CHAPTER

10 The d & f-Block Elements

(iii) 10 elements starting with 57La and from 72Hf to 80Hg in
INTRODUCTION sixth period. (5d series)
Elements of the periodic table in which the differentiating electron (iv) 10 elements starting with 89Ac and from 104Rf to 112Cn in
is filled in d orbital, are called d-block elements. seventh period (6d series)
™ These elements occupy position between s-block and
™ General electronic configuration of these elements is
p-block of the periodic table, and they are members of (n–1) d1–10 ns0–2 (including Pd) & (n–1)d1–10 ns1–2, where n is
III B, IV B, V B, VI B, VII B, VIII (B), I B and II B groups. the number of outermost shell.
According to IUPAC (1984), they occupy 3rd group to 12th
™ Although 40 elements are there in d-block of periodic
group of the periodic table.
table, yet transition elements are only 36. Elements
™ There are four series of these elements, which are order wise
of II B group (Zn, Cd, Hg and Cn) are called d-block
arranged: elements and not transition elements, because they always
(i) 10 elements from 21Sc to 30Zn in fourth period (3d series) exhibit + 2 oxidation state, in which d-orbital is completely
(ii) 10 elements from 39Y to 48Cd in fifth period (4d series) filled, i.e., d orbital does not participate in bond formation.

GENERAL PROPERTIES: ELECTRONIC CONFIGURATION

3d / 1st Series

Sc Ti V Cr Mn Fe Co Ni Cu Zn
Z 21 22 23 24 25 26 27 28 29 30
4s 2 2 2 1 2 2 2 2 1 2
3d 1 2 3 5 5 6 7 8 10 10
nd
4d / 2 Series
Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
Z 39 40 41 42 43 44 45 46 47 48
5s 2 2 1 1 1 1 1 0 1 2
4d 1 2 4 5 6 7 8 10 10 10
rd
5d / 3 Series
La Hf Ta W Re Os Ir Pt Au Hg
Z 57 72 73 74 75 76 77 78 79 80
6s 2 2 2 2 2 2 2 1 1 2
5d 1 2 3 4 5 6 7 9 10 10
th
6d / 4 Series
Ac Rf Db Sg Bh Hs Mt Ds Rg Cn
Z 89 104 105 106 107 108 109 110 111 112
7s 2 2 2 2 2 2 2 2 1 2
6d 1 2 3 4 5 6 7 8 10 10
 PHYSICAL PROPERTIES
Nearly all the transition elements display metallic properties such as high tensile strength, ductility, malleability, high thermal and
electrical conductivity and metallic lustre.
Note: Except Zn, Cd, Hg and Mn, other element have one or more typical metallic structures at normal temperature.

Table : Lattice Structure of Transition Metals

Sc Ti V Cr Mn Fe Co Ni Cu Zn

hcp hcp bcc bcc X bcc ccp ccp ccp X

(bcc) (bcc) (bcc, ccp) (hcp) (hcp) (hcp)

Y Zr Nb Mo Tc Ru Rh Pd Ag Cd

hcp hcp bcc bcc hcp hcp ccp ccp ccp X

(bcc) (bcc) (hcp)

La Hf Ta W Re Os Ir Pt Au Hg

hcp hcp bcc bcc hcp hcp ccp ccp ccp X

(ccp,bcc) (bcc)

(bcc – body centred cubic; hcp-hexagonal close packed; ccp-cubic close packed; X = a typical metal structure).

Atomisation Enthalpy and Metallic Bond In general, greater the number of valence electrons, stronger
is the resultant bonding. Since the enthalpy of atomisation is an
The transition metals (with the exception of Zn, Cd, Hg) are very
important factor in determining the standard electrode potential of
much hard and have low volatility. Their melting and boiling a metal, metals with very high enthalpy of atomisation (i.e., very
points are high. high boiling point) tend to be noble in their reactions.
The high melting points of these metals are attributed to Another generalisation that may be drawn is that metals of the
involvement of greater number of electrons from (n–1) d in 2nd and 3rd series have greater enthalpies of atomisation than the
addition to the ns electrons in the interatomic metallic bonding. corresponding elements of 1st series. This is an important factor in
accounting for the occurrence of much more frequent metal-metal
In any row, the melting points of these metals rise to
bonding in compounds of heavy transition metals.
maximum at d5 except for anamolous behaviour of Mn and Tc
and fall regularly as the atomic number increases. They have high Melting point and Boiling point
enthalpies of atomisation which is shown in figure. (i) Melting and boiling points of these metals are high, which
4 shows strong interatomic attraction.
W (ii) Strength of metallic bond increases from Sc to Cr, because
Re the number of metallic bonds increases upto Cr, due to
Ta which hardness also increases. Thus, melting and boiling
points also increase. Melting and boiling points of Cr are
3 Mo Os
Nb maximum.
Ru
Ir (iii) Mn posses half filled configuration (3d5) but has low
Hf Tc melting point because of complex structure and less
M.p./103K

Cr packing efficiency.
Zr V Rh Pt
2 (iv) Numbers of unpaired electrons decrease from Fe to Cu and
Ti Fe Co Po
therefore, the number of metallic bonds also decrease. Due
Ni to this, strength of bond decreases. Therefore, hardness
Mn Cu decreases and melting and boiling points become low.
1 Ag Au (v) In Zn, weak metallic bonds are formed due to fully-filled
Atomic number (d10) orbitals. Thus, it is a soft metal and its melting and
boiling points are also low.

2 JEE (XII) Module-3 PW

Table : Electronic Configurations and some other Properties of the First Series of Transition Elements
Element Sc Ti V Cr Mn Fe Co Ni Cu Zn
Atomic number 21 22 23 24 25 26 27 28 29 30
Electronic Configuration
M 3d14s2 3d24s2 3d34s2 3d54s1 3d54s2 3d64s2 3d74s2 3d84s2 3d104s1 3d104s2
M+ 3d14s1 3d24s1 3d34s1 3d5 3d54s1 3d64s1 3d74s1 3d84s1 3d10 3d104s1
M2+ 3d1 3d2 3d3 3d4 3d5 3d6 3d7 3d8 3d9 3d10
M3+ [Ar] 3d 1 3d 2 3d 3 3d 4 3d5 3d6 3d7 – –
Enthalpy of atomization, ∆a H°/kJ mol−1
326 473 515 397 281 416 425 430 339 126
Ionisation enthalpy / ∆i H°/kJ mol-1
∆iH° I 631 656 650 653 717 762 758 736 745 906
∆iH° II 1235 1309 1414 1592 1509 1591 1644 1752 1958 1734
∆iH° III 2393 2657 2833 2990 3260 2962 3243 3402 3556 3829
Metallic/ionic M 164 147 135 129 137 126 125 125 128 137
Radii/pm M2+ – – 79 82 82 77 74 70 73 75
M3+ 73 67 64 62 65 65 61 60 – –
Standard M2+/M − −1.63 −1.18 −0.90 −1.18 −0.44 −0.28 −0.25 +0.34 −0.76
Electrode
Potential E°/V M3+/M2+ − −0.37 −0.26 −0.41 +1.57 +0.77 +1.97 − − –
Density/g cm−3 3.43 4.1 6.07 7.19 7.21 7.8 8.7 8.9 8.9 7.1

Train Your Brain Concept Application

Example 1: Why do transition elements have higher boiling
and melting points?
Sol. Transition elements have higher boiling and melting
points because of presence of unpaired electrons. They have
stronger interatomic interaction and hence stronger bonding
between them, strong metallic bonds between the atoms of
these elements attribute to their high melting and boiling
points.
Example 2: Silver atom has completely filled d-orbitals
(4d10) in its ground state. How can you say that it is a
transition element?
Sol. The silver atom’s (4d10) configuration in the ground
state indicates that its d-orbitals are completely occupied.
However, it has a configuration of 4d9 in its most stable
oxidation state (+1) i.e., partially filled d-orbital. According
to definition of a transition element, it can therefore be
regarded as a transition element.
Example 3: In the series, Sc (Z = 21) to Zn (Z = 30), the
enthalpy of atomization of zinc is the lowest i.e. 126 kJ
mol–1. Why?
Sol. Zinc (4d10 5s2) has completely filled d-orbital and
has no unpaired electron to take part in the formation of
metallic bonds. On the other hand, all the other elements
in the transition series have one or more unpaired electrons
and can participate in the formation of these bonds. As a
result, the metallic bonding in zinc is weakest and it has
least enthalpy of atomisation.
1.
Select the group of transition elements.
(a) Pb, Sc, V (b) Pd, Cd, La
(c) Pd, La, Fe (d) Zn, Pd, Bi
2.
Out of the following metals, which has the lowest
melting and boiling point?
(a) Ti (b) Cu
(c) Zn (d) Mn
3.
First IE of 5d series elements are generally higher
than those of 3d and 4d series elements. This is
due to:
(a) Bigger size of atoms of 5d-series elements than
3d-series elements
(b) Greater effective nuclear charge is experienced by
valence electrons because of the weak shielding
of the nucleus by 4ƒ-electrons in 5d series
(c) (A) and (B) both
(d) None of these
Atomic Size
(i) In a given series, the atomic radius decreases from
group 3 elements upto the group 10 elements and
then increases again towards the end of the series.
This anomalous increase in atomic radius towards the

P The d & f-Block Elements

W 3
 end of the series is because of the increased force of
repulsion among the added electrons. Also the d-orbitals
get completely filled in group 11 and 12 elements which
also causes a decrease in force of attraction.
19
18
17
The three terms responsible for the value of ionisation
enthalpy are attraction of each electron towards nucleus,
repulsion between the electrons and the exchange energy.
Exchange energy is responsible for the stabilisation
of energy state. Exchange energy is approximately
proportional to the total number of exchanges possible
when equal number of electrons are present in degenerate

Radius/nm
orbitals (2J energy is released). When several electrons
16
occupy a set of degenerate orbitals, the lowest energy
15
state corresponds to the maximum possible extent
14 of single occupation of orbital and parallel spins
13 (Hund’s rule).
12 The loss of exchange energy increases the stability. As the
Sc Ti V Cr Mn Fe Co Ni Cu Zn
Y Zr Nb Mo Tc Ru Rh Pd Ag Cd stability increases, the ionisation becomes more difficult.
La Hf Ta W Re Os Ir Pt Au Hg There is no loss of exchange energy of d6 configuration.
Trends in atomic radii of transition elements Mn+ has 3d54s1 configuration whereas configuration of Cr+
is 3d5. Due to half filled configuration in Cr+, its ionisation
(ii) Atomic radius increases on going down the group but the
enthalpy is greater than Mn. In the same way, ionisation
very close similarity between the radii of the elements of
enthalpy of iron is lower than Mn. In Fe2+ outermost
second and third transition series is due to lanthanide
contraction. configuration is 3d6 whereas in Mn outermost configuration
is 3d5. Hence, ionisation enthalpy of Fe2+ is lower than that
Density of Mn2+. In other words, we can say that the third ionisation
(i) The density of d-block elements is quite high as compared enthalpy of Fe is lower than that of Mn.
to s-block elements (IA, IIA), because the atomic volume
of d-block element is low. Almost all transition elements Reactivity
show a density higher than 5 gm/cc. Sc, Ti and V have The d-block elements are less reactive due to the following factors:
slightly less density. (i) High ionisation energies:
(ii) Along a group, density of transition metals increases. On account of small size of their atoms, ionisation energies
(iii) The density of third transition series elements is twice as of d-block elements are fairly high.
high as the density of second transition series elements. (ii) Low heat of hydration:
[Atomic volume of second and third transition series
The metal ions are not hydrated easily.
elements (along a group) are almost equal due to lanthanide
contraction]. (iii) High heat of sublimation:
Note: Sc, Ti and Y have density less than 5 g/cm3 while Due to the presence of covalent bonding, these have
other elements have density greater than 5 g/cm3. Densities high heats of sublimation. platinum and gold in the third
of the 2nd row are high and third row values are even higher. transition series are almost unreactive.
Density of Os = 22.57 g/cm3
Oxidation States
Density of Ir = 22.61 g/cm3 (most dense element)
All transition elements except the first and the last member in each
Ionisation Enthalpies series show variable oxidation states. This is because difference of
energy in the (n–1) d and ns orbitals is very little. Hence, electrons
The first ionization energies of d-block elements are higher
from both the energy levels can be used for bond formation.
than those of s-block elements and are lesser than those of
p-block elements. Sc Ti V Cr Mn Fe Co Ni Cu Zn
The irregular trend in the Ist ionisation enthalpy of the +2 +2 +1 +2 +2 +2 +2 +1 +2
3d metals, though of little chemical significance, can be +3 +3 +3 +2 +3 +3 +3 +3 +2
accounted for by considering that removal of one electron
alters the relative energies of 4s and 3d orbitals. +4 +4 +3 +4 +4 +4 +4
These 3d electrons shield the 4s electrons from the +5 +4 +5
increasing nuclear charge somewhat more effectively than +5 +6 +6
the outer shell electrons can shield one another. Therefore,
+6 +7
the atomic radii decreases less rapidly. Thus, ionization
energies increase only slightly along the 3d series. The variability of oxidation states, a characteristic of transition
The lowest common oxidation state of these elements is +2 elements, arises out of incomplete filling of d orbitals in such a
(except Sc and Cu). To form the +2 ion from the gaseous way that their “oxidation states differ from each other by unity,
atoms, the sum of 1st and 2nd ionisation energy is required e.g., VII, VIII, VIV, VV. This is in contrast with the variability of
in addition to the enthalpy of atomisation. oxidation states of non transition elements where oxidation states

4 JEE (XII) Module-3 PW

normally differ by a unit of two. An interesting feature in the of transition metals are low in comparison to elements of group
variability of oxidation states of the d-block elements is noticed 2 (e.g., Ca = –2.87 V, the transition elements have fairly large
among the groups (groups 4 through 10). Although in the p-block, ionisation enthalpies and very large enthalpies of atomisation),
the lower oxidation states are favoured by the heavier members compared to group 2 elements. These reduce their electrode
(due to inert pair effect), the opposite is true in the groups of potentials though their hydration enthalpies are large.
d-block. For example, in group 6, Mo(VI) and W(VI) are found to 2
be more stable than Cr(VI). Thus, Cr(VI) in the form of dichromate
1.5 1.97
in acidic medium is a strong oxidising agent, whereas MoO3 and Co
E°M3+ / M2+
WO3 are not. Low oxidation states are found when a complex 1 1.57
Mn
compound has ligands capable of showing π-acceptor character in 0.77
0.34
Cu
addition to the σ-donation. For example, in Ni(CO)4 and Fe(CO)5, 0.5
–0.37 –0.26 –0.41
Cr
Fe
Ti V E°M2+ / M
the oxidation state of nickel and iron is zero. 0

Note: –0.5 –0.25

–1.18 –0.28
1. Sc does not exhibit oxidation state of +2. V
–0.44 Co Ni
–1 Fe –0.76
2. Ti(II) is more stable than Ti(III) and Ti(IV). –1.63 Zn
Ti –0.9
3. After middle as we approach from left to right, –1.5 Cr –1.18
Mn
higher oxidation state becomes less stable. Fe(II, III),
Co (II, III), Ni(II), Cu(I, II) are typical species. –2

Electrode potential Trend in stability of higher oxidation state

E° M 2+ / M Higher oxidation states are stable with F and O while lower
oxidation states are stable with I.
There is no regular trend in these values. This is attributed to the
V (V) is represented only by VF5, the other halides, however,
irregular variation of ionisation enthalpies (IE1 + IE2), hydration
energies and the sublimation energies in the period. undergo hydrolysis to give oxohalides VOX3. Another feature
of flourides is their instability in the lower oxidation state e.g.
Memory warning : Need not memorize the table but remember VX2 (X = Cl, Br, I) and same applies to CuX. On the other
the comments. hand, all Cu2+ halides are known except the iodide. In this case,
Element Comments Cu2+ oxidises I– to I2.
E° M 3+ / M 2+ E° M 2+ / M
(M) 2Cu2+ + 4I– → Cu2I2 + I2
Ti –0.37 –1.63 +3 Oxidation state is However, many copper (I) compound show disproportionation
more stable. reaction in aqueous medium.
V –0.26 –1.18 +3 Oxidation state is 2Cu+ → Cu + Cu2+
more stable. Now, in aqueous medium, Cu2+ is more stable than Cu+ due to its
Cr –0.41 –0.9 +3 Oxidation state is high hydration energy than Cu+ which compensate for IE2.
more stable. The highest oxidation number is attained in the oxides (Sc2O3 to
Mn 1.57 –1.18 +2 Oxidation states is Mn2O7) because oxygen can form multiple bonds.
more stable
Fe 0.77 –0.44 +2 Oxidation state is
E° Values and Chemical Reactivity
more stable. Transition metals vary widely in their chemical reactivity. Many
of them are sufficiently electropositive to dissolve in mineral acid
Co 1.97 –0.28 +2 Oxidation state is
although a few are noble, it means these do not react with single
more stable.
acid.
Ni – –0.25 +3 Oxidation state does
The metal of 3d series except Cu are relatively more reactive and
not exist for Ni.
are oxidised by 1M H+ though the actual rate at which these metals
Cu – 0.34 +3 Oxidation state react with oxidising agents like hydrogen ion (H+) is sometimes
does not exist for Cu. 0 slow.
Oxidation state is more
For example, Ti and V are passive to dilute non-oxidising acids at
stable.
room temperature. Increase in reduction potential of M2+/M from
Zn – –0.76 +3 Oxidation state does left to right indicate decreasing tendency to form divalent cation
not exist for Zn. along the series.
Comparative graph of E° 2+ and E° 3+ 2+ Note:
M /M M /M

The stability of the half-filled d sub-shell in Mn2+ and the 1. E° value of Mn2+/Mn, Ni2+/Ni and Zn2+/Zn are more
completely filled d10 configuration in Zn2+ are related to their negative than expected. This is due to half filled and full
E° values, whereas E° for Ni is related to the highest negative filled electronic configuration for Mn2+ and Zn2+ respectively
hydration energy. It may be noted that the electrode potentials while for Ni2+ this is because of high enthalpy of hydration.

