Chemistry Notes

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CHAPTER – THE d-BLOCK AND ƒ-Block Elements

General Introduction
 The elements, which are placed between s and p block elements in the long form of
periodic table, are called transition elements. The properties of these elements are
thus intermediate between those of s and p block elements. These elements are called
 transition elements since they represent a change of properties from the most
electropositive s-block elements to the least electropositive p-block elements.
 Transition elements are also called d-block elements simply because the incoming
electrons are filled in the d-orbital. This filling of electrons follows all the rules as for
s and p-block elements, the only difference between them is the last incoming
electron enters (n – 1) sublevel, i.e. the d-sublevel of the penultimate shell. The
general electronic configuration for transition elements is thus written as (n – 1) 1–10
ns0–2 where n is the outermost shell

Classification of d-Block Elements

 Transition elements are conveniently and better discussed by classifying them into
horizontal series rather than columns. The periodic table contains four main series of
transition elements, which correspond to the filling of 3d, 4d, 5d and 6d sublevels.
(i) First transition series or 3d series: This series consists of 10 elements of the 4 th
period for which the filling of 3d sublevel takes place.
Atomic number Element Electronic configuration
21 Sc [Ar] 3d14s2
22 Ti 3d24s2
23 V 3d34s2
24 Cr 3d54s1
25 Mn 3d54s2
26 Fe 3d64s2
27 Co 3d74s2
28 Ni 3d84s2
29 Cu 3d104s1
30 Zn 3d104s2
First (3d) Transition Series (Sc–Zn)

(ii) Second transitions series or 4d series: This series consists of 10 elements of the 5th
period for which the filling of 4d sublevel takes place.
Atomic number Element Electronic configuration
39 Y [Kr] 4d15s2
40 Zr 4d25s2
41 Nb 4d45s1
42 Mo 4d55s1
43 Tc 4d55s2
44 Ru 4d75s1
45 Rh 4d85s1
46 Pd 4d105s0
47 Ag 4d105s1
48 Cd 4d105s2
Second (4d) Transition Series (Y–Cd)

(iii) Third transition series or 5d series: This series consist of 10 elements of 6 th period
for which the filling of 5d sublevel takes place
Atomic number Element Electronic configuration
57 La [Xe] 5d16s2
72 Hf 5d26s2
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 73 Ta 5d36s2
74 W 5d46s2
75 Re 5d56s2
76 Os 5d66s2
77 Ir 5d76s2
78 Pt 5d96s1
79 Au 5d106s1
80 Hg 5d106s2
Third (5d) Transition Series (La–Hg)

(iv) Fourth transition series of 6d series: This series is incomplete and corresponds to
the filling of 6d sublevel.
Atomic number Element Electronic configuration
89 Ac [Rn] 6d17s2
104 Rf 6d27s2
105 Ha 6d37s2
106 Sg 6d47s2
107 Ns 6d57s2
108 Hs 6d67s2
109 Mt 6d77s2
110 Ds 6d87s2
111 Rg 6d107s2
112 Wb 6d107s2
Fourth (6d) Transition Series

 The electronic configuration of transition elements, as shown above, has the following
characteristics
(i) An inner core of electrons with noble gas configuration
(ii) Most of the elements in the four series have two electrons in the outermost s orbital.
Some of the members like Cr, Cu, Nb, Mo, Ag, Pt, Ru etc., have only one electron in
ns orbital whereas Pd has no electron in the ns orbital.
(iii) (n–1) d orbitals are progressively filled-up with electrons.
 Thus, it can be easily seen that the classification of d-block elements is primarily
based on the electronic configuration of their atoms.

Definition of transition (d-block) elements

 Transition elements (d-block) may be defined as those elements, which have partially
filled (n–1) d-subshell in their elementary state. But this definition will exclude
elements like Cu, Ag, Au, etc. which have completely filled (n–1) d-subshell.
 To make the point more clear let us look at the electronic configuration of copper
atom, cuprous ion and cupric ion.
Cu (Z = 29): 1s1 2s2 2p6 3s2 3p6 3d10 4s1
Cu1+ ion :1s 2 2s 2 2p 6 3s 2 3p6 3d10
Cu1+ ion: 1s2 2s2 2p6 3s2 3p6 3d9
 Copper atom or cuprous ion (Cu+ ion) cannot be considered as transition element

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 according to the above definition and in fact they do not exhibit the characteristic
properties of transition elements. But cupric ion (Cu2+ ion), having a d9 configuration
has incomplete d-subshell and hence is a transition ion.
Transition element is thus defined as the element whose atom in ground state or ion
in one of the common oxidation states has incomplete or partially filled (n – 1) d-
subshell.
 This definition again excludes zinc, cadmium and mercury from the transition
elements. These elements do not have partly filled d-subsehll in their atomic state or
their common oxidation state (i.e. Zn 2+ Cd 2+ and Hg 2+ ). These elements do not show
properties of transition elements except for their ability to form complexes. These
elements are still classified with d-block elements so as to maintain the logical form
of the modern periodic table.

Characteristics of d-Block Elements

 The electronic configuration of d-block elements differ from one another only in the
number of electrons present in the (n–1) d-subshell. This difference in their electronic
configuration is reflected in the trends in their physical and chemical properties across
a series.
 Some of the general characteristics of transition elements are discussed below which
distinguish them from other metals of s and p-block elements.
Atomic and ionic radii:
Atomic radii:
 The atomic radii of transition metals lie in between those of s and p-block elements.
The trends in atomic radii being as follows
(i) The atomic radii of transition elements decrease across a series with increase in
atomic number but the decrease is very small after midway.
 The initial decrease in the atomic radius is due to increase in the nuclear charge as the
atomic number increases. This increased nuclear charge pulls the electrons more
towards the nucleus thus resulting in a decrease in atomic radii. The electrons enter
the penultimate shell [(n–1)d–subshell] and the added d-electrons shield (or screen)
the outermost electrons [ns2 electrons] from the nucleus resulting in a decrease in the
attractive forces operating between the nucleus and the electrons. This is called
screening effect. With increase in the number of d-electrons, the screening effect
increases. After middle of the series, this screening effect counter balances the
increased nuclear charge. As a result, the decrease in atomic radii is small after
midway.
Sc Ti V Cr Mn Fe Co Ni Cu Zn
144 132 122 117 117 117 116 115 117 125
Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
162 145 134 129 – 124 125 128 134 141
La Hf Ta W Re Os Ir Pt Au Hg
169 144 134 130 128 126 126 129 134 144

(ii) At the end of the series, there is slight increase in the atomic radii.

