.4 Potassium Permanganate
K 2 Cr2 O 7 + 4KCl + 6H 2SO 4 ——→ 2CrO 2 Cl2 + 6KHSO 4 + (KMnO4) Preparation
3H 2 O
Chromyl chloride
Red vapour
On a large scale, it is prepared from the mineral, pyrolusite,
MnO2. The preparation involves the following two stesp:
8. Reaction with hydrogen peroxide. Acidified K Cr O
2 2 7
solution reacts with H2O2 to give a deep blue solution (i) Conversion of MnO2 into potassium manganate. The
due to the formation of peroxo compound, CrO (O2)2. finely powdered pyrolusite mineral is fused with
potassium
Cr2 O72– + 2 H+ + 4 H2 O2 ——→ 2 CrO + 25 H hydroxide or potassium carbonate in the presence of air
5
O or oxidising agent such as potassium nitrate or
potassium chlorate when green coloured potassium
The blue colour fades away gradually due to the manganate is formed.
decomposition of CrO5 into Cr3+ions and oxygen.
2MnO + 4KOH + O ——→ 2K MnO + 2H O
2 2 2 4 2

The structure of CrO5 is in which Cr is in Potassium manganate

+6
2MnO2 + 2K2CO3 + ——→ 2K
2
MnO
4
+ 2 CO
2

oxidation state. O2
MnO + 2KOH+KNO ——→ K MnO +KNO +H O
Uses. 2 3 2 4 2 2

(i) In volumetric analysis, it is used as a primary standard 3MnO +6KOH+KClO ——→ 3K MnO +KCl+2H
for O
2 3 2 4 2
the estimation of Fe2+ (ferrous ions) and I– (iodides) in
Potassium manganate thus formed undergoes
redox titrations.
disproportionation in the neutral or acidic solution as
Not follows, if allowed to stand for some time :
e VI VII IV

Na2Cr2O7 is not used in volumetric analysis because it is 3 MnO 2–

4
+
+ 4 H ——→ 2 MnO
4
–
+ MnO 2 + 2 H 2 O
deliquescent. Manganateion Permanganate ion

(ii) Oxidation of potassium manganate to potassium

(ii) In industry, it is used
permanganate.
(a) In chrome tanning in leather industry. (a) Chemical oxidation. The fused mass is extracted
(b) In the preparation of chrome alum K SO .Cr (SO ) . with water and the solution after filtration is converted
2 4 2 43
into
24H2O and other industrially important compounds such as Cr O , CrO , CrO Cl , K CrO , CrCl etc.
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d AND f BLOCK ELEMENTS 153
potassium permanganate by bubbling carbon green solution.
dioxide, chlorine
2 3
or ozonised
3 2
oxygen
2 2
through
4 3
the
(c) In calico printing and dyeing. 3K 2 MnO 4 + 2CO2 ——→ 2KMnO 4 + MnO 2 †
(d) In photography and in hardening gelatine +2K 2CO3
film.
2K 2 MnO4 + Cl2 ——→ 2KMnO4 + 2KCl

2K 2 MnO4 + H 2 O + O3 ——→ 2KMnO4 + 2KOH +

O2

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d AND f BLOCK ELEMENTS 147
The carbon dioxide process is uneconomical as one
Presence of ZnSO4 or ZnO catalyses the
third of the original manganate is reconverted to
oxidation.
manganese dioxide. However, this process has the
advantage that the potassium carbonate formed as a by- (ii) It oxidises sodium thiosulphate to sodium sulphate.
product can be 8KMnO4 + 3Na 2S2 O3 + H 2 O ——→3K 2SO 4 + 8MnO 2 +
used for the oxidative fusion of manganese dioxide. In 3Na2SO4 + 2KOH
the chlorine process, potassium chloride obtained as a
by-product is lost. (iii) It oxidises hydrogen sulphide to sulphur.
PROPERTIES 2KMnO4 + 4H 2S ——→ 2MnS + S + K 2SO4 +
1. Colour. Potassium permanganate exists as deep purple 4H2 O
black prisms with a greenish lustre which become dull
in air due to superficial reduction. (b) In alkaline solution. In strongly alkaline solution, MnO
4
2–

2. Solubility. It is moderately soluble in water at room (manganate) ion is produced.

temperature and it is more soluble in hot water. 2KMnO4 + 2KOH ——→2K 2 MnO4 + H2 O + O or
3. Action of heat. When heated to 513 K, it readily –
MnO1–
4 + e ——→ MnO
4
2–

Mol. wt. 158

decomposes giving oxygen. Eq. wt. of KMnO4 = = = 158
1 1
2KMnO 4 ——→ K 2 MnO4 + MnO 2 +
O2
Pot. manganate
Potassium manganate is also further reduced to MnO2
At red heat, potassium manganate formed decomposes
into potassium manganite (K MnO ) and oxygen. when a reducing agent is present.
2 3

2K 2 MnO4 ——→ 2K 2 MnO3 + O2 K 2 MnO4 + H 2 O ——→ MnO2 + 2KOH + O

4. Action of heat in current of hydrogen. When heated in a
current of H2, solid KMnO4 gives KOH, MnO and water or MnO42– + 2H2 O + 2 e – ——→ MnO
2 + 4OH –
vapours.
So the complete reaction is :
2KMnO4 + 5H2 —∆—→2KOH + 2MnO +2 4H O
2KMnO4 + H2 O ——→ 2MnO2 + 2 KOH +
3O
5. Oxidising property. Potassium permanganate is
or MnO – + 2H O + 3 e– ——→ + 4OH–
powerful oxidising agent. The actual course of
MnO 4 2 2
reaction depends
on the use of the permanganate in (a) neutral (b) which is the same as that for neutral medium. Hence,
alkaline or (c) acidic solution. equivalent weight of KMnO4 in weakly alkaline medium is
same as that in the neutral medium, viz., 52.67
(a) In neutral solution. Potassium permanganate acts as a
moderate oxidising agent in neutral aqueous solution Some oxidizing properties of KMnO4 in the alkaline medium.
because of the reaction : These are given below :

2KMnO4 + H 2 O ——→ 2KOH + 2MnO2 + 3O (i) It oxidises potassium iodide to potassium iodate.

or MnO – + 2H O + 3 e– ——→ 2KMnO 4 + H 2 O + KI ——→ 2MnO 2 + 2KOH +

+ 4OH–
MnO 4 2 2
KIO3
Pot. iodate

Thus,
MnO– ion gains 3 electrons. Also, according to or I– + 6OH – ——→ IO – + 3H O + 6 e–
3 2
4
the above equation, in neutral medium, from two moles of In this case, iodine is not liberated unlike the case of acidic
permanganate, three oxygen atoms are available. In medium.
fact, during the course of reaction, the alkali generated
Similar reaction takes place with KBr.
renders the medium alkaline even when we start with
neutral solutions. Hence, Eq. wt. of KMnO4 in neutral (ii) It oxidises olefinic compounds to glycols, i.e., when an
or weakly olefinic compound is shaken with alkaline KMnO4, pink
alkaline medium colour of KMnO4 is discharged.
Mol. wt. 158 medium.
= 3 = 3 = 52.67 These are
Some oxidizing properties of KMnO4 in the neutral given below
 148 d AND f BLOCK ELEMENTS
:
(i) It oxidises hot manganous sulphate to manganese
dioxide.

2KMnO4 + 3MnSO4 + 2H2 O ——→ K 2SO4 + 2H2SO 4 +

5MnO2

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 148 d AND f BLOCK ELEMENTS

Alkaline KMnO4 used for this test is known as Baeyer’s (vii) It oxidises potassium iodide to iodine
reagent. It is used for oxidation of a number of organic
compounds. 2KMnO 4 + 3H 2 SO 4 +10KI ——→ K 2SO 4 + 2MnSO 4 +
(c) In acidic medium. Potassium permanganate in the
8H2O + 5I2
presence of dil. sulphuric acid, i.e., in acidic medium,
acts as a strong oxidising agent because of the reaction (viii) It oxidises HX (where X = Cl, Br, l) to X2

2KMnO4 + 3H 2SO 4 ——→ K 2SO 4 + 2MnSO 4 + 3H 2O + 2KMnO 4 + 3H 2SO4 +10 HX ——→ K 2SO4 + 2MnSO 4 +
5O

or MnO – + 8H + + 5 e– ——→ Mn 2+ + 4H 8H2 O + 5X2

O.
4 2

(ix) It oxidises ethyl alcohol to acetaldehyde

Since in the above reaction, MnO4– ion gains 5 electrons
2KMnO4 + 3H 2SO 4 + 5CH3 CH 2 OH ——→ K 2 SO4 + 2MnSO4 +
of five atoms of oxygen are available from two
molecules of KMnO4. Hence.
5CH3CHO + 8H2O.

Eq. wt. of KMnO4 = Mol. wt. = 158 = 31.6 Uses.

5 5
(i) It is often used in volumetric analysis for the estimation
Some oxidizing properties of KMnO4 in the acidic medium. of ferrous salts, oxalates, iodides and hydrogen
These are given below : peroxide. However, it is not a primary standard because
(i) It oxidises H2S to S. it is difficult to obtain it in the pure state and free from
traces of MnO2. It is, therefore, always first standardised
2KMnO 4 + 3H 2SO 4 + 5H 2 S ——→ K 2SO4 + 2MnSO 4 + 2H 2 O with a standard solution of oxalic acid.
+ 5O
Remember that volumetric titrations inolving KMnO4
(ii) It oxidises sulphur dioxide to sulphuric acid.
are carried out only in presence of dilute H2SO4 but not
2KMnO4 + 5 SO2 + 2H 2 O ——→ K 2 SO4 + 2MnSO 4 + in the presene of HCl or HNO3. This is because oxygen
2H 2SO 4 produced

(iii) It oxidises nitrites from KMnO4 + dill. H2SO4 is used only for oxidizing the
NO– to nitrates NO– , arsenites reducing agent. Moreover, H2SO4 does not give any
2 3
AsO3– to arsentates oxygen of its own to oxidiize the reducign agent. In case
AsO3– and sulphites and
3 4
HCl is used, the oxygen produced from KMnO4 + HCl is
thiosulphates to sulphates. partly used up to oxidize Hcl to chlorine and in case
HNO3 is used, it itself acts as oxidizing agent and partly
2KMnO 4 + 3H 2SO4 + 5KNO2 ——→ K 2SO4 + 2MnSO4 +
oxidizes the reducing agent.
3H2O + 5KNO3 (ii) It is used as a strong oxidising agent in the laboratory
as well as in industry. It is a favourite and effective
(iv) It oxidises oxalates or oxalic acid to CO2
oxidising agent used in organic synthesis Alkaline
potassium
2KMnO + + 5C2 H 2 O 4 ——→ K 2 SO4 + permanganate is used for testing unsaturation in organic
4
3H2SO4 2MnSO 4 + chemistry and is known as Baeyer’s reagent.
(iii) Potassium permanganate is also widely used as a
8H2O +10 CO2
(v) It oxidises ferrous sulphate to ferric sulphate (i.e., disinfectant and germicide. A very dilute solution of
ferrous salt to ferric salt). permanganate is used for washing wounds and gargling
for mouth sore. It is also used for purifying water of
2KMnO 4 + 8H 2SO4 +10FeSO4 ——→ K 2SO4 + 2MnSO 4
stinking wells.
+

5Fe2
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 d AND f BLOCK ELEMENTS 149
SO4 3 (iv) Because of its strong oxidizing power, it is also used
+
8H2O for bleaching of wool, cottong, silk and other textile
fibres
(vi) It oxidises H2O2 to H2O and O2. This is because and also for decolourisation of oils.
acidified KMnO4 is a stronger oxidising agent than
H2O2.

2KMnO 4 + 3H 2SO4 + 5H 2O2 ——→ K 2SO4 + 2MnSO4 +

8H2 O + 5O2

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 150 d AND f BLOCK ELEMENTS

THE LANTHANIDE SERIES

1. INTRODUCTION
These elements are classified by the filling up of the
antipenultimate 4f energy levels.

2. PHYSICAL PROPERTIES

Electronic Configuration and oxidation states

Element Electronic Electronic Oxidation States
Configuration Configuration of
M3+

Lanthanum La [Xe] 5d1 6s2 [Xe] +3

Cerium Ce [Xe] 4f1 5d1 6s2 [Xe] 4f 1 +3 (+ 4)

Praseodymium Pr [Xe] 4f 3 6s2 [Xe] 4f 2 +3 (+ 4)

Neodymium Nd [Xe] 4f 4 6s2 [Xe] 4f 3 (+2) +3

Promethium Pm [Xe] 4f 5 6s2 [Xe] 4f 4 (+2) +3

Samarium Sm [Xe] 4f 6 6s2 [Xe] 4f 5 (+2) +3

Europium Eu [Xe] 4f 7 6s2 [Xe] 4f 6 (+ 2) +3

Gadolinium Gd [Xe] 4f 7 5d1 6s2 [Xe] 4f 7 +3

Terbium Tb [Xe] 4f 9 6s2 [Xe] 4f 8 +3 (+ 4)

Dysprosium Dy [Xe] 4f 10 6s2 [Xe] 4f

4f 10
9
+3 (+ 4)

Holmium Ho [Xe] 4f 11 6s2 [Xe] 4f 11 +3

Erbium Er [Xe] 4f 12 6s2 [Xe] 4f 12 +3

Thulium Tm [Xe] 4f 13 6s2 [Xe] 4f 13 (+ 2) +3

Ytterbium Yb [Xe] 4f 14 6s2 [Xe] 4f 14 (+ 2) +3

Lutetium Lu [Xe] 4f14 5d1 6s2 [Xe] +3

2.1 Oxidation state Oxidation numbers (+II) and (+IV) do occur, particularly
when they lead to :
The sum of the first three ionization energies for each
1. anoblegas configuration e.g. Ce4+ (f 0)
element are low. Thus the oxidation state (+III) is ionic
and Ln3+ dominates the chemistry of these elements. The 2. a half filled f shell, e.g. Eu2+ and Tb4+ (f7)
Ln2+ and Ln4+ ions that do occur are always less stable 3. a completely filled f level, e.g. Yb2+ (f14).
than Ln .3+

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d AND f BLOCK ELEMENTS 151

As we move along the lanthanide series, the nuclear

NOTE charge increases by one unit at each successive element.
The new electron is added into the same subshell (viz., 4f).
The 4f electrons in the antipenultimate shell are very As a result, the attraction on the electrons by the nucleus
effectively shielded from their chemical environment increases and this tends to decrease the size. Further, as
outside the atom by the 5s and 5p electrons. Consequently the new electron is added into the f-subshell, there is
the 4f electrons do not take part in bonding. They are imperfect shielding of one electron by another in this
neither removed to produce ions nor do they take any subshell due to the shapes of these f-orbitals. This
significant part in crystal field stabilization or complexes. imperfect shielding is unable to counterbalance the effect
Crystal field stabilization is very important with the d- block of the increased nuclear charge. Hence, the net result is a
elements. The octahedral splitting of f orbitals ∆o is only contraction in the size though the decrease is very small.
about 1kJ mol–1. Whether the f orbitals are filled or It is interesting to note that in lanthanides, the decrease in
the atomic radius for 14 elements [Ce (58) to Lu (71)] is
empty has little effect on the normal chemical
only 11pm (from 183 to 172 pm).
properties. However, it does affect their spectra and
their magnetic properties. Similarly, decrease in ionic radii from Ce3+ to Lu3+ is only
17 pm (103 to 86 pm)
The contraction is similar to that observed in any
2.2 Atomic radius
transition series. The cause is also similar, just as in the
In lanthanide series, with increasing atomic number, there is transition series where the contraction is due to imperfect
shielding of one d electron by another. But the shielding of
a progressive decrease in the atomic as well as ionic radii of
one 4f electron by another is less than one d electron by
trivalent ions from La3+ to Lu3+. This regular decrease in
another with increase in nuclear charge along the series.
the
atomic and ionic radii with increasing atomic number is
known as lanthanide contraction.
Atomic and Ionic radii (pm) of lanthanum and lanthanoids.

Element La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

Atomic Radii (Ln) 187 183 182 181 181 180 199 180 178 177 176 175 174 173 172

Ionic Radii (Ln3+) 106 103 101 99 98 96 95 94 92 91 90 89 88 87 86

2.3 Magnetic behaviour calculated by considering spin as well as orbital contribution,

i.e,
Paramagnetism is shown by the positive ions of
lanthanides
except La3+ (lanthanum ion, f0) and Lu3+ (lutetium ion, f14). µeff = 4 S (S +1) + L (L + B.M.
This property of the lanthanides is due to presence of 1)
where S is spin quantum number and L is orbital quantum
unpaired electrons in the incomplete 4f subshell.
number.
lanthanides differ from transition elements in the fact that
NOTE
their magnetic moments do not obey ‘spin only’ formula,

viz., n (n + 2) Separation of the Lanthanide Elements

µeff = B.M. where n is the number of
Since the change in ionic radius is very small, the chemical
unpaired electrons. This because in case of transition
properties are similar. This makes the separation of the
elements, the orbital contribution is quenched by the
element in pure state difficult. Separation is done by Ion
electric field of the environment but in case of lanthanides,
Exchange methods which is based on the ionic size.
4f orbitals lie to deep to be quenched. Hence, their
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magnetic moment is

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d AND f BLOCK ELEMENTS 153

2.4 Colour
93 Neptunium Np 5f 4 6d1 7s2
The Lanthanides are silvery white metals. However, most of
+3, +4, +5,+ 6, +7
the trivalent metal ions are coloured, both in the solid
state and in aqueous solution. This is due to the partly 94 Plutonium Pu 5f 6 7s2 +3, +4, +5, +6, +7
filled-f- orbitals which permit f-f transition.
95 Americium Am 5f 7 7s2 +2, +3, +4, +5, +6
NOTE
96 Curium Cm 5f 7 6d1 7s2 +3, +4

Lanthanides ions with x f electrons have a similar colour to 97 Berkelium Bk 5f 9 7s2 +3, +4
those with (14–x) f electrons e.g., La3+ and Lu3+ are 98 Californium Cf 5f 10 7s2 +2, +3
colourless, Sm3+ and Dy3+ are yellow and Eu3+ and Tb3+ are
99 Einsteinium Es 5f 11 7s2 +2, +3
pink.
100 Fermium Fm 5f 12 7s2 +2, +3
2.5 Hydroxides 101 Mendelevium Md 7s2 +2, +3
5f 13
The hydroxides Ln(OH)3 are precipitated as gelationous 102 Nobelium No 5f 14 7s2 +2 ,+3
precipitates by the addition of NH4OH to aqueous
solutions. These hydroxides are ionic and basic. They are 103 Lawrencium Lr 5f14 6d1 7s2 +3
less basic
104 Rutherfordium Rf 4f14 6d2 7s2
than Ca(OH)2 but more basic than Al(OH)3 which is
amphoteric. The metals, oxides and hydroxides all
dissolve
in dilute acids, forming salts. Ln(OH)3 are sufficiently 1. OXIDATION STATE
basic to absorb CO2 from the air and form carbonates. The
basicity decreases as the ionic radius decreases from Ce to Unlike Lanthanides, Actinides show a large number of
Lu. Thus oxidation states. This is because of very small energy gap
between 5f, 6d and 7s subshells. Hence, all their
Ce(OH)3 is the most basic, and Lu(OH3), which is the
electrons can take part in bond formation. The dominant
least basic, is intermediate between Scandium and Yttrium
in basic oxidation state of these element is +3 (similar to
strength. The decrease in basic properties is illustrated by Lanthanides). Besides
+3 state, Actinides also exhibit an oxidation state of +4.
the hydroxides of the later elements dissolving in hot
Some Actinides show still higher oxidation states. The
concentrated NaOH, forming complexes.