P The d & f-Block Elements

W 5
 2. Higher will be E° M3+ / M2+ values, stronger will be oxidising (i) Paramagnetic substances: Substances which are
attracted by magnetic field are called paramagnetic. These
agent. That is why Mn3+ and Co3+ are strongest oxidising substances lose their magnetism on removing the magnetic
agent in aqueous solution. field. Paramagnetism is caused by the presence of unpaired
3. Ti2+, V2+ and Cr2+ are strong reducing agents and liberate electrons and since most of the transition metal atoms have
hydrogen from dilute acids. unpaired d-electrons, they are paramagnetic in behaviour.
2Cr2+(aq) + 2H+ (aq) → 2Cr3+ (aq) + H2 (g) (ii) Diamagnetic substances: Substances which are repelled
4. The trend of reduction potential is not regular because trend by magnetic field are called diamagnetic. This character
of enthalpies of atomisation and (IE1 + IE2) is not regular. arises due to the presence of paired electrons in the atomic
orbital. The examples are Sc3+, Ti4+, Zn2+, Cu+, etc.
which do not contain any unpaired d-electrons and hence
are diamagnetic. The total magnetic moment of a cation
Train Your Brain depends upon the number of unpaired electrons and is
given by the following expression.
Example 4: Why is Cr2+ reducing and Mn3+ oxidising when µM = n (n + 2) B.M. (Bohr magneton)
both have d4 configuration?
Where, n = number of unpaired electrons
Sol. Cr2+ is reducing as the configuration changes from
d4 to d3 having half filled t2g level. On the other hand, When n (the number of unpaired electron) = 1, µM =
1 × 3 = 1.73 B.M.
the change from Mn3+ to Mn2+ results in the half filled d6
configuration which has extra stability. Similary, when n = 2, µM = 2 × 4 = 2.83 B.M.
Example 5: The E°(M2+/M) value for copper is positive When n = 3, µM = 3 × 5 = 3.87 B.M.
(0.34 Volt). What is possible reason for this? Table : Magnetic moments of some transition metal ions of
Sol. Reduction potential depends on 3d-series
(i) Cu(s) → Cu(g); ∆H (atomisation) Ion Electronic Number of Observed
(ii) Cu(g) → Cu2+(g); (IE1 + IE2) configuration unpaired magnetic moment
electrons (Bohr Magneton)
(iii) Cu2+(g) 
H2 O
→ Cu2+(aq.); (∆Hhyd)
Due to high enthalpy of atmisation and low ∆Hhyd Sc3+ d0 0 0
energy, E0(M2+/M) value for copper is positive. Ti2+ d2 2 2.76
V2+ d3 3 3.86
Cr2+ d4 4 4.80

Concept Application
Mn2+ d5 5 5.96
Fe2+ d6 4 5.3–5.5

Standard reduction electrode potential of Zn2+ / Zn

4. Co2+ d7 3 4.4–5.2
is - 0.76 V. This means Ni2+ d8 2 2.9–3.4
(a) ZnO can be reduced to Zn by H2 under standard
Cu2+ d9 1 1.8–2.2
conditions.
(b) Zn can’t liberates H2 with concentrated acids Zn2+ d10 0 0
(c) Zn is generally the anode in an electrochemical Colour
cell
Most of the d-block metal compounds are coloured in the solid
(d) Zn is generally the cathode in an electrochemical or in solution state (different from s and p-block elements whose
cell compounds are generally white). The colour of transition metal
5.
By which of the following species, a transition metal ions is due to the presence of unpaired or incomplete d-obitals.
can be brought into its highest oxidation state? When visible (white) light (λ = 4000–7000 Å) falls on a coloured
(a) F2 (b) Cl2 substance, the matter absorbs certain radiations of white light
(c) Br2 (d) I2 and transmit the remaining ones. The transmitted light has
the complementary colour to that of the absorbed light. This
complementary colour which is actually the colour of the reflected
Magnetic Properties (transmitted) light is the colour of the substance.
On the basis of magnetic properties, substances are classified into The absorption of visible light and hence coloured nature of the
the following two types. transition metal cations is due to the promotion of one or more

6 JEE (XII) Module-3 PW

unpaired d-electron from a lower to a higher level within the
same d-subshell. This promotion requires small amount of energy Example 7: Explain why Cu+ ion is not stable in aqueous
which is available in the visible light. solution?
Note: Sol. Cu+ is less stable than Cu2+ in an aqueous medium.
Along with d-d transition, colour may be due to This is due to the high hydration energy of Cu2+, which
makes up for the energy required to remove one electron
1. Charge transfer spectra.
from Cu+ to form Cu2+. Cu+ ion is hence unstable in an
2. Polarisation aqueous solution, it disproportionates to give Cu2+ & Cu.
There are some compounds in which d0 or d10 configuration are
present and in these cofiguration, no d-d transition is expected.
But still these may be intensely coloured. This colour is due to
charge transfer from ligand to metal or from metal to metal.
MnO–4 is pink coloured due to charge transfer from ligand to metal Concept Application
while Fe4[Fe(CN)6]2 is blue coloured due to charge transfer from
metal to metal. AgBr and AgI are coloured due to polarisation of 6.
Colour of transition metal ions is due to absorption of
Br– or I– by Ag+ ion. some wavelength. This results in
Table : Colours of Ions of the First Transition Series (a) d-s transition (b) s-s transition
(c) s-d transition (d) d-d transition
Ion Outer Number of Colour of the
electronic unpaired ion 7.
Which pair of the compounds is expected to show
configuration electrons similar colour in aqueous solution?
(a) FeCl3 and CuCl2 (b) VOCl2 and CuCl2
Sc3+ 3d0 0 Colourless
(c) VOCl2 and FeCl2 (d) FeCl2 and MnCl2
Ti4+ 3d0 0 Colourless
Ti3+ 3d1 1 purple Catalytic property
V3+ 3d2 2 Green Many of the d-block elements and their compounds act as catalysts
in various reactions. Some common examples are:
Cr3+ 3d3 3 Violet
(i) Pt : Used as a catalyst in the manufacturing of H2SO4.
Mn3+ 3d4 4 Violet (ii) Fe : Used as a catalyst in the manufacture of NH3 by
Haber's process. A small amount of molybdenum is added
Mn2+ 3d5 5 Light Pink as a promoter.
Fe2+ 3d6 4 Green (iii) Ni : Used as a catalyst in the hydrogenation of oils.
(iv) V2O5 : Used as a catalyst for the oxidation of SO2 to SO3 in
Fe3+ 3d5 5 Yellow the manufacturing of H2SO4 in the contact process.
(v) MnO2 : used as a catalyst in the decomposition of KClO3
Co2+ 3d7 3 Pink for preparation of oxygen.
Ni2+ 3d8 2 Green (vi) TiCl4 + (C2H5)3Al : Production of polyethene (Ziegler
Natta catalyst).
Cu2+ 3d9 1 Blue (vii) PdCl2 : Wacker's process
Cu+ 3d10 0 Colourless (viii) Pt/PtO2 : Adam’s catalyst

Zn2+ 3d10 0 Colourless Interstitial Compounds

Train Your Brain
Example 6: Calculate the magnetic moment of a divalent
ion in aqueous solution if its atomic number is 25.
Sol. Element having atomic no (Z = 25) has electronic
configuration 1s2 2s2 2p6 3s2 3p6 4s2 3d5.
As divalent ion is considered here, so it will have d5
configuration i.e. 5 unpaired electrons. The magnetic
moment, µ = 5 ( 5 + 2 ) = 5.92 BM.
P The d & f-Block Elements
W 7
(i) Some space is left between metal atoms in the crystals of
transition metals. Small non-metal atoms (H, C, N, etc.) of
appropriate size can occupy these vacant spaces and the
compounds so formed are called interstitial compounds.
M M Non-metals (like C, N, H etc.) in the
M M vacant space between metal atoms.
(ii) Interstitial compounds are harder than transition metals,
because there is no vacant space in them.
(iii) Laws of simple covalency is not applicable to the interstitial
compounds.
(iv) Interstitial compounds of iron and carbon provide strength
to the steel.
 (v) Their composition is non-stoichiometric, there is no definite Table: Oxides of 3d Metals
ratio of atoms in these compounds.
Oxidation Groups
Non-stoichiometric compounds Number 3 4 5 6 7 8 9 10 11 12
There are known compounds of transition metal elements which +7 Mn2O7
violates the law of definite proportion and form non-stoichiometric +6 CrO3
compounds.
+5 V2O5
e.g. (i) FeO (stoichiometric)  Fe : O  +4 TiO2 V2O4 CrO2 MnO2
 
 1:1  +3 Sc2O3 Ti2O3 V2O3 Cr2O3 Mn2O3 Fe2O3
(non-stoichiometric) [0.84:1] Mn3O4 Fe3O4 Co3O4

(ii) Cu2S [stoichiometric] Cu : S +2 TiO VO (CrO) MnO FeO CoO NiO CuO ZnO
 
 2 :1  +1 Cu2O
(non-stoichiometric) (1.7:1) POTASSIUM DICHROMATE (K2Cr2O7)
Complex compounds O

— —
d-block elements have a marked ability to form complex O— 179pmO— —O
—
compounds. This ability is on account of following three reasons:
Cr O — Cr 126° Cr
16—
—O

(i) Small size
(ii) High nuclear charge
(iii) A number of vacant orbitals of equivalent energy, where,
the electrons donated by ligands can be accommodated.
Ex. [Fe(CN)6]3–, [Cu(NH3)4]2+, [Mn(H2O)4]2+, [CuCl4]2–
Formation of alloys
Atomic sizes of transition metals are almost same. Thus, they
form solid alloys by replacing each other in crystal lattice.
For example, 22 carat gold is an alloy of Cu and Au. 4FeCr2O4 + 16NaOH + 7O2 → 8Na2CrO4
For the formation of an alloy, there should be similarity in the
(i) metallic size,
(ii) crystal structure
(iii) chemical properties of both the metals.
Other examples are
German siliver: 25-30% Cu, 40-50% Ni, 25-30% Zn
Bell Metal: 80 % Cu, 20% Sn
Gun Metal: 80% Cu, 10% Sn, 2% Zn
Brass: 60% Cu, 40% Zn
SOME USEFUL COMPOUNDS
OF TRANSITION METALS
Oxide and Oxoanions of Metals
These oxides are generally formed by the reaction of metals with
oxygen at high temperature. All the metals except Sc form metal
oxides which are ionic.
As the oxidation number of metal increases, ionic character
decreases. In the case of Mn, Mn2O7 is a covalent green oil. Even
CrO3 and V2O5 have low melting points. In these higher oxides,
the acidic character is predominant.
Thus, Mn2O7 gives HMnO4 and CrO3 gives H2CrO4 and H2Cr2O7.
V2O5 is however amphoteric though mainly acidic and it gives
VO43– as well as VO2+ salts. V2O5 react with alkalies as well as
acids to give VO43– and VO4+ respectively. The well characterised
CrO is basic but Cr2O3 is amphoteric.
Oxidising power: VO2+ < Cr2O72– < MnO4–.
—
—
–
O O O–
–1
O — .3p
m
O–1
5 1
Cr posses d s configuration
Preparation
Potassium dichromate is generally prepared from chromite ore
(FeCr2O4). It involves the following steps.
(i) Conversion of chromite ore into sodium chromate:
Chromite ore is fused with sodium hydroxide or sodium
carbonate in the presence of air.
 + 2Fe2O3 + 8H2O
Or 4FeCr2O4 + 8Na2CO3 + 7O2 → 8Na2CrO4 + 2Fe2O3
 + 8CO2
(ii) Conversion of sodium chromate into sodium
dichromate: Sodium chromate is filtered with water and
acidified with sulphuric acid to get sodium dichromate.
2Na2CrO4 + H2SO4 → Na2Cr2O7 + Na2SO4+ H2O
Sodium sulphate crystallises out in the hydrated form due
to common ion effect and is filtered off.
(iii) Conversion of sodium dichromate into potassium
dichromate: Sodium dichromate is more soluble and
less stable than potassium dichromate. Therefore,
when hot saturated solutions of sodium dichromate and
potassium chloride are mixed in equimolar proportions,
orange crystals of potassium dichromate are obtained.
Na2Cr2O7 + 2KCl → 2NaCl + K2Cr2O7
Properties
The important properties of potassium dichromate are given as
follows:
(i) Physical state: Potassium dichromate forms orange red
crystals which melt at 669 K. It is moderately soluble in
cold water but freely soluble in hot water.
(ii) Action of heat: When heated strongly, it decomposes
with the evolution of oxygen.
4K2Cr2O7 → 4K2CrO4 + 2Cr2O3 + 3O2