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 After the middle element in each series, pairing up of d-electrons starts. This pairing
introduces repulsion between the electrons of the same orbital which increases as
pairing increase towards the end of the series. These inter-electronic repulsions tend to
increase the atomic radius while increase in nuclear charge tends to decrease the
atomic radius across a series. For elements like Fe which occur in the middle of the
series, these two opposing tendencies counter balance while as we move towards
right, the electron-electron repulsions increase more rapidly than the attractive force
and hence there is an increase in the atomic radius.
(iii) The atomic radii, increases down the group
 This increase is attributed to the addition of a new shell as we move down the group.
Thus, the electrons are in the energy levels farther away from the nucleus in the
second transition series. Hence, the atomic radii of the element of the second
transition series are larger than those of the elements of the first transition series.
The atomic radii of the elements of the second and third transition series are nearly
same due to lanthanide contraction.

Ionic radii
 The trend followed by ionic radii is the same as that of atomic radii. The ionic radii of
transition metals are different in different oxidation states. As the oxidation state
increases, the effective positive charge on the nucleus increases. This increase in the
effective nuclear charge decreases the ionic radius. Thus, the ionic size of M 3+ cations
is smaller than those of M2+ cations. If oxidation state is same, ionic radii for metal
cations decrease with increase in atomic number.
 The ionic radii of the transition metals are smaller than those of the representative
elements, belonging to the same period. This is because of the poor shielding (or
screening) effect of the d-orbitals. The d-orbitals are more diffused as compared to s
and p-orbitals and hence cannot shield the outermost electrons as effectively as s or p-
orbitals. This results in a greater attraction for the outermost electrons towards the
nucleus and thus decreasing the ionic radii.

Metallic Character
 Transition elements exhibit all the characteristic properties of metals. They are hard,
lustrous, malleable and ductile. Transition elements have high melting and boiling
points, high thermal and electrical conductivity, and high tensile strength as metals.
The metallic character of transition elements is due to their relatively low ionization
energies and large number of vacant d-orbitals in the outermost shell. The availability
of vacant d-orbitals in the outermost shell gives rise to the possibility of excitation of
electrons to these orbitals thus explaining the high thermal and electrical conductivity.
 The unpaired electrons present in d-orbitals of the transition elements interact to form
metallic bonds. Thus, the strength of the metallic bond and consequently metallic
character depend upon the number of unpaired d-electrons. If the number of unpaired
d-electrons is more, the overlapping of such electrons will be more, leading to
stronger bonding. Cr, Mn and W have maximum number of unpaired d-electrons and
thus behave as hard metals while elements like Zn, Cd and Hg are not very hard
metals due to absence of unpaired d-electrons.

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Melting and boiling point
 Transition metals have very high melting and boiling points. As seen above, the
presence of unpaired d-electrons in transition elements give rise to metallic bonds.
Due to these strong metallic bonds, transition metals have high melting and boiling
points.
 The melting points of the transition elements rise to a maximum and then fall as the
atomic number increases across a series. This can be explained as follow. As we move
across a series, the number of unpaired d-electrons increases up to the middle and
then decreases. Consequently the metallic strength increases upto the middle, (i.e. d 5
configuration) and then starts decreasing. Accordingly, the melting points increase up
to the middle of the series and decreases thereafter.

 The elements like Zn, Cd and Hg are soft and have low melting points because of the
absence of unpaired d-electrons.

Ionization Energies
(i) The first ionization energies of d-block elements lie between s-block and p-block
elements. The ionization energy gradually increases with increase in atomic number
across a series. The increase in ionization energy is due to the increase in nuclear
charge with increasing atomic number. As the nuclear charge progressively increases
it becomes more and more difficult to remove the outermost electron from the element
and hence ionization energy increase
 In a given series, the difference in the ionization energy between any two successive
d-block elements is very less as compared to the difference between successive s-
block and p-block elements. This is because in transition elements, the electrons are
being filled in (n–1) d-subshell (penultimate) which screens the outermost ns
electrons from the nucleus. This screening effect opposes the effect of increased
nuclear charge and thus little difference in ionization energy is seen for successive
elements.

(ii) The first ionization energies of 5d elements are higher as compared to those of 3d and
4d elements. It should be noted that in 5d elements, 4f subshell is filled completely.
The electrons in 4f subshell have a very weak shielding effect owing to the highly
diffused nature of f-orbitals. This shielding result in greater effective nuclear charge

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 and hence higher ionization energies for elements of 5d-series.The trends in ionization
energies of 3d and 4d elements are irregular.

(iii) The magnitude of ionization energies of transition metals reflects the thermodynamic
stability of their compounds. A small value of ionization energy means that the
formation of ion from the metal atom is easy and consequently compound formation
is favoured. Thus, smaller the ionization energy of the metal, more stable is its
compound. The significance of the value of ionization energies can be seen from the
following table.
Element (IE1 + IE2) MJ mol–1 (IE3 + IE4) MJ mol–1 Total IE MJ mol–1
Ni 2.49 8.80 11.29
Pt 2.66 6.70 9.36
The sum of the first and second ionization energies (IE 1 + IE2) is less for Ni.
This means that Ni (II) compounds are easily formed as compared to Pt (II)
compounds. Thus, Ni (II) compounds are more stable than Pt (II) compounds
D H
M(S) ��� sub �
� M(g)
Now, the sum of the third and fourth ionization energies (IE 3 + IE4) is less for
Pt. Thus, Pt (IV) is more easily attained while more energy would be required for
obtaining Ni (IV) ion. Hence, Pt (IV) compounds are more stable than Ni (IV)
compounds. For example, K2PtCl6 (Pt in IV oxidation state) is a well-known
compound while corresponding nickel salt is not known.