Yb(OH)3+ 3NaOH → 3Na+ + [Yb(OH)6 ]3–

maximum oxidation state first increases upto the middle of
Lu(OH) + 3NaOH → 3Na+ + [Lu(OH) the series and then decreases, e.g., it increases from + 4
]3–
3 6
from Th to +5, +6, and +7 for Pa, U and Np but decreases in
ACTINIDESSERIES the succeeding elements.
The Actinides resemble Lanthanides in having more
The elements and their Oxidation compounds in +3 state than in the +4 state. However, the
States compounds in the +3 and +4 state tend to undergo
Atomic Element SymbolOuterOxidation hydrolysis.
Further, it may be noted that in case of Actinides, the
electronicstates*
distribution of oxidation states is so uneven that it is of no use
to discuss their
structure chemistry in terms of their oxidation states.

89 Actinium Ac 6d17s2 +3 2. ATOMIC RADIUS

90 Thorium Th 6d2 7s2 +3, +4 The Actinides show Actinide contraction (very much like
Lanthanide contraction) due to poor shielding effect of
91 Protactinium Pa 5f 2 6d1 7s2 +3, +4, +5 the
92 Uraniu U5f 6d1 7s2
3
+3, +4, +5, +6
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 154 d AND f BLOCK ELEMENTS
5f-electrons. As a result, the radii of the atoms or ions of
these metals decrease regularly across the series. The
contraction is greater from element to element in this
series due to poorer shielding by 5f electrons. This is
because 5f orbitals extend in space beyond 6s and 6p
orbitals whereas 4f orbitals are buried deep inside the
atom.

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 d AND f BLOCK ELEMENTS 155

Differences :
3. MAGNETIC BEHAVIOUR
The show differences in some of their characteristics as
Like Lanthanides, the Actinides elements are strongly follows :
paramagnetic. The variation in magnetic susceptibility of
Lanthanides Actinides
Actinides with the increasing number of unpaired
electrons is similar to that of Lanthanides but the values
(i) Besides + 3 oxidation state (i) Besides +3 oxidation state,
are higher for the Actinides than the Lanthanides.
they show + 2 and +4 oxi- they show higher
4. COLOUR oxidation dation states only in few states of +4, +5, +6, +
7 also.
These metals are silvery white. However, Actinide cations
cases.
are generally coloured. The colour of the cation depends
upon the number of 5f-electrons. The cations containing (ii) Most of their ions are (ii) Most of their ions are
no 5f-electron or having seven 5f-electrons (i.e., exactly colourless coloured
half-filled f-subshell) are colourless. The cations (iii) They have less tendency (iii) They have greater
containing 2 to 6 electrons in the 5f-subshell are coloured
tendency towards complex formation towards
both in the crystalline state as well as in aqueous
solution. The colour complex formation.
arises due to f–f transition e.g. Ac3+ (5f 0) = colourless, (iv) Lanthanides compounds are (iv) Actinides compounds are
U3+ (5f 3) = Red, Np3+ (5f 4) = Blue, Pu3+ (5f 5) = Voilet, less basic. more basic
Am3+ (v) Do not form oxocation (v) From oxocations e.g.
(5f 6) = Pink, Cm3+ (5f 7) = Colourless, Th3+ (5f 0) =
Colourless UO2+ , PuO2+ and UO+
2 2
as so on.
(vi) Except promethium, they (vi) They are radioactive.
COMPARISON OF LANTHANIDES AND
are non-radioactive
ACTINIDES
(vii) Their magnetic (vii) Their magnetic
Similarities : properties can be properties cannot be
As both Lanthanides and actinides involve filling of f- explained easily. explained easily, as they
orbitals, they show similarities in many respects as follows are more complex.
:
(i) Both show mainly an oxidation state of +3.
(ii) Both are electropositive and very reactive.
(iii) Both exhibit magnetic and spectral properties.
(iv) Actinides exhibit Actinide contraction like Lanthanide
contraction shown by Lanthanides.

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IMPORTANT COMPOUNDS OF TRANSITION ELEMENTS

1. ZINC SULPHATE (ZnSO4. 7H2O - WHITE VITRIOL) II. REACTIONS :

(a) ZnO + 2HCl ZnCl2 + H2O
I. PREPARATION
:
ZnCO + H SO → ZnSO + H O + CO (dil/conc.)
3 2 4 4 2 2

II. REACTIONS : (b) ZnO + HNO3 Zn (NO3)2 + H2O

(dil/conc.)
(a) ZnSO4 + 2H 2 O ——→ Zn(OH)2 +
(c) ZnO + 2NaOH Na2ZnO2 + H2O
H2SO4
white ppt

(d) ZnO + 2KOH K2ZnO2 + H2O

NaOH
(e) ZnO + CoO CoZnO2
(Rinmann 's green)

III. USES :
Na 2 ZnO2 + Na2SO4 + H2 O
(sodium zincate) (i) As a white paint (It does not get tranished even in
presence of H2S because Zns is also white)
(b) ZnSO4.7H2O ZnSO4.6H2O ZnSO4
(ii) For preparing Rinmann's green (Green Paint)
(iii) As catalyst for preparation of methyl alcohol
(iv) For making soft rubber
(v) For making cosmetic powders, creams and
in medicine

(c) ZnSO + NH OH → Zn 3. ZINC CHLORIDE ZnCl2.2H2O

(OH) + (NH ) SO
4 4 2 4 2 4
Anhydride of zinc chloride cannot be obtained
by heating its aqueous salt.
I. PREPARATION :
(a) ZnO + 2HCl ZnCl2 + H2O
[Zn(NH3)4]SO4
(b) Zn + HgCl2 ZnCl2 + Hg
(d) Lithopone (ZnS + BaSO4) used as a white
pigment. II. PROPERTIES :

2. ZINC OXIDE, ZNO (CHINESE WHITE OR (a) ZnCl2 + H2S → ZnS + 2HCl
(b) ZnCl2+ 2NaOH → Zn(OH) 2 + 2NaCl
PHILOSPHER’S WOOL)
Zn(OH) + 2NaOH → Na ZnO + 2H O
It found in nature as zincite or red zinc ore.
2 2 2 2

I. PREPARATION : (c)2 2Zn(NO )

3 2
2ZnO + 4NO 2
+ O2
4 2 4

(a) 2Zn + O2 2ZnO

(b) ZnCO3 ZnO + CO2

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 d AND f BLOCK ELEMENTS 157
(c) ZnCl + 2NH OH → Zn(OH) + 2NH Cl
[Zn(NH3)4] Cl2 + 4H2O

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 158 d AND f BLOCK ELEMENTS

(b) Fe2O3 + 6HCl 2FeCl3 + 3H2O

4. FERROUS SULPHATE (FeSO4. 7H2O - GREEN
III. USES :
VITRIOL)
(i) As a red pigment
I. PREPARATION :
(ii) As abrasive polishing powder
(a) FeS + H2SO4 → FeSO4 + H2S
(iii) As catalyst

(b)
Fe + H 2SO 4 ——∆ → FeSO 4 + H 2
dil.

2FeS + H O + 6. FERRIC CHLORIDE, FeCl3

7O → 2FeSO + 2H SO
2 2 2 4 2 4
It is known in anhydrous and hydrated form. It is a red
(Commercial preparation)
deliquiscent solid.
II. REACTIONS :
I. PREPARATION :
(a)
2FeSO 4 ——∆ →Fe 2 O 3 + SO 2 + (a) 12FeCl2 (anhydrous) + 3O2 Fe2O3 + 8FeCl3
SO 3
(anhydrous)
(light green) (brown)
6
(b) Fe +2 + [Fe (CN) ]3– —— Fe3[Fe (CN)6 ]2 II. REACTIONS :
Turnbull's blue
→ (used as pigment in ink and paint)
(a) 2FeCl3 2FeCl2 + Cl2
Or Fe4 [Fe (CN)6]3
(b) FeCl3 + 3NH4OH Fe(OH)3 + 3NH4Cl
(Prussian blue)
(Reddish brown)
(c) NO–3 detection :
(c) 4FeCl3 + Fe4[Fe(CN)6 ]3 + 12 KCl
FeSO + NO– + Conc. H SO →
.
[Fe(H O) NO]SO 4

3K4Fe(CN)6 Prussian Blue

4 3 2 4 2 5
Brown ring

(d) 2FeCl3 + Fe[Fe(CNS)6] + 6NH4Cl

6NH4CNS Deep red colour

(d) FeSO4 + 2KCN → Fe(CN)2 +

K2SO4 Deep red colouration is produced due to formation
brown of complex.
(e) Till 750ºC it exists as its dimer Fe2Cl6.

4 6

2+ 3+
(e) 2Hg Cl2 + 2Fe → Hg
2
Cl
2
+ 2Fe +
– III. USES :
2Cl
white

(f) FeSO4 + H2O2 → Fenton’s reagent for oxidation of

(i) Its alcoholic solution is medicine, name (Tincture
alcohols to aldehydes
ferri perchloride)
(g) FeSO4. (NH4)2 SO4. 6H2O → Mohr’s salt
(ii) For detection of acetates and phenols
(iii) For making prussion blue & as an oxidising agent

5. FERRIC OXIDE, Fe2O3 7. COPPER SULPHATE

I. PREPARATION (a) 2FeSO4 II. (CuSO 4. 5H2O - BLUE VITRIOL)
REACTIONS:
:
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d AND f BLOCK ELEMENTS 159

Fe2O3 + SO2 + 3SO3

I. PREPARAT
ION :

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 160 d AND f BLOCK ELEMENTS
(a) Fe2O3 + 2NaOH H2O + 2NaFeO2 (a) CuO + H2SO4 → CuSO4 + H2O

(sodium ferrite) (b) Cu(OH)2.CuCO3 + 2H2SO4 → 2CuSO4 + 3H2O + CO2

Malachite Green

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 d AND f BLOCK ELEMENTS 161

Copper scrape
III. USES :
Cu + H2SO4 + ½O2 (air) → CuSO4 + H2O
(1) Bordeaux Mix → CuSO4 +
(Commerical preparation)
CaO (to kill fungi)
II. REACTIONS :
8. CUPRIC OXIDE, CuO
(a) Effect of heat
It is called black oxide of copper and is found in nature as
CuSO 4 .5H 2 O —1—00—ºC →CuSO 4 .H 2O —2 tenorite.
—30—ºC→ I. PREPARATION :
pale blue. (a) By heating Cu2O in air or by heating copper for a
long time in air (the temperature should not exceed
CuSO ——750—º → CuO +
SO above 1100ºC)
4 3
white
2Cu2O + O2 4CuO (black)
(b)
[CuSO4 + KI → CuI2 + K2SO4 ]× 2 2Cu + O2 2CuO
(Unstable
(b) 2Cu(NO3)2 2CuO + 4NO2 + O2
dirty white)
(c) On a commercial scale, it is obtained by heating
2CuI2 → Cu2 I2 + I2 malachite which is found in nature.
white ppt.

CuCO3 . Cu(OH)2 2CuO + CO2 + H2O

2CuSO4 + 4KI → Cu2I2 + 2K2SO4 + I2
(c) Test of Cu2+ II. REACTIONS :
CuSO 4 + NH 4 OH → C (a) When heated to 1100–1200ºC, it is converted
into cuprous oxide with evolution of oxygen.
u (O H ) 2 + (N H 4 ) 2 SO 4
_ _ _ _ _ _ _,
4CuO 2Cu2O + O2

(Black) (Red)

Uses : Used to impart blue and green colour to glazes and glass.

9. CUPRIC CHLORIDE, CuCl2.2H2O

Schwitzer’s reagent I. PREPARATION :
(Deep blue solution) (a) CuO + 2HCl CuCl2 + H2O
Cu(OH)2 CuCO3 + 4HCl 2CuCl2 + 3H2O+
(d) CuSO 4 + KCN → Cu(CN)2 + K2SO4 CO2

2Cu(CN)2 → Cu 2 (CN)2 + (CN)2 (b) CuCl2 . 2H2O CuCl2 + 2H2O

cyanogen gas

II. REACTIONS :
Cu2 (CN)2 + KCN → K3[Cu(CN)4 ]
excess (a) The anhydrous salt on heating forms Cu2Cl2 and

(e) CuSO4 + K4[Fe(CN)6 ] → Cu2[Fe(CN)6 ] + K2SO4 Cl2 2CuCl2 Cu2Cl2 + Cl2

Chocolate brown ppt.

3CuCl2. 2H2O CuO + Cu2Cl2 + 2HCl

(f) CuSO4 + H2S →

CuS + H2SO4 + Cl + 5H O
(black ppt.) 2 2

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 162 d AND f BLOCK ELEMENTS
(g) In Fehling’s test & Benedict’s test
Dilute solution of CuCl2 is blue but concentrated solution
is green. Its dilute solution on adding HCl becomes
Aldehyde + Cu 2+
→ Cu2O † + acid
yellow.
[Cu(H O) ]2+ → Blue
2 4
(red ppt.)
On adding HCl → [CuCl4 ]2– → green

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 156 d AND f BLOCK ELEMENTS

(g) AgNO3 + 2NH4OH Ag2O + 2NH4 NO3 + H2O

10. AgNO3 (LUNAR CAUSTIC) (brown ppt.)
→
I. Preparation :

(a)
3Ag + 4HNO3 —— 3AgNO3 + NO + 2H2O
∆
→
Colourless crystal
2[Ag(NH3)2] NO3 + 3H2O
II. REACTION:
(h) Ammonical AgNO3 → Tollen’s reagent used to test
(a) 2AgNO3 —— ∆
—→ 2Ag +
red hot + O2 aldehydes
2
2NO (i) It converts glucose to gluconic acid.
(b) 2AgNO 3 — — — — →
T >2 12 ºC

Ag 2O + C6 H12O 6 ——→ 2Ag + C 6 H12 O7

2AgNO 2 + O 2

(c KCN KCN
) AgNO3 ———→ AgCN ———→ K [Ag(CN)2] (j) It oxidises formaldehyde to formic acid
white ppts. soluble
Potassium
Dicyanidoargentate(I) Ag 2 O + HCHO ——→ 2Ag + HCOOH

2AgNO3 + Na 2S2O3 → Ag2S2O3 + 2NaNO3 Very dilute solution of AgNO3 is used as dental antiseptic.
(d)
(limited) white ppt.
(k) Ag2O + H2O2 → 2Ag + H2O + O2
White ppt. of Ag2S2O3 which gracdually changes
11. SILVER BROMIDE, (AgBr)
Ag2S2O3 + H2O → Ag2S + H2SO4
black I. PREPARATION :
(e) AgNO3 + Na2S2O3 → Ag2S2O3 + 2NaNO3 It is prepared by the reaction of silver nitrate with a
soluble bromide.

AgNO3 + NaBr ——→ AgBr + NaNO3

II. PROPERTIES
(a) It is a pale yellow solid. It is insoluble in water and
concentrated acids. It is partially soluble in strong
Sodium argentothic sulphate. solution of ammonium hydroxide due to complex
It is used in photography. formation.

AgBr + 2NH 4 OH ——→ Ag(NH 3 ) 2 Br + 2H 2 O

(b) On heating, it melts to a red liquid.

(f) (c) It is most sensitive to light. It undergoes photoreduction.

2AgBr —L—igh—t → 2Ag

2 + Br

(d) It dissolves in potassium cyanide.

AgBr + 2KCN ——→KAg(CN) 2 + KBr

Potassium argento-
cyanide (Soluble)

(e) It dissolves in sodium thiosulphate.

AgBr + 2Na 2S2 O3 ——→ Na 3 [Ag(S2 O3 )2 ] + NaBr

Sodium argento-
thiosulphate (Soluble)

(f) AgBr is reduced to silver, when treated with zinc and

dilute H2SO4.

Zn + H 2SO 4 ——→ ZnSO 4 + 2H

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d AND f BLOCK ELEMENTS 157
2AgBr + 2H ——→ 2Ag +
2HBr

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 d AND f BLOCK ELEMENTS 157

All above reactions are also observed in the case of

AgCl. However, it is white and fairly soluble in II. REACTION:
ammonium
hydroxide. It is sensitive to light. (a) KI + HgCl2 → KCl + HgI2
red ppts.
III. USES :
It is used for making photographic films and plates (b) HgI2 + KI → K2HgI4
because it is sensitive to light. colourless

Basic solution of K2HgI4 (K2HgI4 + KOH) is called as

12. MERCURY CHLORIDES Nessler’s Reagent.
(c) Test for ammonium ion
12.1 Mercurous Chloride (Hg2 Cl2 -
Calomel) K2HgI4 + NH+4Cl → NH2HgOHgI + KCl
I. PREPARATION
:
Brown ppt.

