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 Chapter - 3
d-BLOCK AND f-BLOCK ELEMENTS
Introduction
The elements of d & f-blocks of periodic table are commonly known as transition and inner transition
elements respectively. The presence of partly filled d or f-orbitals in their elements set the study of these
elements and their compounds, apart from that of the main group elements.

The d-block elements may thus be defined as elements having partly filled d sub-shell in their
elementary form or chemically significant oxidation states.

Zinc, Cadmium and Mercury have a completely filled (n – 1) d sub-shell in their elementary form as well
as in the combined state. According to this definition, these elements cannot be included in the d-block
elements. They do not show much resemblance with other d -block elements except for their ability to
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form complexes with ligands like NH3, amines and halide ions, etc. However, they are generally studied
with the d -block elements in order to maintain a rational classification of elements.

The d -block elements are also called as Transition elements. These are so called because their
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properties are intermediate between those of the s and p -block elements. They make up three
complete rows of 10 elements and an incomplete fourth row in the periodic table as given below
(3) (4) (5) (6) (7) (8) (9) (10) (11) (12)
Sc Zn
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1 2 Ti V Cr Mn Fe Co Ni Cu
3d 4s 3d104s2
Y Cd
Zr Nb Mo Tc Ru Rh Pd Ag
4d1 5s2 4d10 5s 2
La Hg
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1 2 Hf Ta W Re Os Ir Pt Au
5d 6s 5d10 6s 2
Ac
Ku Ha
6d 1 7s2
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The three complete rows of 10 elements mark the filling of 3 d, 4 d and 5 d orbitals respectively, whereas in
the fourth incomplete row the 6 d orbitals start filling.

We are familiar with the regular transition in physical and chemical properties of the s- and p -block
elements in the same period. No such transition in properties is exhibited by the d -block elements in the
same period. This is because the electronic configurations of d -block elements differ only in the number
of electrons in the d -orbitals of their penultimate shell. The number of electrons in their valence shell (ns)
remains the same (it is usually n s 2).

3.1 General Characteristics of d-Block Elements

1. Electronic Configuration of the Atoms and Exchange Energy Effect.– Electronic
configurations illustrate their tendency to have there d-orbitals exactly half-filled or
completely filled. For this purpose one s electron (and sometimes both s electrons) is very
often transferred to d orbitals. For example, Cr (3 d5 4s1), Cu (3d 10 4 s1). Mo (4 d 5 5 s1), Pd

[ 117 ]
d- & f -Block Elements

(4 d 10 5 s0), Ag (4 d 10 5 s1), Pt (5 d 10 6 s0), and Au (5d 10 6 s1). This is because these

configurations have greater stability due to exchange energy effect.

2. Atomic Radii– Some overall trend in the variation of atomic radii across the period are :

(i) The atomic radii of the d -block elements of a given series as given in Table below.
Generally atomic radii decrease with increase in the atomic number. This is because with
an increase in atomic number the effective nuclear charge increases which pulls the
electrons cloud inward resulting in decrease in atomic radius.

(ii) Decrease in radii is, however, very small as we pass from Chromium to Copper. This is
explained in terms of screening effect. Successive addition of d -electrons screens the
outer 4 s electrons from the inward nuclear pull. As a result of this screening, the effective
nuclear charge increase only slightly and the size of the electron cloud does not, change
much as we move from Chromium to Copper.

First Transition Series

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Element Sc Ti V Cr Mn Fe Co Ni Cu Zn
Atomic 21 22 23 24 25 26 27 28 29 30
Number
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Outer
electronic 3d14s2 3d24s2 3d34s2 3d54s1 3d54s2 3d64s2 3d74s2 3d84s2 3d104s1 3d104s2
configuration
Atomic radius 162 147 134 127 126 126 125 124 128 138
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(pm)
Density 3.01 4.51 6.10 7.19 7.43 7.86 8.90 8.90 8.96 7.14
(g cm–3)
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Melting point 1812 1941 2173 2148 1518 1809 1768 1726 1356 693
(K)

Second Transition Series

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Element Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
Atomic 39 40 41 42 43 44 45 46 47 48
Number
Outer
electronic 4d15s2 4d25s2 4d45s1 4d55s1 4d55s2 4d75s1 4d85s1 4d105s0 4d105s1 4d105s2
configuration
Atomic
180 160 146 139 136 140 134 137 144 154
radius (pm)
Density
4.47 6.49 8.40 10.21 11.50 12.20 12.40 12.00 10.51 8.65
(g cm–3)
Melting
1782 2125 2888 2880 2470 2770 2240 1825 233.8 593.9
point (K)

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d- & f -Block Elements

Third Transition Series

Element La Hf Ta W Re Os Ir Pt Au Hg
Atomic 57 72 73 74 75 76 77 78 79 80
Number
Outer
electronic 5d16s2 5d26s2 5d36s2 5d46s2 5d56s2 5d66s2 5d76s2 5d106s0 5d106s1 5d106s2
configuration
Atomic radius
187 158 146 139 137 135 136 138 144 157
(pm)
Density
6.17 13.10 16.60 19.30 21.00 22.60 22.50 21.40 19.30 13.60
(g cm–3)
Melting point
1193 2495 3270 3680 3450 2970 2727 2042 1340 234.6
(K)

(iii) The atomic radius reaches a minimum for the group 8 elements and increases again
towards the end of the series. Because force of repulsion among the added electrons
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which exceeds the attractive force due to the increased nuclear charge and results in the
expansion of the electrons cloud.

(iv)Atomic radius increases on descending the group although the increase is not as significant
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as in the case of s- and p-block elements.

Sc 162 (pm) Ti 147 (pm) V 134 (pm) Cr 127 (pm) Mn 126 (pm)
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Y 180 Zr 160 Nb 146 Mo 139 Te 126

La 187 Hf 158 Ta 146 W 139 Re 137

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Close similarity in atomic radii of second and third transition series has been explained in terms
of Lanthanide contraction. The atomic radii decreases from Zr to Hf .

3. Ionic Radii.– The ionic radii of the d -block elements follow the same trend of atomic radii.
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For ions carrying identical charges, the ionic radius decreases slowly with increase atomic
number in the same transition series as shown below :

Sc2+ Ti2+ V 2+ Cr2+ Mn2+ Fe2+ Co2+ Ni2+ Cu2+ Zn2+

95 91 88 74 84 80 76 74 72 72
Sc3+ Ti3+ V3+ Cr3+ Mn3+ Fe3+ Co3+
81 76 74 69 66 64 63

4. Atomic Volumes and Densities.

(i) Atomic volume of the d -block elements are much lower than those of the neighbouring
s and p -block elements. Atomic volume in the same transition series first decrease and
reach a minimum with 8 group elements. It then starts increasing as v r3, as radius varies
atomic volume varies.

This behaviour can be explained as in the case of atomic radii which follow the same trend.

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d- & f -Block Elements

(ii) Densities of d -block elements are very high as compared with those of groups 1 and 2
elements. In transition series the density increases on moving from left to right and attains a
maximum value on reaching group 8. It starts decreasing as we move further to group 11
and 12.

Density increases substantially on moving down a group. The atomic size of the elements
in the same group but belonging to second and third transition series remains practically
the same but their atomic mass gets almost doubled. As a result of this the densities of
elements in the third transition series and almost double of the corresponding elements of
second transition series, as seen from their values given below :1

Transition Element At. At. Density Element At. At. Density

series Radius Mass (g cm–3) Radius Mass (g cm–3)
(pm) (pm)
Second Nb 146 93 8.4 Mo 139 96 10.4
Third Ta 146 181 16.6 W 139 184 19.3
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Second Te 136 99 11.5 Ag 143 108 10.5

Third Re 137 186 20.5 Au 144 107 19.3
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5. Metallic Character.– All the d -block elements are metals. Unlike s-block metals, these are
hard, malleable and ductile. The melting and boiling points are high. Their hardness along with
their high melting and boiling points suggest the presence of strong binding forces in their
crystals. The metals have close packed structures (fcc, hcp or bcc type).
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Metals of groups 7 and 12 are comparatively softer and more ductile. This is expalined in the
light of their crystals structure. These crystallize giving fcc type crystal lattice whereas others
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crystallize with hcp or bcc structure. In the fcc type crystal lattice of these elements, there
being larger number of planes where deformation can take place, these elements are softer
and more ductile.
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Hardness of these metals suggests the presence of covalent bonds. The unpaired d -electrons
may overlap and form covalent bonds there by giving rise to d p-d p covalent bonding. The
number of such covalent bonds will be a measure of overall bond strength and hardness of
the metals. In a transition series the number of unpaired d -electrons increases as we move
from 3rd group [n – 1) d1, ns2] to 6th group [(n – 1) d5, ns1] after which pairing starts. As
a result, the metallic lattice becomes stronger and stronger up to 6th group (Cr, Mo and W)
and thereafter strength decreases progressively.

These are all good conductors of electricity and possess metallic lustre. Both these properties
are on account of delocalization of their outer s electrons over the entire crystal lattice.

6. Melting and Boiling Points.– Melting and boiling points of transition metals are very high,
which suggests stronger interatomic attraction. Melting and boiling points increase on moving

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d- & f -Block Elements

from left to right across the transition series and reach a maximum near group 5th or 6th group
whereafter they start decreasing.

From the following table it can be seen that the structures of the transition metals are similar
to those of the typical metals. Chromium and Iron, for example, are isostructural with Sodium,
Cobalt with Magnesium and, Copper with Aluminium. It can be said that the structure of the
metals is not greatly influenced by the introduction of d -electrons. However, melting and
boiling points of the transition metals seem to be influenced. With the exception of Zinc, all
the first transition series metals melt at high temperature (at least 400 K higher than the
melting point of Aluminium). The transition metals are also harder and denser than the typical
metals. These distinguishing features of the transition metals are attributed to the stronger
forces that bind their atoms together. It can be concluded that the presence of one or more
unpaired d -electrons contributes to higher interatomic forces, and therefore to high melting
points. Even the most modern theories suggest that strong bonds formed by d -electrons are
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responsible for high melting and boiling points of the transition elements. However, exception
say that the statement is always true. Manganese, for instance, with five unpaired d -electrons
has a lower melting point than that of vanadium or cobalt which have only three. The complex
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structure of Manganese seems to be responsible for this.