Electrode potential
 The stability of compounds in solution does not depend upon ionization energy solely.
It also depends upon factors such as energy of sublimation of the metal and the
hydration energy. All these factors can be chemically depicted as follows:
DH
M(s) ���
sub�
� M(g)
Where, DH sub is the enthalpy of sublimation
IE
M(g) �� � M + (g) + e -
Where, IE is the ionization energy
DH
hyd
M + (g) ���� � M + (aq)

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 Where DH hyd is the enthalpy of hydration. Thus, the total enthalpy change (DHT) when
solid metal, M is brought in the aqueous medium in the form of monovalent ion, M
(aq).
M(s) �� � M + (aq) + e -
will be the sum of the enthalpies of the three reactions involved, i.e.
DH T = DHsub + IE + DH hyd
 The electrode potentials for elements are a measure of DH T . Thus, the stability of the
compounds in solution depends upon the value of electrode potential.
 Since transition elements can occur in more than one oxidation states, the oxidation
state for which the value of DH T is the lowest will be the most stable oxidation state
for that metal in aqueous solution. In other words, the lower the electrode potential
(i.e. more negative the standard reduction potential) of the electrode, more stable is
the oxidation state of the transition metal in the aqueous medium.
 The standard reduction potential of transition metals may be determined by using
standard hydrogen electrode as the counter electrode.
E 0M 2+ / M values for first row transition metals are given as below:
Element V Cr Mn Fe Co Ni Cu
E 0M 2+ / M (V) –1.18 –0.91 –1.18 –0.44 –0.28 –0.25 –0.34
 As seen in the above, there is no regular trend in the values of the reduction potential
as the ionization energies (IE1 + IE2) and sublimation energies of these metals do not
show any regular trend.
Oxidation States
 The valence electrons in transition elements are placed in two sets of orbital viz. (n–1)
d-orbital and ns-orbital. The difference between the energies of these two orbitals is
very less and hence both energy levels are used for bond formation. In ground state,
ns electrons are used to give an oxidation state of +2
Sc Ti V Cr Mn Fe Co Ni Cu Zn
+3 (+2) +2 +2 +2 (+1) (+1) (+1) +1 (+1)
+3 +3 +3 (+3) +2 +2 +2 +2 +2
+4 +4 +4 +4 +3 (+3) (+3) (+3)
+5 (+5) (+6) (+4) (+4)
+6 +7
Y Zr Nb Mo Te Ru Rh Rd Ag Cd
+3 (+3) (+2) +2 +2 +2 +2 +2 +1
+4 (+3) +3 (+4) +3 +3 (+3) (+2) +2
(+4) +4 (+5) +4 +4 +4 (+3)
+5 +5 (+5) (+6)
+6 (+6)
(+7)
(+8)
La Hf Ta W Re Os Ir Pt Au Hg
+3 (+3) (+2) +2 (+2) (+1) +2 +2 +1 +1
+4 (+3) (+3) (+3) (+2) +3 (+3) +3 +2
(+4) +4 +4 +3 +4 +4

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 +5 +5 +5 +4 (+6) (+5)
+6 +6 +6 (+6)
(+6) +8
+7
 Table shows general oxidation states of transition metals (very rare oxidation states
are given in parenthesis)
(i) The most common oxidation state of the first row transition metals is +2 except in
case of scandium. The oxidation state of +2 is obtained by losing ns electrons.
(ii) Bonding is primarily ionic in compounds having transition elements in low oxidation
state like +2 or +3, covalent character increases for higher oxidation states since
bonds are formed by sharing of electrons in higher oxidation states. For example, all
the bonds between manganese and oxygen in MnO 4 are covalent (Mn in + 7 oxidation
state)
(iii) The possibility of having a higher oxidation state increases with increase in atomic
number within group. For example, the common oxidation state for iron (Fe) are +2
and +3 whereas for ruthenium (Ru) and osmium (Os) the oxidation states of +4, +6
and +8 are also observed.
(iv) Transition metals also show low oxidation states of +1 and zero in some of their
compounds. The nature of bonding of such compounds is complex. When many
bonds are formed with a transition metal, the negative charge on the metal increases.
This causes accumulation of charge on the central metal and hence the bonds are not
very stable. In such cases, the transition metals donate their d-electrons to the other
constituents of the compounds. A good example of such bonding is the compounds of
transition metals with sulphur and carbon monoxide which have vacant orbitals to
accommodate the metal’s donated d-electrons. It is important to note that such a
situation of back donation can occur, only if the metal is in a low oxidation state. If
the metal is in high oxidation state the increased nuclear charge will hold the d-
electrons firmly to the nucleus and donation of d-electrons will not be favoured.
(v) A transition metal in solution will have an oxidation state that is most stabilized by the
solvent. Thus, the oxidation state of a metal in solution depends on the nature of the
solvent. A metal in a particular oxidation state may oxidize or reduce in solution under
appropriate conditions. For example, Cu+ is unstable in water and gets oxidized to
Cu2+, which is stable in water. Similarly, Fe2+ is unstable in treated water as it
undergoes oxidation in it.
(vi) The oxidation state of the transition metal also depends on the nature of combining
atoms. The compounds of metals with fluorine and oxygen exhibit the highest
oxidation state as fluorine and oxygen have high electro-negativities.