2HgCl2 + SnCl2 → Hg2Cl2 + SnCl4

II. REACTIONS :

Hg2 Cl2 + SnCl2 → 2Hg+ SnCl4

(a) black /
grey

(b) Hg2Cl2 ——∆ → HgCl2 + Hg (grey

Iodide of Millon’s Base
deposit)

(c) Hg2Cl2 + 2NH3 → H

(d) HgCl2 + 2NH3 → H + NH4Cl
g + H g (N H 2 ) Cl + NH 4Cl
_ _ _ _ _ __, g (N H 2 ) Cl
black _ _ _ ,
white

(e) HgCl2 + Cu → CuCl2 + Hg (grey deposit)

12.2 Mercuric Chloride (Hg Cl2 - Corrosive sublimate)
(f) HgCl2 is sparingly soluble in cold H2O but readily in
I. PREPARATION : hot water.
It is highly corrosive, poisonous and hence is called as
corrosive sublimate.

(a) Hg + 2Cl aqua regia → HgCl2

(b) SnCl2 + 2HgCl2 → Hg2Cl2 † + SnCl4

white ppts.

Hg2Cl2 + SnCl2 → 2Hg + SnCl4

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 158 d AND f BLOCK ELEMENTS

SOLVED EXAMPLES
Example - 1 Reason : d4 → d5 occurs in case of Cr2+ to Cr3+.
Silver atom has a completely filled d orbitals (4d10)
But d6 → d5 occurs in case of Fe2+ to Fe3+. In a medium
in its ground state. How can you say that it is a
(like water) d3 is more stable as compared to d5.
transition element ?

Sol. Silver (Z = 47) can exhibit +2 oxidation state wherein it Example - 8

will have incompletely filled d-orbitals (4d), hence a Calculate the ‘spin only’ magnetic moment of M
(aq)
2+
ion
transition metal. (Z = 27).
Example - 2
Sol. Atomic number (27) = [Ar]3d7 4s2
In the series Sc (Z = 21) to Zn (Z = 30), the enthalpy
n=1
of atomisation of zinc is the lowest i.e., 26, kJ mol.
Why ?
µ= n n+2
Sol. In the formation of metallic bonds no electrons from 3d-
orbitals are involved in case of zinc, while in all other
= 1× 3 = 1.73 BM.
metals of the 3d series, electrons from the d-orbitals are
always involved in the formation of metallic bonds.
Example - 9
Example - 3 Explain why Cu+ ion is not stable in aqueous solutions
Which of the 3d series of the transition metals ?
exhibits the largest number of oxidation states and Sol. Cu+ in aqueous solution undergoes disproportionation
why ? i.e.,
Sol. Manganese (Z = 25), as it atoms has the maximum number
2Cu + aq ——→Cu 2+ aq + Cu s
of unpaired electrons.

Example - 4 The Eo, value for this is favourable.

The Eo (M2+/M) value for copper is positive (+0.34 V). Example - 10

What is possibility the reason for this ?
Actinoid contraction is greater from element to
Sol. Copper has high ∆ Ho and low ∆ Ho. element than lanthanoid contraction. Why ?
a hyd

Sol. The 5f electrons are more effectively shielded from nuclear

Example - 5 charge. In other words, the 5f electrons themselves
How would you account for the irregular variation provide poor shielding from element to element in the
of ionisation enthalpies (first and second) in the first series.
series of the transition elements ?
Example - 11
Sol. Irregular variation of ionisation enthalpies in mainly
On what ground can you say that scandium (Z = 21) is
attributed to varying degree of stability of different 3d-
a transition element but zinc (Z = 30) is not ?
configurations (e.g., d0, d5, d10 are exceptionally stable).
Sol. On the basis of incompletely filled 3d orbitals in case of
Example - 6 scandium atom is its ground state (3d1), it is regarded as
Why is the highest oxidation state of a metal a transition element. On the other hand, zinc atom has
completely filled d orbitals (3d10) in its ground state as
exhibited in its oxide or fluoride only ?
well as in its oxidised state, hence it is not regarded as a
Sol. Because of small size and high electronegativity oxygen transition elements.
or fluorine can oxide the metal to its highest oxidation
state. Example - 12
Why Cr and Cu show exceptional configuration ?
Example - 7
Sol. By deviating from normal configuration, Cr and Cu acquires
Which is a stronger reducing agent Cr2+ or Fe2+ half-filled and fully filled configurations which gives
and why ? them extra stability. Hence they show exceptional
Sol. Cr2+ is strong reducing agent than Fe2+. configuration.
Mahesh Tutorials Science
Cr → [Ar] 3d5 4s1 and Cu → [Ar] 3d10 4s1
 d AND f BLOCK ELEMENTS 159

Example - 13 series (i.e., Cu and Zn). Thus electronic configuration, to

large extent, the existence and stability of oxidation
Why are Zn, Cd and Hg softer and volatile metals ? states.

Sol. Due to their completely filled d-orbitals, they have weak The other factors which determine stability of oxidation
metallic bonding and least compact packing therefore they state are:
all are volatile in nature.
(i) Enthalpy of atomisation (ii) Ionisation energy
(iii) Enthalpy of solvation (iv) E.N. of other element.
Example - 14 Example - 16
Explain briefly how +2 state becomes more an more stable in What may be the stable oxidation state of the transition
the first half of the first row transition elements with element with the following d electron configurations in the
increasing atomic number ? ground state of their atoms : 3d3, 3d5, 3d8 and 3d4 ?
Sol. In transition elements, there are greater horizontal
Sol. The stable oxidation state of transition element with the d
similarities in the properties in constrast to the main
electron configuration in ground state of atoms are as
group elements because of similar ns2 common
follows :
configuration of the outermost shell.
An examination of common oxidation states reveals that
excepts scandium, the most common oxidation state of
first row transition elements is +2 which arises from the
loss of two 4s electrons. This means that after scandium,
d-orbitals become more stable than the s-orbital.
Further, +2 state becomes more an more stable in the
first half of first row transition elements with increasing
atomic number because 3d orbitals acquire only one It should be noted that lower stable oxidation state
electron in each of five 3d orbitals (i.e. remains half filled) generally leads to ionic bond and higher oxidation state
and electronic repulsion is the least and nuclear charge corresponds to covalent bond.
increases. In 2nd half of first row transition elements,
electrons starts pairing up in 3d orbitals. (Ti2+ to Mn2+ Example - 17
electronic configuration changes from 3d2 to 3d5 but in Name the oxometal anions of the first series of the transition
2nd half i.e. Fe2– to Zn2+ it changes from d6 to d10). metals in which the metal exhibits the oxidation state equatl
Example - 15 to its group number.
To what extent do the electronic configurations decide the Sol.
stability of oxidation states in the first series of the transition
elements ? Illustrate your answerwith example.

Sol. One of the main characteristic of a transition element is transition

that it can show large variety of oxidation states in its
compounds. It is due to its characteristic electronic
configuration i.e., (n – 1) d and ns electrons take part in
bond formation either by loosing or by sharing of electrons
with other combining atoms.

The stability of oxidation state depends mainly on

electronic configuration and also on the nature of other
combining atom.

The elements which show largest number of oxidation

states occur in or near the middle of series (i.e., 4s 23d3 to
4s23d7 configuration). For example, Mn exhibits all
oxidation states from +2 to +7 as it has 4s 2 3d 5
configuration. The lesser number of oxidation states at
extreme ends arise from either too few electrons to loose
or share (e.g. Sc and Ti) or too many d electrons (hence
fewer orbitals available in which to share electrons with
others) for higher elements at upper end of first
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 160 d AND f BLOCK ELEMENTS

Sol. A group of fourteen elements following lanthanum i.e. Example - 18

from58Ce to71 Lu placed in 6th period of long form of
periodic talbe is known as lanthanoids (or lanthanide What is lanthanoid contraction ? What are the consequences
series). These of lanthanoid contraction ?
fourteen elements are represented by common general
symbol ‘Ln’. In these elements, the last electron enters
the 4f-subshells (pre pen ultimate shell). It may be
noted that atoms of these elements have electronic
configuration with 6s2 common but with variable
occupancy of 4f level. However, the electronic
configuration of all the tripositive ions (the
most stable oxidation state of all lanthanoids) are of the
form
 d AND f BLOCK ELEMENTS 161

4f n(n = 1 to 14) with increasing atomic number). These (vii) These metals form various alloys with other metals of
elements constitute one of the two series of inner the series.
transition elements or f-block.
(viii) These metals form interstitial compounds with C, N, B
Lanthanoid contraction : In the lanthanoide series with and H.
the increase in atomic number, atomic radii and ionic radii
decrease from one elements to the other, but this The presence of partially filled d-orbitals in the
decrease is very small. the regular small decrease in electronic configuration of atomic and ionic species of
atomic radii and ionic radii of lanthanides with these elements is responsible for the characteristic
increasing atomic number along the series is called properties of transition elements. They are called
lanthanoid contraction. transition elements because of their position in the
periodic table. These elements lie in the middle of
Cause of lanthanoid contraction: When one moves from periodic table between s and p-block (i.e., between
58
Ce to 71Lu along the lanthanide series nuclear charge group 2 and group 13). A transitio element may be
goes on increasing by one unit every time.
Simultaneously defined as a element whose atom or at least one of its
simple ions contain partially filled d-orbitals, e.g., iron,
an electron is also added which enters to the inner f
copper, chromium, nickel etc.
subshell. The shielding effect of f-orbitals in very poor
due to their diffused shape. It results in the stronger The general characteristic electronic configuration may
force of nuclear attraction of the 4f electrons and the be written as (n – 1) d1–10ns1–2.
outer electrons causing decrease in size.
The elements of group 12 i.e., Zinc, Cadmium, and
Consequences of lanthanoid contraction: Mercury are generally not regarded as transition
elements as their atoms and all ions formed have
(i) Similarly in the properties of elements of second and
completely filled d-orbitals i.e., these do not have
third transition series e.g. Sr and Hf; Nb and Ta; Mo and
partially filled d-orbitals in atomic state or common
W. This resemblance is due to the similarity in size due
oxidation state (Zn2+, Cd2+, Hg2+)
to the presence of lanthanoids in between.
Zn (30) = [Ar] 4s23d10 Zn2+ = [Ar] 3d10 4s0
(ii) Similarity among lanthanoids : Due to the very small
change in sizes, all the lanthanoids resemble one another Cd (48) = [Kr] 5s2 4d10 Cd2+ = [Kr] 4d10 5s0
in chemical properties.
Hg (80) = [Xe] 6s2 5d10 Hg2+ = [Xe] 5d10 6s0
(iii) Decrease in basicity : With the decrease in ionic radii,
covalent character of their hydroxides goes on Example - 20
increasing from Ce(OH)3 to Lu(OH)3 and so base
In what way is the electronic configuration of the
strength goes on decreasing.
transition elements different from that of the non-
Example - 19 transition elements ?

What are the characteristics of the transition Sol. Transition elements have incomplete penultimate d-orbitals
elements and why are they called transition elements while penultimate orbitals of representative elements (s -
? Which of the d-block elements may not be and p - block elements) are completely filled up. The
regarded as the transition elements? general valence shell configuration of s-block (group 1
and 2) elements is ns1–2 and for p-block elements (group
Sol. The important characteristics of transition metals are: 13 to 18) is ns2 np1–6. The valence shell configuration of
transition elements can be written as (n – 1) d1–9 ns1–2 .
(i) All transition elements are metallic in nature, e.g., all are
metals. Example - 21
(ii) These metals exhibit variable oxidation states. Explain giving reasons :
(iii) Transition metal atoms or ions generally form the Sol.
complexes with neutral, negative and positive ligands.
(i) Transition metals and many of their compounds show
(iv) Compounds of transition metals are usually coloured. paramagnetic behaviour.
(v) The compounds of these metals are usually (ii) The enthalpies of atomisation of the transition metals are
paramagnetic in nature. high.
(vi) Transition metals and their compounds act as good (iii) The transition metals generally form coloured compounds.
catalysts, i.e., they show catalytic activities. Lakshya Educare
(iv) Transition metals and their many compounds act as
Mahesh Tutorials Science good catalyst.
 d AND f BLOCK ELEMENTS 161

Example - 22 Example - 24
What are interstitial compounds ? Why are such Describe the preparation of potassium dichromate
compounds well known for transition metals ? from iron chromite one. What is the effect of
increasing pH on a solution of potassium dichromate
Sol. Interstitial compounds are those which are formed when ?
small atoms like H, C, N, B etc. are trapped inside the
crystal lattices of metals. They are generally non- Sol. The following steps are involved in preparation of K2Cr2O7
from iron chromite (FeCr2O4) ore :
stoichiometric and neither typically ionic nor covalent.
(i) Preparation of sodium chromate : The chromite ore
Most of transition metals form interstitial compounds
(FeO.Cr2O3) is finely powdered and mixed with sodium
with small non-metal atoms such as hydrogen, boron, carbonate and quick lime and then heated to redness in a
carbon reverberatory furnace with free supply of air.
and nitrogen. These small atoms enter into the void sites 4FeO.Cr O + O → 2Fe O + 4Cr O
2 3 2 2 3 2 3

between the packed atoms of crystalline transition metals. [4Na2CO3 + 2Cr2O3 + 3O2 → 4Na2CrO4 + 4CO2] × 2
For Example, steel and cast iron become hard by forming 4FeO.Cr O + 8Na CO + 7O → 8Na CrO + 2Fe O + 8CO
interstitial compound with carbon. 2 3 2 3 2 2 4 2 3 2

The mass is then extracted with water, when sodium

The exsitence of vacant (n – 1) d orbitals in transition chromate is completely dissolved while Fe2O3 is left
elements and their ability to make bonds with trapped behind.
small atoms in the main cause of interstitial compound (ii) Conversion of sodium chromate into sodium
formation. Other examples are : VH0.56, TiH 1. 7. dichromate (NaCr2O7) : The sodium chromate extracted
Some main with water in previous step is acidified.
characteristics of these compounds are :
3Na 2CrO 4+ H 2SO 4→ Na 2Cr 2O 7 + Na 2SO 4 + H 2O
(i) They have high melting and boiling points, higher than
those of pure metals. On cooling Na SO separates out as Na SO . 10H O and
2 4 2 4 2

(ii) They are very hard. Some borides of transition elements Na2Cr2O7 is remains in solution.
approach diamond in hardness. (iii) Conversion of Na Cr O into K Cr O : The solution
2 2 7 2 2 7

(iii) They are chemically inert but retain metallic containing Na2Cr2O is treated with KCl
conductivity. Na Cr O + KCl → K Cr O + 2NaCl
2 2 7 2 2 7
Example - 23
Sodium chloride (NaCl) being less soluble separates out
How is the variability in oxidation states of on cooling. On crystallising the remaining solution,
transition metals different from that of the non- orange coloured crystals of K2Cr2O7 separate out.
transition metals ? Illustrate with examples
Effect of Change of pH : When pH of solution of K2Cr2O7
Sol. The variability in oxidation states is a fundamental is increased slowly the medium changes from acidic to
characteristic of transition elements and it arises due to basic. The chromates and dichromates are
incomplete filling of d-orbitals in such a way that their interconvertible in aqueous solution depending upon pH
of solution.
oxidation states differ from each other by unity. For
example, vanadium, V show the oxidation states of +2,
+3,
+4 and +5. Similarly, Cr shows oxidation states of +2,
+3,
At low pH (acidic medium), K Cr O7 solution is oranged
+4, +5 and +6; Mn shows all oxidation states from +2 to
+7. 2 2

states. Halogenes like Cl, Br and I show oxidation states of –

This is contrasted with variability of oxidation states of 1, +1, +3, +5 and +7 states. In non-transition elements
non-transition element where oxidation states generally variability of oxidation states is caused due to unpairing of
differ by units of two. For example, S shows oxidation electrons in ns or np orbitals and their promotion to np
states of –2, +2, +4, +6 while P shows +3 and +5 oxidation or nd vacant orbitals.
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162 d AND f BLOCK ELEMENTS
coloured while at higher pH (alkaline medium) it
changes to yellow due to formation of chromate ions.

Describe the oxidising action of potassium Example - 25

dichromate and write the ionic equations for its
reaction with :

(a) iodide (b) iron (II) solution and (c) H2S.

Sol. Potassium dichromate, K2Cr2O7 is a strong oxidising

agent and is used as a primary standard in volumetric
analysis
 d AND f BLOCK ELEMENTS 163
involving oxidation of iodides, ferrous ion and S ions 2–
(a) It oxidises iron(II) salt to iron(III) salts.
etc. In acidic solution, its oxidising action can be
represented as follows : 2MnO 42- + 16+ + 10Fe2+ → 2Mn2+ + 8H2 O + 10Fe3+
Cr O 2–
+ 14H+ + 6e– → 2Cr3+ + 7H O; (E+ = 1.33 V) (b) It oxidised sulphur dioxide to sulphuric acid.
2 7 2

(a) It oxidises potassium iodide to iodine. 2MnO4– + 5SO2 + 2H2 O → 5SO4 2– + 2Mn2+ 4H+
Cr2O72– + 14H+ 6I– → 2Cr3 + 7H2 O + 3I2 (c) It oxidises oxalic acid to CO2 and H2O
(b) It oxidises iron(II) salt to iron (III) salt 2MnO 4– + 16H+ + 5C2O4 2– → 2Mn2+ + 8H2 O + 10CO2
Cr O 2–
+ 14H + 6Fe → 2Cr + 6Fe + 7H O
+ 2+ 3+ 3+
Example - 27
2 7 2

(c) It oxidises H2S to S For M2+/M and M3+/M2+ systems the Eo values for some
metals are as follows :
Cr 2O72– + 8H+ + 3H2 S → 2Cr3+ + 7H2 O +
3S Cr2+/Cr – 0.9 V Cr3+/Cr2+ – 0.4 V

Example - 26 Mn2+/Mn – 1.2 V Mn3+/Mn2+ + 1.5V

Describe the preparation of potassium permanganate.
How does the acidified permanganate solution reacts Fe2+/Fe – 0.4 V Fe3+/Fe2+ + 0.8 V
with (a) iron(II) ions (b) SO2 and (c) oxalic acid ? Use this data to comment upon
Write the ionic equations for the reactions.
(a) The stability of Fe3+ in acid solution as
Sol. Preparation of KMnO4 from pyrolusite ore (MnO2) compared to that of Cr3+ or Mn3+ and
involves the following steps :
(b) In case withwhich iron can be oxidisedas
(i) Fusion of ore with alkali in presence of air : Pyrolusite
compared to the similar process for either
ore is fused with alkali in the presence of air when
chromium or manganese metal.
potassium manganate is obtained as green mass.
2MnO + 4KOH + O → 2K MnO + 2H O Sol
.
2 2 2 4 2
(green mass) (a) We know that higher the reduction potential of a specie,
The green mass is dissolved in water to obtain aqueous there is larger tendency for tis reduction to take place.
solution of potassium manganate. The insoluble Let us represent the reduction potential i.e., Eo values of
impurities of sand and other metal oxides are removed three M3+/M2+ systems on number line.
by filtration. Cr3+ / Cr2+ F3+/Fe2+ Mn3+/Mn2+

(ii) Oxidation of manganate into permanganate : The – 0.4 V 0.8 V 1.5 V

aqueous solution of K2MnO4 is oxidised electrolytically or
by using ozone or Cl2 to obtain potassium
From values of reduction potentials, it is clear that the
permanganate. The
process is carried out till green colour disappear and stability of Fe3+ in acid solution is more than that Cr3+
solution acquires distinct pink colour. but less than that of Mn3+.