Structure and Melting Points of the First Transition Seires

Element Sc Ti V Cr Mn Fe Co Ni Cu Zn
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Structure ccp hcp bcc bcc Complicated bcc hcp ccp ccp hcp
Melting
1812 1941 2173 2148 1518 1809 1768 1726 1356 693
points
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(K)

7. Ionization Energies.– Ionization energies increase as we move from left to right across a
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transition series. The increase, however, is not as pronounced as in the case of s- and p-block
elements in the same period. For example, in the case of first ionization energies of first
transition series is very close to one another. Fe, Co, Ni and Cu have almost similar values.

This is explained in terms of the screening effect of the d -electrons. Increase in the small
ionization energy charge expected on account of the increase in nuclear charge is almost offset
by the extra screening of the nucleus by the inner d-electrons.

The value of their ionization energies lie between those of s-block elements on their left and
p-block elements on their right. In other words, these are less electropositive than the s-block
elements. They form ionic compounds but not so readily as the s-block elements. Unlike
s-block elements d-block elements form covalent compounds as well. Transition metal gives
two series of salts, the lower oxidation one is an ionic compounds and the higher oxidation
one is a covalent compounds.

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d- & f -Block Elements

Ionization Energies of the Elements of the First Transition Series

Element Sc Ti V Cr Mn Fe Co Ni Cu Zn

Ionization Energies (kJ/mol) 632 659 650 652 716 762 758 736 744 906

Ionization energies of the first transition series are given in Table. From this table we find that
second ionization energy increases almost regularly from Sc to Zn. Values for Cr and Cu are,
however, sufficiently higher than those of their neighbours on the left as well as right. This
is due to the stable configuration of Cr+ (3d 5– exactly half filled) and Cu+ (3 d 10 – completely
filled). Removal of one electron means they change from a more stable to less stable
configuration and is hence difficult.

8. Standard Electrode Potentials.– Standard reduction potentials (in volts) of some transition
metals in acid solution at 298 K are given below :
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E0 (volts) E0 (volts)
La3+ + 3 e–  La –2.52 Cd2+ + 2e–  Cd – 0.40
Sc3+ + 3e– Ni2+ + 2e–
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 Sc –2.08  Ni – 0.25
Mn2+ + 2e–  Mn –1.18 Cu2+ + 2e–  Cu + 0.34
Zn2+ + 2e–  Zn –0.76 Fe3+ + e–  Fe2+ + 0.77
Cr3+ + 2e–  Cr –0.74 Hg2 +2+ 2e–  2 Hg + 0.79
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Fe+2 + 2e–  Fe –0.44 2Hg2+ + 2e–  Hg22+ + 0.92

It is seen that standard reduction-potential of a transition element is generally negative, i.e.,

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lower than that of Hydrogen (taken as zero) Only exceptions given above are Copper and
Mercury. All those elements with negative reduction potential liberate Hydrogen from dilute
acids.
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M + 2 H+ – M 2+ + H2 (g)

The rates of evolution of Hydrogen are, however, very low in some cases. Some of these
metals (e.g., Cr) are unreactive due to the formation of the protective film of oxide on their
surface.

Due to high Ionization energy and high heat of atomization they have low oxidations potential.
Inspite of this they have +ve oxidation potential because their hydration energies are high
enough to compensate for the high ionization energy and atomization energy.

9. Reactivity.– Ionization energies of the d-block elements are fairly high on account of the
small size of their atoms. Further these have high heats of sublimation on account of the
presence of covalent bonding. In other words, they require a large amount of energy for
change from the solid to vapour state.

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d- & f -Block Elements

On accounts of (i) their high ionization energies, and (ii) their high heats of sublimation, the
d-block elements have low tendency to react i.e., these are less reactive or unreactive. This
tendency of being unreactive is more pronounced in Platinum and Gold in the third transition
series.

10. Oxidation States.– Oxidation state of an s-block element is its group number. In the case
of p-block elements, variable oxidation state is exhibited due to the participation of valence
electrons. For example, oxidation state of Sn and Pb are + 2 and + 4 while those of As, Sb
and Bi are +3 and +5.

In contrast to the s and p-block elements, the d-block elements exhibit a variety of oxidation
states in due to the participation of both the ns electrons and (n - 1) d-electrons.

Outer electronic configuration of Sc, is 3d 1 4 s2. It exhibits the oxidation state + 2 in the
compounds where as it uses only its two 4 s electrons for bonding. It also exhibits oxidation
state + 3 when it uses its two s-electrons as well as one d-electron for bonding.
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Similarly Ti (3 d 2, 4 s2) exhibits oxidation state +2 when it uses only its two s-electrons, +3
when one d electron is used in addition to two s-electrons and +4 when it uses 2 s-electrons
and 2 d-electrons for bonding.
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Hence we can explain why V (electronic configuration 3 d 3 4 s 2) exhibits oxidation states +2,
+3, +4 and +S. Similarly we can account for the various oxidation states exhibited by Cr (3 d 5
4 s1) and Mn (3 d 5 4 s 2).
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In each case the minimum oxidation state is given by the number of outer s-electrons and
maximum oxidation state is given by the sum of outer s- and d electrons. In other words, both
n s and (n – 1) d electrons are available for bonding. This is possible because there is very
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small difference between the energies of ns and (n – 1) d orbitals. Further, the wide variety
of oxidation states exhibited by d - block elements is due to the availability of both ns and (n
– 1) d-electrons in them for bond formation.
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In the case of Fe (3 d 6 4 s 2), Co (3 d 7 4 s 2), Ni (3 d 8, 4 s2), Cu (3 d 10 4 s1) and Zn (3 d 10

4 s2), the number of 3 d electrons is more than 5. The minimum oxidation state in each case
equals the number of 4 s electrons but the maximum oxidation state is not at all related with
the total of ns and (n – 1) d electrons. Their maximum oxidation state is largely confined to
+2 and +3 as in the case of iron. The +4, +5 and +6 oxidation states are only rare. The +8
oxidation state is important only with Ru and Os.

From Sc to Mn, the highest oxidation state corresponds to the removal of all the 3 d and 4 s
electrons (periodic group number) These oxidation state does not correspond to the removal
of all the 3 d and 4 s electrons. The existence of any particular oxidation state for a properties
of the metal-ligand system. For instance, Vanadium reacts with halogens to form a
pentafluoride VF5, a tetrachloride, VCl4 and a tribromide, VBr3. Vanadium in +5 oxidation state
is too strong as oxidizing agent to exist in sole combination with Br– and I– ions. It converts
them to free halogens.

[ 123 ]
d- & f -Block Elements

Small, highly electronegative anions (such as F– and O2–) are oxidized with great difficulty and
hence can bring out the high oxidation states of element. As we have said earlier, fluorine can
form VF5 but VCl5 and VBr5 are not known. The highest oxidation states achieved by V, Cr
and Mn with O2– ions is compound vanadate VO42–, chromate CrO42– and permanganate
MnO4– are very stable. Fluoride and oxide ions can also form compounds in which Iron and
Cobalt achieve oxidation states greater than +3 or Nickel and Copper acquire oxidation states
greater than +2.

In aqueous solution high oxidation states are favoured in alkaline medium. It follows that to
stabilize the lower oxidation states in aqueous solution, non-oxidizing acids should be used,
Transition metal hydroxides are usually oxidized by atmospheric Oxygen. A familiar example
is that of change of pale green Fe (OH) 2 to brown on standing in air due to oxidation
to Fe (III).

The  acid ligands favour low oxidation states. These ligands are capable of bonding by both
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-donor and -acceptor bonds. The electrons from the ligand are donated along the bond
resulting in the build-up of negative charge on the metal. The charge is then delocalized back
on to the ligand through back-bonding.
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Examples of important -acid ligands are CO, NO, N2 PR3, RNC, bipy and phen.

The uncharged CO ligand forms binary metal carbonyls like Ni(CO)4, Fe(CO)5 and Cr(CO)6
in which the metal is in the zero oxidation state. The bonding involves as M – C bond formed
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by donation of the lone pair of electrons of Carbon and an M – C bond formed to donation
of electron density from metal d orbitals into the vacant antibonding molecular ( * p) on CO.

Similarly, in the complexes containing molecular Nitrogen, the M – N2 bond involves s donation
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and p acceptance by the Nitrogen. The complexs are called dinitrogen complexes. The first
dinitrogen. complex was reported in 1965. Typical examples are provided by
Co(N2), H (PPh3)3 and Fe(N2) H2 (Ph2EtP)3 which contain linear (M – N – N) groupings.
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Dinitrogen complexes with bridging rather than terminal dinitrogen groups are also know. The
[(NH3)5 RuN = NRu(NH3)5]4+ is an example of a complex with bridging dinitrogen group. The
dinitrogen complexes are less stable and less extensive than those of CO.

The elements show more pronounced ionic character in lower oxidation states. As the oxidation
state increases the charge density on the metal increases. This increases the tendency to
polarize the anion charge cloud and hence covalency increases. This is well illustrated in the
following examples of metal halides :

TiCl2 TiCl3 TiCl4

VCl2 VCl3 VCl4 VOCl3
Solids, insoluble in Liquids, s oluble in
Soluble in Benzene ; weak acids Soluble in Benzene ; strong acids

[ 124 ]
d- & f -Block Elements

The increase in oxidation state is also accompanied by increase in acidity. The more covalent
halides are strong Lewis acids and hydrolyse violently in water. The more ionic halides are
weak Lewis acids and they form neutral [M(H2O)6]2+ and acidic [M(H2O)6]2+ aquo-ions.
Similar trends are noticed among metal oxides.