Catalytic properties
 Many transition metals and their compounds can be used as effective catalysts in
various processes. These metals or their compounds provide catalytic effect simply
because they can attain variable oxidation states. This fact is made clearer in the
following points.
(i) Transition elements have unpaired d-electrons and can have variable oxidation states.
This property of showing multiple oxidation state helps them to absorb an electron or
lose an electron to attain low and high oxidation states respectively. Thus, transition

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 metals are capable of absorbing and re-emitting wide range of energies (or electrons)
and providing suitable activation energy for a particular reaction.
(ii) In some cases, transition elements act as catalysts by forming unstable intermediate
compound with one of the reactants. As the reaction proceeds, the intermediate
compound decomposes generating the reactant (in another energy state) so that it can
react with the other reactant. The transition metal is left unchanged after the process,
thus acting as a catalyst.
X + Transition Metal �� � X.Catalyst
One Reactant (catalyst) intermeidate unstable compounds
X.Catalyst + Y ��
� XY + Catalyst
other reactant Product (Transition metal)
(iii) According to adsorption theory of catalysis, the transition metal provides a large
surface area with free valences where the reactants are adsorbed and facilitates the
reaction and a catalytic effect is observed.
Transition metal Process
Vanadium Use as V2O5 in manufacture of H2SO4 by contact process
Cobalt Used as a mixture with thorium in Fischer-Tropsch process for
synthesis of petrol
Nickel Used in finely divided state (Raney nickel) in the hydrogenation
reactions.
Platinum Use of spongy platinum in manufacture of H2SO4 by contact
process and in oxidation of ammonia to HNO3 by Ostwald’s
process
Iron Used in the synthesis of ammonia by Haber’s process
Molybdenum Used as a promoter in Haber’s process
Titanium Use as TiCl4 as Ziegler-Natta catalyst in the production of
polythene
Iron Used as Fenton’s reagent (FeSO4 and H2O2) for oxidizing
alcohols to aldehydes
Platinum Used as Adms catalyst (Pt/PtO) which is used for reduction
Rhodium Used as Wilkinson catalyst (RhCl (PPh)3) in the hydrogenation
of alkenes

Coloured Ions
 Most of the transition metal compounds are coloured both in the solid state and in
aqueous solution. They differ from s and p-block elements in this respect. Colour is
always associated with adsorption of light of a particular wavelength in visible region.
Electrons absorb energy and get promoted to higher energy level. This transition of
electrons is responsible for coloured ions. The transition elements have incomplete d-
orbitals. Though these d-orbitals are degenerate, i.e. have the same energy, for an
isolated ion, but in compounds these orbitals are affected by the combining atoms or
molecules and lose their degeneracy. This loss of degeneracy makes transition of
electron from one d-orbital to another d-orbital which is otherwise forbidden. Such an
effect on the central metal by incoming ligands is called crystal field effect.
 The difference in energy for these d-orbitals is very less and the radiation of light
corresponding to such small amount of energy comes within visible region of light.

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 Hence, transition metal compounds are coloured.
 In solution the transition metal ion is not isolated but surrounded by water molecules
and thus a similar effect is seen in solution. Let us make the point clear by taking an
3+ 3+
example of [Ti(H 2O) 6 ] complex that exists in water [Ti(H 2O) 6 ] as purple color.
This can be explained as follows:
 The d-orbitals of titanium are split into two sets due to crystal field effect offered by
3+
H2O molecules. One set has lower energy than the other. In [Ti(H 2O) 6 ] , Ti has a d1
configuration and the electron is present in the lower energy level in the ground state.
On absorption of yellow wavelength the electron is excited to the high energy set.
Since yellow light is absorbed from visible region of light, the blue and red light will
3+
be transmitted and the solution of [Ti(H 2O) 6 ] will appear purple which is a mixed
effect of blue and red colour. This process can be expressed schematically as follows

Colours of some of the hydrated metal ions are given in the table below:
Oxidation state of the hydrated ions Colour
Sc(III), Ti (IV) Colorless
Ti (III) Purple
V(III) Green
V(II), Cr (III) Violet
Mn (III) Violet
Fe (III) Yellow
Mn (II) Pink
Fe (II) Green
CO (II) Pink
Ni (II) Green
Cu (II) Blue
Zn (II), Cu (I) Colourless
 Sc (III) and Ti (IV) are colourless because they have empty d-orbitals and hence no
electron for promotion to higher level. Cu (I) and Zn (II) are also colourless since they
have completely filled d-orbitals leaving no empty orbital for promotion of electrons.

Magnetic Properties
 Transition metal ions and their compounds show magnetic behaviour due to the
presence of unpaired electrons in (n–1) d-orbitals. A spinning electron has spin as well
as orbital motion. Thus a spinning electron revolving around the nucleus creates a
magnetic field around itself. In other words, an electron behaves as a micro-magnet
having a definite value of magnetic moment. When a substance is placed in an
external magnetic field, the magnetic moment of the electron either aligns or opposes
the external magnetic field. If the magnetic moment aligns itself than the substance
experiences attractive influence in a magnetic field and are said to show paramagnetic
character. The greater the number of unpaired electrons, greater will be the resulting

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 magnetic moment and more will be the paramagnetic character. Iron, cobalt and
nickel are so strongly paramagnetic that they can be magnetized and hence are called
ferromagnetic.
The magnetic moment is expressed in Bohr magneton (B.M.)
eh
B.M = �10 -24 JT -1
4pmc
Where, h is the Planck’s constant
e is the electronic charge
c is the velocity of light
m is the mass of electron
 A paramagnetic substance is characterized by its effective magnetic moment (eff)
which is given by the folling expression.
 eff = n(n + 2) B.M.
Where n is the number of unpaired electrons
 When pairing up of electrons takes place after middle of the series, the magnetic field
created by two electrons in the same orbital with opposite spins are in opposite
direction. Thus the electron pair will not have any residual magnetic field. Such a
compound when placed in an external magnetic field will have induced magnetic
movement whose direction will be in opposite direction to the applied magnetic field.
Such a substance experiences repulsion by the applied magnetic field. This kind of
behaviour is called diamagnetic behaviour. Thus, transition elements which have
paired electrons are diamagnetic in nature.

