d and f block elements -Transition and inner transition Elements:

Transition Elements
Elements having partially filled d-orbitals in ground state or in
excited state or in commonly occurring oxidation state are known
as transition elements. They have been placed in the centre of the
Periodic Table between s-block and p-block elements.

Iron is the most abundant and widely used transition metal.

Cu 29 3d10 4s1 Cu2+ 3d9 so Cu is a transition metal

Zn 30 4s2 3d10 Zn 2+
3d10 but Zn is not.

General Electronic Configuration of Transition Elements

Transition elements have the electronic configuration(n – 1)d1 –10 ns1or 2,

Zn, Cd, Hg, the end members of first three series have general
electronic configuration (n – 1)d10ns2. These elements do not
show properties of transition elements to any extent and are
called non-typical transition elements.

Electronic Configuration of Transition Elements

General Physical Properties of Transition Elements
(i) Atomic and ionic size Ions of the same charge in a given series
exhibit regular decrease in radius with increasing atomic number, because
the new electron enters in a d – orbital and nuclear charge increases by
unity.
In last of the series, a small increase in size is observed due to
electron-electron repulsion. (Atomic and ionic radii increase from
3d-series to 4d-series but the radii of the third (Sd) series elements are
virtually the same as those of the corresponding member of the second
series. It can be explained on the basis of lanthanoid contraction [poor
shielding of 4f ].

Due to lanthanide contraction Zr and Hf Have almost similar radii.

(ii) Ionisation enthalpies In a series as we move from left to right,
ionization enthalpy increases due to increase in nuclear charge but not in
regular trend.
The irregular trend in the first ionisation enthalpy of the 3d metals,
though of little chemical significance, can be accounted by considering
that the removal of one electron alters the relative energies of 4s and
3d-orbitals.

● First Ionization Potentials: IE1 values for the first four 3d block
elements (Sc, Ti, V and Cr) differ only slightly from one another. The
value of IEI for Zn is considerably higher. This is due to the
extra-stability of 3d10 level which is completely filled in Zn-atom.
● Second ionisation potentials: The value of IEII for Cr and Cu are
higher than those of their neighbours. This is due to the fact that the
electronic configurations of Cr+ and Cu+ ions have extra stable 3d5 and
3d10 levels. There is a sudden fall in the values of ionisation potentials
in going from 12 (Zn-group elements) to 13 sub-group.
[If sum of the first and second ionisation enthalpies is greater than
hydration enthalpy standard potential (EoM2+ / M) will be positive and
reactivity will be lower and vice-versa.]
(iii) Oxidation states Transition metals show variable oxidation
state due to two incomplete outermost shells , because electrons
from both s & d orbitals can take part in bonding. Only stable
oxidation states of the first row transition metals are
Sc(+3) , Ti(+4). V(+5), Cr(+3, +6), Mn(+2, +7), Fe(+2. +3).
Co(+2, +3). Ni(+2), Cu(+2), Zn(+2).
The transition elements in their lower oxidation states (+2 and
+3) usually forms ionic compounds. In higher oxidation state
compounds are normally covalent.

Only Os and Ru show +8 oxidation states in fluorides and oxides.

Ni and Fe in Ni(CO)4 and Fe(CO)5 show zero oxidation state.

(iv) Enthalpy of atomisation Transition elements exhibit higher

enthalpies of atomization. Because of the presence of a large number
of unpaired electrons in their atoms, they have stronger interatomic
interactions and hence, stronger bond.

(v) Trends in the M2+ / M standard electrode potentials

EoM2+ / M is governed by three factors. Enthalpy of sublimation,
enthalpy of ionisation and enthalpy of hydration.
The irregular trend in 3d series is due to irregular variation in ionisation
enthalpy and heat of sublimation.

Except copper 3d – elements are good reducing agents.

Cu2+ -3d9 (Cupric) is more stable than Cu+ - 3d10 (cuprous)

e.g Cu SO4 It is due to large Hydration enthalpy.

(vi) Melting and boiling point Due to strong metallic bond, they have
high m.p. and b.p. The m.p. of these elements becomes maximum and
then decreases with the increase in atomic number.
Manganese and technetium show abnormal values in the trend.
Tungsten has the highest m.p. (3410oC).
Mercury is liquid at room temperature (m.p. – 38.9°C) due to
absence of unpaired electrons, and weak metallic bonding.
(vii) Density d-block elements have high density because of their small
atomic size and strong metallic bonding.

Osmium has slightly lower density (22.52 g cm-3) as compared to iridium

(22.61 g cm-2). Thus, iridium has the highest density among transition
metals.

(viii) Atomic volume Atomic volume decreases along the period due to
decrease in atomic size.