TiO Ti2O3 TiO2

VO V2 O 3 V2 O 5
CrO Cr 2 O 3 CrO3
Basic Amphoteric Acidic

Oxidation State Increases

Charge Density on the Metal Increases

Tendency to Polarization of the Anion Charge Increases

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Covalence Increases

Acidity Increases
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Zinc on the extreme right shows only one oxidation state (+2). This is because after losing
two outer 4 s electrons, the Zn2+ ion has a stable 18 electrons configuration and has no
tendency to loss any more electrons.
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The term variable oxidation state is sometimes refered to as variable valency, but the former
is, however, preferred. For example, Iron exhibits variably valence of 2 and 3 as it furnishes
Fe2+ and Fe3+ ions Similarly, Tin is said to exhibit a variable valency of 2 and 4 in Sn2+ and
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Sn4+ salts.

11. Tendency to form Complexes.– A significant feature of the cations of d -block elements
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is their tendency to form complex ions with certain molecules (e.g., CO, NO and NH3) or
ions (e.g., F–, Cl–, CN–, etc.). The molecules or ions attaching themselves with the cations
are termed ligands. These are species with lone pairs of electrons which they can readily
donate. Two factors which accounts for this tendency are :

(i) Transition metal cations because of their small size, and high effective nuclear charge, have
a high charge density. They can accept lone pairs of electrons from other molecules or ions.

(ii) These have vacant inner d-orbitals with appropriate energy to accept lone pairs of
electrons and form coordinate bonds.

Due to the presence of coordinate bonds between the metal cations and the ligands, the
complexes are termed as coordination compounds. The complex ions have in general linear,
square planar, tetrahedral or octahedral structure depending upon the nature of hybridization
of the metal ion orbitals.

[ 125 ]
d- & f -Block Elements

Stability of Coordination Compounds. The donor atoms in ligands possess vacant orbitals
in addition to the lone pair of electrons. The ligand donates a pair of electrons to the metal
cation and thus forms a bond. Then the vacant orbitals of the ligands accept electrons from
the filled metallic ion orbitals forming a bond which adds to the strength of the bond. Stability
of coordination compound is due to the ability of the ligand molecule or ion to accept electrons
pair from the hybrid orbitals of the metal cation.

General trends towards increased stability of complex compounds are :

(a) Stability of complex decreases with the increase in atomic number of the element.

(b) In a particular oxidation state, the stability of a complex increases with decrease in the
size of the atoms.

This is due to greater attraction of metal ion for ligand electrons. For example, Co3+ ion with
NH3 forms a very stable complex [Co(NH3)6]3+ whereas Co2+ does not form stable complex
with ammonia.

12. Reducing Properties.– Transition metals with sufficiently negative standard reduction
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potentials should be good reducing agents. However, they are not good reducing agents when
compared with elements of groups I, II and III Why ?

The reducing property of metals depends on its tendency to form ions. The transition metals
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have less tendency to form ion on account of (i) they have high ionization energies, (ii) their
high heats of sublimation.

13. Colour.– Compounds of s- and p-block elements are almost white always whereas
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compounds of transition metals are usually coloured. Colour is associated with the ability of
a compound to promote an electron from one energy level to another higher energy level by
absorbing light of a particular wavelength.
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The d-orbitals differ from each other in energy, though the energy difference is fairly small.
In the transition elements with partly filled d-orbitals, it is possible to promote electrons from
one d-orbitals to an other. The light absorbed in the visible region ( = 400 – 750 nm) for
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example, hydrated Cu2+ ions and anhydrous cobalt (II) compounds, however absorb therefore,
blue. Hydrated cobalt (II) compounds, however, absorb radiations of wavelengths
corresponding to blue green colour ( = 490 – 500 nm) and, therefore, appear red (d – d
transtion).

Some compounds of transition metals are white, e.g., ZnSO4 and TiO2 are white. This is
because is Zn2+ ion, d-orbitals are fully filled (d10 conf.) and so electronic transitions is
not possible.

In the case of s- and p-block elements, the d-orbitals are either missing or are completely
full. Therefore, for d-d transition of electrons, energy, needed to promote an s or p electron
to a higher energy level is much greater and may correspond to wavelengths of the ultraviolet
region. These absorb no radiations from the visible region. Compound of s- and p-block
elements, therefore, do not appear coloured in the visible region. The colour may also be due
to charge transfer spectra, as in AgBr, AgI, Cr2O72– etc.

Colours exhibited by hydrated ions of the elements of the first transition series.
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d- & f -Block Elements

14. Magnetic Properties.– Many compound of transition elements show magnetic properties.
Those which are attracted by magnetic field are termed paramagnetic while others which are
repelled by magnetic field are called diamagnetic.

Substances which are paramagnetic are those in which there are unpaired electron spins in
the atom. On the other hand, diamagnetic substances are those in which all the electron spins
are paired. In the case of Iron, Cobalt and Nickel the unpaired electron spins are much more
pronounced. As a result these elements are much more paramagnetic which means that they
can be magnetized. Those conditions, are known as ferro magnetism.

A sample of a compound is taken in a small glass tube and weighed. It is weighed again in
the presence of a strong magnetic field show a decrease in mass. Diamagnetic substances
show an increase in mass. Diamagnetic substances have no unpaired electrons. Their
magnetic moment is, therefore, zero. The external magnetic field, however, induces in them
a small magnetic moment which is in opposition to the external magnetic field. The
diamagnetic substances, therefore, repel lines of force and register a slight decrease in mass.
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On the other hand, paramagnetic materials attract lines of force and the sample is pulled down
into the gap between the pole pieces of the magnet. As a result of this attraction the sample
registers an increase in mass.
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The magnetic moment of the material can be calculated from the above change in mass in
the magnetic balance. It gives important information in respect of the number of unpaired
electrons present in the atom and above the orbitals that are occupied. In some cases even
the structure of the molecule or complex is indicated by its magnetic moment.
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Substances are paramagnetic only when there are one or more unpaired electrons in them.

In a number of cases, the orbital contribution is quenched out by the electrostatic fields on
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the surrounding atoms and magnetic moment may be only due to unpaired spins. Taking L = 0
spin only magnetic moment is given by the following formula :
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3 = 4S (S1)

It is measured in Bohr magnetons (BM). In terms of n (number of unpaired spins) magnetic

moment is given by the formula :

3 = n ( n  2)

where n = 1, = 1.73 BM ; n = 2, = 2.83 B.M ;

n = 3, = 3.87 BM ; and so no.

Magnetic moments of some ions of the first transition series.

15. Catalystic Properties : This properties exhibited by Transition metals due to:

(a) Variable oxidation state.

(b) Partially filled d-orbitals.

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d- & f -Block Elements

Transition metals form intermediate products with various reactants in some cases. These
intermediate products with various reactants in some cases. These intermediate products
decompose to give the final product, regenerating the catalyst (Intermediate Compound
Formation Theory).

In other cases, the finely divided metals or their compounds provide a large surface area for
adsorption and the adsorbed reactants react faster due to closer contact (Adsorption Theory).

Many transition metals find use as catalytic agents in the laboratory and in industry. The finely
divided Nickel is used as a catalyst in the manufacture of vegetable ghee as well as in
hydrogenation reactions in the laboratory, finely divided Iron and Molybdenum is used for
catalysing the interaction of Nitrogen. Vanadium pentoxide are employed as contact catalyst
in the manufacture of sulphuric acid.

Some catalysts used in Organic chemistry are : Fenton's reagent (FeSO4 + H2O2) for oxidizing
alcohols to aldehydes ; Pd for hydrogenation of Phenol to cyclohexanone ; Adam's catalyst
(Pt/PtO) used for reduction ; Cu/V used for getting Adipic acid (needed for the manufacture
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of Nylon 6, 6) by oxidation of cyclohexanol/cyclohexanone mixture ; Cu used in the

manufacture of (CH3)2SiCl2 for silicones ; Ziegler Natta catalyst (TiCl4) for the manufacture
of polythene.
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16. Non-stoichiometry–existence of compunds with indefined structure and proportions (termed

as non-stoichiometric compounds) is another feature common with transition metals. For
example, formula of Iron (II) oxide, FeO implies that Iron and Oxygen atoms are present
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exactly in the ratio of 1 : 1. However, the actual analysis has shows that formula varies
between Fe-0.94O and Fe0.84O. To emphasise this fact it should be written with a bar over
the formula as FeO. Another example of such compounds is Vanadium selenide in which the
composition varies from NSe-0.98 to VSe2.
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Non-stoichiometry is due to variable valency of these elements and due to the defects in solid
structures.
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Interstitial compounds of transition metals with small non-metal atoms like H, B, C, N, etc.,
are other examples of non stoichiometric compounds. These small elements fit into the
interstitial sites of the transition metal lattices. Interstitial compounds resemble the parent
transition metals in chemical properties but differ in physical properties. e.g., hardness and
electrical properties.

17. Abundance.–Among the first row of transition elements, those with even atomic numbers are
found to be more abundant in comparison to others with odd atomic numbers. Manganese
appears to be exceptional.

Abundance in parts per million in earth's crust

21 Sc 22Ti 2 3 V 24 Cr 25 Mn 26 Fe 27 Co 28 Ni 29 Cu 30 Zn

5 4400 150 200 1000 50,000 23 80 70 132

Second and third row elements are less abundant than the first row elements.

[ 128 ]
d- & f -Block Elements

Illustration 1: Describe giving reason which one of the following pairs has the property indicated?
(i) Fe or Cu has higher melting point.
(ii) Cu2+ or Ni2+ has lower magnetic moment.

Solution: (i) Fe has higher melting point than Cu. This is because Fe has four unpaired electrons
in 3d-subshell while Cu has only one electron in the 4s-subshell. Hence metallic bonds
in Fe are much stronger than those in Cu.