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 Table showing magnetic moments of some of the transition metal ions

Ion Electronic Name of unpaired Observed Magnetic

Configuration Electrons moments (Bohr magneton)
Sc3+ d0 0 0
Ti 2+ d2 2 2.8 – 3.1
V 2+ d3 3 3.7 – 3.9
Cr 2+ d4 4 4.8 – 4.9
Mn 2+ d5 5 5.9 – 6.0
Fe 2+ d6 5 5.0 – 5.5
Co 2+ d7 3 4.4 – 5.2
Ni 2 + d8 2 2.9 – 3.4
Cu 2+ d9 1 1.8 – 2.2
Zn 2+ d10 0 0
Complex Formation:
 Transition metal ions form a variety of complexes unlike, s and p-block elements.
Complexes are the binary compounds formed by the donation of lone pairs by a
negative ion or neutral molecule (called bonds) to the central metal ion. Transition
elements from complexes easily because
(i) They have small size and thus can accommodate a number of ligands around
them.
(ii) They have large effective nuclear charge due to poor shielding effect of d-orbitals.
(iii) They have vacant d-orbitals of suitable energy so as to accept lone pairs of
electrons from ligands. Availability of low lying vacant orbital is the primary
requirement for complex formation.
 A few examples are [Fe(CN)6 ]3- ,[Cu(NH 3 ) 4 ]2+ ,[Zn(NH) 3 ]2+ ,[Ni(CN) 2 ]2 ,[PtCl4 ]2
Interstitial Compounds:
 Interstitial compounds are those compounds in which small atoms (like hydrogen,
nitrogen carbon. etc.) occupy empty spaces (or interstitial sties) within the lattice
framework of the compound.
 Transition metals form a large number of interstitial compounds. These compounds
are hard and rigid. For example, steel and cast iron, the interstitial compound of iron
and carbon is a hard interstitial compound and is less malleable and ductile than
metals while their density is higher
Alloy Formation:
 Transition metals have similar atomic sizes and thus atoms of one metal can very well
replace the atom of another metal from its position in the crystal lattice. In fact,
transition metal gives alloys on cooling.
 Alloys generally have better properties than individual metals. They are harder than
the constituent metals and have high melting points. Alloys are more resistance to
corrosion.
 The metals chromium, vanadium, molybdenum, tungsten and manganese are used in
the formation of alloy steel and stainless steel.

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General Properties of First Row Transition Metal Compounds
 Transition metals form binary compounds with a number of non-metals like oxygen,
nitrogen, phosphorous, halogens and sulphur. Let us examine a few important classes
of compounds of first row transition metals with respect to their general properties.
Oxides:
(i) The metals of the first transition series form oxides with oxygen at elevated
temperatures
(ii) Several oxides are formed with general formulae MO, M 2O3, MO2, M2O5 and MO3.
Some important oxides of the first transition series are given below:
Transition metal Oxides
Sc Sc 2 O3 (b)
Ti TiO(a)
Ti 2 O3 (b)
TiO 2 (am)
V VO(b)
V2 O3 (b)
VO 2 (am)
V2 O5 (a)
Cr CrO(b)
Cr2O3 (am)
CrO 2 (am)
CrO3 (a)
Mn MnO(b)
Mn 2 O3 (am)
Mn 3O 4 (am)
MnO 2 (am)
Mn 2 O7 (a)
Fe FeO(b)
Fe 2 O3 (b)
Fe3O 4 (b)
Co CoO(b)
Ni NiO(b)
Cu Cu 2 O(b)
CuO(b)
a = Acidic, b = Basic, am = Amphoteric
(iii) In general, the oxides in the lower oxidation states of metals are basic and in their
higher oxidation states, transition metals forms acidic oxides. A transition metal in its
intermediate oxidation state primarily forms amphoteric oxides.
(iv) The basic and Amphoteric oxides dissolves in non-oxidizing acids to form hexaaqua
n+
ions, [M(H 2 O)6 ] . Some of the important compounds like potassium permanganate,

Dr. Brijesh Dabhi

 potassium dichromate and potassium magnates are formed by dissolution of some of
these oxides in acids.
(v) Manganese dioxide (MnO2) in its purified form is used in dry cells.

Halides:
(i) Transition elements react slowly with halogens at high temperature to form halides.
(ii) The order of reactivity of the halogen in the formation of halides of transition metal is
F > Cl > Br > I.
(iii) Transition metals attain their highest oxidation state in their fluorides owing to the
electronegativity of fluorine.
(iv) Halides of transition metals in higher oxidation state are not stable to hydrolysis and
are readily hydrolyzed to oxides. For example, TiCl4 reacts with water to give TiO2.
TiCl4 + 2H 2 O ��� TiO 2 + 4HCl
(v) Fluorides of transition metals are ionic in nature. The ionic character of halides
decrease with increase in the mass of the halogen. For example, CuF 2 is ionic whereas
CuCl2 and CuBr2 are covalent.

Sulphides:
(i) Sulphides of the transition metals can either be obtained by direct combination of
metals with sulphur or by the action of H2S or Na2S on the salts of these metals.
(ii) Transition metals are generally found in lower oxidation states in their Sulphides
since sulphur is not a good oxidizing agent.
(iii) The sulphides of transition metals are usually dark coloured or black and are insoluble
in water.

General Group trends in the Chemistry of Transition Metals

Group 4 elements:
(i) Group 4 consists of titanium, zirconium and hafnium.
(ii) The most common oxidation state is +4 for these elements the +3 oxidation state is
known for titanium only.
(iii) The typical compounds of this group are chlorides, TiCl4, ZrCl4 and HfCl4 and oxides
TiO2, ZrO2 and HfO2.
(iv) Zr and Hf are silvery white metals and occur together in minerals, since they have
nearly same ionic radii ( (Zr 4+ = 79 pm, Hf 4 = 78 pm) as a consequence of lanthanide
contraction.
(v) Zirconium oxides are used as refractory materials.

Group 5 elements:
(i) Group 5 consists of vanadium, niobium and tantalum.
(ii) The most stable oxidation state of this group is +5. Vanadium also shows oxidation
states of +3 and +4 in its compounds.
(iii) Niobium and tantalum have similar chemical properties.
(iv) Niobium alloys are used in jet engines.
(v) Tantalum is resistant to corrosion and hence it is used in analytical weights and in
instruments used in surgery of veins.

Dr. Brijesh Dabhi

Group 6 elements:
(i) Group 6 consists of chromium, molybdenum and tungsten.
(ii) The elements of group 6 show variable oxidation states in their compounds. The most
important oxidation states exhibited by chromium in its compounds are +3 and +6.
(iii) Chromium is used in stainless steel and in chrome plating while molybdenum is used
in X-ray tubes.
(iv) Molybdenum and tungsten also find use as catalysts.