8 JEE (XII) Module-3 PW

 (iii) Action of alkalies: When an alkali is added to an orange
red coloured dichromate solution, a yellow solution is
obtained due to the formation of chromate ions.
K2Cr2O7 + 2KOH → 2K2CrO4 + H2O
On acidifying the above yellow solution containing
chromate ions, it again changes to orange red colour due
to the formation of dichromate ions.
(iv) Oxidising properties: Potassium dichromate is a
powerful oxidising agent. In acidic solution, its oxidising
action can be represented as follows.
Ionic equation
Cr2O72– + 14H+ + 6e– → 2Cr3+ + 7H2O
Molecular equation
K2Cr2O7 + 4H2SO4 → K2SO4 + Cr2(SO4)3 + 4H2O + 3[O]
Following some reaction are those in which potassium
dichromate behaves as an oxidising agent.
(a) It oxidises iodides to iodine:
K2Cr2O7+ 7H2SO4 + 6KΙ → 4K2SO4 + Cr2(SO4)3
+ 7H2O + 3Ι2
The above reaction is used in the estimation of iodide
ions in volumetric analysis.
(b) It oxidises ferrous salts to ferric salts:
K2Cr2O7 + 7H2SO4 + 6FeSO4 → K2SO4 + Cr2(SO4)3
 + 3Fe2(SO4)3 + 7H2O
(c) It oxidises H2S to S:
K2Cr2O7 + 4H2SO4 + 3H2S → K2SO4 + Cr2(SO4)3
 + 7H2O + 3S
(d) It oxidises sulphites to sulphates:
K2Cr2O7 + 4H2SO4 + 3Na2SO3 → K2SO4 +
Cr2(SO4)3 + 4H2O + 3Na2SO4
(e) It oxidises sulphur dioxide to sulphuric acid:
K2Cr2O7 + 3SO2 + H2SO4 → K2SO4 + Cr2(SO4)3
 + 4H2O
(f) It oxidises halogen acids to halogens:
K2Cr2O7 + 14HCl → 2KCl + 2CrCl3 + 7H2O+ 3Cl2
Note: Cr2(SO4)3 is green coloured compound
(v) Chromyl chloride test: When potassium dichromate is
heated with sodium chloride and concentrated sulphuric
acid, reddish brown vapour of chromyl chloride
(CrO2Cl2) are obtained.
K2Cr2O7 + 4NaCl + 6H2SO4 → 2CrO2Cl2 +
 2KHSO4 + 4NaHSO4 + 3H2O
This reaction is used for the detection of chloride ions in
qualitative analysis. The vapours of chromyl chloride are
passed through the aqueous solution of sodium hydroxide
which becomes yellow. To the yellow solution, a few
drops of acetic acid are added and this is followed by
addition of lead acetate, when a yellow precipitate of
lead chromate is formed.
P The d & f-Block Elements
W 9
CrO2Cl2 + 2NaOH → Na2CrO4 + 2HCl
Yellow
Na2CrO4 + Pb(CH3COO)2 → PbCrO4 +
 2CH3COONa
(vi) With hydrogen peroxide: Acidified potassium
dichromate forms a deep blue colour with hydrogen
peroxide due to the formation of CrO5.
K2Cr2O7 + H2SO4 + 4H2O2 → 2CrO5 + K2SO4
 + 5H2O
The blue colour fades away gradually due to
decomposition of CrO5 into Cr3+ ions and oxygen.
Structure of CrO5
O
O O
—
—
Cr
O O
POTASSIUM PERMANGANATE (KMnO4)
Preparation: Potassium permanganate is prepared on a large
scale from the mineral pyrolusite, MnO2. The preparation
involves the following steps:
(i) Conversion of pyrolusite into potassium manganate:
Finely powdered pyrolusite is fused with potassium
hydroxide or potassium carbonate in the presence of air
or an oxidising agent like potassium nitrate or potassium
chlorate.
2MnO2 + 4KOH + O2 → 2K2MnO4 + 2H2O
2MnO2 + 2K2CO3 + O2 → 2K2MnO4 + 2CO2
In actual practice, solid pyrolusite is generally fused with
caustic potash. The melt is well stirred in contact with
air to obtain a green coloured fused mass containing
potassium manganate.
(ii) Conversion of potassium manganate into potassium
permanganate: The fused mass is extracted with water
and the solution after filtration is converted into potassium
permanganate either by chemical oxidation or by
electrochemical oxidation.
(a) Chemical oxidation: Chemical oxidation of
potassium manganate can be carried out by bubbling
carbon dioxide, chlorine or ozonised oxygen through
the green coloured solution in the first step.
3K2MnO4 + 2CO2 → 2KMnO4 (ppt.) + MnO2 +
2K2CO3
2K2MnO4 + Cl2 → 2KMnO4 + 2KCl
2K2MnO4 + H2O + O3 → 2KMnO4 + 2KOH +  O2
Ex.: What is meant by 'disproportionation' of an
oxidation state? Give an example.
Sol. When a particular oxidation state becomes less
stable relative to other oxidation states, one lower, one
higher, it is said to undergo disproportionation. For
example, manganese (VI) becomes unstable relative to
manganese (VII) and manganese (V) in acidic solution.
3MnVIO42– + 4H+ → 2MnVII O4– + MnIVO2 + 2H2O
 (b) Electrolytic oxidation: Green coloured solution or 2MnO4– + H2O → 2MnO2 + 2OH– + 3[O]
containing potassium manganate is electrolysed using (Ionic equation)
nickel anode and iron cathode. This is the same reaction as that for the neutral medium.
K2MnO4  2K+ + MnO42– Some oxidising properties of KMnO4 in the alkaline
medium are given below:
H2O  H+ + OH–
(i) It oxidises potassium iodide to potassium iodate,
At anode: MnO42– → MnO4– + e– KIO3:
Manganate ion Permanganate ion
(Green) (Purple) 2KMnO4 + KI + H2O → 2MnO2 + 2KOH + KIO3
At cathode: 2H+ + 2e– → 2[H] or H2 (ii) Alkaline KMnO4 (Baeyer’s reagent)
(From water) It is used for the testing of unsaturated organic compounds
After the oxidation is complete, the purple coloured solution in the laboratory.
is filtered and concentrated by evaporation under controlled CH2 CH2—OH

—
—
conditions.  The less soluble potassium permanganate crystallizes 1% Alkallne KMno 4

out on cooling the concentrated solution.
Properties
Potassium permanganate exists as dark purple black prismatic
crystals having a greenish metallic lustre. It melts at 523 K. It is
moderately soluble in water at room temperature giving a purple
solution.
(i) Action of heat: When heated strongly to a temperature
above 745 K, it readily decomposes to give oxygen.
2KMnO4  
heat
→ K2MnO4 + MnO2 + O2
(ii) Oxidising nature: Potassium permanganate acts as a
powerful oxidising agent in neutral, alkaline and acidic
medium.
(a) Oxidation in neutral solution : It acts as a moderately
powerful oxidising agent in neutral solution.
2KMnO4 + H2O → 2KOH + 2MnO2 + 3[O]
or MnO4– + 2H2O + 3e– → MnO2 + 4OH–
The important reaction in which neutral KMnO4 act as
an oxidising agent is as follows:
It oxidises H2S to S:
2KMnO4 + 3H2S → 2KOH + 2MnO2 + 2H2O + 3S
(b) Oxidation in alkaline solution : In the presence of
concentrated alkali, purple coloured permanganate
ions are reduced to green coloured manganate ions,
with the evolution of oxygen.
O– O–
— —
—
+ H2O + [O]  
CH2 CH2—OH
(c) Oxidation in acidic medium:
Acidified KMnO4 solution is frequently used as a strong
oxidising agent in the laboratory. The best acid is dilute
H2SO4, since HNO3 is itself an oxidising agent and HCl
is oxidised by permanganate ions to chlorine.
2KMnO4 + 3H2SO4 → K2SO4 + 2MnSO4 + 3H2O +
5[O]
or MnO4– + 8H+ + 5e– → Mn2+ + 4H2O
The important reaction in which acidified KMnO4 acts as
an oxidising agent is as follows:
(i) Iodine is liberated from potassium iodide:
10I– + 2MnO4– + 16H+ → 2Mn2+ + 8H2O + 5I2
(ii) Fe2+ ion (green) is converted to Fe3+ (yellow):
5Fe2+ + MnO4– + 8H+ → Mn2+ + 4H2O + 5Fe3+
(iii) Oxalate ion or oxalic acid is oxidised at 333 K:
5C2O42– + 2MnO4– + 16H+ → 2Mn2+ + 8H2O + 10CO2
(iv) Hydrogen sulphide is oxidised, sulphur being
precipitated:
H2S → 2H+ + S2–
5S2– + 2MnO4– + 16H+ → 2Mn2+ + 8H2O + 5S
(v) Sulphurous acid or sulphite is oxidised to a sulphate or
sulphuric acid:
5SO32– + 2MnO4– + 6H+ → 2Mn2+ + 3H2O + 5SO42–

— —

(vi) Nitrite is oxidised to nitrate:

Mn Mn 5NO2– + 2MnO4– + 6H+ → 2Mn2+ + 5NO3– + 3H2O
—
—

—
—

—
—

—
—

–
O O
O O
O O
Green Purple
F-BLOCK ELEMENTS (INNER
4KMnO4 + 4KOH → 4K2MnO4 + 2H2O + O2
TRANSITION ELEMENTS)
or
4MnO4– + 4OH– → 4MnO42– + 2H2O + O2 Introduction
(Ionic equation) (i) Those elements in which the differentiating electron
In the presence of a reducing agent, the manganate enters in (n – 2) f-orbital are called f-block elements.
ions are further reduced to MnO2. Thus, the reduction (ii) Elements having three outer shells incomplete are
of permanganate ions in alkaline medium occurs in the known as inner transition or f-block elements, i.e., they
following two steps:
have configuration (n–2)f1–14 (n – 1)d0–1ns2.
2KMnO4 + 2KOH → 2K2MnO4 + H2O + [O]
(iii) There are two series of f-block elements corresponding
(K2MnO4 + H2O → MnO2 + 2KOH + [O]) × 2 to the filling of 4f and 5f-orbitals.


10 JEE (XII) Module-3 PW

Lanthanoids starts after Lanthanum which is a transition element.
57 Lanthanum La 4f05d16s2 4f05d1 4f0 187 106

LANTHANOID SERIES
Electronic configurations* Radii/pm
Atomic
Name Symbol Ln Ln2+ Ln3+ Ln4+ Ln Ln3+
Number

58 Cerium Ce 4f15d16s2 4f2 4f1 4f0 183 103

59 Praseodymium Pr 4f36s2 4f 3 4f2 4f1 182 101
60 Neodymium Nd 4f46s2 4f4 4f3 4f2 181 99
61 Promethium Pm 4f56s2 4f5 4f4 181 98
62 Samarium Sm 4f66s2 4f6 4f5 180 96
63 Europium Eu 4f76s2 4f7 4f6 199 95
64 Gadolinium Gd 4f7 5d16s2 4f75d1 4f7 180 94
65 Terbium Tb 4f96s2 4f9 4f8 4f7 178 92
66 Dysprosium Dy 4f106s2 4f10 4f9 4f8 177 91
67 Holmium Ho 4f116s2 4f11 4f10 176 89
68 Erbium Er 4f126s2 4f12 4f11 175 88
69 Thulium Tm 4f136s2 4f13 4f12 174 87
70 Ytterbium Yb 4f146s2 4f14 4 f13 173 86
71 Lutetium Lu 4f145d16s2 4f145d1 4f14 — — —

Atomic Size and Ionic Size

Note: In their chemical behaviour, in general, the earlier
Decrease in size from La to Lu is a unique feature in chemistry of members of the series are quite reactive similar to
lanthanoids. This is due to lanthanoid contraction. The decrease calcium but with increasing atomic number, they behave
in atomic radii is not quite regular as it is regular in M3+ ions. This more like aluminium.
contraction is similar to that observed in an ordinary transition Reactions
series and is attributed to the same cause, the imperfect shielding
Ln2O3
of one electron by another in the same sub-shell. However,
shielding of one 4f electron by another is less than one d electron Burn H2
by another with the increase in nuclear charge along the series. Ln2S3
in O2
He cid
wit ated A
Oxidation state hS
With halo
In the lanthanoids, La(II) and Ln(III) compounds are predominant. Ln ge n
ted LnX3
However, some elements may show oxidation state of III and IV. Hea 2
Wi

h N
wit
th

Ce, Pr, Nd, Tb and Dy can exhibit +4 O.S. only in MO2 oxide. LnN
H2

With C
O

Eu2+ is formed by losing the two s-electron. However, Eu2+ is a 2773 K

strong reducing agent changing to the common +3 state. TbIV has
half filled f-orbital and is an oxidant. Sm also exhibit +2 oxidation
state. The only +4 oxidation state of Lanthanides which oxists in
solution and has aqueous chemistry is Ce4+.
General Characteristics
1. All the lanthanoids are silvery white soft metals and
tarnish rapidly.
2. Hardness increases with increasing atomic number,
samarium (Sm) being steel hard.
3. These are good conductor of electricity.
4. Density and other properties change smoothly except for
Eu and Yb and occasionally for Sm and Tm.
P The d & f-Block Elements
W 11
Ln(OH)3+H2
LnC2
Ionisation enegry and electropositive nature : Lanthanoids
have low values of first and second ionisation energy (IE1 and IE2)
which are closer to alkaline earth metals, specially to calcium.
On account of fairly low ionisation enegry and large atomic size,
lanthanoids are strong electropositive elements.
IE1 of the lanthanoids are around 600 kJ/mole and IE2 is about 1200
kJ/mole comparable with those of Ca. A detailed discussion of
IE3’s variation indicates that the exchange enthalpy considerations
(as in 3d orbitals of the first transition series) appear to impart
a certain degree of stability to empty, half filled and completely
filled orbitals of f level. This is indicated from the abnormally low
value of the IE3 of La, Gd and Lu.
Coloured cations and paramagnetism: Most of the lanthanoid
ions are coloured and exhibit paramagnetic nature due to partially ACTINOIDS SERIES
filled f-orbitals. The unpaired electrons involve f-f transition in
(i) The differentiating electron occupies 5f-subshell and
lanthanoid ion which is responsible for the colour in solid as well thus these elements also have three outermost shells not
as in solution state. Also, the number of unpaired electrons give filled to their capacity as well. These are called actinoids.
rise to paramagnetism in them. 0 2 6 1 2
89Ac :...........5f , 6s 6p 6d ,7s
Lanthanoids have similar chemical properties and similar radii, 0 2 6 2 2
90Th :...........5f , 6s 6p 6d ,7s
therefore difficult to separate from each other. However, due to :      :
lanthanoid contraction, their ability to form complexes, varies 14 2 6 1 2
103Lr:...........5f , 6s 6p 6d ,7s
slightly. This slight variation is utilised to separate lanthanides by
(ii) The members of actinoid series are radioactive and
ion-exchange method.
majority of them are not found in nature. The elements
Uses of lanthanoids from atomic number 93 and onwards are called
transuranic elements and have been prepared by
Lanthanoids are commonly used as: artificial means using nuclear reactions. G.T. Seaburg
(i) Pyrophoric alloys, known as Misch metal, contain has maximum contribution in the discoveries of these
lanthanoids about 90–95% (Ce 40.5%, lanthanum and elements.
neodymium 44%), iron 4.5%, calcium, carbon and (iii) The name actinoid is derived from actinium, the first
silicon about 10.5% and are used in cigarette and gas member of the series.
lighters, flame throwing tanks, toys, tanks and tracer (iv) Thus the 5f-series includes fourteen elements from
bullets as well as in shells. thorium to lawrencium.
(ii) Any alloy containing 30% Misch metals and 1% Zr are (v) Some of the properties of actionoids are listed below in
used for making parts of jet engines. table.
(iii) Cerium salts are commonly used as catalyst in petroleum (vi) The electronic configuration of actinoids is [Rn] 5f0–
14, 6d0–2, 7s2 where [Rn] stands for radon core. Like
cracking (cerium phosphate), volumetric analysis and as
lanthanoids, these are placed together because of similar
oxidising agent (ceric sulphate). In dying cotton, in lead
chemical nature.
accumulators etc.
(vii) Like lanthanoid contraction, these too show actinoid
(iv) Oxides of praseodymium (Pr2O3) and neodymium contraction due to poor shielding effect of 5f-subshells.
(Nd2O4) are used in the preparation of coloured glasses Therefore, atomic size of actinoids too decreases
and standard filters. gradually from Ac to Lr.
(v) Oxides of cerium and thorium are used in the preparation (viii) Actinoids show a range of oxidation states which is due
of gas lamp mantles. to comparable energies of 5f, 6d and 7s-orbitals. The
(vi) Cerium oxide is used to prepare sun glasses as cerium general oxidation state of actinoids is +3; the elements in
cuts off heat and ultraviolet light. the first half of the series show higher oxidation states.
Actinium is a transition element and actinoids comes after actinium
Actinium Ac 89 [Rn] 6d1,7s2 +3
Some properties of actinoids
Element Symbol Atomic number Configuration Oxidation states
Thorium Th 90 [Rn] 6d2, 7s2 +3,+4
Protactinium Pa 91 [Rn] 5f2, 6d1, 7s2 +3, +4, +5
Uranium U 92 [Rn] 5f3, 6d1, 7s2 +3, +4, +5, +6
Neptunium Np 93 [Rn] 5f4, 6d1, 7s2 +3, +4, +5, +6, +7
Plutonium Pu 94 [Rn], 5f6, 7s2 +3, +4, +5, +6, +7
Americium Am 95 [Rn], 5f7, 7s2 +2,+3, +4, +5, +6
Curium Cm 96 [Rn], 5f7, 6d1, 7s2 +3, +4
Berkelium Bk 97 [Rn] 5f9, 7s2 +3, +4
Californium Cf 98 [Rn] 5f10, 7s2 +2, +3
Einsteinium Es 99 [Rn] 5f11, 7s2 +2, +3
Fermium Fm 100 [Rn] 5f12, 7s2 +2, +3
Mendelevium Md 101 [Rn] 5f13 , 7s2 +2, +3
Nobelium No 102 [Rn] 5f14 , 7s2 +2, +3
Lawrencium Lr 103 [Rn] 5f14, 6d1, 7s2 +3