(ix) Reactivity d-block elements are less reactive due to high ionisation
energies. Some are almost inert and known as noble metals, e.g., Au; Pt,
Os, Ir, etc

(xii) Complex formation They are well known to form a large number of
complex compounds mainly due to
(a) small atomic size and high nuclear charge

(b) presence of partly filled or vacant d-orbitals, e.g.,K4[Fe(CN)6]

(xiii) Coloured ions Colour exhibited by transition metal ions is due

to the presence of unpaired electrons in d-orbitals and is due to
the d-d transitions of electrons, when invisible light is incident on the
ion.
Colour of a complex depends on the metal, its oxidation state and its
ligands, e.g., [Cu(H2O)4]2+ is pale blue while [Cu(NH3)4]2+ is dark blue.
CuSO4· 5H2O is blue in colour and anhydrous CuSO4 is colourless.
Charge transfer also give intense colour e.g., MnO–4 ion does not contain
any unpaired d-electron. Its purple colour is due to charge transfer from
O to MD, thus O-2 change to O– and Mn(VII) to Mn(Vl). Charge transfer is
possible only when the energy levels on the two different atoms involved
are fairly close.

(xiv) Magnetic properties

(a) Paramagnetic nature is due to the presence of unpaired
electrons in d-orbitals. Paramagnetic character increases with
increase in the number of unpaired electrons and highest for Mn(II)
[among 3d-series].
(b) Diamagnetic substances are repelled by applied magnetic field and
have no unpaired electron.

(c) In ferromagnetism, permanent magnetic character is acquired by

substance e.g., Fe.

Magnetic moment is given by μ = √n (n + 2) BM,

Where, n = number of unpaired electrons and BM = Bohr magneton (unit
of magnetic moment).

(xv) Catalytic properties The transition metals and their compounds

behave like catalyst due to
(a) the presence of partly filled d-orbitals resulting in variable
oxidation states.

(b) formation of intermediate complex with reactants by lowering

the energy of activation.

(c) their rough surface area which provides active sites for
adsorption of reactant molecules.

Iron in the preparation of NH3 (Haber’s process), finely divided nickel for
hydrogenation, Pt in the preparation of nitric acid (Ostwald’s process)
Some important catalysts having transition metals are

1. Ziegler Natta catalyst : TiCI4 + (C2H5)3 AI

2. Lindlar’s catalyst : Pd / BaSO4
3. Wilkinson’s catalyst : [Ph3P3RhCI
4. Adam’s catalyst : Pt / PtO

5. Brown’s catalyst or P-2 catalyst: Nickel boride

(xiv) Formation of alloys d-block elements have a strong tendency to

form alloys, because their atomic radii and size are similar and in the
crystal lattice one metal can be readily replaced by another. Alloys so
formed have high m.p.. The metals Mo, W, Cr, Ni, and V are used for the
production of stainless steel.
Amalgam is an alloy formed by mercury with other metals, Iron and
platinum do not form any alloy with mercury.

List of Alloys
(xv) Interstitial compounds The vacant space present in a crystal
lattice is known as interstitial site or void. The non-metal atoms (e.g., H,
N, C, etc.) due to their small size when occupy such place, the resulting
compound is known as interstitial compound. Such compounds are hard
and rigid, e.g., cast iron and steel.

(xvi) Non-stoichiometric compounds The compounds not navm the

elements in the exact ratio as in the ideal crystal are known
non-stoichiometric compounds e.g., in Fe0.94O1 the Fe : O is approx 0.94 :
1 and not exactly 1 : 1. It is due to the variability of Oxidation state in the
transition metal. These elements form such compound by trapping H, B, C
and N etc.

(xvii) Spinel These are the mixed oxides in which oxygen atoms
constitute a fcc lattice e.g., ZnFe2O4 It is a normal spinel in which the
trivalent ions occupy the octahedral holes and divalent ions occupy the
tetrahedral holes.
In inverse spinel, the trivalent ion occupy the tetrahedral holes and
divalent ion occupy the octahedral holes. e.g., FeFe2O4 or Fe3O4.
Some important reagents having transition metals

1. Baeyer’s reagent Dilute alkaline KMnO4 used to test the presence of

unsaturation.
2. Tollen’s reagent Ammoniacal solution of AgNO3, i.e., [Ag(NH3)2]OH.
used to test the aldehyde group.
3. Nessler’s reagent Alkaline solution of K2HgI43 (g) and NH: .
4. Benedict’s solution CuSO4 solution + sodium citrate + Na2CO3, used
to test the aldehyde group.
5.Lucas reagent HCl (cone.) + anhydrous ZnCl2, used to distinguish
between 1°, 2° and 3° alcohols.

Applications of transition elements

1. A mixture of TiO2 and BaSO4 is called titanox and a mixture of ZnS +
BaSO4 is called lithopone.
2. TiCI2 and TiO2 are used in smoke screens. TiO2 is also used as white
pigment of paints.
3. Tantalum is used in surgical venables and analytical weights.