(ii) 27Co = [Ar]3d74s2,Co2+ = [Ar]3d7 (3 unpaired electron)

28 Ni = [Ar]3d84r2, Ni2+ = [Ar]3d8 (2 unpaired electrons)

Hence, Ni has lower magnetic moment than Co.

Illustration 2: Give reasons for the following features of transition metal chemistry:

(i) The lowest oxide of a transition metal (say, chromium, atomic number 24) is basic
whereas the highest oxide is usually acidic.
JE

(ii) Transition metals sometimes exhibit very low oxidation state such as +1 and 0.

Solution: (i) Lowest oxide of Cr is CrO which is basic. The highest oxide is CrO3 which is acidic
(In between, Cr 2O3 is amphoteric). Higher the oxidation state of the metal, more
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easily it can accept electrons and hence greater is the acidic character.

(ii) +1 oxidation state is shown by Cu because after loss of one electron, it acquires
stable configuration of 3d10. Zero oxidation state is shown in forming metal carbonyls,
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e.g., Ni(CO)4 because p-electrons donated by the ligands are accepted into the empty
d-orbitals.

Illustration 3: The 4d and 5d series of transition metals have more frequent metal-metal bonding in their
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compounds than do the 3d metals. Explain.

Solution: In the same group of d-block elements, the 4d and 5d transition elements have larger size
than that of 3d element. Thus, the valence electrons are less tightly hold and hence can
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form metal bond more frequently. (That is why melting points of 4d and 5d series as well
as enthalpies of atomisation are higher than those of 3d series).

Illustratioi 4: A mixed oxide of iron and chromium, FeO.Cr 2O3, is fused with sodium carbonate in
presence of air to form a yellow colorued compound (A). On acidification, the compound
(A) form an orange coloured compound (B) which is a strong oxidizing agent. Identify
(i) the compounds (A) and (b) (ii) Write balanced chemical equations for each step.

Solution: 4FeO.Cr2O3  O2 
 2Fe2 O3  4Cr2 O3
4Na 2CO3  2Cr2O3  3O2 
 4Na 2CrO4  4CO3 ]  2
______________________________________________

4FeO.Cr2O3  8Na 2CO3  7O 2 

 8Na 2 CrO4  2Fe 2O3  8CO 2
(A )
Sodium chromium

2Na 2CrO 4  H 2SO 4 

 Na 2 Cr2O 7  Na 2SO 4  H 2O
(B)
Sodium dichromate

[ 129 ]
d- & f -Block Elements

Illustration 5: (a) A blackish brown coloured solid ‘A’ when fused with alkali metal hydroxides in
presence of air, produces a dark green coloured compond ‘B”, which on electrolytic
oxidation in alkaline medium gives a dark purple coloured compound C. Identify A,
B and C and write the reactions involved.

(b) What happens when an acidic solution of the green compound (B) is allowed to stand
for same time? Give the equation invovled. What is this type of reaction called?
Fuse
MnO 2  4KOH  O 2   2K 2 MnO 4  2H 2O
Solution: (a) Pyrolusite Potassiuim manganate
(A) Blackish brown (B)-Green coloured

Alkaline
2K 2 MnO4  H 2O  2KMnO 4  2KOH
medium
(B) Potassium manganate
(C)-Purpole coloured

2  
or MnO 
 MnO  e 4 4

(b) When acidic solution of green compound (B), i.e., potassium manganate is allowed
to stand for ome time, it disproportionates to give permanganate as follows:
3MnO24  4H  
 2MnO4  MnO2  2H2O
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This reaction is called disproportionation reaction.

SAMPLE PROBLEMS 3.1 (MCQ)

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Problem 1: The number of d-electron in Fe2+ is not equal to that of

(a) p-electron in neon (b) s-electron in Mg
(c) d-electrons in Fe (d) p-electrons in Cl– ion

Solution: (d) Fe2+ : [Ar]3d6. (6 d-electrons); p-electrons in Cl– = 11.

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Problem 2: Zr and Hf have almost equal atomic and ionic radii because
(a) of actinide contraction (b) of diagonal relationship
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(c) of lanthanoide contraction (d) both belong to same transition series

Solution (c) Due to lanthanoid contraction

Problem 3: Which ion is not colooured?

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(a) Ni(DMG)2 (b) [Co(SCN)4]2–

(c) [Fe(H2O)5 SCN]2+ (d) [Al(OH)4 ]–

Solution: (d) Al3 has no unpaired d-electrons.

Problem 4: The most stable oxidation state of +3 is shown by

(a) Mn (b) Co
(c) Ni (d) Fe

Solution: (d) Fe3+ : [Ar]3d5. Half fileld d-subshell is very much stable.

Probem 5: Of the following elements whcih is not expected to display on oxidation state of +6 in any of
its compounds?
(a) Ti (b) Cr
(c) Mn (d) W

Solution: (a) ti = [Ar]3d24s2. The highest oxidation state will be +4.

[ 130 ]
d- & f -Block Elements

Problem 6: Which of the following compounds is expected to be coloured?

(a) Ag2 SO 4 (b) Cu2Cl2
(c) MgF2 (d) CuF2

Solution: (d) Cu2+ has one unpaired electron (3d9).

Problem 7: The electronic configuration of the element which is just above the element with atomic
number 42 in the same periodic group is
(a) (Ar)3d4 4s2 (b) (Ar)3 3d34s1
(c) (Ar)3d5 4s1 (d) (Ar)3s10 4s1

Solution: (c) Atomic number of the elemnet = 42 – 18 = 24 (chromium)

Problem 8: Paramagnetism of Cr(Z = 24), Mn2+ (Z = 25) and Fe3+ (Z = 26) are x, y and z respectively.
They are in the order
(a) x = y = z (b) x > y > z
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(c) x = y > z (d) x > y – z

Solution: (d) Number of unpaired electrons in Cr, Mn2+ and Fe3+ are 6, 5 and 5 respectively.

Problem 9: Maximum oxidation states of Cr, Mn and Os are respectively

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(a) +3, –5 and +6 (b) –6, –5, + 7

(c) +6, +7, +8 (d) None of these

Solution: (c) Conceptual

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Problem 10: Which is not correct about FeO?

(a) It is non-stoichiometric compond
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(c) Some of Fe2+ ions get repalced by as many two third Fe3+ ions
(c) It is metal excess solid
(d) It is metal deficient solid
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Solution: (c) Non-stoichiometric compound FeO is metal deficient solid.

3.2 f-Block Elements

General Characteristics of Lanthanides (Lanthanons) – 4f Block Series – First Inner
Transition Series

In these elements differentiating electrons goes to 4f-orbitals. This series consists of Lanthanum (Z
= 57) and the next fourteen elements (Z = 58 to 71) from Ce58 to Lu71.

Strictly speaking according to this definition only thirteen elements from Ce58 (4f1 5d1 6s2) to Yb70
(4f13 5d1 6s2) should be members of this series, because Lu71 (4f14 5d1 6s2) has completely filled f-
subshell. It should be noted that fifteen elements starting from La57 to Lu71 are generally considered
as 4f block elements because they resemble one another closely. The name lanthanide has been
derived from lanthanum which is the prototype of Lanthanides.

[ 131 ]
d- & f -Block Elements

Originally these elements were called rare earth metals because for many years pure compounds of
these elements were difficult to Obtain. Now a days, the term rare earth is avoided because many of
these elements are far from rare.

1. These are hard metals with high melting points.

2. Oxidation state. The lanthanides, too display variable oxidation states. The characteristic and
the most stable oxidation state of lanthanides is +3(La3+) because in this case we have ns and
(n – 1)d-subshell fully empty. Even certain metals show +2 and +4 oxidation states so as to attain
f0, f7 and f14 configurations.

Samarium and Thulium also show +2 state although M2+ ions so formed have f6 and f13
configurations respectively. These metals donot show +1 oxidation state, although in that
case their M+ ions would have acquired stable f7 and f14 configurations respectively.

3. Ionic radii-Lanthanide contraction. There is a regular decrease in the size of atoms/ions with
increase in atomic number as we move across from La to Lu. Thus among Lanthanides, Lanthanum
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has the largest and Lutetium has the smallest radii. This gradual decrease in size is known as
lanthanide contraction.

Cause of Lanthanide Contraction

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The configuration of lanthanides show that the additional electron enters the 4f-subshell. The
shielding of one 4f-electron by another is very little (imperfect), being even smaller than that
encountered in case of d-electrons (d-transition series). The imperfect shielding of f-electrons is
due to the shape of f-orbitals which is very much diffused. Thus as the atomic number increases,
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the nuclear charge increases by unity at each step, while no comparable increase in the mutual
shielding effect of 4f-electrons occurs. This causes a contraction in the size of 4f-subshell.
Consequently the atomic and ionic size goes on decreasing systematically from La to Lu.
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It must be noted that the decrease in size, although continuous, is not regular. The decrease is
much more in the case of first six elements than in the subsequent elements. Hence the properties
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of Lanthanide compounds show some divergence from regularity.

Consequences of Lanthanide Contraction

(i) Separation of Lanthanides. Separation of lanthanides is possible only due to lanthanide

contraction. All the lanthanides have quite similar properties and due to this reason they are
difficult to separate. However, because of lanthanide contraction their properties (such as
ability to form complexes) vary slightly. This slight variation in properties is utilized in the
separation of lanthanides by ion exchange methods.

(ii) Variation in basic strength of hydroxides. The basic strength of oxides and hydroxides
decreases from La(OH)3 to Lu(OH)3. Due to lanthanide contraction size of M 3+ ions
decreases and there is increase in the covalent character in M–OH bond.

(iii) Similarity of second and third transition series. The atomic radii of second row of
transition elements are almost similar to those of the third row of transition elements. For
example, among the elements of group 3, there is normal increase in size from Sc to Y to La.