12 JEE (XII) Module-3 PW

 (ix) All these elements are strong reducing agents and are very
reactive metals. Actinoids are radioactive and, therefore,
it is difficult to study their chemical nature. However,
relatively more stable isotopes of these elements beyond
Concept Application
uranium have been discovered and the chemistry of 8.
Actinides:
these elements has been studied to an extent by using
(a) are all synthetic elements
radiotracer techniques.
(b) includes element 104
Like lanthanoids, they react with oxygen, halogens,
(c) have only short lived isotopes
hydrogen, sulphur and acids.
(d) have variable valency
(x) Difficulties in studying chemical nature of actinoids: The
chemical nature of actinoids (beyond uranium) has not 9.
The most common lanthanide is:
been studied to a greater extent due to following reasons: (a) lanthanum (b) cerium
(a) All are radioactive and the radioactive decay gives (c) samarium (d) Plutonium
out extremely energetic particles which may break bond
and disrupt crystal structure. Difference between Lanthanides and Actinides
(b) The breaking up of bonds by emitted particles, due Lanthanides Actinides
to higher energy associated with them also develops the
process of self oxidation and it is, therefore, difficult to 1. In addition to +3 1. In addition to +3
decide the more stable oxidation state. oxidation state, they oxidation state, they
exhibit +2 and +4 show +4, +5, +6 and +7
Uses of actinoids: Only U, Th and Pu members of oxidation states also. oxidation states.
this series have found application in nuclear reactions,
undergoing nuclear fission to produce nuclear power and 2. Most of their ions are 2. Most of their ions are
nuclear bomb. colourless. coloured.
3. They do not form 3. They have much greater
complexes easily. tendency to form
complexes.
Train Your Brain 4. They do not form oxo
cations.
4. They form oxocations
such as UO22+, PuO22+
Example 8: Sm2+ , Eu2+ and Yb2+ ions in solutions are good and UO+.
reducing agents but an aqueous solution of Ce4+ is a good 5. Their compounds are 5. Their compounds are
oxidising agent. Why? less basic. more basic.
Sol. Sm2+, Eu2+ and Yb2+ ions in solutions are good 6. Except promethium, 6. They are radioactive.
reducing agents as they tend to acquire common oxidation they are non-
state of +3 shown by lanthanoids by the loss of one electron radioactive.
while Ce4+ gains one electron to attain +3. Hence, Ce4+ is
7. Their magnetic 7. Their magnetic properties
an oxidising agent.
properties can be easily can not be easily
Example 9: The chemistry of the actinoid elements is not explained. explained.
so smooth as that of the Lanthanoids. Justify this statement
by giving some examples from the oxidation state of these Some Applications of D & F-Block Elements
elements. 1. Iron and steel are the most important construction
Sol. Lanthanoids primarily show three oxidation states material, their production is based on the reduction of
(+2, +3, +4). Among these oxidation states, +3 state is the iron oxides, removal of impurities and the addition of
most common. Lanthanoids display a limited number of carbon and alloying metals like Cr, Mn and Ni to them.
oxidation states because the energy difference between 4f, 2. Some compounds are manufactured for special purpose
5d, and 6s orbitals is quite large. On the other hand, the such as TiO for the pigment industry and MnO2 for use
energy difference between 5f, 6d, and 7s orbitals is very in dry cell along with use of Zn.
less. Hence, actinoids display a large number of oxidation 3. Many of the elements or compounds of this block are
states. For example, uranium and plutonium display +3, +4, important catalysts.
+5 and +6 oxidation states while neptunium displays +3, 4. AgBr is an important chemical used in photography.
+4, +5 and +7 oxidation states. The most common oxidation Along with AgBr. Agl can also be used.
state in case of actinoids is also +3. 5. Some compounds like MnO4– & CrO42– are good
oxidising agents.

P The d & f-Block Elements

W 13
 Short Notes

Definition Density in a Group: 3d < 4d << 5d

Transition elements are those d-block elements which have Metallic character: They are solid, hard, ductile, malleable,
partially filled (n – 1)d subshell either in their ground state or in good conductor of heat and electricity and exhibit metallic
their most stable oxidation states. Therefore, Zn, Cd & Hg are lusture, high tensile strength. Hg is a liquid.
d-block elements and not transition elements. Electrical conductivity:-
Ag > Cu > Au
 > p – block
Al
General electronic configuration 
d – block
ns0–2 (n–1)d1–10 Oxidation State
Cr = 3d 4s
5 1
Transition elements exhibit variable oxidation states due to small
Exceptions  energy difference of ns and (n–1)d orbitals.
Cu = 3d 4s , Pd = 4d 5s
10 1 10 0

™ Sc(+3) and Zn(+2) exhibit only one oxidation state.

Transition Series ™ Common oxidation state is +2 & +3.

1st 3d series Sc21 — Zn30 9 + 1 = 10 ™ In 3d series, highest oxidation state is +7 (Mn).

™ In d-block series, highest oxidation state is +8 (Os, Ru).

2nd 4d series Y39 — Cd48 9 + 1 = 10
™ In carbonyl compounds, oxidation state of metals is zero due
3rd 5d series La57, Hf72 — Hg80 9 + 1 = 10
to synergic effects.
4th 6d series Ac89, Unq104 — Uub112 9 + 1 = 10 ™ Their higher oxidation states are more stable in fluorides and
oxides.
Atomic Radius ™ Higher oxidation states in oxides are normally more stable
3d series: Sc > Ti > V > Cr > Mn ≥ Fe  Co  Ni ≤ Cu < Zn. In a than fluorides due to capability of oxygen to form multiple
group from 3d to 4d series, atomic radius increases but 4d and 5d bonds.
series have nearly same atomic radius due to poor shielding of f
Eg. stable fluoride in higher oxidation state of Mn is MnF4
electrons (Lanthanide contraction).
while oxide is Mn2O7.
3d < 4d  5d ™ Mn shows maximum number of oxidation states (+2 to +7)

Smallest radius – Ni among 3d series.
e.g :Ti < Zr  Hf ™ Beyond Mn, trihalides are not observed except in FeX3 (X = Cl/
Largest radius – La
Br/I) & CoF3.
Melting point : s-block metals < d-block metals
⇒ V2O3 V2O4 V2O5
In a series, on increasing number of unpaired electrons, melting Basic Basic Amphoteric
point increases upto Cr and then decreases. ⇒ CrO Cr2O3 CrO3
Sc < Ti < V < Cr > Mn < Fe > Co > Ni > Cu > Zn Basic Amphoteric Acidic
↓ ↓ ⇒ MnO MnO2 Mn2O7
Basic Amphoteric Acidic
Half filled d 5 Fully filled d10
⇒ CuI2 does not exist as it decomposes to give CuI & I2 at room
∴weak metallic bond    ∴weak metallic bond
temperature
Zn > Cd > Hg 1
Melting point (data based) CuI 2 → CuI + I 2
Cu > Ag ≤ Au 2

E.N. Exception: Zn < Cd < Hg
Density : s − block metals < d − block metals.
3d series
Sc < Ti < V < Cr < Mn < Fe < Co ≤ Ni < Cu > Zn
⇒ In aqueous solution, Cu+ disproportinates into Cu & Cu2+. In
p-block, lower oxidation states of heavier elements are more
stable, while in d-block higher oxidation state of heavier
elements are more stable.
Eg. In VIB group, Mo(+6) & W(+6) are more stable than
Cr(+6).

14 JEE (XII) Module-3 PW

 Magnetic Property Important reactions of d-block elements
All transition elements are paramagnetic due to the presence of (a) Cu2+ + 4I–→ Cu2I2(s) + I2
unpaired electrons. Magnetic moment of unpaired electrons is due (b) CuSO4 + KCN → K2SO4 + Cu(CN)2
to spin and orbital angular momentum. Excess Unstable
2Cu(CN)2 → 2CuCN + (CN)2
“Spin only” magnetic moment can be calculated by using the formula, Cyanogen

=µ n(n + 2) Bohr magneton. (n is the number of unpaired e–s) CuCN + 3KCN → K3[Cu(CN)4]
H2O + CO2
If n is 1, m = 1.73 BM (c) Cu CuCO3.Cu(OH)2
moist air Green
n is 2, m = 2.84 BM Aqua regia
Au(3HCl H[AuCl4] + NOCl + H2O
n is 3, m = 3.87 BM + HNO ) 3

n is 4, m = 4.90 BM 1
Heating
(d) AgNO3(s) Ag + NO2 + O 2
n is 5, m = 5.92 BM 2
Substances, that are not attracted by applied magnetic field are Heating 1
Ag2CO3(s) Ag + CO2 + O 2
diamagnetic. They have all the electrons paired. d-block elements 2
and ions, having d0 and d10 configuration are diamagnetic. (e) CuSO4.5H2O 100ºC CuSO4.H2O 720ºC
Light greenish blue
Colour 230ºC 1
CuSO4 CuO + SO2 + O 2
Colour in transition metal ions is associated with d-d transitions of Colourless 2
unpaired electrons from t2g to eg set of energies. This is achieved NH2
by absorption of light in the visible spectrum, rest of the light is (f) Hg2Cl2 + NH4OH Hg + Hg
Cl Black

no longer white.
(g) NO3–/NO– FeSO4 + H2SO4 [Fe(H O) NO+]SO
Colourless – Sc3+, Ti4+, Zn2+ etc. 2 2 5
Brown ring complex
4

Coloured – Fe3+ yellow, Fe2+ green, Cu2+ blue, Co3+ blue etc. (h) AgBr + 2Na2S2O3 Na3[Ag(S2O3)2] + NaBr
Photographic complex
Alloys (i) Chemical volcano:
Solid mixture of metals in a definite ratio (15% difference in (NH4)2Cr2O7 →D
N2 + 4H2O + Cr2O3
metallic radius). They are hard and have high melting point. orange solid Green residue

Eg. Brass (Cu + Zn) Reactions of Cr2O72–

Bronze (Cu + Sn) etc. Cr2O72– (Orange)
Hg when mixed with other metals form semisolid amalgam except
Fe, Co, Ni, Pt. SO2 SO42–

Interstitial compound H2S S

SO3 2–
When less reactive non-metals of small atomic size eg. H, B, N, C SO42–
are trapped in the interstitial space of transition metals, interstitial NO2 –
NO3–
compounds are formed, like: TiC, Mn4N, Fe3H etc.
I– I2
They are non-stoichiometric compounds.
Br– Br2
They have high melting point than the metals from which
they are formed. S2O32– S + SO42–
They are chemically inert. C2H5OH CH3COOH
Sn2+ Sn4+
Catalytic Properties
Most of the d-block compounds act as catalyst due to their variable Fe2+ Fe3+
oxidation state, complex formation tendency and adsorption of
Cr3+(green)
gases on their surface.
H+
Example: 

CrO 24 − 
−
2−
 Cr2 O7
OH
Contact process = V2O5
Yellow Orange

Cr2O7 –2/H+ (Orange)

Haber's process = Fe2O3 + Al2O3 + K2O
Fenton’s reagent = FeSO4 + H2O2
Decomposition of KClO3 = MnO2
H2O2 H2O
Ostwald's process = Pt/Rh
Zeigler Natta = TiCl4 + (C2H5)3 Al
Hydrogenation of Alkene = Ni/Pd
Wilkinson’s catalyst = RhCl + PPh3 CrO5
(Blue)

P The d & f-Block Elements 15

W
Reaction of MnO4– 3. Copper sulphate, CuSO4.5H2O (Blue vitriol)
Also known as ‘Nilathotha’
MnO4–(Purple)
Physical Properties: Blue crystalline compound, soluble in
C2O42– CO2 water.
CuSO4.5H2O  → CuSO4.4H2O 
100° C
→
air
SO2 SO42– effloresces
H2S S 250° C 750° C
CuSO4.H2O → CuSO4 → CuO + SO2 + O2
S2O32– S + SO42–
NO2– NO3– Cu + H 2SO 4 + O 2  → CuSO 4
− H2 O
I– I2
CuSO 4 
NaOH / Na 2 CO3
→ Cu ( OH )2 ↓
Br– Br2 − Na 2 SO 4 / − Na 2 SO 4 , CO 2
blue
Cl– Cl2 KSCN + SO + H O
CuSO 4  → CuSCN ↓ (white) + K 2SO 4 + H 2SO 4
2 2

C2H5OH CH3COOH
Sn+2 Sn+4 4. Ferric Chloride, FeCl2
Fe+2 Fe+3 FeCl2(anhyd.) + O2 
–Fe2O3
Mn+2(Purple colour is decolourised) Fe + Cl2 (dry)  FeCl3
Strongly ∆
MnO4– →Basic MnO42– FeCl3.6H2O+SOCl2 –HCl, SO2

Purple Green
Solution
It sublimes at 300°C giving a dim eric gas.
MnO4–/OH– Cl Cl Cl

I– IO3– Fe Fe
Cl Cl Cl
CH2 = CH2 CH2 – CH2 Two 3C-4e– bond
Four 2C-2e– bond
OH OH 5. Zinc Chloride
Prepration of hydrated ZnCl2(ZnCl2.2H2O)
MnO2
ZnCl2.  
(Brown PPT)
ZnO +HCl Zn(OH)Cl ZnO+HCl
2H2O –HCl, H2O
Some important d-Block metal compounds
Ferrous sulphate, FeSO4.7H2O (Green Vitriol) 6. Cupric chloride, CuCl2, 2H2O
150° C
Commonly known as harkasis. Heating effect: CuCl2.2H2O →
HCl gas CuCl2 + 2H2O
Heating effect: 7. Silver nitrate, AgNO3 (Lunar Caustic)
140° C Heating above
FeSO4.7H2O 
→ FeSO4.H2O 
→ 2FeSO4 300° C
M.pt.
AgNO2 + O2
 
High
→ Fe2O3 + SO2↑ + SO3↑ 
Temp. Ag+HNO3 (dil.) AgNO3
Red Hot
Fe (from iron scrap)  FeSO 4
H 2 SO4
 H2  Ag + NO2 + O2

FeSO 4 
KCN
− K 2 SO4
→ K 4 [Fe ( CN )6 ] Photography
(i) A photographic film consists of a light sensitive emulsion
FeSO 4 
Hydrolysis
→ Fe(OH) 2 + H 2SO 4 of fine particles (grains) of silver salts in gelatin, spread