4. Chromium is used in stainless steel and chrome plating.

5. Mo is used in X-rays tubes. Pt is used in resistance thermometers.

6. Cd is used for making joints in jewellery.

7. Ce is used as a scavenger of oxygen and sulphur in many metals-

8. Alkaline solution of K2HgI4 is called Nessler’s reagent and is used to test

the presence of ammonium ion (NH+4).

1. Potassium Dichromate (K2 Cr2 O7)

Ore Ferrochrome or chromite (FeO· Cr2O3) or (FeCr2O4)
Preparation

Sodium dichromate is more soluble than potassium dichromate.

Chromates and dichromates are interconvertible in aqueous solution

depending upon pH of the solutions.

Properties Sodium and potassium dichromates are strong oxidising

agents, thus, acidified K2Cr27 will oxidise iodides to iodine, sulphides to
sulphur, tin (ll) to tin (IV) and iron (ll) salts to iron (III).
Uses
1. K2Cr27 is used as oxidising agent in volumetric analysis.
2. It is used in mordant dyes, leather industry, photography (for
hardening of film).

3. It is used in chromyl chloride test.

4. It is used in cleaning glassware.

2. Potassium Permanganate (KMnO 4)

Ore Pyrolusite (MnO2)
Preparation

Commercial preparation

Properties KMnO4 acts as strong oxidising agent.

1. In the presence of dilute H2SO4, KMnO4 is reduced to manganous salt.

Acidic KMnO4 solution oxidises oxalates to CO2, iron(II) to iron (lll),

nitrites to nitrates and iodides to iodine. The half-reactions of reductants
are
To acidify KMnO4, only H2SO4 is used and not HCI or HNO3 because HCI
reacts with KMnO4 and produce Cl2 while HNO3, itself acts as oxidising
agent.
2. In alkaline medium, KMnO4 is reduced to insoluble MnO2.

Alkaline or neutral KMnO4 solution oxidises I– to IO–3, S2O2-3 to SO2-4,

Mn2+ to MnO2, etc.
Aqueous KMnO4, reacts with NH$ to liberate N2 gas.
2KMnO4 + 2NH3 → 2KOH + 2MnO2 + N2 + 2H2O
Uses
KMnO4 is used
(i) in laboratory preparation of CI2.
(ii) as an oxidising agent and disinfectant.

(iii) in making Baeyer’s reagent.

Structures

3. Copper Sulphate (CUSO4 ·5H2O)

It is also known as blue vitriol.

Method of preparation It is obtained by the action of dil H2SO4 on

copper scrap in the presence of air.

Properties
1. On heating it turns white due to loss of water of crystallisation.

At 1000 K, CuSO4 decomposes into CuO and So3

2. It gives blue solution with NH4OH and white ppt of Cu2I2 with KI.
Uses It 1S used in electroplating, as mordant in dyeing, in making
bordeaux mixture [(Ca(OH) 2 + CuSO4)], etc.
4. Silver Nitrate (AgNO3)
It is also called Lunar caustic.

Method of preparation It is prepared by heating silver with dilute nitric

acid

Properties
1. It is colourless, crystalline compound which blackens when comes in
contact of organic substances (skin, cloth, etc.)

2. With potassium dichromate, it gives red ppt of Ag2CrO4.

3. On strong heating, it decomposes to metallic silver.

4. Ammoniacal solution of silver nitrate is known as Tollen’s

reagent.

Uses It is used as laboratory reagent, in silvering of mirror, in the

preparation of inks and hair dyes, etc.

Inner-Transition Elements
The elements in which the filling of atomic orbitals by electrons take place
inner subshells i.e two levels inside the outer subshell, are known as
inner-transition elements. They are also known as f-block elements

Classification of f-block Elements

They have been classified into two series.

(a) 4f-series (first inner-transition series) The last electron enters in

4f-orbital. The elements belonging to this series are also known
as lanthanoids.
(b) 5f-series (second inner-transition series) The last electron enters
in 5f-orbital. The elements belonging to this series are also known
as actinides.

Lanthanides
The fifteen elements from lanthanum (at. no. 57) to lutetium (at. no. 71)
are known as lanthanides or rare earths. Their properties are as follows :

1. Electronic configuration
The general electronic configuration of these elements is
[Xe]4f 0 – 14
5d0-1 6s2. The lanthanum, electronic configuration
[Xe]4f0 5d1 6s2 and lutetium, electronic configuration [Xe]4f14 5d1 6s2,
have no partially filled 4f-orbital in their ground state, are considered as
lanthanides due to their properties close to these elements.