MnO 42 – ——→ MnO –

+ e–
4
(oxidation at anode)
at anode
green coloure pink (b) Mn2+/Mn Cr2+/Cr Fe2+/Fe
H O + e– → 1/2H + (OH)– (reduction at cathodes)
2 2
– 1.2 V 0.9 V –0.4 V 0V
(at cathode)
The lower the reduction potential of a species, its
or 2K 2 MnO4 + oxidation will take place more readily.
→ 2KMnO4 + 2KCI
CI2 pink colour
Mn is oxidised most readily to Mn2+ and Fe is oxidised
green colour

Potassium permanganate is crystallised out from the least readily among given metals Mn, Cr and Fe.
solution.
Example - 28 Lakshya Educare
Oxidising Properties : It acts as a powerful oxidising
agent in different media differentily. In acidic medium, it Write the electronic configurations of the elements with
oxidises iron(II) salts to iron(III) salts, SO2 to H2SO4 and the atomic numbers 61, 91, 101 and 109.
oxalic acid Sol. Atomic number (61) = [X ] 4f5 6s2.
to CO and H O.
 164 d AND f BLOCK ELEMENTS
a
2 2

Mahesh Tutorials Science Atomic number (91) = [rn] 5f2 6d1 7s2
d AND f BLOCK ELEMENTS 163
Atomic number (101) = [Rn] 5f 14

7s1 3CrO4 3– + → 2–
+ Cr3+ + 4H2O
2CrO4
8H+
Atomic number (109) = [Rn] 5f14 6d7 7s2. Cr in + 5 o.s. Cr in + o.s.

.
3MnO 43– + 4H+ → 2MnO 4– + MnO 2+ 2H 2 O
Mn in + 6 o.s. Mn in Mn in
+7 o.s +4 o.s.
Example - 29
How would you account for the following : Here, we can say that Cr in +5 oxidation state undergo
disproportionation into its +6 and +3 states. Similarly, Mn
(a) Of the d4 species Cr2+ is strongly reducing while in +6 oxidation state undergo disproportionation into +7
manganese(III) is strongly oxidising. and +7 oxidation states.

(b) Cobalt(II) is stable in aqueous solution but in Example - 31

the presence of complexing reagents it is easily
Give reasons for the following :
oxidized.
(a) Transition metals have high enthalpies of
(c) The d1 configuration is very unstable in ions?
atomisation.

Sol (b) Among the lanthenoids Ce(III) is easily oxidised

. to Ce(IV).
(a) Of d4 species, Cr2+ has 3 d4 configuration and tends to
loose one electron to acquire d3 configuration as it is (c) Fe3+/Fe2+ redox couple has less positive electrode
highly stable and best metallic specie available for potential than Mn3+/Mn2+ couple.
complex formation. Cr3+ can accommodate six lone pair of
electrons (d) Copper (I) has d10 configuration while copper(II) hs
from ligands due to sp3d2 hybridisation e.g. [Cr(NH ) ]3+
3 6
Mn3+ although have d4 configuration but tends to become d9 configuration, still copper(II) is more stable
in
Mn2+ stable specie by acquiring one electron to attain d 5 aqueous solution than copper(I).
configuration. It becomes exactly half filled on one hand
(e) The second and third transition series elements
and more energy is released in gain of electron due to
higher nuclear charge. have almost similar atomic radii.

Sol.
(b) Co2+ is stable in aqueous solution because it get
surrounded and weakly bonded to water molecules. In (a) The metallic bonds in transition elements are very strong
presence of strong ligands and air it gets oxidised tc due to participation of (n – 1) d electrons along with
Co(III) as strong ligands get co-ordinated more strongly valence s-electrons in the bond formation. Therefore, the
with Co(III). The electronic configuration of Co(II) and cleavage of these bonds is extremely difficult and
Co(III) are : consequently, enthalpies of atomization are high.

Co(II) = [Ar]18
4s03d7 and Co(III) = [Ar] 18 4s03d6
Ce 3+ —— 4+
+ e–
→Ce
In Co(III) specie, 6 lone pairs of electrons from ligands 4f 5do 6so 4f o 5do 6so

are accommodated by sp3d2 hybridisation which is not

possible in Co(II). sol e transition metal species in same oxidation state
uti undergo a chemical change in such a way that some
(c) Some species with d1 configuration are reducing and tends on. species get oxidised and some other get reduced. For
to loose one electron to acquire d4 stable configuration. example, Cr(V) and Mn(VI) species undergo
Some other species with d1 configuration like Cr(V) and disproportionation reaction
Sol.
Mn(VI) undergo disproportionation. in acidic medium as follows:
So
Example - 30 m
e
What ismeant by disproportionation ? Give two ti
examples of disproportionation reaction in aqueous m
Lakshya Educare
 164 d AND f BLOCK ELEMENTS
Sp 3e– ——→Mn + 2+
on
tan
eo (more spontaneous due to higher stability of Fe3+)
us
(c) ox Fe3+ + e– ——→Fe 2+
ida
tio
n (less spontaneous due to higher stability of Fe3+)
du
e Due to stability of half filled d-orbitals, Mn2+ is more
to stable than Mn3+ and thus its reduction is more
m
or spontaneous. Similarly Fe3+ is more stable than Fe2+ and
e thus its reduction is less spontaneous.
sta
bil
ity
of
Ce
4+

io
n
as
co
m
pa
re
d
to
Ce
3+

io
n
du
e
to
m
or
e
sta
bl
e
co
nfi
gu
-
rat
io
n
of
C
e4+
io
n.

M
n
3

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 d AND f BLOCK ELEMENTS 165
(d) Copper (II) has lower reduction electrode potential than
copper (I), hence. Copper(I) is oxidised to copper (II) in An important alloy which contains some of the lanthanoid
the presence of strong ligands and air. is mischmetall. Mischmetall consists of a lanthanoid metal
(~95%) and iron (~5%) and traces of S, C, Ca and Al.
(e) It is due to lanthanoid contraction. It arises due to poor
shielding effect of d and f electrons. Uses : (i) Mischmetall is used in Mg based alloy to
produce bullets, shell and lighter flint.
Example - 32
Some individual Ln oxides are used as phosphorus in
Indicate the steps in the preparation of : television screens and similar fluorescing surfaces.
(a) K Cr O from chromite ore
Example - 34
2 2 7

(b) KMnO4 from pyrolusite The Chemistry of the actinoid elements is not so
smooth as that of the lanthanoids. Justify this
ore.
Sol. statement by giving some examples fromthe oxidation
state of these elements.

(a) The preparation of potassium dichromate from chromite

involves the following main steps : Sol. Among the actinoids, there is a greater range of oxidation
states as compared to lanthanoids. This is in part due to
(i) The chromate ore is finely ground and heated strongly
the fact that 5f, 6d and 7s levels are of very much
with molten alkali in the presence of air.
comparable energies and the frequent electronic
transition
2FeCr O + 8NaOH + 7 / 2O → 4Na Cr among these three levels is possible. This 6d-5f transition
O → Fe O + 4H O
2 4 2 2 2 4 2 3 2
Chromite Sodium chromate and larger number of oxidation states among actinoids
(ii) The solution of sodium chromate is filtered and acidified make their Chemistry more complicated particularly among
with dilute sulphuric acid so that sodium dichromate is
the 3rd to 7th elements. following examples of oxidation
obtained.
states of actinoids. Justify the complex nature of their

2Fe2Cr2O4 + H3SO4 Chemistry.

Sodium Chromate → Na 2Cr2O7 + Na2SO4 + H2O
Sodium dichromate
(i) Uranium exhibits oxidation states of +3, +4, +5, +6 in its
(iii) A calculated quantity of potassium chloride is added to a compounds. However, the dominant oxidation state in
hot concentrated solution of sodium dichromate.
actinoides is +3.
Potassium dichromate is less soluble therefore it
crystallizes out first. (ii) Nobelium, No is stable in +2 state because of
Na2Cr2O7 + 2KCl → K2Cr2O7 + 2NaCl completely filled f14 orbitals in this state.
Sodium Potassium
dichromate dichromate (iii) Berkelium, BK in +4 oxidation state is more stable due to f7
(b) (i) Pyrolusite ore is fused with alkali in the presence of (exactly half filled) configuration.
air when potassium manganate is formed.
(iv) Higher oxidation states are exhibited in oxoions are UO 22+,
2MnO2 + 4KOH + O2 → 2K2MnO4 + 2H2O PuO 22+, NpO+ etc.
Potassium manganate

Example - 35
(ii) Potassium manganate is oxidised by using either CO2,
ozone or chlorine to potassium permanganate. Use Hund’s rule to derive the electronic configuration
2K2MnO4 of Ce3+ ion, and calculate its magnetic moment on the
+ → 2KMnO4 + 2KCl
Cl2 Potassium basis of ‘spin only’ formula.
permanganate

(iii) Potassium permanganae is crystallized from the What are alloys ? Mention an important alloy which
solution. contains some of the lanthanoid metals. Mention its uses.

Example - 33 Sol. An alloy is a mixture of a metal with other metals or non-

metals.
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 166 d AND f BLOCK ELEMENTS
Sol. The electronic configuratio of Ce and Ce3+ ion is :

Ce(Z = 58) = [Xe] 4f15d16s2 54

Ce3+ = [Xe] 4f1 54

The no. of unpaired electron = 1

‘Spin only’ formula for magnetic moment of a specie,

Mahesh Tutorials Science

d AND f BLOCK ELEMENTS 167

(i) Because of their variable oxidation states transition

µ = n n + 2 B.M.
metals form unstable intermediate compounds and
provide a new path with lower activation energy for the
Magnetic moment of Ce3+ reaction.

(ii) In some cases, the transition metal provides a suitable

µ = 1 1+ 2 B.M. large surface area with free valencies on which reactants
are adsorbed.
= 3 B.M. = 1.732 B.M. (b) Because they have strong metallic bonds due to greater
number of unpaired d electrons.
Example - 36
(c) this is due to d-d transition.
Name the members of the lanthanoid series which
exhibit Example - 38
+4 oxidation states and those which exhibit +2
Discuss the relative stability in aqueous solutions of
oxidation state. Try to correlate this type of
+2 oxidation state among the elements: Cr, Mn, Fe
behaviour with the electronic configurations of these
and Co. How would you justify this situation ?
elements.
(At. Nos. Cr = 24, Mn = 25, Fe = 26, Co = 27)
Sol. Cerium (Ce) and Terbium (Tb) show +4 oxidation state.
Their electronic configurations are given below : Sol. On the basis of electrochemical series the standard
electrode potential shows the following order
Ce = [Xn] 4f1 5d1 6s2
E o Mn < Eo Cr < E o Fe < E o Co
Tb = [Xn] 4f0 6s2 2+
/ Mn 2+
/ Cr 2+
/ Fe 2+
/ Co

It is clear from the configuration of Ce that Ce +4 is favoured Therefore Co2+ gets easily reduced to metallic cobalt while
by its noble gas configuration i.e., [Xn] 4f0 5d0 5s0, but it is difficult to reduce Mn2+. Hence Mn2+ will be most
can be easily converted into Ce3+ ([Xn]) 4f1 5d0 6s0). Due stable and the increasing stability order will be
to this reason Ce+4 is an oxidising agent. Tb4+ ion is Co2+ < Fe2+ < Cr2+ < Mn2+
stabilized due to half filled f-subshell i.e., [Xn] 4f7. It
also acts as an oxidant. Example - 39
Europium (63) and ytterbium (70) show +2 oxidation Which metal in the first series of transition metals
state, this acts as reducing agents because they can be exhibits +1 oxidation state most frequently and why
converted into common oxidation state +3. The ?
electronic configuration of Eu and Y are as follows :
Sol. Copper metal (Cu, at, no. 29) shows + 1 oxidation state
Eu = [Xn] 4f 6s
7 2
i.e., it exists as Cu+ in large number of copper compounds
e.g., cuprous oxide (Cu2O), coprous sulphide 9Cu2S);
Y = [Xn] 4f14 cuprous chloride (Cu Cl ) etc. The electronic
2 2
configuration of Cu+ is [Ar] 3d10 4s0.
6s2

Formation of Eu2+ ion leaves 4f7 configuration and Y2+

ion
leaves 4f14 configuration. These configurations can stable (c) t coloured complexes.
r
due to half filled and full filled f-subshell. Samarium, a
n
Sm s
(62) 4f6 6s2 also shows both +2 and +3 oxidation states like i
t
europium. i
o
n
Example - 37
m
Explain the following facts e
t
a
(a) transition metals act as catalysts. l
s
(b) chromium group elements have the highest f
melting points in their respective series. o
r
m
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 168 d AND f BLOCK ELEMENTS
Sol. This configuration is very stable as all five 3d orbitals are
fully filled.

Example - 40
Assign a reason for each of the following :

(i) The third ionization energy of Mn(Z = 25) is

higher than that of either Cr (Z = 24) or Fe (Z
= 26).

(ii) Simple copper (I) salts are not stable in

aqueous solutions.
(i) This is because Mn2+ is more stable as it has exactly half
Sol. filled configuration 3d5 4s0.

(a) The catalytic activity of transition metals is attributed to

the following reasons :

Mahesh Tutorials Science

 d AND f BLOCK ELEMENTS 169
(ii) Cu (aq) is much more stable than Cu (aq). This is
2+ +

because, although second ionization enthalpy of copper

is large but for Cu2+ (aq) is much more negative than that
of Cu+ (aq) and therefore, it more compensate for the
second ionisation enthalpy of copper. Therefore, Cu+ ion
aqueous solution undergoes disproportionation.

2Cu 2+ aq —— aq + Cu s
→Cu 2+

Example - 41 Example - 42

Describe the trends in the following properties of the Complete the following chemical reaction
first series of the transition elements: equations:

(i) Oxidation states

(i) MnO–
4 aq + C2 O2–
4 aq + H+ aq ——→

(ii) Atomic sizes 2 7

(ii) Cr O2– aq + Fe2+ aq + H + aq ——→
(iii)Magnetic behaviour of dipositive gaseous ions
(M2+).
Sol. (i) MnO–4
+ 8H+ + 5e– ——→ Mn2+ + 4H O]× 2
2
Sol. 2– ——→ + 2– ]× 5
C O 2CO
(i) As there is very little energy difference between 4s and 2 4 2

3d orbitals, electrons from both energy levels can be 2MnO–4 + 5C2 O42– +16H + ——→ 2Mn 2+ +10CO + 8H O
2 2
used for chemical bond formation. Therefore all elements
except Sc and Zn, of the first transition series show a
number of oxidation states as shown in table. (ii) Cr2 O72– + 14H + + 6e – ——→ 2Cr 3+ + 27H O
–
Fe2+ ——→ Fe + e ]× 6
3+
Sc Ti V Cr Mn Fe Co Ni Cu Zn
+2 +2 +2 +2 +2 +2 +2 +1
+3 +3 +3 +3 +3 +3 +3 +3 +2 +2 Cr O2– + 6Fe2+ +14H+ ——→2Cr3+ + 6Fe3+ + 7H O
+4 +4 +4 +4 +4 +4 +4 2 7 2

+5 +5 +5 Example - 43
+6 +6 +6
+7 How would you account for the following :

(ii) Atomic radii of the first transition series decreases from (i) Many of the transition elements and their
Sc to Cr, then reamins almost constant till Ni and then compounds can act as good catalysts.
increases from Cu to Zn.
(ii) The metallic radii of the third (5d) series of
The reason of this variation in atomic radii has been
transition elements are virtually the same as
attributed to the increase in nuclear charge in the
beginning of the series. But as the electrons continue to those of the corresponding members of the
be filled in d-orbitals, they screen the outer 4s electrons second series.
from the influence of nuclear charge. When the
(iii) There is a greater range of oxidation states
increased nuclear charge. When the increased nuclear
charge and the increased screening effect balance each among the actinoids than among the
Sol. lanthanoids.
other in the middle of transition series, the atomic radii
becomes almost
constant (Mn to Fe). Towards the end of the series, the transition series can be calculated with the unpaired
repulsive interaction between electrons in d orbitals electrons (n) by the spin-only formula
become very dominant. As a result there is an expansion
of then nelectron
+2 cloud; consequently, the atomic size µ B.M.
increases.
(iii) Except Zn2+, all other divalent gaseous ions of the first
series of the transition elements contain unpaired
electrons in their 3d subshell and are therefore
paramagnetic in nature.
The magnetic moment (µ) of the elements of the first
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 170 d AND f BLOCK ELEMENTS
(i) The catalytic activity of transition metals is attributed
to the following reasons:

(a) Because of their variable oxidation states

transition metals form unstable intermediate
compounds and provide a new path with lower
activation energy for the reaction.

(b) In some cases, the transition metal provides a

suitable large surface area with free vacancies on
which reactants are adsorbed.

(ii) This due to filling of 4f orbitals which have poor

shielding effect or due to lanthanoid contraction.