(Solution is acidic) on a clear celluloid strip or a glass plate. AgBr is mainly
used as the light sensitive material.
Uses : For making laboratory reagents, like Mohr’s salt etc.
(ii) The film is placed in a camera. When the photograph is
FeSO4 + (NH4)2 SO4 + 6H2O → FeSO4.(NH4)2 SO4.6H2O exposed, light from the subject enters the camera and is
(Mohr’s salt) focussed by the lens to give a sharp image on the film.
The light starts a photochemical reaction by exciting a
FeSO4 + H2O2 known as Fenton’s reagant is used as catalyst. halide ion, which loses an electron. The electron moves
2. Zinc Sulphate, ZnSO4.7H2O (White Vitriol) in a conduction band to the surface of the grain, where it
reduces Ag+ ion to metallic silver. To remove the excess
ZnSO 4 NaOH
− Na 2 SO4
→ Zn(OH) 2 ↓  NaOH
− H2 O
→ Na 2 ZnO 2
White Soluble Complex of AgBr, hypo solution is used.
ZnSO  ° ° 800°C 2AgBr(s)  light
→ 2Ag + Br2
100
→ ZnSO ⋅ 6H O 
4
200
4 → ZnSO
2 4
AgBr + Na2S2O3(aq.) 
light
→ Na3[Ag (S2O3)2] + NaBr
ZnO + SO3

16 JEE (XII) Module-3 PW

f-block elements
Lanthanoids are a series of elements that involve the filling of
4f- subshell. These are fourteen elements, following lanthanum,
from Cerium to Lutetium. Actinoids are a series of elements
that involve filling of 5f-subshell. These are fourteen elements
following Actinium from Thorium to Lawrencium. The common
oxidation state of lanthanoids and actinoids is +3.
Solved Examples
1.
What is the position of d-block elements in the periodic
table?
Sol. The d-block elements are in the middle of s and p blocks,
comprising the groups 3 to 12. There are four rows of
elements in the periods 4th (3d series), 5th (4d series), 6th
(5d series) and 7th ( 6d series).
2. An unknown inorganic compound (X) gave the following
reactions:
(i) The compound (X) on heating gave a residue, oxygen
and oxide of nitrogen.
(ii) An aqueous solution of compound (X) on addition to
NaCl gave a turbidity which did not dissolve in HNO3.
(iii) The turbidity dissolved in NH4OH.
Identify the compound (X) and give equations for the
reactions (i), (ii) & (iii).
∆
Sol. 2AgNO3  → 2 Ag + 2NO2 + O2
AgNO3 (aq.) + Cl– → AgCl↓ (white) + NO3–
AgCl + 2NH3 → [Ag(NH3)2 ]+ (soluble complex)
X = AgNO3
3.
Zinc, cadmium and mercury of group 12 are not regarded
as transition metals, why?
Sol. Zinc, cadmium and mercury of group 12 have fully filled
d10 configuration (d orbitals are completely filled) in their
ground state as well as in their common oxidation states
hence, are not regarded as transition metals.
Which of the following is true for the species having 3d4
4. good catalyst.
configuration?
(a) Cr2+ is reducing in nature
(b) Mn3+ is oxidising in nature
(c) Both (a) and (b)
(d) None of these
Sol. Cr2+ is reducing as its configuration changes from d4 to d3,
3 energy level of 3d orbitals
the latter having a half-filled t2g
in octahedral crystal field spliting. On the other hand, the
change from Mn3+ to Mn2+ results in the half-filled (d5)
configuration which has extra stability.
P The d & f-Block Elements
W 17
Some Applications of d- and f-Block Elements
Iron and steels are the most important construction materials. Their
production is based on the reduction of iron oxides, the removal of
impurities and the addition of carbon and alloying metals, such as
Cr, Mn and Ni. TiO for the pigment industry and MnO2 for use in
dry battery cells. The battery industry also requires Zn and Ni/Cd.
The ‘silver’ UK coins are Cu/Ni alloy.
The outer electronic configuration of Cu is 3d104s1 instead
5.
of 3d94s2, why?
Sol. Completely filled (3d10) orbitals are relatively more stable,
hence one electron of 4s orbital jumps to 3d orbital.
6.
To what extent do the electronic configurations decide the
stability of oxidation states in the first series of the transition
elements? Illustrate your answer with examples.
Sol. The oxidation states with the maximum number (+2 to +7)
are exhibited by the elements of Mn oxidation states that are
in the first half of the transition series. Ti with the increase in
atomic number,the stability of +2 oxidation state increases.
Once more electrons are filled in the d-orbital, this happens
to a great extent. The +2 oxidation state is not shown by Sc.
Its electronic configuration is 4s2 3d1 . It loses all the three
electrons to form Sc3+, +3 oxidation state of Sc is very stable
as by losing all three electrons, it attains stable noble gas
configuration, [Ar], Ti (+ 4) and V (+5) are very stable for
the same reason. For Mn, +2 oxidation state is very stable as
after losing two electrons, its d-orbital is exactly half-filled,
[Ar] 3d5.
7. Explain giving reasons
(i) Transition metals and many of their compounds show
paramagnetic behaviour.
(ii) The enthalpies of atomisation of the transition metals
are high.
(iii) The transition metals generally form coloured
compounds.
(iv) Transition metals and their many compounds act as
Sol. (i) Transition metals show paramagnetic behaviour.
Paramagnetism arises due to the presence of unpaired
electrons with each electron having a magnetic
moment associated with its spin angular momentum
and orbital angular momentum. However, in the first
transition series, the orbital angular momentum is
quenched. Therefore, the resulting paramagnetism is
only because of the unpaired electron.
(ii) Transition elements have high effective nuclear charge
and a large number of valence electrons. Therefore,
they form very strong metallic bonds. As a result, the
enthalpy of atomization of transition metals is high.
 (iii) Most of the complexes of transition metals are 14. Describe the preparation of potassium dichromate from
coloured. This is because of the absorption of radiation iron chromite ore. What is the effect of increasing pH on a
from visible light region to promote an electron from solution of potassium dichromate?
one of the ‘d’orbitals to another. In the presence of
Sol. From iron chromite ore, potassium dichromate is prepared
ligands, the d-orbitals split up into two sets of orbitals
in the following steps:
having different energies. Therefore, the transition of
electrons can take place from one set to another. The Step 1: Preparation of sodium chromate.
energy required for these transitions is quite small 4FeCr2O4 + 16NaOH + 7O2 → 8Na2CrO4 + 2Fe2O3
and falls in the visible region of radiation. The ions + 8H2O
of transition metal absorb the radiation of a particular Step 2: Conversion of sodium chromate into sodium
wavelength and the rest is reflected, imparting colour dichromate.
to the complex.
2Na2CrO4 + conc. H2SO4 → Na2Cr2O7 + Na2SO4
(iv) The catalytic activity of the transition elements can + H2O
be explained by two basic facts. (a) Transition metals
Step 3: Conversion of sodium dichromate to potassium
provide a suitable surface for the reactions to occur.
dichromate.
(b) Owing to their ability to show variable oxidation
states and form complexes, transition metals form Na2Cr2O7 + 2KCl → K2Cr2O7 + 2NaCl
unstable intermediate compounds. Thus, they provide Potassium dichromate being less soluble than sodium
a new path with lower activation energy, Ea, for the dichromate is obtained in the form of orange coloured
reaction. crystals and can be removed by filtration.
8.
What is the most common oxidation state of lanthanoids and The dichromate ion (Cr2O72–) exists in equilibrium with
actionoids? chromate (CrO42–) ion at pH 4.
Cr2O72– + 2OH– → 2CrO42– + H2O
Sol. The most common oxidation state of lanthanoids and (Orange) (Yellow)
actionoids is +3. On increasing the pH; K2Cr2O7 changes into K2CrO4
9.
What is actinoid contraction? (orange to yellow).
Sol. There is a gradual decrease in the size of atoms or M3+ ions 15. Among the following statements, choose the true or false
across the series. This is known as the actinoid contraction. statement(s).
10. Actinoid contraction is more than lanthanoid contraction. (A) K2Cr2O7 on heating with charcoal gives metallic
Give reason. potassium and Cr2O3.
Sol. The actinoid contraction is more than lanthanoid contraction (B) On heating in current of H2 , the crystalline KMnO4 is
due to poor shielding by 5f electrons than that by 4f electrons converted into KOH and Mn3O4.
in lanthanoids. (C) Hydrated ferric chloride on treatment with 2, 2–
11. Actinoids show larger number of oxidation states than dimethoxypropane gives anhydrous ferric chloride.
lanthanoids. Why? (D) Interstitial compounds have high melting points,
Sol. In actinoids 5f, 6d and 7s levels are of comparable energies, higher than those of pure metals.
hence electrons from these orbitals are available to lose or (E) Permanganate titrations in presence of hydrochloric
share. acid are unsatisfactory.
12. Which of the following statement(s) is (are) not correct with (F) KMnO4 does not act as an oxidising agent in strong
reference to ferrous and ferric ions? alkaline medium.
(a) Fe3+ gives brown colour with potassium ferricyanide (G) KMnO4 on heating in a current of H2 gives MnO.
(b) Fe2+ gives blue precipitate with potassium
ferricyanide Sol. (A) False (B) False (C) True (D) True (E) True (F) False (G)
(c) Fe3+ gives red colour with potassium thiocyanate True
∆
(d) Fe2+ gives brown colour with potassium thiocyanate (A) K2Cr2O7 + 2C (charcoal)  → Cr2O3 + K2CO3 +
Sol. Fe3+ produces red colouration with KSCN but Fe2+ does not CO↑.
∆
give brown colour with KSCN. Therefore, (d) option is not (B) 2KMnO4 + 5H2  → 2KOH + 2MnO + 4H2O.
correct.
OCH3
— —

13. What is the composition of mischmetal alloy and what are

it’s uses? (C) FeCl3.6H2O + 6CH3 —C—CH3 
→ FeCl3(anhydrous)

Sol. Mischmetal alloy consists of lanthanoid metal (~95%) and OCH3

iron (~5%) and traces of S,C,Ca and Al. Mischmetal is used + 12CH3OH + 6CH3COCH3
in Mg based alloys to produce bullets, shell and lighter flint. (D) Due to strong interatomic forces.

18 JEE (XII) Module-3 PW

 (E) Some of the hydrochloric acid is oxidised to chlorine 0 +V

and thus we get less volume of KMnO4 than the actual (A) 5AgNO3 (aq) + 3I 2 (excess) + 3H 2 O 
→ HIO3 +
one. −1

−
 5Ag I + 5HNO3
MnO −4 + e − 
(F) OH
→ MnO 24 −
So, it is a redox and disproportionation reaction. Agl is
∆
2KMnO 4 + 5H 2 
(G) → 2KOH + 2MnO + 4H 2 O insoluble in water.
+ VI + VII + IV
16. Match the reactions in Column-I with nature of the reactions/ 3K 2 MnO 4 ( aq ) + 2CO 2 (g) 
(B) → 2KMnO 4 + MnO 2 +
type of the products in Column-II.
2K2CO3
Column-I Column-II
So, it is a redox and disproportionation reaction. MnO2 is

A. AgNO3(aq) + I2 (excess) + p. Disproportionation insoluble in water.
H2O → 0
∆
+VI + III + IV + II
2 C + Na 2Cr2 O7 
(C) → Cr2 O3 + Na 2CO3 + CO ↑
B. K2MnO4(aq) + CO2(g) 
→ q. Conproportionation
So, it is a redox reaction. Cr2O3 (green pigment) is
C. ∆
Na2Cr2O7 + C  → r. Redox insoluble in water.
+ II 0 +l
D. CuCl2(aq) + Cu(s) 
→ s. One of the products Cu Cl2 (aq) + C u(s) 
(D) → Cu 2 Cl2 (s)
is insoluble in water
So, it is a redox and conproportionation reaction. Cu2Cl2
Sol. (A → p,r, s); (B → p, r, s); (C → r, s); (D → q, r, s)
is insoluble in water.

P The d & f-Block Elements

W 19
 Exercise-1 (Topicwise)

GENERAL PROPERTIES OF TRANSITION
ELEMENTS
What is the general electronic configuration for 2nd row
1.
transition series?
(a) [Ne] 3d1–10, 4s2 (b) [Ar] 3d1–10, 4s1–2
1–10
(c) [Kr] 4d , 5s 1–2 (d) [Xe] 5d1–10, 5s1–2
2. The general electronic configuration of transition elements
is
(a) (n – 1)d1–5 (b) (n – 1)d1–10ns1
(c) (n – 1)d1–10ns1–2 (d) ns2(n – 1)d10
3. Highest (+7) oxidation state is shown by
(a) Co (b) Cr
(c) V (d) Mn
4.
The metallic bond strength in first transition series increases
from
(a) Sc to Mn (b) Sc to Cr
(c) Cr to Zn (d) Sc to Cu
5.
Which of the following is diamagnetic?
(a) Zn2+ (b) Ni2+
(c) Co2+ (d) Cu2+
6.
If n is the number of unpaired electrons, the magnetic
moment (in B.M.) of transition metal/ion is given by
(a) n (n + 2) (b) 2n (n +1)
(c) n (n – 2) (d) 2n (n –1)
µ = 15 is true for the pair
7. 17. Which of the following is not a characteristic property of
(a) Co2+, Cr3+ (b) Fe2+, Cr3+
(c) Fe3+, Cr2+ (d) Mn2+, Fe2+
8.
The tendency towards complex formation is maximum in
(a) s-block elements (b) p-block elements
(c) d-block elements (d) f-block elements
9.
Variable valency is shown by
(a) Na (b) Cu
(c) Mg (d) Al
10. The coinage metals are
(a) Iron, Cobalt, Nickel
(b) Copper and Zinc
(c) Copper, Silver and Gold
(d) Gold and Platinum
11. The number of unpaired electrons in Cr+ ion is
(a) 3 (b) 4
(c) 5 (d) 6
12. The ionic radius of Cr is minimum in which of the following
compounds?
(a) CrF3 (b) CrCl3
(c) Cr2O3 (d) K2CrO4
13. Which of the given ion is not coloured?
(a) Cr3+ (b) Co2+
(c) Cr2+ (d) Cu+
14. In a transition series, as the atomic number increases,
paramagnetism
(a) Increases gradually.
(b) Decreases gradually.
(c) First increases to a maximum and then decreases.
(d) First decreases to a minimum and then increases.
15. Ionic character of halides of metals (3d-transition series)
decreases in the order
(a) M-I > M-Br > M-Cl > M-F
(b) M-Cl > M-Br > M-l > M-F
(c) M-Br > M-Cl > M-F > M-I
(d) M-F > M-Cl > M-Br > M-I
16. The reason for the formation of complex compounds by
transition metals is
(a) Availability of empty d-orbitals
(b) Completely filled d-orbitals
(c) Paramagnetism
(d) Bigger size
transition metals?
(a) High enthalpy of atomisation.
(b) Formation of interstitial compounds.
(c) Diamagnetism
(d) Variable oxidation state.
18. Of the ions Zn2+, Ni2+ and Cr3+
[atomic number of Zn = 30, Ni = 28, Cr = 24]
(a) Only Zn2+ is colourless and Ni2+ and Cr3+ are coloured.
(b) All three are colourless.
(c) All three are coloured.
(d) Only Ni2+ is coloured and Zn2+ and Cr3+ are colourless.
19. Transition metals ions form interstitial compounds because
(a) Vacant sites are available in their crystal lattice.
(b) They have empty d-orbitals.
(c) They have high value of ionic potential.
(d) They show variable oxidation states.