2. Oxidation state
The most common and most stable oxidation state of lanthanides is +3
but some elements also exhibit +2 and +4 oxidation states in which they
leave behind stable ions, e.g.,

An aqueous solution of Ce4+ is a good oxidising agent. The Eu2+ and

Yb2+ can exist in aqueous solution and are good reducing agents. But
there are exceptions also e.g.,

3. Magnetic properties
Magnetic properties have spin and orbit contributions. Hence, magnetic
moments are given by the formula

μ = √4S(S + 1)+ L (L + 1)
Where, L = orbital quantum number, S = spin quantum number

All lanthanide ions with the exception of La3+, Lu3+ and Ce4+, are
paramagnetic in nature.

4. Lanthanoid contraction
Steady decrease in the atomic and ionic (Ln3+) radii as the atomic Dumber
of the lanthanide elements increases is called lanthanide contraction.
Causes: As we move down the group from left to right in a lanthanide
series, the atomic no. increases and for every proton in the nucleus the
extra electron goes to 4f orbital. The 4f orbital is too diffused to shield the
nucleus effectively, thus there is a gradual increase in the effective
nuclear charge experienced by the outer electrons. Consequently , the
attraction of the nucleus for the electrons in the outermost shell increases
with the increase of atomic number, thus size decreases.

Consequence of Lanthanide Contraction:

Separation of Lanthanides: Due to the similar sizes of the lanthanides,
it is difficult to separate them but due to lanthanide contraction their
properties slightly vary (such as ability to form complexes). The variation
in the properties is utilized to separate them.
Basic Strength of Hydroxide: Due to the lanthanide contraction, size of
M3+ ions decreases and there is increase in covalent character in M–OH
and hence basic character decreases.
Similarity of second and third transition series: The atomic radii of
second row transition elements are almost similar to those of the third
row transition elements because the increase in size on moving down the
group from second to third transition elements is cancelled by the
decrease in size due to the lanthanide contraction

5. Colour
The species containing unpaired electrons are coloured and so on in the
case of lanthanide ions. The f- f transitions are possible due to absorption
of light from the visible region

6. Melting and boiling points

Lanthanides have high melting and boiling points but there is no regular
trend.

7. Density
Lanthanides have densities varying . from 6.67 to 9.7 g cm-3, but there IS
no regular trend for these values.

8. Electronegativity
For lanthanides the electronegativity values are almost same as that of
$-block elements. Lanthanides form ionic compounds.

9. Ionisation energies
The ionisation energy values of lanthanoids are not very high due to their
large size and comparable with those of alkaline earth metals.

10. Complex compound

Due to their large ionic SIze, they have little tendency to form complexes.

11. Reactivity
Due to their low values of ionisation energies, the lanthanides are very
reactive.

12. Alloys
They form alloy especially with iron e.g., misch metal rare earths 94 _
95%, iron ~ 5% and S, C, Ca and AI in traces. Mg mixed with 3% misch
metal is used for making jet engine parts.

Actinides
The fifteen elements from actinium (at. no. 89) to lawrencium (at. no.
103) are known as actinides and constitute the 5f series.

From neptunium to onwards the elements are man-made

(artificially prepared) and also known as transuranic elements.

1. Electronic configuration
The last electron in such elements enters in the 5f atomic orbital.

Their general electronic configuration is

[Rn]5 f0 – 14 6d0 – 1 7s2

There is not much difference between the energies of 5f and 6d, so it is
difficult to predict whether the electron has entered in 5f or 6d.

2. Oxidation state
The common oxidation state is +3 but other oxidation states are also
exhibited by actinides upto the maximum being +7.

3. Magnetic properties
The magnetic moments of actinide ions are smaller than theoretical
values. It is hard to interpret due to large spin orbit coupling.

4. Actinide contraction
It is similar to lanthanide contraction due to poor shielding or 5f –
electrons

5. Melting and boiling points

They have high values for melting and boiling points but there is no
regular trend.

6. Density
The value of density vary from 7.0 gcm-3 to 20 gcm-3. Again there is no
regular trend in density.

7. Reducing character
They are strong reducing agents as they have high E° values
approximately 2.0 V.

8. Reactivity
Actinide are very reactive in nature and combine with oxygen and
halogens like lanthanoids.

9. Coloured ions
Actinide ions are coloured due to the presence of unpaired electrons and
f-f transitions.

10. Complex formation

They have higher tendency to form complex compounds.
 Lanthanum La 57 [Xe] 5d1 6s2

3 d series elements
Scandium Sc 21 [Ar] 4s23d1
Titanium Ti 22 [Ar] 4s23d2
Vanadium V 23 [Ar] 4s23d3
Chromium Cr 24 [Ar] 4s13d5
ManganeeseMn 25 Ar] 4s23d5
Iron Fe 26 [Ar] 4s23d6
Cobalt Co 27 [Ar] 4s23d7
Nickel Ni 28 [Ar] 4s23d8
Copper Cu 29 [Ar] 4s13d10
Zinc Zn 30 [Ar] 4s23d10