Mahesh Tutorials Science

 d AND f BLOCK ELEMENTS 171
(iii) This is due to comparable energies of 5f, 6d and 7s
Cerium can lose four electrons (4f1 5d1 6s2) in aqueous
orbital in actinoids.
solution to acquire stable configuration of rare gas
xenon. Moreover due to small size and high charge, Ce4+
Example - 44
ion has high hydration energy.
In transition series, with an increase in atomic
number, the atomic radius does not change very (ii) The second and third members in each group of transition
much. Why is it so ? elements have very similar atomic radii due to lanthanoid
contraction. It arises due to poor shielding effect of ∆f
Sol. With the increase in atomic number along a transition electrons.
series the nuclear charge increases which tends to
decrease the size of the atom. But the addition of Example - 47
electrons in the d subshell increases the screening Among the ionic species Sc3+, Ce4+ and Eu2+ which one
effect which counterbalances the increased nuclear is a good oxidising agent? Give a suitable reason for
charge. Hence, along a transition series the atomic radius your answer. (Atomic numbers ; Sc = 21; Ce = 58;
does not change very much. Eu = 63).
Example - 45 Sol. The electronic configurations of given species are:
Decide giving reasons which one of the following
pairs exhibits the property indicated: 21 Sc ——→18 Sc3+

(i) Sc3+ or Cr3+ exhibits paramagnetism.

Ar 3d1 4s2 Ar 3d0 4s0
(ii) V or Mn exhibits more number of oxidation
Ce ——→54
states. (Atomic Numbers: Sc = 21; Cr = 24; V = 23; 58

Mn = 25) Ce4+ [Xe] 4f1 3d1

Sol. 6s2 [Xe]

(i) The electronic configurations of Sc3+ and Cr3+ are given
Eu ——→61 Eu2+
below. 63

Xe 4f 7 6s2 Xe 4f 7
Sc3+ : Ar 3d0 4s0 Cr3+ : Ar 3d3 4s0
Ce4+ is a good oxidising agent because it can readily
Because of the presence of three unpaired electrons in change to the most stable +3 oxidation state by gaining
the 3d subshell Cr3+ is paramagnetic. Sc3+ is diamagnetic one electron.
as it does not have any unpaired electrons.
Ce4+ + e– ——→Ce3+
(ii) The electronic configurations of V and Mn are given
below: Because of their stable configuration Sc 3+ and Eu2+ cannot
gain electrons.
23
V : Ar 3d3 4s2 25
Mn : Ar 3d5 4s2
Example - 48
Mn exhibits more number of oxidation states than V
Write complete chemical equations for :
because of the greater number of electrons in its valence
shell. (i) Oxidation of Fe2+ by Cr2 O7 2– in acid medium.

Example - 46 (ii) Oxidation of S2O 32– by MnO– in neutral aqueous

Account for the following: solution.

(i) Cerium (atomic number = 58) forms tetra

Sol. (i) 6Fe2+ + Cr2 O7 2– + 14 H+ ——→ 6Fe3+ + 2Cr3+ +2 7H O
positive ion, Ce4+ in aqueous solution.
(ii) The second and third members in each group of (ii) 2MnO – + 3S O 2– + H O ——→ 2MnO + 3SO 2– +
4 2 3 2 2 4
transition element have similar atomic 3S + 2OH–.
radii.
Sol.

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 172 d AND f BLOCK ELEMENTS
(i) The electronic configuration of Ce (Z = 58) is 58Ce =
[Xe] 4f1 5d1 6s2

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 d AND f BLOCK ELEMENTS 173

Example - 49 Sol.
What are the different oxidation states exhibited by (i) 8MnO4– aq + 3S2 O32– aq + H2 O l ——→6 SO
4
2–

the lanthanoids ? (aq) + 8MnO 2+ 2OH– (aq)

Sol. The most common oxidation states shown by lanthanoids
(ii) Cr2O2–
7
aq + 6Fe2+ aq +14H+ aq ——→ 2 Cr 3+
is +3. In some exceptional cases it may be +2 or +4 (+2 (aq) + 6 Fe3+ (aq) + 7H 2O (l)
in Eu and Yb; +4 in Ce).
Or
Example - 50
(i) Cu2+ (aq) is much more stable than Cu+ (aq. This is due
What is meant by ‘lanthanoid contraction’ ? to more negativehyd
∆ H more than compensates fori ∆2 H .
Sol. The regular decrease (contraction) in the atomic and ionic As a result Cu(I) is unstable in aqueous solution and
radii with increasing atomic number from lanthanum to undergoes disproportionation as below :
lutetium along the lanthanoid series is called lanthanoid
contraction. 2Cu + ——→ Cu 2+ + Cu

Example - 51 (ii) The valence shell electronic configuration of Cr3+, Mn2+,

Fe3+ is d3, d5 respectively. Due to symmetrical distribution
How would you account for the following :
of electrons (Either t32g or t3
2g
e2
g ) they form stable
(i) Cr2+ is reducing in nature while with the same
d- orbital configuration 9d4) Mn3+ is an cationic complexes. The atomic radii of 4d and 5d
oxidising agent. transition metal at elements are more than those of 3d
(ii) In a transition series of metals, the metal which series. Hence. they generally do not form stable cationic
exhibits the greatest number of oxidation states complexes.
occurs in the middle of the series.
Example - 53
Sol. Explain giving reasons :
(i) Transition metals and their compounds generally
(i) Eo value of Cr3+/Cr2+ is negative (–0.04V) while that of exhibit a paramagnetic behaviour.
Mn3+/Mn2+ is positive (1.5 V). This means Cr 2+ can lose
electrons to form Cr3+ and thus is reducing in nature while (ii) The Chemistry (XII) (XII) of actinoids is not so
Mn3+ can gain electrons to form Mn2+ and is thus smooth as that of lanthanoids.
oxidising in nature.
Sol.
(ii) In a transition series of maximum number of oxidation
states
are shown by that element which has maximum number of (i) Paramagnetism is a property due to presence of unpaired
unpaired electrons. This is so in the element present in electrons. In case of transition metals, as they contain
the middle of the series. That is why the metal in the unpaired electrons in (n – 1) d orbitals, most of the
middle of the series exhibits maximum number of transition metal ions and their compounds are
oxidation states. For example, manganese, present in the paramagnetic.
middle of the first transition series exhibits maximum
(ii) The general electronic configuration of lanthanoids is
oxidation states i.e., +2,
+3, +4, +5, +6, +7. [Xe]54 4f0–4 5d0–1 6s2 and that of actinoids is [Rn]86 5f1–14
6d0–1 7s2. Unlike 4f orbitals, 5f orbitals are not deeply
burried and participate in bonding to a greater extent. In
Example - 52
actinoids due to poor shielding effect of 5f orbitals, the
Complete the following chemical equations : effective nuclear charge experienced by valence shell
(i) MnO–4 aq + S2 O2–
3
aq + 2H O l → electrons is more than those in lanthanoids. As a result
the Chemistry
(ii) Cr2 7
aq + Fe2+ aq + aq → (XII) (XII) of actinoids is not so smooth as that of
O2– +
lanthanoids.
Or H
State reasons for the following : M2+ ions of the 3d series of elements, the 4d and the
(i) Cu (I) ion is not stable in an aqueous solution. 5d series metals generally do not form stable
cationic species.
(ii) Unlike Cr3+, Mn2+, Fe3+ and the subsequent other
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 174 d AND f BLOCK ELEMENTS
Example - 54
Assign reasons for the following :
(i) Copper (I) ion is not known in aqueous solution.
(ii) Actinoids exhibit greater range of oxidation
states than lanthanoids.

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 d AND f BLOCK ELEMENTS 175
Sol. Sol.
(i) Cu (I) ion is not known in aqueous solution because
(i) CuF2 and CCl2 compounds will be coloured because they
Cu2+(aq) is much more stable than Cu+(aq). This is due incompletely filled d-orbitals and unpaired electrons,
to they
more negative ∆ hydH for Cu2+ (aq) than Cu+(aq) although can undergo d-d transition by absorbing colour from
∆ i H2 for Cu is large. Thus, ∆ hydH more than compensates
2+
visible region and radiating complementary colour.
for high value of ∆ i H2 . As a result Cu (I) is unstable in
(ii) Zr and H have identical sizes because passing of electrons
aqueous solution and undergoes disproportionation as f

below : takes place in d-orbitals causing repulsion and effective

nuclear charge does not increase apprecialby.
2Cu + ——→Cu 2+ + Cu
(iii) Manganese (Z = 25) exhibits the largest number of
(ii) Actinoids exhibit greater range of oxidation states than oxidation states because its atoms has the maximum
lanthanoids. this is because of very small energy gap number of npaired electrons. The lowest oxidation state
between 5f, 6d and 7s subshells. Hence, all their electrons of manganese is basic while the highest is acidic.
can take part in bond formation.
(iv) Mn(II) shows maximm paramagnetic character amongst
Example - 55 the divalent ions of the first transition series because it
Assign reasons for each of the following : has the largest number of unpaired electrons.

(i) Transition metals generally form coloured Example - 57

compounds.
Explain the following facts :
(ii) Manganese exhibits the highest oxidation state of
+7 among the 3d series of transition elements. (a) Transition metals acts as catalyst.

Sol. (b) Chromium group elements have highest

meeting points in their respectively series.
(i) Transition metals generally form coloured compounds. The
colour of compounds of transition metals may be (c) Transition metals form coloured complexes.
attributed to the presence of incomplete (n – 1) d
subshell. In the compounds of transition metals the d– Sol.
orbitals split into

two sets-t2g
dx 2 2
–y
, dz of lower energy and eg (a) Transition metals acts as catalyst due to the following
2
reasons :
dxy , dyz , dxz
of high energy. The electron can jump from
lower energy t2g orbitals to higher energy eg orbitals (d–d (iii) The lowest oxidation state of manganese is basic
transition) by absorption of light of some particular while the highest is acidic.
wavelength from visible light. The remainder light is
emitted (iv) Mn (II) shows maximum paramagnetic character
as coloured light and the compound appears coloured. amongst the divalent ions of the first transition
series.
(ii) In a transition series the element with maximum
oxidation state occurs in or near the middle of the
transition series and maximum oxidation state exhibited
is equal to sum of (n – 1) d and ns electrons. In Mn
(3d5 4s2) the sum of (n – 1) d and (ns) electron is 7 and
therefore it exhibits maximum o.s. of + 7. The lesser no.
of oxidation states on extreme ends are either due to too
few electrons to lose or share or too many d-electrons so
that fewer orbitals are available to share electrons with
others.

Example - 56
Explain:
(i) CrO 42– is astrongoxidizing agent while MnO
4
2–
is
not.
(ii) Zr and Hf have identical sizes.
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 176 d AND f BLOCK ELEMENTS
(i) Their partially empty d-orbitals provide surface area
for reactant molecules.

(ii) They combine with reactant molecules to form

transition states and lowers their activation energy.

(iii) They show multiple oxidation states and by giving

electrons to reactants they form complexes and lower
their energies.

(b) The melting point of chromium groups elements have

the highest melting points in their respective serves due
to presence of strong intermetallic bonds (formed by
valence electrons and covalent bonds formed due
to d–d overlapping of impaired d-elelctrons.)

(c) Their colour due to the presence of incomplete d-

subshell. The electrons can be excited from one energy
lavel to another with in the d-subshell. The energy
required to cause such d–d promotions or transition
falls within the visible range for all transition elements.
When white light falls on an ion or compound, some of
its wave lengths are absorbed due to d–d transition
and others are reflected.

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 d AND f BLOCK ELEMENTS 177

Therefore, coloure of the transition metal ion is that of the

Example - 60
reflected light.
What happens when ?
Example - 58
(i) Ferric chloride is added to potassium ferrocyanide.
Give reasons :
(ii) Iron reacts with cold dilute nitric acid.
(i) Among transition metals, the highest oxidation
state is exhibited in oxoanins of a metal. (iii) Potassium ferricyanide is added to ferrous sulphate.
(ii) Ce is used as an oxidising agent in volumetric
4+
(iv) Excess of potassium iodide is added to mercuric
analysis. chloride.
(iii) Transition metals form a number of
(v) Green vitriol is strongly heated.
interstitial compounds.
(vi) Silver chloride is treated with aqueous sodium
(iv) Zn2+ salts are white while Cu2+ salts are blue.
cyanide and the product thus formed is allowed to
Sol react with zinc in alkaline medium.
.
(i) Highest oxidation state is shown in flourides and oxides
because F2 and O2 are strong oxidising agents. (vii) Zinc oxide is treated with excess of sodium
hydroxide solution.
(ii) Ce4+ = [Xe], 4f0, 5d0, 6s0
Ce4+ has the tendency to accept one electron to get the +3 (viii) Ammonium thiocyanate is added to ferric
oxidtion state, hence Ce4+ is a good oxidising agent. chloride solution.
(iii) In these compounds small size atoms like hydrogen,
Sol. (i) Prussian blue is formed.
carbon, nitrogen, boron, etc. occupy the empty space of
metal lattice (interstices). The small entrapped atom in
the interstices form the bonds with metals due to which 4FeCl3 + 3K 4Fe(CN)6 → Fe4[Fe(CN)6 ]3 +12KCl
Prussian blue
mobility and ductility of the metals decrease, when as (Ferri ferrocyanide)
tensile strength increases. Example : steel is the
interstitial compound of iron and carbon. (ii) Ammonium nitrate is formed.
(iv) In Cu2+ salts (3d9) d–d transition is possible. Therefore
Cu2+ salts are coloured. [Fe + 2HNO3 → Fe(NO3)2 + 2H] ×
In Zn2+ salts (3d ) no. d–d transition is possible due to
10
4 HNO + 8H → NH + 3H O
3 2
completely filled d-orbitals. Hence Zn2+ salts are white. 3

Example - 59 NH 3 + HNO3 → NH4 NO3

Write the main differences in lanthanides and 4Fe + 10HNO 3→ 4Fe(NO ) + NH 4NO + 3H O
actinides. 23 2

Sol (iii) Ferrous ion is first oxidised to ferric ion while

. ferricyanide ion is reduced to ferrocyanide ion.
Then, ferric ions react with ferrocyanide ions to
form potassium ferric ferrocyanide (Turnbull's
blue).

Fe2+ + K [Fe (CN) ]3– → KFe [Fe(CN)6]

3 6 (Turnbull's Blue)

(iv) First scarlet precipitate is formed which then

dissolves in excess of potassium iodide forming a
complex.

HgCl2 + 2KI → HgI2 +

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 178 d AND f BLOCK ELEMENTS
2KCl HgI2 + 2KI → K2HgI4

Potassiumtetraiodomercurate(II)

(colourless)

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d AND f BLOCK ELEMENTS 179

(v) When heated strongly, a mixture of gases consisting

K2Cr2O7 + 4H2SO4 → K2SO4 + Cr2(SO4)3 + 4H2O + 3 [O]
of SO2 and SO3 is evolved and a red residue, Fe2O3 is
[Na 2SO 3+ [O] → Na 2SO 4] × 3
formed.
[FeSO 4.7H 2O → FeSO4 + 7H 2O] × 2 K2Cr2O7 + 3Na2SO3 + 4H2SO4 → K2SO4 + Cr2(SO4)3
Green
2FeSO → Fe O + SO + SO
4 2 3 2 3
+ 3Na2SO4 + 4H2O
SO 3+ H 2O → H 2SO 4 (ii) When zinc is exposed to moist air, the surface is
2FeSO .7H O → Fe O + SO + H SO + 13H O affected with the formation of a film of basic zinc
4 2 2 3 2 2 4 2
carbonate on it. Due to this zinc becomes dull.
Green vitriol Red [2Zn + 2H 2O + O2 → 2Zn (OH)2 ] × 2
(vi) AgCl dissolves in KCN forming a complex, Zn(OH)2 + CO2 → ZnCO3 + H2O
potassium
argentocyanide. The addition of zinc precipitates
ZnCO + 3Zn(OH) → ZnCO .3Zn (OH)
silver. 3 2 3 2
4Zn + 3H O + CO + 2O → ZnCO .3Zn(OH)
AgCl + 2KCN → KAg(CN)2 + KCl 2 2 2 3 2
Basic zinccarbonate
2KAg(CN)2 + Zn → K2Zn(CN)4 + (iii) Ferrous sulphate is a salt of a weak base and a
2Ag strong acid. Thus, its hydrolysis occurs when it is
Potassium zincocyanide dissolved in water and solution becomes turbid due
to formation of ferrous hydroxide.
(vii)ZnO dissolves in NaOH forming sodium
FeSO + 2H O Fe(OH) + H SO
zincate. ZnO + 2NaOH → Na2ZnO2 + H2O
4 2 2 2 4
(viii) Deep red colouration due to the formation of a Addition of a small amount of acid shifts the
complex is developed. equilibrium towards left and thus prevents hydrolysis.
FeCl + NH CNS → Fe(CNS)Cl + NH Cl (iv) On addition of NaOH, a white precipitate of Zn (OH)2
3 4 2 4
is formed which dissolves in excess of NaOH forming
or FeCl 3+ 3NH 4CNS → Fe(CNS)3 + 3NH4 Cl sodium zincate.
Example - 61 ZnCl2 + 2NaOH → Zn(OH)2 + 2NaCl
Zn (OH)2 + 2NaOH → Na2ZnO2 +
Explain the following :
2H2O
(i) Acidified K2Cr2O7 solution turns green when Soluble
sodium sulphite is added to it. (v) NH4OH is a weak hydroxide. It ionises slightly
(ii) Zinc becomes dull in moist air. furnishing OH– ions. However, the OH– ions are
(iii) A little acid is always added in the preparation sufficient to cause the precipitation of Zn(OH)2 as its
solubility product is exceeded.
of aqueous ferrous sulphate solution.
ZnSO4 + 2NH4OH → Zn(OH)2 +
(iv) The addition of NaOH solution to a solution of zinc (NH4)2SO4
white ppt.
In presence of NH4Cl, the ionisation of NH 4OH is
chloride produces a white precipitate which –
further suppressed and sufficient OH ions are not
dissolves on further addition of NaOH. available to cause precipitation as the solubility
(v) The addition of NH4 OH to ZnSO4 solution product is not exceeded.
produces white precipitate but no (vi) Zinc is cheaper as well as stronger reducing agent in
comparison to copper.
precipitate is formed if it contains NH4Cl. Zn + 2[Ag(CN)2 ]– → 2Ag + [Zn(CN) 4 ]
2–

(vi) Zinc and not copper is used for the recovery of silver

from complex [Ag(CN) ]–. (vii) Copper sulphate dissolves in the ammonium hydroxide
2
(vii)Copper sulphate dissolves in NH4OH solution due to formation of a copper complex. Ferrous
sulphate
but FeSO4 does not.
reacts with NH4OH to form insoluble Fe(OH)2. It does
not form any complex with NH4OH.
CuSO + 4NH OH → [Cu(NH ) ]SO + 4H O
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 180 d AND f BLOCK ELEMENTS
(viii) Copper hydroxide is soluble in ammonium 4 4 3 4 4 2
Deep blue solution
hydroxide but not in sodium hydroxide. FeSO + 2NH OH → Fe(OH) + (NH ) SO
4 4 2 4 2 4
Insoluble
Sol. (i) Na2SO3 is a reducing agent. It reduces acidified
(viii) Cu(OH)2 dissolves in NH4OH by forming a complex.
K2CrO7
to chromic sulphate which is green in colour.
Cu(OH) + 4NH OH → [Cu(NH ) ] (OH) + 4H O
2 4 3 4 2 2

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 172 d AND f BLOCK ELEMENTS

the compound (A) is ferrous sulphate, FeSO4.7H2O.