[ 132 ]
d- & f -Block Elements

But after lanthanides the atomic radii from second to third transition series do not increase
as shown below for group 4 and group 5 i.e., for Zr – Hf and Nb – Ta pairs which have same
atomic radii. After group 5 the effect of lanthanide contraction is not so predominant.

4. Colour. The lanthanide metals are silvery white metals and the trivalent lanthanide ions are
coloured both in the solid state and in the aqueous solution.

5. Magnetic properties. La 3+ (4f0) and Lu3+ (4f14) having no unpaired electron do not show
paramagnetism while all other tripositive ions of lanthanides are paramagnetic.

6. They have low ionisation energy and are highly electropositive. Their ionisation energy values
are quite comparable with those of alkaline earth metals particularly Calcium.

7. These metals do not have much tendency to form complexes.

8. The lanthanides are highly reactive. This is in agreement with the low values of their ionisation
energies and electronegativity.
JE

9. The solubility of compounds of lanthanides follow the same order as group 2 elements. Their
fluorides, oxides, hydroxides, carbonates are insoluble in water. However halides (except fluorides),
nitrates, acetates are soluble in water.
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General Characteristics of Actinides – 5f Block Series – Second Inner Transition

Series
1. These are silvery white metals with high melting and boiling points.
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2. Besides the most common oxidation state of +3, Actinides show +4, +5 and +6 oxidation states
in certain elements.

3. All the actinides are radioactive in nature.

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4. All the actinides are highly electropositive and as such are strong reducing agent.

5. Actinides have a strong tendency towards complex formation and form oxocations like UO22+,
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PuO22+, UO+ etc.

6. Most of the cations of Actinides are coloured.

7. Actinides show actinide contraction i.e., decrease in ionic radii along the series.

Some Important Properties of Iron and its Compounds

Properties
(1) Grey white lustrous metal

(2) Fe reacts with steam liberating hydrogen gas

3Fe + 4H2O  Fe3O4 + 4H2

(3) Iron reacts with hydrochloric acid in dilute conditions

Fe + 2HCl  FeCl2 + H2
[ 133 ]
d- & f -Block Elements

(4) With dilute sulphuric acid also it liberates hydrogen.

Fe + H2SO4  FeSO4 + H2
(dil)

(5) With conc H2SO4 in cold conditions it forms SO2 and ferrous sulphate.

Fe + 2H2SO4  FeSO4 + SO2 + 2H2O

(Conc.)

(6) With hot concentrated sulphuric acid it forms sulphur dioxids and ferric sulphate.

2Fe + 6H2SO4  Fe2(SO4)3 + 3SO2 + 6H2O

(7) It reacts with nitric acid in different ways in under different conditions

4Fe + 10HNO3  4Fe(NO3)2 + NH4NO3 + 3H2O

(Cold & dil)
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Fe + 6HNO3  Fe (NO3)3 + 3NO2 + 3H2O

(Mod. conc.)

(8) It displaces less reactive metals from their metallic salt solution.
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Fe + CuSO4  FeSO4 + Cu

Fe + 2AgNO3  Fe(NO3)2 + 2Ag

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(9) It reacts with carbon monoxide to form iron pentacarbonyl.

Fe + 5CO  Fe(CO)5
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(10)Rusting of iron

Fe  Fe2+ + 2e–
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2H2O + O2 + 4e–  4OH–

Fe+2 + 2OH–  Fe(OH)2

O2
2Fe(OH)2 Fe2O3.xH2O.(rust)
H2 O

Ferrous sulphate (FeSO4.7H2O)

Preparation

(1) Ferrous sulphide reacts with sulphuric acid to form ferrous sulphate

FeS + H2SO4  FeSO4 + H2S

(2) Ferrous sulphate is formed by the oxidation of Ferrous sulphide.

2FeS2 + 2H2O + 7O2  2FeSO4 + 2H2SO4

[ 134 ]
d- & f -Block Elements

Properties
(1) Light green crystalline solid.

(2) Heptahydrated ferrous sulphate on heating to 140ºC gives ferrous sulphate monohydrated
which on further heating forms anhydrous Ferrous sulphate at 300ºC.

FeSO4.7H2O 140ºC FeSO4.H2O 300ºC FeSO4 (white)

Heating above 300ºC gives Fe2O3 and SO2 & SO3

High
2FeSO4 Temp.
Fe2 O3 + SO2 + SO3

(3) It reacts with water and Oxygen to forms Ferric hydroxy sulphate.

4FeSO4 + 2H2O + O2  4Fe(OH) SO4

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(4) It forms a complex with nitric oxide.

FeSO4 + NO  FeSO4.NO

(5) It reacts with ammonium sulphate to forms Ferrous ammonium sulphate.

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FeSO4 + (NH4)2SO4 + 6H2O  FeSO4. (NH4)2SO4.6H2O

(6) With potassium cyanide it forms ferrous cyanide

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FeSO4 + 2KCN  Fe(CN)2 + K2SO4

Ferrous cyanide further form potassium hexacyanoferrate

Fe(CN)2 + 4KCN  K4[Fe (CN)6]

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(7) It decolourises acidified KMnO4 and turns dichromate solution green.

2KMnO4 + 10FeSO4 + 8H2SO4  K2SO4 + 2MnSO4 + 5Fe2(SO4)3 + 8H2O

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K2Cr2O7 + 6FeSO4 + 7H2SO4  K2SO4 + Cr2(SO4)3 + 3Fe2(SO4)3 + 7H2O

(8) It decomposes nitric acid to nitric oxide.

2HNO3 + 3H2SO4 + 6 FeSO4  2NO + 3Fe2(SO4)3 + 4H2O

Ferric oxide (Fe2O3)

Preparation
(1) Decomposition of FeSO4 gives Fe2O3.

2FeSO4  Fe2O3 + SO2 + SO3

(2) Ferric hydroxide on decomposition gives Fe2O3

2Fe(OH)3  Fe2O3 + 3H2O

[ 135 ]
d- & f -Block Elements

(3) When Ferrous sulphide is reacted with excess of Oxygen it forms Ferric oxide.

4FeS2 + 11O2  2Fe2O3 + 8SO2

Properties
(1) It is red powder

(2) Ferric oxide decomposes at 1300ºC to mixed oxide Fe3O4.

6Fe2O3 1300ºC 4Fe3O4 + O2

(3) Ferric oxide form Ferric chloride with hydrochloric acid.

Fe2O3 + 6HCl  2FeCl3 + 3H2O

(4) With Sodium carbonate it forms complex

Fe2O3 + Na2CO3  2NaFeO2 + CO2

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(5) It dissolves in alkali

Fe2O3 + 2NaOH  2NaFeO2 + H2O

(6) Other reaction of Fe2O3

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Fe2O3 + 3H2  2Fe + 3H2O

Fe2O3 + 3C  2Fe + 3CO

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Fe2O3 + 3CO  2Fe + 3CO2

Ferric Chloride (FeCl3)

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Preparation
(1) Ferric chloride is obtained by the action of HCl on Fe2O3.

Fe2O3 + 6HCl  2FeCl3 + 3H2O

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(2) Ferric hydroxide on reaction with HCl gives Ferric chloride.

Fe(OH)3 + 3HCl  FeCl3 + 3H2O

(3) When Fe is dissolved in aqua regia it forms Ferric chloride

3HCl + HNO3  NOCl + 2Cl + 2H2O

Fe + 2Cl  FeCl2
2FeCl2 + Cl2  2FeCl3

(4) Anhydrous Ferric chloride is prepared by passing dry Chlorine gas through Fe.

2Fe + 3Cl2  2FeCl3 (Anhydrous)

(5) When hydrated Ferric chloride is reacted with Thionyl chloride then anhydrous Ferric chloride is
obtained

FeCl3.6H2O + 6SOCl2  FeCl3 (Anhydrous) + 12 HCl + 6SO2

[ 136 ]
d- & f -Block Elements

Properties
(1) Hydrated FeCl3 is a yellow deliquescent crystalline solid.

(2) Ferric chloride on heating decomposes to form Ferrous chloride and Chlorine.

2FeCl3  2FeCl2 + Cl2

(3) It reacts with Ammonia to form a complex.

FeCl3 + 6NH3  FeCl3.6NH3

(4) Ferric chloride is hydrolysed to ferric hydroxide

FeCl3 + 3H2O  Fe(OH)3 + 3HCl

(5) It reacts with NaOH to form Fe(OH)3

FeCl3 + 3NaOH  Fe(OH)3 + 3NaCl

(6) With NH4OH it forms ferric hydroxide

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FeCl3 + 3NaOH  Fe(OH)3 + 3NH4Cl

(7) With ammonium sulphocyanide it forms Ferric sulphocyanide.

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FeCl3 + 3NH4CNS  Fe(CNS)3 + 3NH4Cl

(8) Ferric chloride reacts with potassium ferrocyanide to form ferriferrocyanide.

4FeCl3 + 3K4 [Fe(CN)6]  Fe4 [Fe(CN)6] + 12 KCl

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Prussian blue

(9) It is reduced to FeCl2 by SO2

FeCl3 + SO2 + 2H2O  2FeCl2 + H2SO4 + 2HCl

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(10) It is reduced by H2S to FeCl2

2FeCl3 + H2S  2FeCl2 + 2HCl + S

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FeCl3 + H  FeCl2 + HCl

(11)Stannous chloride reduces FeCl3 to FeCl2

2FeCl3 + SnCl2  FeCl2 + SnCl4

(12) Sodium thiosulphate reduces Ferric chloride to Ferrous chloride.

2FeCl3 + 2Na2S2O3  2FeCl2 + Na2S4O6 + 2NaCl

Potassium Ferrocyanide K4[Fe(CN)6]

Preparation
(1) Potassium Ferrocyanide is obtained by heating Ferrous sulphate with Potassium cyanide.