Groups 7 elements:
(i) Group 7 consists of manganese, technetium and rhenium.
(ii) The common oxidation states of manganese, the most important element of this group
are +2, +4 and +7.
(iii) Technetium occurs in traces in nature and is radioactive. Rhenium is also rare.
(iv) Manganese along with chromium is used in the manufacture of steel.
(v) Manganese dioxide is used as a catalyst while potassium permanganate is a very
common laboratory reagent.
(vi) Rhenium is used in electronic filaments, flash bulbs and high temperature
thermocouples.

Group 8, 9 and 10 elements:

(i) The elements of group 8, 9 and 10 are studied by classifying them as triads.
Group 8 Group 9 Group 10
First Triad Iron Cobalt Nickel
Second Triad Ruthenium Rhodium Palladium
Third Triad Osmium Iridium Platinum
(ii) The elements of the first triad are known as ferrous metals. Iron and cobalt show
oxidation states of +3 and +2 in their compounds whereas nickel generally exhibits +2
oxidation states in its compounds.
(iii) The elements of the second and third triad are known as platinum metals. They
generally show lower oxidation state in their compounds.

Group 11 elements:
(i) Group 11 consists of copper, silver and gold. These metals are known as coinage
metals.
(ii) The most stable oxidation state for copper is +2 whereas for silver and gold +1 is the
most stable oxidation state.
(iii) These elements form alloys with many metals.
(iv) Silver and gold are used in jewellery.

Potassium Dichromate
Preparation of Potassium Dichromate:
Potassium dichromate is prepared from chromates which in turn are prepared from
iron chromate, FeCr2O4. The various steps involved are as follows:

Dr. Brijesh Dabhi

(i) Preparation of Sodium Chromate :
The ore, FeCr2O4 is finely powdered, mixed with sodium carbonate and quick
lime and then heated to redness in presence of air to evolve carbon dioxide. The
reaction involved can be written as follows:
4FeO.Cr2 O3 + O 2 ��� 2Fe 2 O3 + 4Cr2 O3
4Na 2 CO3 + 2Cr2 O3 ��
� 4Na 2 CrO 4 + 4CO 2 ] �2
___________________________________________________
4FeO.CrO3 + 8Na 2CO3 + 7O 2 �� � 8Na 2CrO 4 + 2Fe 2 O3 + 8CO 2
The roasted mass is then extracted with water when sodium chromate is
completely dissolved while Fe2O3 is left behind.
(ii) Conversion of sodium chromate into sodium dichromate :
Sodium chromate solution obtained is filtered and treated with concentrated
sulphuric acid to obtain sodium dichromate as shown below:
2Na 2CrO 4 + H 2SO 4 ��� Na 2 Cr2O 7 + Na 2SO 4 + H 2O
Sodium sulphate being less soluble crystallizes and then filtered off.
(iii) Conversion of sodium dichromate into potassium dichromate :
Sodium dichromate is more soluble and less stable than potassium dichromate
and it is converted to potassium dichromate easily upon treatment with potassium
chloride
Na 2 Cr2 O7 + 2KCl �� � K 2 Cr2 O7 + 2NaCl
Potassium dichromate being much less soluble than sodium salt crystallizes
out on cooling.

Properties of potassium dichromate:

Potassium dichromate is an orange-red crystalline solid which melts at 669 K. It is
moderately soluble in cold water but freely soluble in hot water. Some important properties
are as follows:
(i) Action of heat: When heated potassium dichromate decomposes with evolution of
oxygen
D
4K 2Cr2O7 �� � 4K 2 CrO 4 + 2Cr2 O3 + 3O2
(ii) Action of alkalis: An orange-red solution of potassium dichromate turns yellow upon
treatment with alkali due to the formation of chromate.
K 2 Cr2 O7 + 2KOH �� � 2K 2CrO 4 + H 2O
The reaction is reversed on acidification.
Thus, the inter-conversion of chromate and dichromate is an equilibrium
process which is pH dependent.
���
2CrO 24- + 2H + �� � 2HCrO 4 ��
-
��� 2-
� Cr2 O7 + H 2 O
Chromate Hydrogen Dichromate
(Yellow) Chromate (Orange)
In acidic conditions (low pH), dichromate is more stable while under alkaline
conditions (high pH) chromate is more stable. Structure of chromate and dichromate
ions are shown below:

Dr. Brijesh Dabhi

(iii) Action of concentrated sulphuric acid: Red crystals of chromic anhydride
(chromium trioxide) are formed when potassium dichromate is treated with cold
concentrated sulphuric acid
K 2 Cr2 O7 + 2H 2SO 4 �� � 2CrO 3 + 2KHSO 4 + H 2O
(Re d)
On the other hand, heating of potassium dichromate with concentrated
sulphuric acid results in evolution of oxygen
2K 2Cr2 O 7 + 8H 2SO4 �� � 2K 2SO 4 + 2Cr2 (SO 4 ) 3 + 8H 2O + 3O 2
(iv) Oxidizing properties: Potassium dichromate is a powerful oxidizing agent. In the
presence of dilute sulphuric acid, one mole of potassium dichromate produces three
moles of oxygen atoms as indicated by the equation.
K 2 Cr2 O7 + 4H 2SO 4 ��
� K 2SO 4 + Cr2 (SO 4 )3 + 4H 2O + 3[O]
Cr2O 72- + 14H + + 6e - ��
� 2Cr 3+ + 7H 2 O
2-
Where chromium in +6 oxidation state in Cr2 O 7 ion is being reduced to Cr 3+
(+3 oxidation state)
Let us examine the action of acidified potassium dichromate solution as an
oxidizing agent by taking few examples:

 It liberates I2 from KI
K 2 Cr2 O7 + 4H 2SO 4 ��� K 2SO 4 + Cr2 (SO 4 )3 + 4H 2O + 3[O]
6KI + 3H 2SO 4 + 3[O] �� � 3K 2SO 4 + 3I 2 + 3H 2O
_______________________________________________________
K 2 Cr2 O7 + 7H 2SO 4 + 6KI ��
� 4K 2SO 4 + Cr2 (SO 4 )3 + 3I 2 + 7H 2O
or Cr2 O72- + 14H + + 6I - ��
� 2Cr 3+ + 3I 2 + 7H 2 O

 It oxidizes ferrous salts to ferric salts.