20 JEE (XII) Module-3 PW

 20. Transition elements act as catalyst because
(a) Their melting points are higher.
(b) Their I.P. values are higher.
(c) They have high density.
(d) They can show variable oxidation states.
21. In acidic medium, one mole of MnO4– accepts how many
moles of electrons in a redox process?
(a) 1 (b) 3 (c) 5 (d) 6
22. Acidified potassium dichromate is treated with hydrogen
sulphide. In the reaction, the oxidation number of chromium
(a) Increases from + 3 to + 6.
(b) Decreases from +6 to +3.
(c) Remains unchanged.
(d) Decreases from +6 to +2.
23. When KMnO4 reacts with acidified FeSO4
(a) Only FeSO4 is oxidised.
(b) Only KMnO4 is oxidised.
(c) FeSO4 is oxidised and KMnO4 is reduced.
(d) None of these.
24. AgCl dissolves in a solution of NH3 but not in water, because
(a) NH3 is a better solvent than H2O.
(b) Ag+ forms a complex ion with NH3.
(c) NH3 is a stronger base than H2O.
(d) The dipole moment of water is higher than NH3.
25. Which one of the following is reduced by hydrogen peroxide
in acid medium?
(a) Potassium permanganate
(b) Potassium iodide
(c) Ferrous sulphate
(d) Potassium ferrocyanide
26. Which one of the following oxide is ionic?
(a) MnO (b) Mn2O7 (c) CrO3 (d) P2O5
27. Equivalent weight of KMnO4 acting as an oxidant in acidic
medium is equal to
(a) Molecular weight of KMnO4
1 (b) Cr2+ (aq.) is more stable than Cr3+ (aq.).
(b) × Molecular weight of KMnO4
2 (c) Mn3+ (aq.) is more stable than Mn2+ (aq.).
1 (d) None of these.
(c) × Molecular weight of KMnO4
3 K2Cr2O7 and KMnO4
1
(d) × Molecular weight of KMnO4
5
28. FeSO4.(NH4)2SO4.6H2O is called
(a) Mohr’s salt (b) Green salt
(c) Alum (d) Glauber’s salt
29. V2O5 is useful as catalyst in
(a) Manufacture of H2SO4
(b) Manufacture of HNO3
(c) Manufacture of Na2CO3
(d) It is not a catalyst
P The d & f-Block Elements
W
30. When metallic copper comes in contact with moisture,
a green powdery/pasty coating can be seen over it.
This is chemically known as
(a) Copper sulphide - Copper carbonate
(b) Copper carbonate - Copper sulphate
(c) Copper carbonate - Copper hydroxide
(d) Copper sulphate - Copper sulphide
31. Which of the following is used in photography?
(a) AgCl (b) AgBr
(c) AgI (d) Ag2O
32. Which of the following is least soluble in water?
(a) AgI (b) AgCl
(c) AgBr (d) Ag2S
33. While extracting an element from its ore, the ore is ground
and leached with dilute KCN solution to form the soluble
product potassium argentocyanide. The element is
(a) Lead (b) Chromium
(c) Manganese (d) Silver
34. Amongst which of the following pair of ions, the lower
oxidation state is more stable than the higher oxidation state
in aqueous solution?
(a) Ti+, Ti3+ (b) Cu+, Cu2+
(c) Cr2+ , Cr2+ (d) V2+, VO2+
35. To significantly increase the concentration of free Zn2+ ions
in a solution of the complex ion [Zn(NH3)4]2+, some_____
solution need to be added Zn 2+ (aq) + 4NH 3 (aq) 
[Zn(NH3)4]2+ (aq)
(a) H2O (b) HCl (aq)
(c) NH3(aq) (d) NH4Cl (aq)
36. VCl5 undergoes hydrolysis with water and forms
(a) VOCl2 (b) VOCl3
(c) V(OH)2 (d) [V(H2O)6]3+
37. E° values for the couples Cr3+/Cr2+ and Mn3+/Mn2+ are –0.41
and + 1.51 volts, respectively. Considering these values
select the correct option from the following statements.
(a) Cr2+ acts as a reducing agent and Mn3+ acts as an
oxidising agent in their aqueous solutions.
38. The equilibrium Cr2O72–  2CrO42– is shifted to right in
(a) An acidic medium (b) A basic medium
(c) A neutral medium (d) It does not exist
39. The number of moles of acidified KMnO4 required to
convert one mole of sulphite ion into sulphate ion is
(a) 2/5 (b) 3/5 (c) 4/5 (d) 1
40. When MnO2 is fused with KOH, a coloured compound is
formed, the product and its colour is
(a) K2MnO4, green (b) KMnO4, purple
(c) Mn2O3, brown (d) Mn3O4 , black
21
 41. K2Cr2O7 is preferred over Na2Cr2O7 for use in volumetric 48. Lanthanoid contraction implies
analysis as a primary standard becasuse (a) Decrease in density
(a) Na2Cr2O7 is hygroscopic while K2Cr2O7 is not. (b) Decrease in mass
(b) K2Cr2O7 is hygroscopic while Na2Cr2O7 is not. (c) Decrease in ionic radii
(c) K2Cr2O7 is pure while Na2Cr2O7 is impure. (d) Decrease in radioactivity
(d) None of these. 49. Which of the following statement is not correct?
42. Which of the following compound has colour but no (a) La(OH)2 is less basic than Lu(OH)3.
unpaired electrons? (b) In lanthanide series, ionic radius of Ln3+ ions
(a) KMnO4 (b) K2MnO4 decreases.
(c) MnSO4 (d) MnCl2 (c) La is actually an element of transition series rather
43. The correct formula of permanganic acid is than lanthanide series.
(a) HMnO4 (b) HMnO5 (d) Atomic radii of Zr and Hf are same because of
(c) H2MnO4 (d) H2MnO3 lanthanide contraction.

44. Which oxide of manganese is acidic in nature? 50. Lanthanide contraction is due to increase in
(a) MnO (b) Mn2O7 (a) shielding by 4f electrons
(c) Mn2O3 (d) MnO2 (b) atomic number
(c) effective nuclear charge
45. Which of the following compounds are coloured due to
charge transfer spectrum? (d) size of 4f orbitals
(a) K2Cr2O7 (b) KMnO4 51. Which of the following element is not an actinide?
(c) [Fe(H2O)5NO]SO4 (d) All of these (a) Curium
46. The product of oxidation of I– with MnO4– in alkaline (b) Californium
medium is (c) Uranium
(a) IO3– (b) I2 (d) Terbium
(c) IO– (d) IO4– 52. The correct statement(s) among the following
is/are
f - Block (i) all the d and f-block elements are metals.
47. General electronic configuration of lanthanides is (ii) all the d and f-block elements form coloured ions.
(a) (n–2)d0–1 (n–1)f 0–14 ns1 (iii) all the d and f-block elements form paramagnetic ions.
(b) (n–2)f 0–14 (n–1)d0–1 ns1–2 (a) (i) only (b) (i) and (ii)
(c) (n–2)f0–14 (n–1)d10 ns2 (c) (ii) and (iii) (d) All of these
(d) (n–2)f1–14 (n–1)d0–1 ns2

Exercise-2 (Learning Plus)

1.
The atomic volumes of the transition elements are low increase in atomic number because of poor shielding of
compared with elements in neighbouring groups 1 and 2, nuclear attraction by (n – 1)d electrons.
because (c) Second and third transition series elements have nearly
(a) The nuclear charge is poorly screened and so attracts the same size.
all the electrons more strongly. (d) Their densities are higher and densities of the 5d series
(b) The extra electrons added occupy inner orbitals. elements are higher than those of 4d series elements.
(c) (a) and (b) both 3.
The melting point of Zn is lower as compared to those of
(d) None of these the other elements of 3d series, because
2.
The wrong statement regarding transition metals among the (i) The d-orbitals are completely filled.
following is (ii) The d-orbitals are partially filled.
(a) 4s electrons penetrate towards the nucleus more than (iii) d-electrons do not participate in metallic bonding.
3d electrons. (iv) Size of Zn atom is smaller.
(b) Atomic radii of transition metals increases rapidly with (a) (i), (iii) (b) (ii) (c) (iv) (d) (ii), (iv)

22 JEE (XII) Module-3 PW

 4.
The Ziegler-Natta catalyst used for polymerisation of 11. Which of the following has the maximum number of
ethene and styrene is TiCl4 + (C2H5)3Al, the catalysing unpaired d-electron?
species (active species) involved in the polymerisation is (a) Zn2+ (b) Fe2+
(a) TiCl4 (b) TiCl3 (c) Ni2+ (d) Cu2+
(c) TiCl2 (d) TiCl
12. The highest magnetic moment is shown by the transition
5.
The electrons which take part in order to exhibit variable metal ion with the outermost electronic configuration
oxidation states by transition metals are
(a) 3d5 (b) 3d2
(a) ns only 7
(c) 3d (d) 3d9
(b) (n – 1)d only
(c) ns and (n – 1)d only but not np 13. Magnetic moment of Cr2+ (Z =24), Mn2+ (Z = 25) and
(d) (n –1)s and np orbital Fe2+(Z = 26) are x,y,z. They are in the order
(a) x < y < z (b) x > y > z
6.
First IE of 5d series elements are higher than those of 3d and
4d series elements. This is due to (c) z < x = y (d) x = z < y
(a) Bigger size of atoms of 5d-series elements than 14. Which of the following group of ions is paramagnetic in
3d-series elements. nature?
(b) Greater effective nuclear charge is experienced by (a) Cu+, Zn2+, Sc3+ (b) Mn2+, Fe3+, Ni2+
Valence electrons because of the weak shielding of 2+ 3+ 3+
(c) Cr , Mn , Sc (d) Cu2+, Ni2+, Ti4+
the nucleus by 4ƒ-electrons in 5d series.
(c) (a) and (b) both 15. The colour of transition metal ions is attributed to
(d) None of these (a) Exceptionally small size of cations.
(b) Absorption of ultraviolet rays.
7.
Which of the following statement is correct?
(a) The lesser number of oxidation states in 3d-series in the (c) Incomplete (n–1) d-subshell.
beginning of the series is due to the presence of too few (d) Absorption of infrared radiations.
electrons to loose or share. 16. Transition elements have more tendency to form complex
(b) The lesser number of oxidation states in 3d-series than representative elements (s and p-block elements) due
towards the end of the series is due to the presence of to
too many electrons and thus fewer empty orbitals to (a) Availability of d-orbitals for bonding.
share electrons with the ligands.
(b) Variable oxidation states are not shown by transition
(c) (a) and (b) both elements.
(d) None is correct
(c) All electrons are paired in d-orbitals.
Ionisation energies of Ni and Pt in kJ mol–1 are given below.
8. (d) ƒ-orbitals are available for bonding.
(IE)1 + (IE) 2 (IE) 3 + (IE) 4 17. Transition elements are usually characterized by variable
      
Ni 2.49 8.80 oxidation states but Zn does not show this property because
Pt 2.60  6.70 of
Select the correct statement: (a) Completion of np-orbitals
(a) nickel (II) compounds tend to be thermodynamically (b) Completion of (n–1) d orbitals
more stable than platinum (II). (c) Completion of ns-orbitals
(b) platinum (IV) compounds tend to be more stable than (d) Inert pair effect
nickel (IV).
18. The d-block element which is liquid at room temperature,
(c) (a) and (b) both
having high specific heat, less reactivity than hydrogen and
(d) None is correct its chloride (MX2) is volatile on heating
9.
Maximum oxidation sate is shown by (a) Cu (b) Hg
(a) Os (b) Mn (c) Cr (d) Co (c) Ce (d) Pm
10. Which of the following statement is correct? 19. When acidified KMnO4 is added to hot oxalic acid solution,
(a) Transition elements exhibit higher enthalpies of the decolourization is slow in the beginning, but becomes
atomization as they have stronger interatomic very rapid after some time. This is because
interaction. (a) Mn2+ acts as autocatalyst.
(b) ΙE2 of 23V < 24Cr > 25Mn and 28Ni < 29Cu > 30Zn. (b) CO2 is formed as the product.
(c) Ni(II) compounds are more stable than Pt(II) whereas (c) Reaction is exothermic.
Pt(IV) compounds are more stable than nickel (IV).
(d) MnO4– catalyses the reaction.
(d) All of these.
P The d & f-Block Elements 23
W
 20. Which one of the ionic species will impart colour to an
aqueous solution?
(a) Ti4+ (b) Cu+
2+
(c) Zn (d) Cr3+
21. MnO4– is of intense pink colour, though Mn is in (+7)
oxidation state. It is due to
(a) Oxygen gives colour to it.
(b) Charge transfer when Mn gives its electron to oxygen.
(c) Charge transfer when oxygen gives its electron to Mn
making it Mn(+VI) hence coloured.
(d) None is correct.
22. The yellow colour of chromates changes to orange on
acidification due to formation of
(a) Cr3+ (b) Cr2O3
2-
(c) Cr2O7 (d) CrO4–
23. KMnO4 is the oxo-salt of
(a) MnO2 (b) Mn2O7
(c) MnO3 (d) Mn2O3
24. During estimation of oxalic acid vs KMnO4, self indicator is
(a) KMnO4 (b) oxalic acid
(c) K2SO4 (d) MnSO4
Org.solvent
25. Acidified chromic acid + H2O2  → X + Y; X
(Blue colour)
and Y are
(a) CrO5 and H2O
(b) Cr2O3 and H2O
(c) CrO2 and H2O
(d) CrO and H2O
26. Cl2 gas is obtained by various reactions but not by
∆
(a) KMnO 4 (s) + conc.HCl  →
∆ _____________
(b) KCl(s) + K 2 Cr2 O7 (s) + conc.H 2SO 4 
→
∆
(c) MnO 2 (s) + conc.HCl  →
(d) KCl (s) + F2 (l) 
→ 37. Interstitial compounds are formed by
27. When acidified solution of K2Cr2O7 is shaken with aqueous
solution of FeSO4, then
(a) Cr2O72– ion is reduced to Cr3+ ions.
(b) Cr2O72– ion is converted to CrO42– ions.
(c) Cr2O72– ion is reduced to Cr.
(d) Cr2O72– ion is converted to CrO3.
28. Which of the following compounds is used as the starting
material for the preparation of potassium dichromate?
(a) K2SO4.Cr2(SO4)3.24H2O (chrome alum)
(b) PbCrO4 (chrome yellow)
(c) FeCr2O4 (chromite)
(d) PbCrO4.PbO (chrome red)
29. (NH4)2Cr2O7(ammonium dichromate) is used in fire works.
The green coloured powder blown in air is
(a) Cr2O3 (b) CrO2
(c) Cr2O4 (d) CrO3
24
30. The final products obtained for the following reaction is:
KMnO4 (excess) + H2SO4 (concentrated and cold) 
→
(a) Mn2 O7 (b) MnO
(c) Mn3O4 (d) MnO3+
31. The compound that gets oxidised even on exposure to
atmosphere is
(a) Co2(SO4)3 (b) NiSO4
(c) KMnO4 (d) FeSO4
32. Bayer’s reagent used to detect olifinic double bond is
(a) Acidified KMnO4
(b) Aqueous KMnO4
(c) 1% alkaline KMnO4 solution
(d) KMnO4 in benzene
33. CrO3 dissolves in aqueous NaOH to give
(a) Cr2O72– (b) CrO42–
(c) Cr(OH)3 (d) Cr(OH)2
34. During estimation of oxalic acid Vs KMnO4, self indicator
is
(a) KMnO4 (b) oxalic acid
(c) K2SO4 (d) MnSO4
35. Correct statement(s) is/are
(a) An acidified solution of K2Cr2O7 liberates iodine from
KI.
(b) K2Cr2O7 is used as a standard solution for estimation
of Fe2+ ions.
(c) In acidic medium, M = N/6 for K2Cr2O7.
(d) (NH4)2Cr2O7 on heating decomposes to yield Cr2O3
through an endothermic reaction.
36. Iron becomes passive by ___________ due to formation of
(a) dil. HCl, Fe2O3 (b) 80% conc. HNO3, Fe3O4
(c) conc. H2SO4, Fe3O4 (d) conc. HCl, Fe3O4
(a) Co (b) Ni
(c) Fe (d) Ca
38. Pick out the incorrect statement:
(a) MnO2 dissolves in conc. HCl, but does not form Mn4+
ions.
(b) MnO 2 oxidizes hot concentrated H 2SO 4 liberating
oxygen.
(c) K 2MnO 4 is formed when MnO 2 in fused KOH is
oxidised by air, KNO3, PbO2 or NaBiO3.
(d) Decomposition of acidic KMnO4 is not catalysed by
sunlight.
39. The metals present in insulin and haemoglobin are
respectively
(a) Zn, Hg (b) Zn, Fe
(c) Co, Fe (d) Mg, Fe
JEE (XII) Module-3 PW
 40. Solid CuSO4·5H2O having covalent, ionic as well as 46. On addition of small amount of KMnO4 to concentrated
co-ordinate bonds. Copper atom/ion forms ___________ H2SO4, a green oily compound is obtained which is highly
co-ordinate bonds with water. explosive in nature. Identify the compound from the
(a) 1 (b) 2 following.
(c) 3 (d) 4 (a) Mn2O7 (b) MnO2
(c) MnSO4 (d) Mn2O3
41. Acidified KMnO4 can be decolourised by
(a) SO2 (b) H2O2 47. Which of the following reactions are disproportionation
reactions?
(c) FeSO4 (d) Fe2(SO4)3
(A) 2Cu+ → Cu2+ + Cu
42. Ion(s) having non-zero magnetic moment (spin only) is/are
(B) MnO42– + 4H+ → 2MnO4– + MnO2 + 2H2O
(a) Sc3+ (b) Ti3+
(C) 2KMnO4 → K2MnO4 + MnO2 + O2
(c) Cu2+ (d) Zn2+
(D) 2MnO4– + 3Mn2+ + 2H2O → 5MnO2 + 4H+
43. The correct order of E0M2+/M values with negative sign for (a) A, B  (b)  A, B, C  (c)  B, C, D  (d)  A, D
the four successive elements Cr, Mn, Fe and Co, is 48. KMnO4 acts as an oxidising agent in acidic medium.
(a) Mn > Cr > Fe > Co (b) Cr > Fe > Mn > Co The number of moles of KMnO4 that will be needed to react
(c) Fe > Mn > Cr > Co (d) Cr > Mn > Fe > Co with one mole of sulphide ions in acidic solution is
44. Which series of reactions correctly represents chemical 2 3
(a) (b)
relations related to iron and its compound? 5 5
(a) Fe  dill H SO
2
→ FeSO 4 
4 H SO , O
2
→ Fe 2 (SO 4 )3 
4 2