FeSO4 + 2KCN  Fe(CN)2 + K2SO4

Fe (CN)2 + 4KCN  K4 [Fe(CN)6]

[ 137 ]
d- & f -Block Elements

(2) It can also be prepared by first converting KOH to KCN and then making the KCN formed to
react with FeSO4.
KOH + HCN  KCN + H2O
6KCN + FeSO4  K4 [Fe(CN)6] + K2SO4

Properties
(1) Lemon yellow soft crystalline solid.
(2) Potassium ferrocyanide decomposes on heating giving Potassium cyanide and Iron carbide.

K4 [Fe(CN)6]  4KCN + FeC2 + N2

(3) Potassium ferrocyanide reacts with dilute sulphuric acid.
2K4 [Fe(CN)6] + 3H2SO4 (dil)  3K2SO4 + K2 Fe[Fe(CN)6] + 6HCN
(4) It is decomposed by conc. H2SO4 to Ammonium sulphate and Carbon monoxide
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K4 [Fe(CN)6] + 6H2SO4 (Conc.) + 6H2O  2K2SO4 + 3(NH4)2SO4 + FeSO4 + 6CO

(5) It is oxidised to Potassium ferricyanide by chlorine
K4 [Fe(CN)6] + Cl2  2K3 [Fe(CN)6] + 2KCl
ES

(6) It forms a green coloured complex Ferric Ferro cyanide when reacted with ferric chloride.
3K4 [Fe(CN)6] + 4FeCl3  Fe4 [Fe(CN)6]3 + 12 KCl
(7) It forms a brown ppt with Copper sulphate due to the formation of Copper ferrocyanide
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K4 [Fe(CN)6] + 2CuSO4  Cu2 [Fe(CN)6] + 2K2SO4

(8) Zinc Salts form complex with Potassium ferrocyanide.
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K4 [Fe(CN)6] + 2ZnCl2  Zn2 [Fe(CN)6] + 4KCl

Potassium Ferricyanide K3[Fe(CN)6]

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Preparation
Potassium ferricyanide is obtained by oxidising potassium ferrocyanide solution.
2K4 [Fe(CN)6] + Cl2  2K3 (Fe(CN)6] + 2KCl

Properties
(1) Dark red crystalline solid.
(2) The different reactions of potassium ferricyanide are given below :
2K3[Fe(CN)6] + 8HCl  2H4[Fe(CN)6] + 6KCl + Cl2

(3) 2K3[Fe(CN)6] + 2KOH  2K4[Fe(CN)6] + H2O + [O]

Cr2O3 + 4KOH + 3[O]  2K2CrO4 + 2H2O

PbO + [O]  PbO2
MnO + [O]  MnO2

[ 138 ]
d- & f -Block Elements

(4) With ferrous salts it forms Ferroferricyanide complex

3FeSO4 + 2K3 [Fe(CN)6]  Fe3[Fe(CN)6]2 + 3K2SO4

Some Important Properties of Copper and its Compounds

Properties
(1) Red coloured lustrous metal

(2) Copper reacts with air to form basic copper carbonate

2Cu + H2O + CO2 + O2  CuCO3. Cu(OH)2 (verdigris)

(3) It reacts with Sulphur dioxide forming brochanite

8Cu + 6H2O + 2SO2 + 5O2  2[CuSO4. 3Cu(OH)2]

(4) Copper reacts with oxygen in different ways

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Below
2Cu + O2 1100ºC 2CuO

Above
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4Cu + O2 1100ºC 2Cu2O

(5) With conc HCl it form cupric Chloride

2Cu + 4HCl + O2  2CuCl2 + 2H2O

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(Conc.)

(6) 2Cu + 2H2SO4 + O2  2CuSO4 + 2H2O

(Dil.)
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With Conc. H2SO4 Cu reacts to form copper sulphate and Sulphur dioxide

Cu + 2H2SO4  2CuSO4 + SO2 + 2H2O

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(Conc.)

(7) Copper reacts with dilute nitric acid liberating Nitric oxide but with conc. HNO3 it reacts liberating
Nitrogen dioxide.

3Cu + 8HNO3  3Cu(NO3)2 + 2NO + 2H2O

(Dil.)
Cu + 4HNO3  Cu (NO3)2 + 2NO2 + 2H2O
(Conc.)

(8) Copper displaces silver from silver salts.

2Ag+ + Cu  Cu+2 + Ag

However Copper is displaced from its aqueous salt solution by Fe

Cu+2 + Fe  Fe+2 + Cu
[ 139 ]
d- & f -Block Elements

(9) It reacts with Chlorine to form Cupric chloride.

Cu + Cl2  CuCl2

(10) It reacts with Sulphur to form Copper sulphide

Cu + S  CuS.

Copper sulphate (CuSO4.5H2O)

Preparation
(1) Copper sulphate is prepared by the action of dilute sulphuric acid on Cupric oxide and Copper
carbonate.

(a) CuO + H2SO4  CuSO4 + H2O

(b) CuCO3 + H2SO4  CuSO4 + H2O + CO2

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(2) It can also be prepared by oxidation of CuS by Oxygen.

CuS + 2O2  CuSO4

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(3) When Copper reacts with sulphuric acid in the presence of air we get Copper sulphate

Cu + 2H2SO4 + O2 (air)  2CuSO4 + 2H2O

Properties
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(1) Deep blue crystalline solid

(2) Effect of Heat on CuSO4.5H2O

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Cu SO4. 5H2O 100ºC CuSO4. H2O 230ºC CuSO4 (anhydrous)

(Blue) (Pale-blue) (White)
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(3) Copper sulphate decomposes at high temperature to form SO2 and CuO.

2CuSO4  2CuO + 2SO2 + O2

(4) Being an acidic salt it reacts with bases. It form a Deep blue coloured complex with ammonia.

CuSO4 + 2NH4OH  Cu(OH)2 + (NH4)2 SO4

Cu (OH)2 + (NH4)2SO4 + 2NH4OH [Cu(NH3)4] SO4 + 4H2O

(5) Copper sulphate reacts with KI to form Cuprous iodide liberating Iodine.

2CuSO4 + 4KI  Cu2I2 + I2 + 2K2SO4

(6) It reacts with Sodium hydroxide to from a precipitate of Cu(OH)2

CuSO4 + 2NaOH  Cu(OH)2 + Na2SO4

[ 140 ]
d- & f -Block Elements

(7) It reacts with KCN to form Potassium tetracyanocuprate (II).

CuSO4 + 4KCN  K2 [Cu(CN)4] + K2SO4

(8) When reacted with excess of KCN it form dicyanogen and potassium tetracyano cuprate (I).

2CuSO4 + 10 KCN  2K3 [Cu(CN)4] + 2K2SO4 + (CN)2

(9) With Potassium Sulphocyanide, it forms Copper sulphocyanide in the presence of SO2.

2CuSO4 + 2KSCN + SO2 + 2H2O  2CuSCN + K2SO4 + 2H2SO4

Some important properties of Silver and its Compounds

Properties
(1) White lustrous metal.

(2) Silver reacts with hydrogen sulphide to form a black ppt of Ag2S

(a) 4 Ag + 2H2S + O2  2 Ag2S + 2H2O

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(b) 2Ag + H2S  Ag2S + H2

(3) It reacts with Chlorine directly to form Silver chloride.

ES

2Ag + Cl2  2AgCl

(4) With dil HNO3 it librates nitric oxide where as with conc HNO3 it liberates nitrogen dioxide.
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3Ag + 4HNO3 (dil)  3AgNO3 + 2H2O + NO

Ag + 2HNO3 (Conc.)  AgNO3 + H2O + NO2

(5) It reacts with H2SO4 to give Ag2SO4

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2Ag + 2H2SO4  Ag2SO4 + 2H2O + SO2

(6) With Sodium cyanide it forms a complex, Sodium dicyanoargentate (I)

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4Ag + 2H2O + O2 + 8NaCN  4Na [Ag (CN)2] + 4NaOH

(7) With dilute HCl in the presence of Oxygen it forms AgCl.

4Ag + 4HCl + O2  4AgCl + 2H2O

Silver Nitrate (AgNO3) (Lunar Caustic)

Preparation
Silver nitrate is prepared by dissolving Silver metal in dil. HNO3.

3Ag + 4HNO3 (dil)  3AgNO3 + 2H2O + NO

Properties
(1) Colourless crystalline solid

(2) On heating at different temperatures it form different compounds

[ 141 ]
d- & f -Block Elements

Above
2AgNO3 2Ag NO2 + O2
m.p.
Red
2AgNO3 heat 2Ag + 2NO2 + O2

(3) With sodium hydroxide it forms silver oxide

2 AgNO3 + 2NaOH  Ag2O + 2NaNO3 + H2O

(4) With drops of NH4OH it form Ag2O which on adding excess of NH4OH dissolves to form a
complex.(Tollen’s Reagent).

2AgNO3 + 2NH4OH  Ag2O + 2NH4NO3 + H2O

Ag2O + 4NH4OH  2[Ag(NH3)2] OH + 3H2O

(5) It reacts with Copper to give silver

2Ag NO3 + Cu  Cu (NO3)2 + 2Ag

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(6) With Potassium chromate it forms Silver chromate.