K 2Cr2O 7 + 4H 2SO 4 ��
� K 2SO 4 + Cr2 (SO 4 ) 3 + 4H 2O + 3[O]
{2FeSO 4 + H 2SO 4 + [O] ��� Fe 2 (SO 4 ) 2 + H 2 O}�3
K 2Cr2O 7 + 7H 2SO 4 + 6FeSO 4 ��� K 2SO 4 + Cr2 (SO 4 ) 3 + 3Fe 2 (SO 4 ) 3 + 7H 2O
________________________________________________________________
or Cr2 O72- + 14H + + 6Fe 2+ ��
� 2Cr 3+ + 6Fe3+ + 7H 2O
The above two reactions are used in the volumetric estimation of iodine and iron (II).

 In oxidizes H2S to sulphur.

Dr. Brijesh Dabhi

 K 2 Cr2 O7 + 4H 2SO 4 ��
� K 2SO 4 + Cr2 (SO 4 )3 + 4H 2O + 3[O]
{H 2S + [O] ��
� H 2O + S}�3
_____________________________________________________________________
K 2 Cr2 O7 + 4H 2SO 4 + 3H 2S ��
� K 2SO 4 + Cr2 (SO 4 )3 + 3S + 7H 2O
or Cr2 O72- + 8H + + 3H 2S ��
� 2Cr 3+ + 3S + 7H 2 O
 It oxidizes ethyl alcohol to acetaldehyde and acetic acid
K 2 Cr2 O7 + 4H 2SO 4 ��
� K 2SO 4 + Cr2 (SO 4 )3 + 4H 2O + 3[O]

CH 2CH 2 OH + [O] ��
� CH 3CHO + H 2O
Etheyl alcohol Acetaldehyde
CH3CHO + [O] �� � CH 3COOH
Acetaldehyde Acetic acid
 It oxidizes sulphides to sulphates
K 2 Cr2 O7 + 4H 2SO 4 ��� K 2SO 4 + Cr2 (SO 4 )3 + 4H 2 O + 3[O]
{Na 2SO3 + [O] �� � Na 2SO 4 } �3
_________________________________________________
K 2 Cr2 O7 + 4H 2SO 4 + 3Na 2SO3 ��
� K 2SO + Cr2 (SO 4 )3 + 4H 2O + 3Na 2SO 4
or Cr2 O 72- + 8H + + 2SO32- ��
� 2Cr +3 + 3SO24- + 7H 2 O

 It oxidizes SO2 to sulphuric acid

K 2 Cr2 O7 + 4H 2SO 4 ��� K 2SO 4 + Cr2 (SO 4 )3 + 4H 2O + 3[O]
{SO 2 + [O] + H 2O �� � H 2SO 4 }�3
_______________________________________________
K 2 Cr2 O7 + H 2SO 4 + 3SO 2 ��
� K 2SO 4 + Cr2 (SO 4 )3 + H 2O
or Cr2 O 72- + 2H + + 3SO 2 ��
� Cr2 (SO 4 )3 + H 2 O

 It oxidizes halogen acids to halogen.

K 2 Cr2 O 7 + 14HCl ��
� 2KCl + 2CrCl3 + 7H 2O + 3Cl 2

 Chromyl chloride test: When potassium dichromate is treated with a concentrated

sulphuric acid and a chloride, reddish-brown vapours of chromyl chloride are formed
K 2 Cr2 O7 + 2H 2SO 4 ��
� 2KHSO 4 + 2CrO3 + H 2O
{KCl + 4HCl �� � KHSO 4 + HCl}�4
2CrO3 + 4HCl �� � 2CrO 2Cl 2 + 2H 2O
_________________________________________________________
K 2 Cr2 O7 + 4KCl + 6H 2SO 4 ��
� 2CrO 2Cl 2 + 6KHSO 4 + 3H 2O
Chromyl chloride
(Re d)

NOTE
NOTE
 This test is used in detection of chloride ions in qualitative analysis.

Dr. Brijesh Dabhi

Potassium Permanganate
Preparation of potassium permanganate:
Potassium permanganate is prepared on large scale from mineral pyrolusite (MnO 2).
The preparation involves following steps.
(i) Conversion of MnO2 to potassium manganate :
Pyrolusite is fused with potassium hydroxide and the molten liquid is stirred well in
the presence of air.
2MnO 2 + 4KOH + O 2 �� � 2K 2 MnO 4 + 2H 2O
Oxidizing agents like potassium nitrate can also be used instead of air.
MnO 2 + 2KOH + KNO3 �� � K 2 MnO4 + KNO 2 + H 2 O
(ii) Oxidation of potassium manganate to potassium permanganate :
Potassium manganate can be chemically oxidized to permanganate by bubbling CO 2,
Cl2, etc, through the solution of potassium manganate.
3K 2 MnO4 + 2CO2 �� � 2KMnO4 + MnO2 �+2K 2 CO3
2K 2 MnO 4 + Cl2 �� � 2KMnO4 + 2KCl
These chemical processes are not very economical at the industry scale and hence
electrolytic oxidation is preferred over them.
Potassium manganate is oxidized electrochemically to permanganate. The
electrode reactions taking place are:
At anode:
2K 2 MnO4 + H 2O + O �� � 2KMnO 4 + 2KOH
MnO 24- ��
� MnO 4- + e -
or Green Purple

At cathode: 2H + + 2e- �� � H2 �
 Oxidation by potassium permanganate in neutral solution:
(i) It oxidizes hot manganese sulphate to manganese dioxide
2KMnO 4 + H 2 O �� � 2KOH + 2MnO 2 + 3[O]
3MnSO 4 + 3H 2 O + 3[O] �� � 3MnO 2 + 3H 2SO 4
2KOH + H 2SO 4 �� � K 2SO 4 + 2H 2 O
__________________________________________________
3MnSO 4 + 2KMnO 4 + 2H 2 O �� � 5MnO 2 + K 2SO4 + 2H 2SO 4