Cu(OH)2 is insoluble in NaOH as no such complex
is formed. Reactions :
FeSO4.7H2O ——Hea—t → FeSO H Fe O + SO + SO
——→
eat —
Example - 62 ( A)
–7H2O 4 2 3 2 3

(B)
A metal chloride (x) shows the following reactions : Blackish
(C) ( D)

brown powder
(a) When H2S is passed in an acidified solution of (x)
a Fe2O3 + 6HCl 2FeCl3 + 3H2O
——→
black precipitate is obtained. (B) (E)
Yellow solution

(b) The black precipitate is not soluble in ammonium

sulphide. 2FeCl3 + H2S ——→ 2FeCl 2 + S
(F)

(c) The solution of stannous chloride is added to an 2HCl + White

turbidity
(G)
aqueous solution of (x), a white precipitate is Apple
green solution
obtained which turns grey on addition of more FeCl3 + 3CNS– ——→ Fe(CNS) + 3Cl–
3
stannous chloride. (E) Blood red
coloured solution

(d) When aqueous solution of KI is added to an aqueous

solution of (x), a red precipitate is obtained which Example - 64
dissolves on addition of excess of KI. A black mineral (A) on treatment with dilute sodium cyanide
Identify (x) and write down the equations for the solution in presence of air gives a clear solution of (B) and (C).
reactions. The solution (B) on reaction with zinc gives precipitate of a
Sol. The acidified solution of (x) gives a black sulphide with metal (D).
H2S indicates that the chloride is of a basic cation of (D) is dissolved in dilute HNO3 and the resulting solution gives
second group. The sulphide in insoluble in ammonium a white precipitate (E) with dilute HCl.
sulphide, hence, the cation belongs to IIA group of (E) on fusion with sodium carbonate gives (D).
mixture analysis.
(E) dissolves in ammonia solution giving a colourless solution
It gives white precipitate with SnCl2 which turns to
grey in excess of SnCl2 suggests that (x) is HgCl2. It is of (F). Identify (A) to (F) and give chemical equations for
further confirmed by the reaction with KI. reactions at steps (i) to (v).
Reactions :
HgCl 2+ H 2S → HgS + 2HCl Sol. On the basis of the given data, the black mineral (A) is
Black silver glance, Ag2S. It is confirmed by the following :
2HgCl 2+ SnCl 2→ Hg 2Cl 2 + SnCl 4 (i) It dissolves in sodium cyanide solution in presence of air.
white
Hg Cl + → 2Hg + SnCl Ag2S + 4NaCN + 2O2 → 2[NaAg(CN)2 ] + Na2SO4
SnCl
2 2 2 4 Sodium Sodium
argento cyanide sulphate
Grey (B) (C)

HgCl2 + 2KI → HgI2 + 2KCl

Red ppt. (ii) 2[NaAg(CN)2 ] + Zn → Na2 Zn(CN)4 + 2Ag
(D)
HgI2 + 2KI → (B)

K2HgI4
Soluble
(iii) 3Ag
(D)
+ 4HNO3 → 3AgNO3 + NO + 2H2O
Example - 63
A certain inorganic compound (A) on heating loses its water of AgNO3 + HCl → AgCl + HNO3
(E)
crystallisation. On further heating, a blackish brown powder
(B) and two oxides of sulphur (C and D) are obtained. The 2AgCl+ Na CO 1
powder (B) on boiling with hydrochloric acid gives a yellow →
CO2Ag+ 2NaCl + + O
solution (E). When H2S is passed in (iv) 2 3
2 2
(E) (D)
2
(E), a white turbidity (F) and apple green solution (G) are
su ay be a sulphate. The solution (E) on treatment
obtained. The solution (E) on treatment with thiocyanate ions lp with thiocyanate ions gives blood red coloured
gives a blood red coloured compound (H). Identify the h compound
compounds from (A) to (H). ur (H) indicates that the solution (E) consists Fe3+
, ions. Thus,
it Lakshya Educare
Sol. The compound (A) on strong heating gives two oxides of
m
 d AND f BLOCK ELEMENTS 173
Silver chloride, AgCl
Ag
(v) (F) = Diamminsilver (I) chloride, Ag (NH3)2Cl
Cl
+
2N
H4
O
H
→
Ag
(N
H3
)2
Cl
+
2H
2O
(
E)
(F
)

(A)
=
Sil
ver
gla
nce
,
Ag2
S
(B)
=
So
diu
m
arg
ent
ocy
ani
de,
Na
Ag
(C
N)2
(C)
=
So
diu
m
sul
pha
te,
Na2
SO
4
(D)
=
Sil
ver
me Lakshya Educare
tal,
Ag
(E)
=
 d AND f BLOCK ELEMENTS 173

EXERCISE − 1 : BASIC OBJECTIVE QUESTIONS

D & F Block 9. Transition elements
1. Transition elements have (a) exhibit inert-pair effect
(a) completely filled d levels (b) show nonmetallic character
(b) completely filled s levels and d levels (c) do not form complex compounds
(c) incompletely filled s levels and completely filled d (d) exhibit variable oxidation states
levels
10. The oxidation states shown by transition elements is
(d) incompletely filled d levels related to their
2. The general electronic configuration of the transition (a) electropositive characters
elements is
(b) electronic configurations
(a) (n – 1)d10 (n + 1)s2
(c) atomic weights (d) atomic sizes
(b) (n – 1)d1–10
(n + 1)s 1–2
11. The electronic configuration of chromium is4 actually
5 1 2

(c) (n – 1)d1–10 np6 ns2 [Ar]3d 4s instead of normally expected [Ar]3d 4s . This
is because
(d) (n – 1)d1–10 ns0–2
(a) an exactly half-filled d level gives additional
3. Which of the following transition elements has stability, according to the Hund rule of maximum
completely filled d orbitals (the d10 configuration) multiplicity

(a) Co (b) Cr (b) the 4s orbital has higher energy than the 3d orbitals

(c) Hg (d) Ni (c) the 4s orbitals has lower energy than the 3d orbitals

4. In which of the following transition elements are the d (d) the 3d and 4s orbitals have equal energies and hence
orbitals not completely filled ? electron migration occurs readily

(a) Zn (b) Hg 12. Identify the species having an atom in +6 oxidation state.
(a)
MnO– (b) Cr(CN)3–
(c) Cd (d) Ag 4 6

5. The electronic configurations of the first four members (c)

NiF63– (d)
CrO2Cl2
of
the actinide series cannot be written accurately in a 13. Which of the following is not true about the transition
regular manner because of elements ?
(a) small difference in energy between 5f and 6d orbitals (a) They show variable oxidation states
(b) large difference in energy between 5f and 6d orbitals (b) Their ions have a strong tendency to form complexes
(c) small difference in energy between 5f and 6s orbitals (c) Their compounds usually do not absorb ultraviolet
(d) violation of the Pauli exclusion principle and visible lights

6. The electronic configuration of silver is (d) Their ions and complex ions usually possess magnetic
moments.
(a) [Ar]3d10 4s1 (b) [Ar]4d10 4s1
14. What of the following is an incorrect statement?
(c) [Kr]4d 5s
10 1
(d) [Kr]4d 5s
8 2
(a) The lowest oxide of a transition metal is acidic
7. The electronic configuration of palladium whereas the highest one is usually basic.
(b) A transition metal usually exhibits higher oxidation
is (a) [Ar]3d84s2 (b) [kr]4d85s2
states in its fluorides than it its iodides.
(c) [kr]5d86s2 (d) [Ar]4d105s0 (c) Transition metal halides become more covalent with
8. The electronic configuration of platinum is the increasing oxidation state of the transition metal
and are more susceptible to hydrolysis.
(a) [Ar] 4f145d96s1 (b) [Ar] 4f145d106s2
(d) The highest oxide of a transition metal is acidic
(c) [Ar] 4f 6d 7s
14 10 2
(d) [Ar] 4f 6d 7s
14 9 1 whereas the lowest one is usually basic.
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 174 d AND f BLOCK ELEMENTS
15. Which of the following transition metals does not show 25. Which of the following compounds is expected to be
variable oxidation states ? coloured ?
(a) Mercury
(b) Zinc (a) Ag2SO4 (b) CuF2
(c) Gold
(d) Silver (c) MgF2 (d) CuCl
16. Which of the following ions is colourless in solution ? 26. The covalent radii of transition metals decrease from
left to right in a period because
(a) V3+ (b) Cr3+
(a) the densities of the metals decrease with increasing
(c) Co2+ (d) Sc3+ atomic number due to poor shielding of electrons

17. Which of the following ions has the maximum number of

(b) the screening of nuclear charge by d electrons is
unpaired d electrons ?
poor and hence the nuclear charge attracts all the
electrons strongly, causing a decrease in size
(a) Fe3+ (b) V3+
(c) the ionization energies also decrease correspondingly
(c) Ti 3+
(d) Mg 2+
(d) the metallic character decreases as the atomic number
18. Which of the following ions possesses the maximum increases
number of unpaired electrons ?
27. The highest possible oxidation state shown by osmium
in its compounds is
(a) Ni2+ (b) Fe2+
(a) +4 (b) +8
(c) Cu +
(d) Zn 2+
(c) +6 (d) +10
19. Which of the following does not possess unpaired
28. Which of the following oxides of chromium is
electrons ?
amphoteric in nature ?
(a) Co3+
(b) Cu2+ (a) CrO (b) CrO3
(c) Ti 2+
(d) Hg2+ (c) Cr2O3 (d) CrO5

20. Which one of the following ionic species will impart 29. Permanent magnetic are generally made from the alloy of
colour to an aqueous solution ?
(a) Co (b) Zn
(a) Ti 4+
(b) Cu+ (c) Al (d) Pb
(c) Zn2+ 30. CrO3 dissolves in aqueous NaOH to give
(d) Cr3+
21. Which of the following elements shows the maximum (a)
CrO2– (b) Cr(OH)
4 2
number of different oxidation states in its compounds ?
(c) Cr O2– (d) Cr(OH)
(a) Eu (b) La
2 7 3

31. Lanthanide elements have

(c) Gd (d) Am
(a) similar lattice energies but widely different solvation
22. Which of the following electronic configurations and ionization energies
represents Fe3+ ? (a) similar lattice and solvation energies but widely
different ionization energies
(a) [Ar]3d64s2 (b) [Ar]3d54s1 (c) similar lattice and ionization energies but widely
different hydration energies
(c) [Ar]3d54s2 (d) [Ar]3d54s0
(d) similar lattice energies, solvation energies and
23. The last electron of a d-block element occupies the orbital ionization energies
(a) (n – 1)d (d) (n – 1)s
(b) nd
(c) np
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d AND f BLOCK ELEMENTS 175
32. A n e transition metals, the melting points of Zn, Cd and Hg
m g are relatively low because
o th
(a) their d shells are not completely filled
24. Which of the following ions is expected to the coloured
(b) their d electrons do not participate in metallic bonding
in solution ?
(a) Cu+ (c) their densities are higher
(b) Cu2+
(c) Ti4+ (d) of all the above
(d) Sc3+

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 176 d AND f BLOCK ELEMENTS
33. The noble character of platinum and gold is favoured by 39. Which of the following compounds is green in colour ?
(a) high enthalpies of sublimation, high ionization
(a) KMnO4 (b) (NH4)2Cr2O7
energies and low enthalpies of solvation
(b) high enthalpies of sublimation, low ionization energies (c) MnO2 (d) K2MnO4
and low enthalpies of solvation 40. Cr 2O2–7 reacts with OH– as
(c) low enthalpies of sublimation, high ionization
energies and low enthalpies of solvation Cr 2O2–7 + 2(OH– ) → 2CrO2–
4 + H2 O

(d) high enthalpies of sublimation, high ionization The change in oxidation number of Cr is
energies and high enthalpies of solvation
(a) +6 (b) +3
34. The transition elements are
(c) zero (d) +4
(a) more reactive than group 1 elements
41. CrO 2–4 reacts with H+ as
(b) more reactive than group 2 elements
(c) less reactive than group 1 elements but more 2CrO2–4 + 2H+ → Cr2 O2–
7 + H2 O
reactive than group 2 elements
The change in oxidation number of Cr is
(d) less reactive than group 1 and 2 elements
(a) +5 (b) +7
35. Transition metals
(c) +6 (d) zero
(a) form only ionic compounds
(b) form exclusively covalent compounds easily
(c) may form either ionic or covalent compounds (d) Zn2+ ions absorb light of the visible range
depending on the condition
(d) exclusively form coordination compounds but no
simple compounds
36. Which of the following statements is incorrect ?
(a) The compounds formed by the 3d transition metals
in lower valence states are ionic but those in higher
valence states are covalent.
(b) The 4d and 5d transition metals form less ionic
compounds than do the 3d transition metals.
(c) The compounds formed by the 3d transition metals
are less ionic than the corresponding compounds
formed by the 4d and 5d transition metals.
(d) The ionization energies of 3d, 4d and 5d transition
metals are greater than those of group 1 and 2
metals.
37. Which of the following compounds is colourless?

(a) K2MnO4 (b) HgI2

(c) ZnSO4 (d) FeSO4

38. The compound ZnSO4 is white because

(a) charge is transferred from the metal to the oxygen
atoms
(b) electron transfer to d level does not occur as the
level is already filled to capacity in zinc

(c) Zn2+ has d10 configuration and d–d transition occurs

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 d AND f BLOCK ELEMENTS 177
42. Which of the following ions is paramagnetic ?

(a) Zn2+ (b) N3–

(c) Mn4+ (d) Cu+

43. Which of the following ions is diamagnetic ?

(a) Ni2+ (b) Ti4+

(c) Cr3+ (d) Co3+

44. The value of magnetic moment (µ spin only) for Cu2+

in CuSO4.5H2O is
(a) 5.92 BM (b) 4.92 BM
(c) 2.83 BM (d) 1.73 BM
45. For a given ion, the magnetic moment is 2.83 BM.
The total spin (s) of all the unpaired electrons is
(a) 2 (b) 1
(c) 3/2 (d) 1/2
46. Wilkinson's catalyst consists of

(a) (C2H5)3 Al and TiCl4 (b) RhCl3 and Ph3P

(c) HCo(CO)4 (d) trans-[(Rh(CO)(H)(PPh3)3]

47. Which of the following mixture is known as
Fenton's reagent ?

(a) FeSO4 + K4[Fe(CN)6] (b) FeSO4 + PdCl2

(c) FeSO4 + H2O2 (d) TiCl4 + (C6H5)3P

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 178 d AND f BLOCK ELEMENTS
48. Which of the following is known as Adams catalyst ?
55. Deep red-yellow vapour of CrO2Cl2 is passed into an
(a) Pt/PtO (b) V O /TiCl aqueous solution of NaOH. The solution turns
2 5 4

(c) Cu/V (d) Pt/Rh (a) yellow due to the formation of Na2Cr2O7

49. The transition metals sometimes form

(b) yellow due to the formation of Na2CrO4
nonstoichiometric compounds. These compounds have
(a) definite structures and definite proportions (c) green due to the formation of CrCl3
(b) indefinite structures and definite proportions (d) red due to the formation of Na2CrO4
(c) definite structures and indefinite proportions
56. Acidified K2Cr2O7 on treatment with KI produces
(d) indefinite structures and indefinite proportions
(a) KIO3 (b) I2
50. Which of the following statements is correct ?
(a) The second-row elements have smaller radii than the (c) KIO4 (d) I–3
corresponding third-row ones. 57. Na CrO on treatment with lead acetate gives a precipitate.
2 4
(b) Because of lanthanide contraction, the radii of the This precipitate is dried and the solid is used as a pigment
third-row elements are almost the same as those of the for road signs and markings. The solid is known as
first-row elements.
(a) white lead (b) chrome green
(c) Because of lanthanide contraction, the radii of the
third-row elements are almost the same as those of the (c) chrome yellow (d) red lead
second-row elements. 58. Which of the following ores is known as pyrolusite ?
(d) Because of lanthanide contraction, the separation of
second-row elements from one another is easier. (a) Fe2O3 (b) SnO2

51. Sodium chromate is prepared by (c) MnO2 (d) PbS

(a) fusing chromite (FeCr2O4) with sodium chloride in
59. Which of the following oxides of manganese is
air amphoteric ?
(b) fusing chromite (FeCr2O4) with sodium hydroxide (a) MnO (b) Mn2O3
in air

(c) fusing (NH4)2Cr2O7 with sodium hydrogen sulphate (c) Mn2O7 (d) MnO2
in nitrogen 60. Which of the following oxides of manganese is stable
(d) fusing sodium dichromate with carbon as well as strongly acidic ?
52. When hydrogen peroxide is added to an acidic solution
of a dichromate, the most probable product is (a) MnO2 (b) Mn2O7

(a) K2CrO4 (c) MnO3 (d) Mn2O3

(b) CrO3
(c) Cr2O3
(d) CrO(O2)2 61. KMnO4 is manufactured on a large scale by

53. Which of the following statements is incorrect for CrO3 ?

(a) fusing MnO2 with KOH and then oxidizing the
(a) It is a bright orange solid. fused mixture with KNO3
(b) It is commonly called chromic acid. (b) fusing MnO2 with Na2CO3 in the presence of O2
(c) It is prepared by adding concentrated H2SO4 to a
saturated solution of sodium dichromate. (c) fusing MnO2 with KOH and KNO3 to form K2MnO4
which is then electrolytically oxidized in an alkaline
(d) The colour arises due to d–d transition. solution
54. Chromyl chloride, CrO Cl , is prepared byheating a mixture (d) fusing MnO2 with KNO3 and then acidifying the fused
of
2 2
mixture
(a) NaCl, K2Cr2O7 and NaOH
62. MnO– 4is prepared by treating a solution containing Mn2+
(b) NaCl, K2Cr2O7 and concentrated H2SO4 ions with a very strong oxidizing agent such as
Mahesh Tutorials Science
d AND f BLOCK ELEMENTS 179
(c) NaCl, K2Cr2O7 and MnO2
(a) PbO2 (b) C2 O2–
4
(d) CrO3 and NaCl
(c) I2 (d) Fe3+

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 180 d AND f BLOCK ELEMENTS
63. Which of the following is an incorrect statement ? 71. Which of the following statements is correct for the
lanthanoids ?
(a) In a redox reaction in acidic medium, KMnO4
produces Mn2+ ions. (a) The 4f electrons do not take part in bonding.