K2CrO4 + 2AgNO3  Ag2CrO4 + 2KNO3

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(7) With Sodium sulphide it forms black ppt. of Ag2S

2AgNO3 + Na2S  Ag2S + 2NaNO3

(8) With Sodium phosphate it form Silver phosphate

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3AgNO3 + Na3PO4  Ag3PO4 + 3NaNO3

(9) It reacts with Iodine forming either AgIO3 or HIO3

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(a) 6AgNO3 + 3I2 + 3H2O  5AgI + AgIO3 + 6HNO3

(b) 5AgNO3 + 3I2 + 3H2O  5AgI + HIO3 + 5HNO3

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(10) Along with ammonium hydroxide i.e. Tollen’s reagent, it acts as a mild oxidising agent

2AgNO3 + 2NH4OH  Ag2O + 2NH4NO3 + H2O

Ag2O + HCOOH  2Ag + H2O + CO2

Silver Halides
All the halides of silver (I) are known. The fluoride is soluble whereas the chloride, bromide and
iodide are insolube in water. Silver fluoride may be prepared by the action of hydrofluoric acid on
silver (I) oxide. The white chloride and yellow bromide and iodide are most conveniently made by
double decomposition :

Ag+ (aq) + X– (aq)  AgX (s) (X = Cl, Br or I)

The chloride and bromide are soluble in ammonia (chloride very readily) to give a solution containing
linear complex ion, [Ag(NH3)2]+. Silver halides darken in light due to photochemical decomposition,

[ 142 ]
d- & f -Block Elements

a property which is primarily responsible for their use in photography. all the silver halides dissolve in
thiosulphate and dicyano complexes of Silver (I).
–
3
O O
S O
S Ag S
O S O O

[N  C — Ag — C  N]–

Dicyanoargentate (I) ion

Silver chloride is used in photography chiefly for printing paper and lantern slides, the bromide is used
in large quantities for the production of photographic film and plates and the iodide chiefly for the
production of colloidal emulsion plates in photography.

Preparation
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Silver Bromide is prepared by the action of NaBr on AgNO3

AgNO3 + NaBr  AgBr + NaNO3

Properties
ES

(1) It is pale yellow solid which melts to red liquid on heating

(2) AgBr dissolves in excess of NH4OH forming a complex.

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AgBr + 2NH4OH  [Ag(NH3)2] Br + 2H2O

(3) It decomposes to Silver and Bromine or heating.

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2AgBr  2Ag + Br2

(4) With potassium cyanide it form potassium argento cyanide and potassium bromide.

AgBr + 2KCN  K[Ag(CN)2] + KBr

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(5) It reacts with sodium thiosulphate to form sodium argentothiosulphate.

AgBr + 2Na2S2O3  Na3[Ag(S2O3)2] + NaBr

Use of Silver & Gold

1. Silver is used for making ornaments. Silver being very soft is alloyed with Copper. Silver Copper
alloy used for making ornaments contains about 80% Silver and 20% Copper. The composition
of Silver alloy is expressed as its “fineness”. i.e., the number of parts by mass of Silver in 1000
parts by mass of the alloy. ‘900 fine silver’ means an alloy containing 90% Silver and 10%
Copper.

2. Silver is used in silver plating.

3. Silver salts are extensively used in photography.

4. Silver-Tin alloy is used for filling teeth.

[ 143 ]
d- & f -Block Elements

Some important alloys of Silver along with their uses are given below :

Alloy Percentage Uses

Composition
1. Coinage alloy Ag 50% For making coins
Cu 40 – 50%
Ni 5 – 10%
2. Palladium silver alloy Pd 60% Potentiometer, winding of some
Ag 40% special instruments
3. Dental alloy It contains tin, silver For filling teeth
and mercury
4. Silver copper alloy Ag 92.5% Silver wares, coins and jewellery.
Cu 7.5%

Use of Silver & Gold

1. For preparing ornaments.

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2. For electrogilding (i.e., gold plating by electrolysis).

3. For preparing alloys.

ES

Pure Gold is soft and is generally hardened by adding Silver or Copper to it for the purpose of making
ornaments. The weight of Gold in Gold ornaments is expressed in terms of ‘carats’. Pure Gold is
taken as 24 carats. 18 carat Gold means that it contains 18 parts by weight of Gold in 24 parts by
weight of the given alloy. The percentage of Gold in this sample may be calculated as :
an

18
Percentage of gold in 18 carat Gold =  100  75%
24
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Most jewellery is made out of 22 carat Gold.

Compounds of Zinc and Mercury

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1. Zinc Sulphate ZnSO4.7H2O (White Vitriol)

Preparation : It is prepared by treating metallic zinc, zinc oxide or zinc carbonate with dilute
H2SO4.

ZnO + H2SO4 
 ZnSO4 + H2O

ZnCO3 + H2SO4 
 ZnSO4 + CO2 + H2O

The solution thus obtained is heated to crystallization.

Properties : On heating ZnSO4.7H2O to 373 K, the molecules of water of crystallization are

lost and at 723 K it becomes anhydrous. On further heating, the anhydrous salt decomposes as:

2ZnSO4 
 2ZnO + 2SO2 + O2

[ 144 ]
d- & f -Block Elements

Uses :

1. It is used to prepare lithopone (BaSO4 + ZnS), a white pigment.

ZnSO4 + BaS (BaSO4 + ZnS)

Lithopone

2. It is also used in galvanising iron.

3. As mordant in dyeing.

2. Mercury (II) Chloride,HgCl2 (Corrosive Sublimate)

Preparation : It is formed when chlorine is passed over heated mercury or mercury (I) chloride.

Hg + Cl2 
 HgCl2

Hg2Cl2+Cl2 
 2HgCl2

It is manufactured by heating a mixture of mercury (I) sulphate and sodium chloride in the
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presence of a little MnO2 which oxidizes any Hg2Cl2 salt formed during the reaction.

HgSO4 + 2NaCl 
 HgCl2 + Na2SO4
ES

Properties:

1. It is white crystalline solid, sparingly soluble in cold water, but soluble in hot water. It is
readily soluble in organic solvents, such as ethanol and ether. This indicates that HgCl2 has
an

appreciable covalent character.

2. Reaction with stannous chloride. An aqueous solution of mercury (II) chloride on reaction
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with stannous chloride solution gives at first a white ppt. of mercurous chloride which turns
grey due to formation of mercury.

2HgCl2 + SnCl2 
 Hg2Cl2 + SnCl4
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Hg2Cl2 + SnCl2 
 Hg + SnCl4

3. Reaction with ammonia. It reacts with ammonia to give white precipitate of amino
mercuric chloride, (NH2)HgCl.
HgCl 2  2NH 3 
 Hg (NH 2 )Cl  NH 4 Cl
White ppt.

4. Reaction with potassium iodide. It reacts with KI solution to form scarlet red precipitate of
mercuric iodide which dissolves in excess of KI solution to give a colourless solution.

HgCl2 + 2KI 
 HgI2 + 2KCl

HgI2 + 2KI 
 K2[HgI4]
Potassium tetraiodomercurate (II)

Alkaline solution of K2[HgI4] is known as Nessler’s reagent.

[ 145 ]
d- & f -Block Elements

Mercury (II) chloride is poisonous. Its best antidote is the white of an egg which gives an
alternative protein material for it to act upon.

Uses : A very dilute solution of mercury (II) chloride is sometimes used as an antiseptic. It is
also used for preseving wood.

3. Mercury (II) Iodide,HgI 2

Preparation : It is obatained as scarlet red precipitate when a requisite amount of potassium

iodide solution is added to a solution of mercury (II) chloride.

HgCl2 + 2KI 
 HgI2 + 2KCl

Mercury (II) iodide readily dissolves in an excess of potassium iodide solution and forms the
(HgI4)2– complex ion.

HgI2 + 2KI 
 K2[HgI4]
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The tetraiodo complex forms light yellow crystals K2[HgI4].2H2O. These crystals are freely
soluble in water and alcohol.

Uses :
ES

1. An alkaline solution of K2[HgI4] is called Nessler’s reagent. It is used to test the presence of
ammonia or ammonium ion. It gives a brown precipitate with ammonia.

2. In the form of ointment it is used for the treatment of skin infections.

an

4. Mercury (I) Chloride,Hg2Cl2 (Calomel)

Preparation : It precipitates out as a white solid when solutions containing a mercury (I) salt
and chloride ions are mixed.
ka

Hg2(NO3)2 + 2NaCl 
 Hg2Cl2 + 2NaNO3

It can also be obtained by heating HgCl2 and Hg in an iron vessel. Hg2Cl2 thus obtained is
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purified by sublimation.

HgCl2 + Hg 
 Hg2Cl2

Properties :

1. Mercury (I) chloride is a white amorphous powder, insoluble in water. On heating, it dissociates
into mercury (II) chloride and mercury.

Hg2Cl2 
 HgCl2 + Hg

2. Reaction with ammonia. It is blackened by ammonia due to formation of amino-mercuric

chloride and finely divided mercury.

Hg2Cl2 + 2NH3 
 Hg(NH3) + Hg + NH4Cl

Uses : Calomel is used in medicine as a purgative.

[ 146 ]
d- & f -Block Elements

Compounds of Transition Elements

1. Potassium Dichromate (K 2Cr2O7)

The structure of dichromat ion is consists of two tetrahedra sharing an oxygen atom at the
common coner.

The dichromate ion (Cr2O72–) and chromate ion (CrO42–) exists in equilibrium with each other at
a pH of about 4. They are interconvertible by changing the pH. The chromate ions, on addition
of acid, change into dichromate ion while the dichromate ions, on addition of alkali, change into
chromate ion.

Acid Acid
2CrO42– + 2H+ 2 HCrO4– Cr2 O 72 – + 2H2O
Alkali Alkali
Hydrogen Dichromate
chromate (orange)
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Properties :
1. It is an orange crystalline solid with melting point 670 K.
2. It is appreciably soluble in hot water but modertely soluble in cold water.
3. Action of Heat : On heating K2Cr2O7 decomposes to give potassium chromate and chromic
oxide.