heat
→ Fe 1
(c) 4 (d)
(b) Fe →
O , heat2
FeO 
dillH SO
→ FeSO 4 
2

heat
4
→ Fe 5 5
(c) Fe 
Cl2 , heat
→ FeCl3 →
heat, air
FeCl2 
Zn
→ Fe 49. Which of the following are an amphoteric oxide?
CO, 600° C
(d) Fe → Fe3O 4 → FeO  Co, 700° C Mn2O7, CrO3, Cr2O3, CrO, V2O5, V2O4
O2 , heat
→ Fe
(a) V2O5, Cr2O3 (b) Mn2O7, CrO3
45. The colour of KMnO4 is due to
(c) CrO, V2O5 (d) V2O5, V2O4
(a) M → L charge transfer transition
(b) d - d transition 50. When acidified K2Cr2O7 solution is added to Sn2+ salts then
(c) L → M charge transfer transition Sn2+ changes to
(a) Sn (b) Sn3+
(d) σ – σ* transition
(c) Sn4+ (d) Sn+

Exercise-3 (JEE Advanced Level)

MULTIPLE CORRECT TYPE QUESTIONS 3.

The lanthanide contraction is responsible for the fact that
(a) Zr and Hf have same atomic size.
1.
The catalytic activity of transition elements is related to
their (b) Zr and Hf have same properties.
(a) Variable oxidation states (c) Zr and Hf have different atomic size.
(b) Surface area (d) Zr and Hf have different properties.
(c) Complex formation ability 4.
Which of the following statements are correct when a
(d) Magnetic moment mixture of NaCl and K2Cr2O7 is gently warmed with conc.
H2SO4?
2.
Correct statements about transition metals are that they
(a) Deep red vapours are liberated.
(a) Form complexes
(b) Deep red vapours dissolve in NaOH (aq.) forming a
(b) Show variable oxidation states yellow solution.
(c) Show magnetic properties (c) Greenish yellow gas is liberated.
(d) Do not form coloured compounds (d) Deep red vapours dissolve in water forming yellow
solution.
P The d & f-Block Elements
W 25
 5.
Mercury is a liquid at 0°C because of 12. Which of the following statements is/are correct?
(a) Very high ionisation energy (a) Tendency to form complexes: Sc3+ > Y3+ > La3+.
(b) Weak metallic bonds (b) Most of Ln3+ complexes are coloured.
(c) High heat of hydration (c) Ln(II) hydroxides are mainly basic in character.
(d) High heat of sublimation (d) Lanthanoids release H2 gas on reaction with strong
6.
The correct statement(s) about transition elements is/are acids.
(a) The most stable oxidation state is +3 and its stability 13. Which of the following statements is/are correct?
decreases across the period. (a) Transition elements exhibit higher enthalpies of
(b) Transition elements of 3d- series have almost same atomization as they have stronger interatomic
atomic sizes from Cr to Cu. interaction.
(c) The stability of +2 oxidation state increases across the (b) IE2 of 23V < 24 Cr >25 Mn and 28Ni < 29Cu > 30Zn.
period. (c) Ni(II) compounds are more stable than Pt(II) where as
(d) Some transition elements like Ni, Fe, Cr may show Pt(IV) compounds are more stable than nickel (IV).
zero oxidation state in some of their compounds. (d) The elements which give the greatest number of
7.
Amphoteric oxide(s) is/are oxidation states do not occur in or near the middle of
(a) Al2O3 the series.
(b) SnO 14. Which of the following is/are soluble in excess of NaOH?
(c) ZnO (a) Al(OH)3 (b) Cr(OH)3
(d) Fe2O3 (c) Fe(OH)3 (d) Zn(OH)2
8.
Which of the following statement(s) is/are correct? 15. Which of the following ions give(s) coloured aqueous

(a) S2O82– oxidises Ag+ in presence of pyridine and give solution?
red colour compound. (a) Ni2+ (b) Fe2+
(b) MnO42– disproportionates to yield MnO4– and MnO2 (c) Cu2+ (d) Cu+

in presence of H+ ions. 16. Which of the following chemical reaction(s) is/are involved
(c) In Cr2O72– each Cr is linked to four oxygen atoms. in developing of photographic plate?
(d) Ti2+ is purple while Ti4+ is colourless. (a) C6H4(OH)2 + 2AgBr → 2Ag + C6H4O2 + 2HBr
9.
Following reaction(s) is/are involved in the iodometric (b) AgBr + 2Na2S2O3 → Na3 [Ag(S2O3)2] + NaBr
estimation: (c) 2AgNO3 + Na2S2O3 → Ag2S2O3 + 2NaNO3
(a) Cr2O72– + H+ + Ι– 
→ 2Cr3+ + Ι2 ; (d) AgNO3 + KCN → AgCN + KNO3
17. Which of the following compound has oxidation state of
Ι2 + S2O32– 
→ S4O62– + Ι–
metal atom greater than 4?
(b) MnO4– + H+ + Ι– 
→ Mn2+ + Ι2 ; (a) K2MnO4 (b) K2Cr2O7
Ι2 + S2O32– 
→ S4O62– + Ι– (c) K3[Fe(CN)6] (d) K3[Co(CN)6]

(c) MnO4– + OH– + Ι– 

→ MnO2 + Ι2 ; COMPREHENSION BASED QUESTIONS
Ι2 + S2O3 2– 
→ S4O6 + 2– Ι– Comprehension–1 (Q. No. 18 to 20): Paramagnetism is a
property due to the presence of unpaired electrons. In case of
(d) Cr2O72– + OH– + Ι– 
→ 2Cr3+ + Ι2 ;
transition metals, as they contain unpaired electrons in the (n – 1)d
Ι2 + S2O32– 
→ S4O62– + Ι– orbitals, most of the transition metal ions and their compounds are
10. Acidified KMnO4 can be decolourised by paramagnetic. Paramagnetism increases with increase in number
(a) SO2 (b) H2O2 of unpaired electrons. Magnetic moment is calculated from ‘Spin
only formula’ viz.
(c) FeSO4 (d) Fe2(SO4)3
11. Pyrolusite in MnO2 is used to prepare KMnO4. Steps are µ = n (n + 2) B.M, n = number of unpaired electrons
MnO2 
→ MnO4
I 2– 
→ MnO4
II – Similarly, the colour of the compounds of transition
metals may be attributed to the presence of incomplete
Steps I and II are respectively (n–1)d sub-shell. When an electron from a lower energy of d-orbital
(a) Fuse with KOH / air, electrolytic oxidation. is excited to a higher energy d-orbital, the energy of excitation
(b) Fuse with KOH / KNO3 , electrolytic oxidation. corresponds to the frequency of light absorbed. This frequency
(c) Fuse with concentrated HNO3 / air, electrolytic generally lies in the visible region. The colour observed corresponds
reduction. to complementary colour of the light absorbed. The frequency of
(d) Dissolve in H2O, oxidation. the light absorbed is determined by the nature of the ligand.

26 JEE (XII) Module-3 PW

 18. Titanium shows magnetic moment of 1.73 BM in its
compound. What is the oxidation state of titanium in the
compound?
(a) +2 (b) +1
(c) +3 (d) +4
19. The colourless species is
(a) VCl3 (b) VOSO4
(c) Na3VO4 (d) [V(H2O)5SO4]2H2O
20. Identify the incorrect statement amongst the following.
(a) Mn2+ has the highest paramagnetism amongst the
bivalent cations of the Ist transition series.
(b) The coloured ions or compounds of transition elements
are due to d-d transition and charge transfer spectrum.
(c) In 3d series, the paramagnetic character first increase
to maximum & then starts decreasing.
(d) None of these.
Comprehension – 2 (Q. No. 21 to 23):
(i) A powdered substance (A) on treatment with fusion
mixture gives a green coloured compound (B).
(ii) The solution of (B) in boiling water on acidification
with dilute H2SO4 gives a pink coloured compound
(C) and brown coloured compound (D).
(iii) The aqueous solution of (A) on treatment with NaOH
and Br2–water gives the compound (D).
(iv) A solution of (D) in concentrated HNO3 on treatment
with lead peroxide at boiling temperature produced a
compound (E) which was of the same colour at that of (C).
(v) A solution of (A) on treatment with a solution of
barium chloride gave a white precipitate of compound
(F) which was insoluble in concentrated HNO3 and
concentrated HCl.
21. Which of the following is true for compound (C)?
(a) It oxidises ammonia to nitrogen dioxide in neutral
medium.
(b) It’s pink colour is due to d-d transition.
(c) It can be oxidised by ozone.
(d) It is obtained by alkaline fusion of pyrolusite followed
by electrolytic oxidation.
22. The oxidation state of central metal ions of (A), (B) and (C)
compounds are respectively
(a) +II , +VI and +VII
(b) +II , +VI and +VI
(c) +II , +VII and +VII
(d) +VI , +VII and +VII
23. Consider the following statements;
(I) Anions of both (B) and (C) are diamagnetic and have
tetrahedral geometry.
(II) Anions of both (B) and (C) are paramagnetic and have
tetrahedral geometry.
(III) Anion of (B) is paramagnetic and that of (C) is
diamagnetic but both have tetrahedral geometry.
P The d & f-Block Elements
W 27
(IV) Green coloured compound (B) in a neutral or acidic
medium disproportionates to give (C) and (D). Below
these select the correct one from the codes given.
(a) I and III only (b) II and III only
(c) II and IV only (d) III and IV only
Comprehension – 3 (Q. No. 24 to 26): Pyrolusite ore on oxidation
with KClO3/KNO3 in basic medium produces dark green coloured
compound (A), which on electrolysis produces a purple coloured
compound (B). The purple coloured compound can be crystallised
to deep purple rhombic prisms. It shows different reactions in
different mediums. Excess of compound (B) on heating with
concentrated H2SO4 gives an explosive oil (C), which on heating
decomposes to gives another compound (D) along with oxygen.
24. On passing CO2 in the solution of (A), a purple coloured
solution along with brown precipitate is observed.
Select the correct statement
(a) This is a disproportionation reaction where oxidation
number changes from +6 to +7 and +4.
(b) This is a comproportionation reaction where
oxidation number changes from +3 to +2.
(c) Both (a) and (b)
(d) None of these
25. The nature of compound (C) is
(a) Basic (b) Acidic
(c) Neutral (d) Amphoteric
26. Identify (D)
(a) Mn2O7 (b) MnO2
(c) MnSO4 (d) Mn2O3
Comprehension – 4 (Q. No. 27 to 28): An aqueous solution of
metal ion M1 reacts separately with reagents Q and R in excess
to give tetrahedral and square planar complexes, respectively. An
aqueous solution of another metal ion M2 always forms tetrahedral
complexes with these reagents. Aqueous solution of M2 on reaction
with reagent S gives white precipitate which dissolves in excess of S.
The reactions are summarized in the scheme given below:
Scheme:
Tetrahedral ←Q
excess
 M1 R
excess
→ Square planar
Tetrahedral ←Q
 M2 R
→ Tetrahedral
excess excess
S, stoichiometric amount
White precipitate S
→ precipitate dissolves
excess
27. M1, Q and R, respectively are
(a) Zn2+, KCN and HCl
(b) Ni2+, HCl and KCN
(c) Cd2+, KCN and HCl
(d) Co2+, HCl and KCN
28. Reagent S is
(a) K4[Fe(CN)6] (b) Na2HPO4
(c) K2CrO4 (d) KOH
NUMERICAL TYPE QUESTIONS In this sequence how many species (from M to T) show green
colour?
29. The oxidation state of Cr in K3CrO8 is _____.
43. How many of the following show variable oxidation states
30. The number of unpaired electrons in Cr+ is _____.
in their compounds? Sc, Cr, Cu, Zn, Fe, Hg, La
31. A metal ion from the first transition series has a magnetic ∆
moment (calculated) of 3.87 B.M. How many unpaired 44. FeC2O4  → products.
electrons are expected to be present in the ion? Number of diamagnetic products = x. Number of unpaired
32. In acidic medium, one mole of MnO4– accepts how many electrons in paramagnetic product = y. Report your answer as
moles of electrons in a redox process? (x + y)
33. The equivalent weight of K2Cr2O7 in acidic medium is
45. The number of water molecule(s) directly bonded to the
_____.
metal centre in CuSO4.5H2O is –
34. Magnetic moment value for a d-block ion is 4.90 BM.
Determine value of total spin for it (consider clock wise
spin). MATCH THE COLUMN TYPE QUESTIONS
35. Number of following reagents in which ppt A is soluble, is 46. Match the salts/mixtures listed in column-I with their
AgNO3 + NaCl → A respective names listed in column-II.
(i) Aq. NH3 (ii) Aq. KCN Column–I Column–II
(iii) Na2S2O3 (iv) Conc. HCl
(v) Aq. NaOH (vi) Aq. KI A. K2SO4.Cr2(SO4)3.24H2O p. Blue vitriol
36. Total number of 3d-series transition elements that contain
either 3d1 or 4s1 orbital in their ground state electronic B. FeSO4.(NH4)2SO4.6H2O q. Green vitriol
configuration is _____.
+
C. CuSO4.5H2O r. Chrome alum
37. KMnO 4 H
Reducing Agent
→ Mn a +
D. FeSO4.7H2O s. Mohr’s salt
OH − (weakly alkaline)
KMnO 4 
→ Mn b +
Reducing Agent
(a) A → r ; B → s ; C → p ; D → q
OH − c+
K 2 Cr2 O7 
→ Cr (b) A → s ; B → s ; C → r ; D → q
a + b + c is: (c) A → p ; B → s ; C → s ; D → r
38. An element of 1st transition series X3+ has highest magnetic (d) A → r ; B → s ; C → r ; D → p
moment in series and X2+ has non magnetic nature as low
spin complex. If Atomic number of X is ‘p’ and number of 47. Match the reactions listed in column-I with the characteristic(s)
unpaired e– in free state if X2+ and X3+ is ‘q’ and ‘r’, then of the products/type of reactions listed in column-II.
calculate p + q + 2r.
Column–I Column–II
39. In neutral or faintly alkaline solution, 8 moles of permanganate
anion quantitatively oxidize thiousoulphate anions to produce A. MnO42– + CO2 → p. A pungent smelling
X moles of sulphur containing product. The magnitude of X gas is liberated.
is _____.
40. The heavier members of lanthanoid series metal react with B. CrO42– + H+ → q. Shows
following non-metal. disproportionation
N2 reaction.
P