(b) In a redox reaction in strongly alkaline medium, (b) The 4f electrons can neither be removed to produce
KMnO4 produces MnO2– ions. ions nor be made to take part in crystal field
4 stabilization of complexes.
(c) In a redox reaction in neutral medium, KMnO (c) The 4f electrons in the antepenultimate shell are very
produces
MnO2. 4
effectively shielded by the 5s and 5p electrons.
(d) All of these
(d) In a redox reaction in alkaline medium, KMnO4
produces Mn O . 72. The most common and stable oxidation state of a
2 7
lanthanide is
64. KMnO4 in an acidic medium
(a) +II (b) +IV
oxidizes
(a)
CrO2– to CO
4 2
(b)
N2H to N2 (c)
+VII (d) +III
4

(c) S O2– to SO2– (d) all of these

73. The atomic and ionci radii (M3+ ions) of lanthanide
2 3 4
65. KMnO4 in an acidic medium will not oxidize elements decrease with increasing atomic number. This
effect is called
(a)
NO– (b) SO2–
(a) lanthanide contraction
2 4
(b) lanthanide expansion
(c) HN3 (d) H2O2 70. The electronic configuration of cerium is

66. Dilute and slightly alkaline KMnO4 is called (a) [Xe]4f15d16s2 (b) [Xe]4f25d06s1

(a) Fenton's reagent (b) Lucas reagent (c) [Xe]4f15d26s2 (d) [Xe]4f25d06s2
(c) Baeyer's reagent (d) Tollens reagent
67. Which one of the following oxides of chromium is
amphoteric in nature ?

(a)CrO (b) Cr2O3

(c) CrO3 (d) CrO5

68. The electronic configuration of-block elements is
represented by

(a) (n – 2)f1–14 (n – 1)d0–1ns2

(b) (n – 2)f1–14 (n – 1)d0–5ns0–2

(c) (n – 2)f1–14 (n – 1)d0–10ns1–2

(d) (n – 2)f1–14 (n – 1)d0–2 (n – 1)s2

69. Lanthanides are characterized by the filling of the
(a) penultimate 4f energy level
(b) antepenultimate 4f energy level
(c) penultimate 3f energy level
(d) antepenultimate 3f energy level

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d AND f BLOCK ELEMENTS 181
(c) actinide contraction
(d) none of these
74. Lanthanide contraction occurs because
(a) the 4f electrons, which are gradually added, creat a
strong shielding effect
(b) the 4f orbitals are greater in size than the 3d and
3f orbitals
(c) the 5f orbitals strongly penetrate into the 4f orbitals
(d) the poor shielding effect of 4f electrons is coupled
with increased attraction between the nucleus and
the added electrons
75. The hardness, melting point and boiling point of
elements increase from Ce to Lu because
(a) the attraction between the atoms increases as the
size increases
(b) the attraction between the atoms decreases as the
size increases
(c) the attraction between the atoms increases as the
size decreases
(d) the attraction between the atoms remains the same
as the size increases

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 178 d AND f BLOCK ELEMENTS

EXERCISE − 2 : PREVIOUS YEAR COMPETITION QUESTIONS

2013
(c) It has no Cr – Cr bond and has six O – O bonds
1. Which of the following lanthanoid ions is diamagnetic ?
(d) It has one Cr – Cr bond and seven Cr – O bonds
(Atoms, Ce = 58, Sm = 62, Yb = 70) [CBSEAIPMT] 3+
2+ 2+ 7. The spin only magnetic moment of Fe ion (in BM) is
(a) Yb (b) Ce approximately [KCET]
2+ 2+
(c) Sm (d) Eu (a) 4 (b) 7
2. KmnO4 can be prepared from K2MnO4 as per the reaction
(c) 5 (d) 6
:
8. Which of the following species is/are paramagnetic ?
3MnO42– + 2H2 O v— —~— 2MnO
4
–
+2 MnO + 4OH– 2+ 0 2+ 4+
Fe , Zn , Hg , Ti [Kerala
–
The reaction can go to compition by removing OH ions by CEE]
addings :- [CBSEAIPMT] 2+ 0 4+
(a) Fe only (b) Zn and Ti
2+ 2+ 0 2+
(a) SO2 (c) Fe and Hg (d) Zn and Hg
(b) HCl
(c) KOH (d) CO2 9. The acidic, basic or amphoteric nature of Mn2O7, V2O5
2012 and CrO are respectively, [Kerala
CEE]
3. Which of the statements is not true ? [CBSEAIPMT]
(a) acidic, acidic and basic
(a) K2Cr2O7 solution becomes yellow on increasing the
(b) basic, amphoteric and acidic
pH beyond 7
(c) acidic, amphoteric and basic
(b) On passing H2S through acidified K2Cr2O7 solution, a
(d) acidic, basic and amphoteric
milky colour is observed
10. Ammonia will not form complex with [Kerala CEE]
(c) Na Cr O 2+ 2+
is preferred over K Cr O in volumetric (a) Ag (b) Pb
2 2 7 2 2 7 2+ 2+
analysis (c) Cu (d) Cd
(d) K2Cr2O7 solution in acidic medium is orange
11. The titanium (atomic number 22) compound that does
Transition Elements and Their Compounds not exist is [Kerala
2011 CEE]

4. For the four successive transition elements (Cr, Mn, Fe and (a)TiO (b) TiO2
Co), the stability of +2 oxidation state will be there in (c) K2TiF6 (d) K2TiO4
which of the following order ? [CBSEAIPMT]
12. Copper exhibits only +2 oxidation state in its stable
(At. no. Cr = 24, Mn = 25, Fe = 26, Co = 27)
compounds. Why ? [Guj.
(a) Cr > Mn > Co > Fe (b) Mn > Fe > Cr > Co CET]
(c) Fe > Mn > Co > Cr (d) Co > Mn > Fe > Cr (a) Copper is transition metal in +2 state.
(b) +2 state compounds of copper are formed by
exothermic reactions.
5. Acidified K Cr O 9
solution turns green when Na SO is (c) Electron configuration of copper in +2 state is [Ar]3d
2 2 7 2 3
0
added to it. This is due to the formation of 4s .
[CBSEAIPMT] (d)
Copper gives coloured compounds in +2 state.
(a) CrSO4 (b) Cr2(SO4)3 13. When dil. H2SO4 is added to aqueous solution of potassium
chromate, yellow colour of solution turns to orange
(c)
CrO 2–
(d) Cr2 (SO3 )3
4
colour. It indicates [Guj.
Which is the correct statement about Cr 2O2–7 structure ? CET]
6.
(a) chromate ions are reduced
d AND f BLOCK ELEMENTS 179

[DUMET] (b) chromate ions are oxidised

(a) It has neither Cr – Cr bonds nor O–O bonds (c) mono centric complex is converted into dicentric complex

(b) It has one Cr – Cr bond and six O – O (d) oxygen gets removed from chromate ions
bonds
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 d AND f BLOCK ELEMENTS 179

14. German silver alloy contains [Guj. CET]

23. In Cu (at. no. 29) [RPMT]
(a) zinc, silver and copper
(a) 13 electrons have spin in one direction and 16
(b) nickel, silver and copper
electrons in other direction
(c) germanium, silver and copper
(b) 14 electrons have spin in one direction and 15
(d) zinc, nickel and copper electrons in other direction
2+
(c) one electron can have spin only in the clockwise
15. Experimental value of magnetic moment of Mn complex is
direction
5.96 BM. This indicates [Guj. CET]
(d) None of the above is correct
(a) axial and orbital motion of electron in same direction
24. Which one of the following ions is colourless ?
(b) axial and orbital motion of electron in opposite
direction [Manipal, BVP]
+ 2+
(c) electron does not exhibit orbital motion, it only (a) Cu (b) Co
exhibits axial motion 2+ 3+
(c) Ni (d) Fe
(d) electron does not axial motion, it only exhibits orbital
motion 25. Which of the following statements concerning transition
2010
elements is false ? [Manipal, JCECE]
16. Which of the following pairs has the same size ?
(a) They are all metals
[CBSEAIPMT]
2+ 4+ 2+ 2+ (b) They easily form complex coordination compounds
(a) Zn , Hf (b) Fe , Ni
4+ 4+ 4+ 4+
(c) They form compounds containing unpaired electrons
(c) Zr , Ti (d) Zr , Hf and their ions are mostly coloured
17. Which of the following ions will exhibit colour in (d) They show multiple oxidation states always differing
aqueous solutions ? [CBSEAIPMT] by units of two
3+ 3+
(a) Sc (Z = 21) (b) La (Z = 57) 26. Choose the correct reaction to prepare mercurous chloride
3+
(c) Ti (Z = 22) (d) Lu3+ (calomel). [Guj. CET]
(Z = 71)
18. Which of the following transition metal ions is not (a)
HgCl + Hg —∆—→ (b) Hg + Cl ——→
coloured?
2 2
[AFMC]
+ 3+ (c) HgCl2 + SnCl 2 ——→
(a) Cu (b) V
2+
2+ (d) Both options (a) and (c)
(c) Co
(d) Ni 4
27. A transition element X has the configuration [Ar]d in its
19. Maximum number of unpaired electrons are present in
+3 oxidation state. Its atomic number is [JCECE]
[CPMT]
(a) 25 (b) 26
2+ 2+
(a) Fe (b) Mn (c) 22 (d) 19
+ 2+
(c) Cu (d) Cr 28. In haemoglobin, the metal ion present is [WB JEE]
20. The colour of zinc sulphide is [MPPMT] 2+ 2+
(a) Fe (b) Zn
(a) white (b) black 2+ 2+
(c) Co (d) Cu
(c) brown (d) red
21. The formula of mercurous ion is [MPPMT] 29. When Zn is treated with excess of NaOH, the product
obtained is [BVP]
+
(a) Hg (b) Hg+2 (a) Zn(OH)2 (b) ZnOH
(c) Hg2+ (d) None of these
2 (c) Na2ZnO2 (d) None of these
22. Which of the following has maximum unpaired d-electrons? 30. Which of the following is magnetite ? [VMMC]
[RPMT]
(a) Fe2CO3 (b) Fe2O3
2+ 2+
(a) Zn (b) Fe (c) Fe O (d) Fe O . 3H O
2+ 3 4 2 3 2
+
(c) Ni (d) Cu
180 d AND f BLOCK ELEMENTS

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 180 d AND f BLOCK ELEMENTS

2009
39. The maximum number of unpaired electrons is preent in
31. Out of TiF2– , CoF3– , Cu Cl and NiCl2– (Z of Ti =
22, [MHTCET]
6 6 2 2 4

Co = 27, Cu = 29, Ni = 28), the colourless species are (a) Fe (b) Cu

[CBSEAIPMT, AMU] (c) CO (d) Ni
(a)
TiF2– and CoF3– 40. The ion of least magnetic moment among the following is
6 6
(b)
Cu 2 Cl 2 and NiCl2–
4
[J & K CET]
(c)
TiF6 and Cu 2Cl 2
2– (d)
CoF6 and NiCl 4
3– 2– 3+ 2+
(a) Ti (b) Ni
2+ 2+
32. Transition metals show paramagnetic behaviour. This is (c) Co
because of their (d) Mn
[AFMC
(a) high lattice energy ] 41. The atom of which one of the following elements has the
(b) variable oxidation state highest number of unpaired electrons ? [J & K CET]
(c) characteristic configuration (a) 25Mn (b) 24Cr
(d) unpaired electrons (c) 96Cm (d) 26Fe

33. For which of the following pairs, magnetic moment is same? 42. The amphoteric oxide among the following is
[AIIMS] [J & K CET]
(a) MnCl2, CuSO4
(b) CuCl2, TiCl3 (a) Cr2O3 (b) Mn2O7
(c) TiO2, CuSO4
(d) TiCl3, NiCl2 (c) V2O3 (d) CrO
34. Which compound is expected to be coloured ? [CPMT] 43. Which one of the following is a d-block element ?
(a) CuCl
(b) CuF2 [J & K CET]
(c) Ag2SO4 (a) Gd (b) Hs
(d) MgF2

35. The magnetic moment of a transition metal ion is 15 BM. (c) Es (d) Cs
Therefore, the number of unpaired electrons present in it 2+ 2+ 2+ 2+
44. Out of Cu , Ni , Co and Mn those dissolve in dil.
is
HCl only one gives a precipitate when H2S is passed.
[KCET]
Identify
(a) 4 the corresponding one. [OJEE]
(b) 1
2+ 2+
(c) 2 (a) Ni (b) Cu
(d) 3
36. The solid product formed on heating AgNO3 strongly to 2+ 2+
(c) Co (d) Mn
3+
980 K is [Kerala 45. Number of unpaired electrons in Mn is [OJEE]
CEE]
(a) silver (b) silver
(a) 2 (b) 3
carbonate nitride
(c) 4 (d) 5
(c) silver oxide (d) silver metal
37. The maximum oxidation state shown by Mn in its 2008
compounds is [Kerala
(a) +4 (b) +5 CEE] 46. What is the correct order of spin only magnetic moment
2+
(in BM) of Mn 2+, Cr2+ and Ti ? [AFMC]
(c) +6 (d) +7
2+ 2+ 2+ 2+ 2+ 2+
38. Which one of the following sets correctly represent the (a) Mn > Ti > Cr (b) Ti > Cr > Mn
increase in the paramagnetic property of the ions ? 2+ 2+ 2+ 2+ 2+ 2+
(c) Mn > Cr > Ti (d) Cr > Ti > Mn
[EAMCET]
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 d AND f BLOCK ELEMENTS 181
47. Which of the following compounds is coloured ? [AIIMS]
2+ 2+
(a) Cu 2+ < < Mn (a) TiCl (b) FeCl
<V 2+
Cr
2+ 3 3
2+
(b) Cu 2+
< Cr < V < Mn (c) CoCl2 (d) All of these
2+
2+ 2+ 2+ 2+
(c) Cu > V > Cr > Mn
(d)
2+ < 2+
< Cr < Mn
2+
V 2+
Cu

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 182 d AND f BLOCK ELEMENTS

48. An aqueous solution of CoCl2 on addition of excess of 55. The highest oxidation state exhibited by transition metals
conc. HCl turns blue due to the formation of [DUMET] is [J&K CET]
(a) [Co(H O)]Cl 2– (a) +7 (b) +8
2 2
(b) [Co(H2O)2Cl4]
2– (c) +6 (d) +5
(c) [CoCl4] (d) [Co(H2O)2Cl2]
56. Which one of the following statements is not true with
49. Mercury is a liquid metal because [KCET]
regard to transition elements ? [J&K CET]
(a) it has a completely filled s-orbital
(a) They readily form complex compounds
(b) it has a small atomic size
(b) They show variable oxidation states
(c) it has a completely filled d-orbital that prevents d-d
(c) All their ions are colourless
overlapping of orbitals
(d) Their ions contain partially filled d-electrons
(d) it has a completely filled d-orbital that causes d-d
overlapping 2007
50. A transition metal ‘A' has ‘spin-only' magnetic moment 57. Which one of the following ions is the most stable in
value of 1.8 BM. When it is reacted with dilute sulphuric aqueous solution ? (At. no. Ti = 22, V = 23, Cr = 24, Mn =
acid in the presence of air, a compound ‘B' is formed. ‘B' 25)
reacts with compound ‘C' to give compound ‘D' with [CBSEAIPMT]
liberation of iodine. Then, the metal A and compounds B, C 3+ 3+
and D are respectively [Kerala CEE] (a) Cr (b) V
3+ 3+
(a) Ti, TiSO4, KI and TiI2 (c) Ti (d) Mn

(b) Zn, ZnSO4, KI and Zn2I2 58. Acidified potassium permanganate solution is
decolourised by [AFMC]
(c) Cu, CuSO4, KI and Cu2I2
(a) bleaching powder (b) white vitriol
(d) Cu, CuSO4, Cu2I2 and CuI2
(c) Mohr's salt (d) microcosmic salt
51. Which of the following pairs of transition metal ions are 59. Assertion : Mercury vapour is shining silvery in
the stronger oxidising agents in aqueous solutions ? appearance.
[Kerala CEE] Reason : Mercury is a metal with shining silvery
2+ 2+ 2+ appearance.
(a) V2+ and Cr (b) Ti and Cr
[AIIMS]
(a) Both Assertion and Reason are true and Reason is the
3+
(c) Mn 3+ 2+ 2+ correct explanation of Assertion.
and Co (d) V and Fe
(b) Both Assertion and Reason are true but Reason is not
52. Which of the following group of transition metals is the correct explanation of Assertion.
called coinage metals ? [RPMT]
(c) Assertion is true but Reason is false.
(a) Cu, Ag, Au (b) Ru, Rh, Pd
(d) Both Assertion and Reason are false.
(c) Fe, Co, Ni (d) Os, Ir, Pt
60. Which of the following ions has the least magnetic moment?
53. Potassium dichromate is used [Guj. CET]
[AMU]
(a) in electroplating 2+ 2+
(b) as a reducing agent (a) Cu (b) Ni

(c) oxidise ferrous ions into ferric ions in acidic media as (a) HgO (b) Hg2O
an oxidising agent
(c) NH2 – Hg – Hg – Cl (d) HgNH2Cl
(d) as an insecticide
54. Calomel on reaction with ammonium hydroxide gives
[JCECE]
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d AND f BLOCK ELEMENTS 183
3+ 2+
(c) Co (d) Fe

61. CuSO4 when reacts with KCN forms CuCN which is

insoluble
in water. It is soluble in excess of KCN, due to
formation of the following complex [Punjab
PMET]
(a) K2[Cu(CN)4] (b) K3[Cu(CN)4]