4K2Cr2O7   4K2CrO4 + 2Cr2O3 + 3O2

4. Oxidizing Properties : It acts as strong oxidizing agent in acid medium.

K2Cr2O7 + 4H2SO4 
 K2SO4 + Cr2(SO4)3 + 4H2O + 3[O]

Since Cr2O72– ions take up electrons so they get reduced and act as oxidizing agent. Some
of the oxidizing reactions of K2Cr2O7 are given below :

[ 147 ]
d- & f -Block Elements

(a) It oxidizes iodide to iodine

Cr2O72– + 6I– + 14H+ 
 2Cr3+ + 3I2 + 7H2O

(b) It oxidizes acidified ferrous sulphate to ferric sulphate

Cr2O72– + 14H+ + 6Fe2+ 
 2Cr3+ + 6Fe3+ + 7H2O

(c) It oxidizes H2S to sulphur

Cr2O72– + 3H2S + 8H+ 
 2Cr3+ + 3S + 7H2O

Similarly, it oxidizes sulphites to sulphates, chlorides to chlorine, nitrites to nitrates, thiosulphates

to sulphates and sulphur and stannous salts (Sn2+) to stannic salts (Sn4+) according the
equation given below

3SO23   Cr2 O27   8H  

 3SO 24   2Cr 3  4H 2 O
Sulphite Sulphate

3NO 2  Cr2 O 72   8H  
 3NO 3  2Cr 3  4H 2 O
Nitrite Nitrate
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3S O  Cr2 O72   8H  
2 3
2
 3SO 42   3S  2Cr 3  4H 2 O
Thiosulphate Sulphate

3Sn 2  Cr7 O 72  14H  

 3Sn 4  2Cr 3  7H 2 O
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Stannous Stannic

5. Chromyl Chloride Test : When any chloride is heated with K2Cr2O7 and conc. H2SO4
orange red fumes of chromyl chloride (CrO2Cl2) are formed.
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K2Cr2O7 + 4NaCl + 6H2SO4 

 2KHSO4 + 4NaHSO4 + 2CrO2Cl2 + 3H2O

6. Reaction with H2O2 : Acidified solution of dichromate ions forms a deep blue colour
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with H2O2 due to the formation of [CrO(O2)2].

The blue colour fades away gradually due to decomposition of CrO5 into Cr3+ ions and Oxygen.
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2. Potassium Permanganate (KMnO 4)

Properties : Potassium permanganate is violet crystalline solid having m.p. 523 K. It is

soluble in water and its aqueous solution is purple in colour.

1. Effect of Heat : On heating, potasium permanganate changes into manganate and oxygen
gas is evolved.

2KMnO4 
 K2MnO4 + MnO2 + O2

2. Effect of Alkalies : On heating with alkalies, potassium permanganate changes into

manganate and oxygen gas is evolved.

4KMnO4 + 4KOH 
 4K2MnO4 + 2H2O + O2

In acidic medium potassium permanganate oxidizes :

[ 148 ]
d- & f -Block Elements

(a) Ferrous salts to ferric salts

MnO4– + 5Fe2+ + 8H+ 
 Mn2+ + 5Fe3+ + 4H2O

(b) Oxalates to CO2

2MnO4– + 5C2O42– + 16H+ 

 2Mn2+ + 10CO2 + 8H2O

(c) Iodides to iodine

10I– + 2MnO4– + 16H+ 

 2Mn2+ + 5I2 + 8H2O

(d) Sulphites to sulphates

5SO32– + 2MnO4– + 6H+ 

 2Mn2+ + 5SO42– + 3H2O

Illustration 1: The electronic configuration of actinide elements are not known with certainty. Explain.

Solution: In actinides, 5f and 6d subshells are close in energy. The outermost 7s orbital remains filled
with 2 electrons (7s2). The electron can easily jump from 5f to 6d or vice versa. Further,
irregularities in electronic configuration are also related to the stabilities of f0, f7 and f14
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occupancy of the 5f orbitals. Hence, they show a large number of oxidation states (Moreover,
they are radioactive with short half-lives. Hence, their properties cannot be studied easily).
ES

Illustration 2: The actinide contraction differs from lanthanide contraction? Explain.

Solution: Lanthanide contraction refers to the gradual decrease in the size of the lanthanides and their
trivalent ions. (Z = 58 to 71) whereas actinoid contraction refers to the gradual decrease in
the size of the actinoids or their ions (M3+ or M4+) (Z = 90 to 103). They differ in the fact that
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in the actinoid series, the contraction is greater from element to element due to poor shielding
by 5f electrons than by 4f electrons.

Illustration 3: How is the variability of oxidation states of the transition elements different from that of the
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non-transition elements? Illustrate with examples.

Solution: The variability in oxidation states of transition metals is due to the in complete filling of
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d-orbitals in such a way that their oxidation states differ from each other by unity, e.g., Fe2+
and Cu+ and Cu2+ etc. In case of non-transition elements, the oxidation states differ by units
of two, e.g.,. Pb2+ and Pb4+, Sn2+ elements in a group. For example, in group 6, Mo (VI) and
W (VI) are more stable than Cr (VI). In p-block elements, the lower oxidation states are
more stable for heavier members due to inert pair effect, e.g., in group 16, Pb (II) is more
stable than Pb (IV).

Illustration 4: How would your account for the increasing oxidising power in the series

VO 2  Cr2O 72  MnO4 ?

Solution: This is due to the increasing stability of the species with lower oxidation state of the metal
atom to which they are reduced

V IV V III VII UII

e.g., V O 2 
 V O 2 ; Cr2 O 72 
 C r 3 ; M nO 4 
 M n 2

[ 149 ]
d- & f -Block Elements

Illustration 5: Name the members of the lanthanoid series which exhibit +4 oxidation states and those
which exhibit +2 oxidation states. Try to correlate this type of behaviour with the electronic
configuration of these elements.

Solution: + 4 = 58Ce, 59Pr, 60Nd, 65Th, 66Dy

+ 2 = 60Nd, 62Sm, 63Eu, 69Tm, 70Yb

+ 2 oxidation state is exhibited when the lanthanoid has the configuration 5d06s2 so that 2
electrons are easily lost +4 oxidation sate is exhibited when the configuration left is close to
4f0 (3.g. 4f0, 4f1, 4f2) or close to 4f7 (e.g. 4f7 or 4f8)

SAMPLE PROBLEMS 3.2 (MCQ)

Problem 1: The compound that gets oxidised even on exposure to air, is
(a) FeSO4.(NH4)2SO4.6H2O (b) Hg2Cl2
(c) FeSO4.7H2O (d) Cu2Cl2

Solution: (c) Hydrated ferrous sulphate acquires brownish-yellow colour due to the formation of
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basic ferric sulphate by atmospheric oxygen.

4FeSO 4  2H 2O  O 2 
 4Fe(OH)SO 4
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Problem 2: Chromyl chloride test can be used to confirm the presence of Cl– ion in the compound
(a) HgCl2 (b) AgCl
(c) BaCl2 (d) PbCl2
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Solution: (c) Other chlorides are not volatile enough to form CrO2Cl2.

Problem 3: Pyrolusite when fused with K2CO3 in presence of air gives a green mass A. When Cl2 is
passed into the solution of A, another coloured product B is obtained A and B are respectively.
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(a) K2Mn(OH)4 and Mn2O3 (b) K2Mn(OH)4 and Mn3O4

(c) MnO(OH) and Mn2O7 (d) K2MnO4 and KMnO4

Solution: (d)
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Problem 4: Which of the following is false about the stability of oxidation states of manganese?
(a) Mn (II) > Mn (VII) (acidic solution)
(b) Mn (II) < Mn (IV) (alkaline solution)
(c) Mn (VI) > Mn(IV) (acidic soluton)
(d) Mn (VI) > Mn (VII) (alkaline solution)

Solution (c) Mn (VI) disproportionates to Mn (VII) and Mn(IV) even in weakly acidic solution.

Problem 5: Atomic size of Zr and Hf is almost the same because of

(a) both have (n – 1)d2m2 configuration
(b) both have the same number of d-electrons in penultimate energy level.
(c) lanthamide contraction
(d) large screening effect of 4f-electrons over the valence shell.

Solution: (c)

[ 150 ]
d- & f -Block Elements

Problem 6: Which of the following is correct?

I. [Cu(NH3)4]Cl Blue and paramagnetic
II. [Cu(NH3)4Cl2 Deep blue and paramagnetic
III. CuO34 Colourless and diamagnetic
IV. [Cu(NH3)4]Cl Colourless and diamagnetic
(a) I only (b) II only
(c) II and III (d) II, III and IV
Solution: (c) Due to absence of unpaired electron.

Problem 7: A metal gives two chlorides ‘X’ and ‘Y’. The chloride ‘X’ gives a black precipitate with
NH4OH. the chloride ‘Y’ gives a white precipitate with NH4OH. ‘Y’ gives red precipitate
with KI which is soluble in excess of KI. The formula of chlorides ‘X’ and ‘Y’
respectively are:
(a) Hg2Cl2 and HgCl2 (b) HgCl2 and ZnCl2
(c) ZnCl2 and Hg2Cl2 (d) None of these
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H2N
Hg 2 Cl2  NH 4OH 
 Hg  Hg  NH 4 Cl  2H 2O
X
Solution: (a) Cl
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Black ppt.
H2N
HgCl2  2NH 4 OH 
 Hg  NH 4Cl  2H 2 O
Cl
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White ppt.

Problem 8: Consider the following oxides of transition elements and choose the correct order of their
basic character.
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I. VO II. CrO
III. TiO IV. FeO
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Solution: (d) Considering the size of metal atom we find that it decreases in the order Ti, V, Cr, Fe
(atomic number increases). The basic character of monoxides also decreases in the
same order as their atomic size.
Problem 9: A transition metal with low oxidation number is most likely to act as
(a) a base (b) an acid
(c) an oxidising agent (d) none of the above
Solution: (b) During complex formation, the transition metal atom is most likely to act as Lewis acid
and the liquid acts as Lewis base.
Problem 10: Select the one that represents chlorodising roasting
(a) PbS  2O 2 
 PbSO 4 (b) 4Hg  2AgCl 
 2HgAg  Hg 2 Cl2
(c) 2NaCl  Ag 2S 
 2AgCl  Na 2S (d) Both (b) and (c)

Solution: (d) The conversion of metal or as one to metal chloride by heating metal or its one with a
chloride salt is called chlorodising roasting.

[ 151 ]
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