S C. ∆
r. Dimeric bridged
Ln Q FeSO4  →
 tetrahedral metal
R ion in the product.
Halogen
D. ∆ s. One of the products
The summation of atomicity of compound P, Q and R is? CuCl2.2H2O  →
has central atom in
41. The sum of the oxidation states of Mn in KMnO4, K2MnO4, its highest possible
and K3MnO4 is ______________ . oxidation state.
42. Chromite ore is processed through the following sequence:
+ (a) A → r, s ; B → p, s ; C → p, s ; D → r
FeCr2O4 
Na 2 O2
Fuse
→ {(M) + (N)} 
Boil
→ N (aq.) 
excess H
→ (O)
H2 O
(b) A → q, s ; B → r, s ; C → p, s ; D → r
H2O2
(c) A → q, s ; B → q, s ; C → p, s ; D → r

(T) ←
H 2 O2
→ (S) ←
NaOH
excess
→ (R) ←
NH3 little Warm H +
 (Q) ←
− O2
 (P) (d) A → q, s ; B → r, s ; C → r, s ; D → r

28 JEE (XII) Module-3 PW

 48. Match the pairs of complex/compounds listed in column-I 49. Match the reactions in Column-I with nature of the reactions/
with the characteristic(s) of the reaction products listed in type of the products in Column-II.
column-II.
Column–I Column–II
Column–I Column–II
A. O −2 → O 2 + O 22 − p. Redox reaction
A. Cu(I) and Zn(II) p. Pair of compound having
complexes similar colour and same but
non→zero magnetic moment B. CrO 24 − + H + → q. One of the products
has trigonal planar
B. KMnO4 and q. Pair of compounds having structure
diamagnetic character but
K2Cr2O7
coloured
C. MnO −4 + NO 2− + H + → r. Dimeric bridged
C. Cu2O and HgI2 r. Pair of compounds having
tetrahedral metal
metals in the highest stable
ion
oxidation state
D. [ C u ( N H 3 ) 4 ] 2 + s. Pair of compounds which D. NO3− + H 2SO 4 + Fe 2 + → s. Disproportionation
and [Ni(NH3)4]2+ show diamagnetism and are
colourless
(a) A – p, s; B – r; C – p, q; D – p
(a) A → r ; B → q, r ; C → q ; D → q (b) A – r, s; B – q; C – p, q; D – p
(b) A → s ; B → p, r ; C → q ; D → s (c) A – p, s; B – s; C – p, q; D – r
(c) A → s ; B → q, r ; C → q ; D → q (d) A – p, s; B – r; C – p, r; D – s
(d) A → s ; B → q, r ; C → s ; D → r

Exercise-4 (Past Year Questions)

JEE MAIN 6. A →

2
2B + 2H 2 O
4KOH,O

(green)
1.
Which of the following compounds is metallic and
ferromagnetic? (2016) 3B → 2C + 2MnO 2 + 2H 2 O

4HCl
(purple)
(a) TiO2 (b) CrO2
(c) VO2 (d) MnO2 2C 
H 2 O,KI
→ 2A + 2KOH + D
2.
In the following reactions, ZnO is respectively acting as a/ In the above sequence of reactions, A and D , respectively

an  (2017)
are : (2019)
(A) ZnO + Na2O → Na2ZnO2
(a) KI and KMnO4 (b) MnO2 and KIO3
(B) ZnO + CO2 → ZnCO3
(c) KIO3 and MnO2 (d) KI and K2MnO4
(a) Base and Acid (b) Base and Base
7.
The lanthanide ion that would show colour is (2019)
(c) Acid and Acid (d) Acid and Base 3+ 3+ 3+ 3+
(a) Sm (b) La (c) Lu (d) Gd
3.
The highest value of the calculated spin-only magnetic
moment (in BM) among all the transition metal complexes 8.
Thermal decomposition of a Mn compound (X) at 513 K results
is: (2019) in compound Y, MnO2 and a gaseous product. MnO2 reacts
with NaCI and concentrated H2SO4 to give a pungent gas Z.
(a) 5.92 (b) 6.93
X, Y and Z, respectively are (2019)
(c) 3.87 (d) 4.90
(a) K2MnO4, KMnO4 and SO2
4.
The transition element that has lowest enthalpy of atomisation (b) K2MnO4, KMnO4 and Cl2
is (2019)
(c) K3MnO4, K2MnO4 and Cl2
(a) Fe (b) Cu (c) V (d) Zn
(d) KMnO4, K2MnO4 and Cl2
5.
The element that usually does NOT show variable oxidation
9.
The alloy used in the construction of aircrafts is (2019)
states is: (2019)
(a) Mg – Sn (b) Mg – Mn
(a) Cu (b) Ti
(c) Mg – Al (d) Mg – Zn
(c) Sc (d) V
P The d & f-Block Elements
W 29
 10. The pair that has similar atomic radii is (2019)
(a) Sc and Ni (b) Ti and HF
(c) Mo and W (d) Mn and Re
11. The highest possible oxidation states of uranium and
plutonium, respectively, are (2019)
(a) 6 and 4 (b) 7 and 6
(c) 4 and 6 (d) 6 and 7
12. The atomic radius of Ag is closest to (2020)
(a) Au (b) Hg
(c) Ni (d) Cu
13. The electronic configurations of bivalent europium and
trivalent cerium are
(atomic number : Xe = 54, Ce = 58, Eu = 63) (2020)
(a) [Xe] 4f 4 and [Xe] 4f 9
(b) [Xe] 4f 7 and [Xe] 4f 1
(c) [Xe] 4f 7 6s2 and [Xe] 4f 2 6s2
(d) [Xe] 4f 2 and [Xe] 4f 7
14. The sum of the total number of bonds between chromium
and oxygen atoms in chromate and dichromate ions is _____.
 (2020)
15. The incorrect statement is (2020)
(a) Manganate and permanganate ions are paramagnetic.
(b) Manganate and permanganate ions are tetrahedral.
(c) Manganate ion is green in colour and permanganate
ion is purple in colour.
(d) In manganate and permanganate ions, the π-bonding
takes place by overlap of p-orbitals of oxygen and
d-orbitals of manganese.
16. The incorrect statement(s) among (A) - (C) is (are)
 (2020)
(A) W(VI) is more stable than Cr (VI).
(B) In the presence of HCl, permanganate titrations provide
satisfactory results.
(C) Some lanthanoid oxides can be used as phosphors.
(a) (A) and (B) only (b) (A) only
(c) (B) and (C) only (d) (B) only
17. Mischmetal is an alloy consisting mainly of (2020)
(a) Lanthanoid and actinoid metals
(b) Actinoid and transition metals
(c) Lanthanoid metals
(d) Actinoid metals
18. The lanthanoid that does NOT show +4 oxidation state is
 (2020)
(a) Tb (b) Dy
(c) Ce (d) Eu
19. The secondary valency and the number of hydrogen bonded
water molecule(s) in CuSO4.5H2O , respectively are(2021)
(a) 5 and 1 (b) 4 and 1
(c) 6 and 5 (d) 6 and 4
30
20. Given below are two statements:
Statement-I: Potassium permanganate on heating at 573K
forms potassium manganate.
Statement-II: Both potassium permanganate and potassium
manganate are tetrahedral and paramagnetic in nature.
In the light of the above statements, choose the most
appropriate answer from the options given below
 (2021)
(a) Statement-I is true but statement-II is false.
(b) Statement-I is false but statement-II is true.
(c) Both statement-I and statement-II are false.
(d) Both statement-I and statement-II are true.
21. Among Co3+, Ti2+, V2+ and Cr2+ ions, one if used as a
reagent cannot liberate H2 from dilute mineral acid solution,
its spin-only magnetic moment in gaseous state is _____
B.M. (2022)
22. The spin-only magnetic moment value of the compound
with strongest oxidizing ability among MnF4, MnF3 and
MnF2 is ______ B.M. (2022)
23. The total number of Mn = O bonds in Mn2O7 is______.
 (2022)
(a) 4 (b) 5
(c) 6 (d) 3
24. Which of the following pair is not isoelectronic species?
(At. No. Sm, 62; Er, 68: Yb, 70: Lu, 71: Eu, 63: Tb, 65; Tm,
69) (2022)
2+ 3+
(a) Sm and Eu
(b) Yb2+ and Lu3+
(c) Eu2+ and Tb4+
(d) Tb2+ and Tm4+
25. The difference in oxidation state of chromium in chromate
and dichromate salts is________. (2022)
26. Cerium (IV) has a noble gas configuration. Which of the
following is correct statement about it? (2022)
(a) It will not prefer to undergo redox reactions.
(b) It will prefer to gain electron and acts as an oxidizing
agent.
(c) It will prefer to give away an electron and behave as
reducing agent.
(d) It acts as both, oxidizing and reducing agent.
27. The spin-only magnetic moment value of the most basic
oxide of vanadium among V2O3, V2O4 and V2O5 is
__________B.M (2022)
28. The most common oxidation state of lanthanoid elements is
+3. Which of the following is likely to deviate easily from
+3 oxidation state? (2022)
(a) Ce (At. No. 58) (b) La (At. No. 57)
(c) Lu (At. No. 71) (d) Gd (At. No. 64)
JEE (XII) Module-3 PW
JEE ADVANCED (a)  Ag ( S2 O3 )2 
3−
, Ag 2S2 O3 , Ag 2 S
29. The colour of light absorbed by an aqueous solution of 5−
CuSO4 is: (2012) (b)  Ag ( S2 O3 )3  , Ag 2SO3 , Ag 2 S
(a) Organge-red (b) Blue-green 3−
(c)  Ag ( SO3 )2  , Ag 2S2 O3 , Ag
(c) Yellow (d) Violet
3−
30. Which of the following halides react(s) with AgNO3(aq) to (d)  Ag ( SO3 )3  , Ag 2SO 4 , Ag
give a precipitate that dissolves in Na2S2O3(aq)?
35. Among the species given below, the total number of
(2012) diamagnetic species is____.
(a) HCl (b) HF (c) HBr (d) HI H atom, NO2 monomer, O2– (superoxide), dimeric sulphur
31. Consider the following list of reagents: in vapour phase,
Acidified K2Cr2O7, alkaline KMnO4, CuSO4, H2O2, Cl2, O3, Mn3O4, (NH4)2[FeCl4], (NH4)2[NiCl4], K2MnO4, K2CrO4
FeCl3, HNO3 and Na2S2O3. The total number of reagents (2018)
that can oxidise aqueous iodide to iodine is _____.(2014) 36. Consider the following reactions (unbalanced)(2019)
32. The correct statement(s) about Cr2+
and Mn3+ is
(are): Zn + hot conc. H2SO4 → G + R + X
(2015) Zn + conc. NaOH → T + Q
[Atomic numbers of Cr = 24 and Mn = 25] G + H2S + NH4OH → Z (a precipitate) +X +Y
(a) Cr2+ is a reducing agent. Choose the correct options(s)
(b) Mn3+ is an oxidizing agent. (a) The oxidation state of Zn in T is + 1
(c) Both Cr2+ and Mn3+ exhibit d4 electronic (b) Bond order of Q is 1 in its ground state
configuration. (c) Z is dirty white in colour
(d) When Cr2+ is used as a reducing agent, the chromium (d) R is a V- shaped molecule
ion attains d5 electronic coniguraton. 37. In the chemical reaction between stoichiometric quantities of
33. Fe3+ is reduced to Fe2+by using (2015) KMnO4 and KI in weakly basic solution, what is the number
(a) H2O2 in presence of NaOH. of moles of I2 released for 4 moles of KMnO4 consumed?
(b) Na2O2 in water.  (2020)
(c) H2O2 in presence of H2SO4. 38. An acidified solution of potassium chromate was layered
(d) Na2O2 in presence of H2SO4. with an equal volume of amyl alcohol. When it was shaken
after the addition of 1 mL of 3% H2O2, a blue alcohol layer
34. In the following reaction sequence in aqueous solution, the
was obtained. The blue color is due to the formation of
species X,Y and Z respectively are (2016)
a chromium (VI) compound ‘X’ . What is the number of
S2 O3  → X  → Y  → Z
+ +
2- Ag Ag with time
oxygen atoms bonded to chromium through only single
clear white black
solution precipitate precipitate bonds in a molecule of X? (2020)

P The d & f-Block Elements

W 31
 ANSWER KEY

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

EXERCISE-1 (TOPICWISE)
1. (c) 2. (c) 3. (d) 4. (a) 5. (a) 6. (a) 7. (a) 8. (c) 9. (b) 10. (c)
11. (c) 12. (d) 13. (d) 14. (c) 15. (d) 16. (a) 17. (c) 18. (a) 19. (a) 20. (d)
21. (c) 22. (b) 23. (c) 24. (b) 25. (a) 26. (a) 27. (d) 28. (a) 29. (a) 30. (c)
31. (b) 32. (d) 33. (d) 34. (a) 35. (b) 36. (b) 37. (a) 38. (b) 39. (a) 40. (a)
41. (a) 42. (a) 43. (a) 44. (b) 45. (d) 46. (a) 47. (d) 48. (c) 49. (a) 50. (c)
51. (d) 52. (a)

EXERCISE-2 (LEARNING PLUS)

1. (c) 2. (b) 3. (a) 4. (b) 5. (c) 6. (b) 7. (c) 8. (c) 9. (a) 10. (d)
11. (b) 12. (a) 13. (d) 14. (b) 15. (c) 16. (a) 17. (b) 18. (b) 19. (a) 20. (d)
21. (c) 22. (c) 23. (b) 24. (a) 25. (a) 26. (b) 27. (a) 28. (c) 29. (a) 30. (a)
31. (d) 32. (c) 33. (b) 34. (a) 35. (a,b,c) 36. (b) 37. (a,b,c) 38. (d) 39. (b) 40. (d)
41. (a,b,c) 42. (b,c) 43. (a) 44. (d) 45. (c) 46. (a) 47. (a) 48. (a) 49. (a) 50. (c)

EXERCISE-3 (JEE ADVANCED LEVEL)

1. (a,b,c) 2. (a,b,c) 3. (a,b) 4. (a,b,d) 5. (a,b) 6. (a,b,c,d) 7. (a,b,c) 8. (a,b,c,d) 9. (a,b) 10. (a,b,c)
11. (a,b) 12.
(a,b,c,d) 13. (a,b,c) 14. (a,d) 15. (a,b,c) 16. (a,b) 17. (a,b) 18. (c) 19. (c) 20. (d)
21. (d) 22. (a) 23. (d) 24. (a) 25.
(b) 26.
(b) 27. (b) 28. (d) 29. [5] 30. [5]
31. [3] 32. [5] 33. [49] 34. [2] 35. 4 [(i), (ii), (iii), (iv)] 36. [3] 37. [14] 38. [36]
39. [6] 40. [11] 41. [18] 42. [3] 43. [4] 44. [6] 45. [4] 46. (a) 47. (b) 48. (c)
49. (a)

EXERCISE-4 (PAST YEAR QUESTIONS)

JEE Main
1. (b) 2. (d) 3. (a) 4. (b) 5. (c) 6. (b) 7. (a) 8. (d) 9. (c) 10. (c)
11. (d) 12. (a) 13. (b) 14. [12.00] 15. (a) 16. (d) 17. (c) 18. (d) 19. (b) 20. (a)
21. [5] 22. [5] 23. (c) 24. [d] 25. [0] 26. (b) 27. [3] 28. (a)

JEE Advanced
29. (a) 30. (a,c,d) 31. [7] 32. (a,b,c) 33. (c,d) 34. (a) 35. [1] 36. (b,c,d) 37. [6] 38. [4]

32 JEE (XII) Module-3 PW