(c) CuCN2 (d) Cu[K Cu(CN)4]

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 184 d AND f BLOCK ELEMENTS

62. Formula of ammonium manganate is [DUMET] 72. A transition metal ion exists in its highest oxidation state. It
(a) NH MnO
(b) (NH ) MnO is expected to behave as [KCET]
4 4 4 2 4
(a) a chelating agent
(c) NH4(MnO4)2 (d) NH4Mn2O4 (b) a central metal in a coordination compound
63. The dark blue colour of the solution formed when excess of
ammonia is added to a solution of copper(II) sulphate is (c) an oxidising agent (d) a reducing agent
due to the presence of the ion [Kerala 73. The following is known as “bordeaux mixture” [Kerala CEE]
CEE]
2– 2+
(a) [Cu(OH)4 (H2O)2] (a) Borax and copper sulphate
(b) [Cu(H2O)6]
(c) [Cu(NH 3)2 (H 2O)4]
4+ 2+ (b) Orthoboric acid and ferrous sulphate
(d) [Cu(NH3)4 (H2O)2]
(c) Sodium borate and zinc sulphate
64. Among the following series of transition metal ions, the
2 6 (d) Copper sulphate and lime
one in which all metal ions have 3d , 3p electronic
74. Wich of the following metals form amphoteric oxide ?
configuration is (At. no. Ti = 22 ; V = 23 ; Cr = 24, Mn = 25)
[Manipal] [MPPMT]
3+ 2+ 3+ 4+ + 4+ 6+ 7+
(a) T i , V , Cr , Mn (b) Ti , V , r , Mn (a) Fe (b) Cu
C
(c) Zn (d) Ca
(c) Ti 4+, V3+, Cr2+ , Mn3+ (d) Ti 2+, V 3+, Cr 4+, Mn 5+
75. The stability of ferric ion is due to [BCECE]
65. Among K, Ca, Fe and Zn, the element which can form more
(a) half-filled f-orbitals (b) hal-filled d-orbitals
than one binary compound with chlorine is [Manipal]
(a) Fe (b) Zn (c) completely filled f-orbitals
(c) K (d) Ca (d) completely filled d-orbitals
66. Blue vitriol is [RPMT] 76. Which of the following is red in colour ? [JCECE]

(a) MgSO4 (a) Cu2O (b) CuF

. 7H2O (b) CuSO4 . 5H2O
(c) CaSO . 2H O (d) ZnSO . 7H O (c) ZnF2 (d) ZnCl2
4 2 4 2
67. Reason of passivity of iron is [RPMT] 77. Fenton's reagent is [JCECE]
(a) Fe O
(b) Fe O (a) SnCl2 + HCl (b) AgNO3 + NH4OH
2 3 3 4

(c) FeO (d) Fe2O4 . 3H2O (c) CuSO4 + NaOH (d) FeSO4 + H2O2

68. Essential component of amalgam is [RPMT] 78. The coordination number in an.......complex may increase
(a) Fe to 8. [J&K CET]
(b) Pb
(c) Hg (a) cobalt (b) osmium
(d) Cr
69. In which of the following ions, d–d transition is not (c) nickel (d) iron
possible? [Guj. 79. Which of the following is used as indelible ink ?
3+ 4+ CET] [J&K CET]
(a) Cr (b) Ti
2+
(c) Cu 2+ (a) Aqueous CuSO4 solution
(d) Mn
70. Which of the following is used as purgative ? [BCECE] (a) Aqueous AgNO3 solution
(a) HgS
(b) Hg Cl (c) Aqueous NaCl solution
2 2
(d) Aqueous NaOH solution
(b)HgCl2 (c) ZnSO4
2005
2006
80. Four successive members of the first row transition elements
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 d AND f BLOCK ELEMENTS 185
71. 4K Cr O —H—eat—→ 4K + 3O + X . In the above are listed below with their atomic numbers. Which one of
CrO
2 2 7 2 4 2
them is expected to have the highest third ionisation
reaction X is [AMU]
enthalpy ? [CBSEAIPMT]
(a) CrO3 (b) Cr2O7 (a) Vanadium (Z = 23) (b) Chromium (Z = 24)
(c) Cr2O3 (d) CrO5 (c) Iron (Z = 26) (d) Manganese (Z = 25)

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 186 d AND f BLOCK ELEMENTS

81. Which of the following is a highly corrosive salt ?

2004
[AFMC]
89. The transition metal used as a catalyst is [Punjab PMET]
(a) FeCl2 (b) PbCl2
(a) nickel (b) platinum
(c) Hg2Cl2 (d) HgCl2
(c) cobalt (d) All of these
82. Which of the following is obtained when auric chloride
90. Vanadium (III) oxide is the strong [Kerala CEE]
reacts with sodium chloride ?
[AMU] (a) drying agent (b) oxidising agent

(a) Na[AuCl] (b) Na[AuCl2] (c) reducing agent (d) wetting agent

(c) Na[AuCl3] (d) Na[AuCl4] (e) precipitating agent

83. Green vitriol is formed by [Punjab PMET] 91. Which element is not found in nature ? [RPMT]

(a) FeS2 + H2O + O2 (b) FeS2 + H2O + CO2 (a) Tc (b) Y

(c) FeS2 + CO + CO2 (b) FeS2 + CO (c) Sr (d) Pt

84. Which of the following pairs of elements cannot form an 92. Mohr's salt is [JCECE]
alloy ? [KCET] (a) Na2SO4 . Al2(SO4)3 . 24H2O
(a) Zn, Cu (b) Fe, Hg
(b) CuSO4 . Al2(SO4)3 . 24H2O
(c) Fe, C (d) Hg, Na
3+
(c) FeSO . (NH ) SO
. 6H O
85. Assertion : The spin only magnetic moment of Sc is 1.73 4 4 2 4 2
BM (d) K2SO4 . Fe2(SO4)3 . 24H2O
Reason : The spin only magnetic moment (in BM) of an
ion 2003
is equal to n(n + 2) , where n is the number of unpiared
93. The basic character of the transition metal monoxides
electrons present in the ion. [EAMCET] follows the order
(a) Both Assertion and Reason are true and Reason is the (At. no. Ti = 22, V = 23, Cr = 24, Fe = 26)
correct explanation of Assertion.
[CBSEAIPMT]
(b) Both Assertion and Reason are true but Reason is not
(a) TiO > FeO > VO > CrO
the correct explanation of Assertion.
(c) Assertion is true but Reason is false. (b) TiO > VO > CrO > FeO

(d) Assertion is false but Reason is true. (c) VO > CrO > TiO > FeO

86. The magnetic moment µ, of transition metals is related to (d) CrO > VO > FeO > TiO
the number of unpaired electrons, n as [JCECE] 94. The colourless species is [AIIMS]
(a) µ = n (n + 2)2 (b) µ = n2 (n + 2) (a)VCl3 (b) VOSO4

n (c) Na3VO4 (d) [V(H2O)6]SO4 . H2O

(c) µ = (d) µ = n(n + 2) 95. Assertion : Solution of Na2CrO4 in water is intensely
(n + 2)

87. CrO3 dissolves in aqueous NaOH to give [J&K CET] (a)

Cr (b) CrO3
(a)
CrO2– (b) Cr(OH)–3 (c) Cr2O3 (d) CrO(O2)
4

(c) Cr2 O2–

7
(d) Cr(OH)

88. Which of the following is the green coloured powder

produced when ammonium dichromate is used in fire
works?
[J&K CET]
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 d AND f BLOCK ELEMENTS 187
coloured.
Reason : Oxidation state of Cr in Na2CrO4 is +VI.
[AIIMS]
(a) Both Assertion and Reason are true and Reason is the
correct explanation of Assertion.
(b) Both Assertion and Reason are true but Reason is not the
correct explanation of Assertion.
(c) Assertion is true but Reason is false.
(d) Both Assertion and Reason are false.

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96. Copper sulphate is commercially made from copper scrap

Lanthanides and Actinides
by [AMU]
2010
(a) heating with sodium sulphate
104. Which of the ions is colourless inspite of the presence of
(b) heating with sulphur unpaired electrons ? [MHTCET]
3+ 3+
(c) action of dilute sulphuric acid and air (a) La (b) Eu
3+ 3+
(d) dissolving in hot conc. sulphuric (c) Gd (d) Lu
acid 4+
[Punjab PMET] 105. Ce in stable. This is because of [MHTCET]
97. Lunar caustic is
(a)AgCl
(b) AgNO3 (a) half-filled d-orbitals
(c) NaOH (b) all paired electrons in d-orbitals
(d) KNO3
98. Which of the following is called white vitriol ? (c) empty orbitals
[DUMET] (d) fully filled d-orbitals
(a) ZnCl2 (b) MgSO4 . 7H2O
106. The lanthanoid contraction relates to [CMCLudhiyana]
(c) ZnSO4 . 7H2O (d) Al2(SO4)3 (a) atomic radii
99. Which gas is evolved, when ammonium dichromate is 3+
(a) atomic as well as M radii
heated ? [DUMET
] (c) valence electrons
(a) Hydrogen (b) Ammonia
(d) oxidation states
(c) Oxygen (d) Nitrogen
107. Across the lanthanide series, the basicity of the lanthanide
100. All the following statements about the transitional elements hydroxides [BVP]
are true except that [Kerala CEE] (a) increases
(a) all of the transitional elements are predominantly
(b) decreases
metallic
(c) first increases and then decreases
(b) in aqueous solution many of their simple ions are
coloured. (d) first decreases and then increases

(c) most of the transitional elements show pronounced 108. More number of oxidation state are exhibited by the
catalytic activity. actinoids than by the lanthanoids. The main reason for this
is
(d) most of the transitional elements show only one valence
[VMMC]
state.
(a) lesser energy difference between 5f- and 6d-orbitals
101. Which of the following is more soluble in ammonia ?
than that between 4f- and 5d-orbitals.
[MHTCET]
(b) greater metallic character of the lanthanoids than that of
(a) AgCl the corresponding actionoids.
(b) AgBr
(c) AgI (c) more active nature of the actinoids.
(d) None of these
(d) more energy difference between 5f and 6d-orbitals than
102. On going left to right in a period, in transition metals, that between 4f and 5d-orbitals.
their
atomic volume [MPPMT
] 2009
(a) decreases (b) increases
109. Which of the following is man-made element ? [AFMC]
(c) remain same (d) None of
(a) Ra (b) U
these

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 d AND f BLOCK ELEMENTS 189
103. Addition of HgCl2 to SnCl2 gives a black colour due to
(c) Np (d) C
[JCECE] 110. The pair, that referred as ‘chemical twins' is [MHTCET]

(a) oxidation of Sn
(a) Ac, Cf (b) Hg, Ta
(b) reduction of HgCl2
(c) formation of amalgam (d) oxidation of Hg (c) Tc, Re (d) La, Ac

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 d AND f BLOCK ELEMENTS 185

111. Most basic hydroxide among the following

is (c) As a result of lanthanoid contraction, the properties of
[MHTCET] 4d-series of the transition elements have no
similarities with the 5d-series of elements.
(a) Lu(OH)3 (b) Eu(OH)3
(d) Shielding power of 4f electrons is quite weak.
(c) Yb(OH)3 (d) Ce(OH)3 119. General electronic configuration of lanthanides are
2008
[Punjab PMET]
112. Which of the following is not an actinide ? [AMU]
1–14 2 6 0–1 2
(a) Curium (b) Californium (a) (n – 2) f (n – 1) s p d ns
10–14 0–1 2
(c) Uranium (d) Terbium (b) (n – 2) f (n – 1) d ns
113. Identify the incorrect statement among the following. 0–14 10 2
(c) (n – 2) f (n – 1) d ns
[BHU] 0–1 1–14 2
(d) (n – 2) (n – 1) ns
(a) d-block elements show irregular and erratic chemical
d f
3+ 3+ 3+ 3+
properties among themselves. 120. The correct order of ionic radii of Y , La , Eu and Lu
(b) La and Lu have partially filled d-orbitals and no other is
[Kerala CEE]
partially filled orbitals. 3+ 3+ 3+ 3+
(a) Y < La < Eu < Lu
(c) The chemistry of various lanthanoids is very similar.
3+ 3+ 3+ 3+
(d) 4f- and 5f - orbitals are equally (b) Lu < Eu < La < Y
shielded.
3+ 3+ 3+ 3+
114. The point of dissimilarity between lanthanides and (c) La < Eu < Lu < Y
actinides
is [MHTCET] (b)Lanthanoid contraction is the accumulation of
(a) three outermost shells are partially filled. successive shrinkages.
(b) they show oxidation state of +3 (common).
(c) they are called inner-transition elements.
(d) they are radioactive in nature.
115. Most common oxidation states of Ce (cerium) are
[MHTCET]
(a) +3, +4 (b) +2, +3
(c) +2, +4 (d) +3, +5
116. On which factors, the stability of an oxidation state of
lanthanoide elements depends ? [Guj.
CET]
(a) Enthalpy
(b) Internal energy
(c) Combined effect of hydration energy and ionisation
energy
(d) Electronic configuration
117. Differentiating electron in inner-transition elements
enters in the ........ orbital. [J&K CET]
(a) s (b) p
(c) d (d) f
2007
118. Identify the incorrect statement among the following
[CBSEAIPMT]
(a) There is a decrease in the radii of the atoms or ions as
one proceeds from La to Lu.
 186 d AND f BLOCK ELEMENTS
3+ 3+ 3+ 3+
(d) Y < Lu < Eu < La
121. Lanthanides are [Manipal]
(a) 14 elements in the sixth period (atomic no. = 90 to
103) that are filling 4f sub-level.
(b) 14 elements in the seventh period (atomic no. = 90
to 103) that are filling 5f sub-level.
(c) 14 elements in the sixth period (atomic no. = 58 to
71) that are filling 4f sub-level.
(d) 14 elements in the seventh period (atomic no. = 58 to
71) that are filling 4f sub-level.
2006
122. Which of the following is not an actinoid ?
[DUMET]
(a)Am (b) Cm
(c) Fm (d) Tm
123. The lanthanoid contraction is responsible for the fact that
[Guj. CET]
(a) Zr and Y have about the same radius
(b) Zr and Nb have similar oxidation state
(c) Zr and Hf have about the same radius
(d) Zr and Zn have the same oxidation state
2005
124. Europium is
[DUMET]
(a) s-block element (b) p-block element
(c) d-block element (d) f-block element
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 186 d AND f BLOCK ELEMENTS

125. Which belongs to the actinide series ? [J&K CET]

(a) Ce (b) Cf
(c) Ca (d) Cs
2004
126. Lanthanides and actinides resemble in [AFMC]
(a) electronic configuration
(b) oxidation state
(c) ionisation energy
(d) formation of complexes
127. Which of the following lanthanide is commonly used in
the manufacture of alloys ? [Manipal]
(a) Lanthanum
(b) Nobelium
(c) Thorium (d) Cerium
128. The atomic size of cerium and promethium is quite close,
because [JCECE]
(a) they are in same period in Periodic Table
(b) their electronic configuration is same
(c) f-electrons have poor shielding effect
(d) nuclear charge is higher on cerium than promethium
2003
129. Lanthanide for which +II and +III oxidation states are
common is [AIIMS]
(a) La (b) Nd
(c) Ce (d) Eu

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d AND f BLOCK ELEMENTS 187

ANSWER KEY

Exercise - 1 : (Basic Objective Questions)

1. (d) 2. (d) 3. (c) 4. (d) 5. (a) 6. (c) 7. (d) 8. (a) 9. (d) 10. (b)

11. (a) 12. (d) 13. (c) 14. (a) 15. (b) 16. (d) 17. (a) 18. (b) 19. (d) 20. (d)
21. (d) 22. (d) 23. (a) 24. (b) 25. (b) 26. (b) 27. (b) 28. (c) 29. (a) 30. (a)
31. (d) 32. (b) 33. (a) 34. (d) 35. (c) 36. (c) 37. (c) 38. (b) 39. (d) 40. (c)
41. (d) 42. (c) 43. (b) 44. (d) 45. (b) 46. (b) 47. (c) 48. (a) 49. (d) 50. (c)
51. (b) 52. (d) 53. (d) 54. (b) 55. (b) 56. (b) 57. (c) 58. (c) 59. (b) 60. (b)
61. (c) 62. (a) 63. (d) 64. (d) 65. (b) 66. (c) 67. (b) 68. (a) 69. (b) 70. (a)
71. (d) 72. (d) 73. (a) 74. (d) 75. (c)

Exercise - 2 : (Previous Year Competition Questions)

1. (a) 2. (d) 3. (c) 4. (b) 5. (b) 6. (a) 7. (d) 8. (a) 9. (c) 10. (b)
11. (d) 12. (b) 13. (c) 14. (d) 15. (a) 16. (d) 17. (c) 18. (a) 19. (b) 20. (a)
21. (c) 22. (b) 23. (b) 24. (a) 25. (d) 26. (d) 27. (a) 28. (a) 29. (c) 30. (c)
31. (c) 32. (d) 33. (b) 34. (b) 35. (d) 36. (d) 37. (d) 38. (a) 39. (a) 40. (a)
41. (c) 42. (a) 43. (b) 44. (b) 45. (c) 46. (c) 47. (d) 48. (c) 49. (c) 50. (c)
51. (c) 52. (a) 53. (c) 54. (d) 55. (b) 56. (c) 57. (d) 58. (c) 59. (d) 60. (a)
61. (b) 62. (b) 63. (d) 64. (d) 65. (a) 66. (b) 67. (b) 68. (c) 69. (b) 70. (b)
71. (c) 72. (c) 73. (d) 74. (c) 75. (b) 76. (a) 77. (d) 78. (b) 79. (b) 80. (d)
81. (d) 82. (d) 83. (a) 84. (b) 85. (d) 86. (d) 87. (a) 88. (c) 89. (d) 90. (c)
91. (a) 92. (c) 93. (b) 94. (c) 95. (b) 96. (c) 97. (b) 98. (c) 99. (d) 100. (d)
101. (a) 102. (d) 103. (b) 104. (c) 105. (c) 106. (b) 107. (b) 108. (a) 109. (c) 110. (c)
111. (d) 112. (d) 113. (d) 114. (d) 115. (a) 116. (c) 117. (d) 118. (c) 119. (a) 120. (d)

121. (c) 122. (d) 123. (c) 124. (d) 125. (b) 126. (b) 127. (d) 128. (c) 129. (d)

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