(ii) It oxidizes sodium thiosulphate to sodium sulphate

3Na 2S2 O3 + 8KMnO 4 + H 2 O �� � 3Na 2SO 4 + 8MnO 2 + 3K 2SO 4 + 2KOH
(iii) It oxidizes hydrogen sulphide to sulphur
2KMnO 4 + 4H 2S �� � 2MnS + S + K 2SO 4 + 4H 2O

Properties of potassium permanganate:

Potassium permanganate is a purple crystalline solid melting at 523 K. It is slightly
soluble in cold water. The solubility increases in hot water.
(i) Action of heat: Potassium permanganate decomposes to oxygen, potassium
manganate and manganese dioxide when heated to 746 K.

Dr. Brijesh Dabhi

 D
2KMnO 4 �� � K 2 MnO4 + MnO2 + O2
(ii) Action of concentrated sulphuric acid: When treated with cold concentrated
sulphuric acid potassium permanganate is converted to Mn2O7 (green oil) which
decomposes on warming to MnO2 (The reaction is highly explosive)
2KMnO 4 + 2H 2SO 4 �� � Mn 2O7 + 2KHSO 4 + H 2O
D
2Mn 2 O7 �� � 4MnO 2 + 3O 2
(iii) Oxidizing properties: Potassium permanganate is a strong oxidizing agent and the
reaction is pH dependent.
2-
In alkaline solution: In strongly alkaline solution, MnO 4 ion is produced as shown
in the reaction.
2KMnO 4 + 2KOH �� � 2K 2 MnO 4 + H 2O + [O]
or MnO -4 + e - ��
� MnO 24-
2-
The MnO 4 ion gets further reduced to MnO 2 ,
K 2 MnO4 + H 2 O ��
� MnO 2 + 2KOH + [O]
or MnO 24- + 2H 2 O + 2e - ��
� MnO 2 + 4OH -
Thus, the complete reaction is
2KMnO 4 + H 2 O �� � 2MnO2 + KOH + 3O
or MnO-4 + 2H 2 O + 3e- ��
� MnO2 + 4OH -

A few examples of oxidation by KMnO4 in alkaline medium are:-

(a) Potassium iodide is oxidized to potassium iodate
2KMnO 4 + H 2O + KI �� � 2MnO 2 + 2KOH + KIO3
or I - + 6OH - ��
� IO3- + 3H 2 O + 6e-
(b) Potassium permanganate is used in oxidation of olefinic compounds to glycols. It is
known by the name of Baeyer’s reagent in these reactions.
CH 2 C H 2O H
+ H 2O + [O ]
CH 2
C H 2O H
In acidic medium: In the presence of dilute sulphuric acid, the following reaction
takes place,
2KMnO 4 + 3H 2SO4 �� � K 2SO4 + 2MnSO 4 + 3H 2 O + 5[O]
or MnO -4 + 8H + + 5e - ��
� Mn 2+ + 4H 2O
Potassium permanganate acts as a very strong oxidizing agent in acidic
medium. Few examples of oxidation by acidic potassium permanganate solution are:

(a) Oxidation of H2S to S

2KMnO 4 + 3H 2SO 4 ��
� K 2SO 4 + 2MnSO 4 + 3H 2O + 5[O]
{H 2S + O ��
� H 2 O + S} �5

Dr. Brijesh Dabhi

 ____________________________________________________
2KMnO 4 + 3H 2SO4 + 5H 2S ��
� K 2SO 4 + 2MnSO4 + 8H 2 O + 5S
or 2MnO -4 + 16H + + 5S2- �� � 2Mn 2+ + 8H 2O + 5S
(b) Oxidation of ferrous sulphate to ferric sulphate
2KMnO 4 + 3H 2SO 4 �� � K 2SO 4 + 2MnSO 4 + 3H 2O + 5[O]
{2FeSO 4 + H 2SO 4 + [O] ��
� Fe 2 (SO 4 )3 + H 2O}�5
_____________________________________________________________
2KMnO 4 + 8H 2SO4 + 10FeSO 4 �� � K 2SO4 + 2MnSO4 + 5Fe2 (SO 4 )3 + 8 H 2O
or 2MnO -4 + 16H + + 10Fe 2+ ��� 2Mn 2+ + 18H 2O + 10Fe3+
(c) Oxidation of potassium iodide to iodine:
2KMnO 4 + 3H 2SO 4 �� � K 2SO 4 + 2MnSO 4 + 3H 2O + 5[O]
{2KI + H 2SO 4 + [O] ��
� K 2SO 4 + I 2 + H 2O}�5
_____________________________________________________
2KMnO 4 + 8H 2SO 4 + 10KI ��� 6K 2SO 4 + 2MnSO 4 + 8H 2 O + 5I 2
or 2MnO-4 + 16H + + 10I - ��
� 2Mn 2+ + 8H 2O + 5I 2

In neutral medium: In neutral medium, potassium permanganate is weakly oxidizing

and the reaction involved is
2KMnO 4 + H 2O ��
� 2KOH + 2MnO 2 + 3[O]
or MnO-4 + 2H 2 O + 3e- �� � MnO2 + 4OH -
The alkali (KOH) produced renders the solution basic as the reaction proceeds and the
reaction given above is then essentially same as that for alkaline medium.

Uses:
(i) Potassium permanganate is used in volumetric analysis for estimation of ferrous salts,
oxalates, iodide and hydrogen peroxide.
(ii) It is used as a strong oxidizing agent in the laboratory.
(iii) It is also used as a disinfectant and germicide.

Structure of permanganate ion:

 The four oxygen atoms are arranged tetrahedrally around manganese in MnO -4 as
manganese is sp3 hybridized

Inner Transition Elements (Lanthanides)

 The elements in which the last electron enters (n–2) f-orbitals are called f-block
elements. These elements are also known as inner transition elements. This is

Dr. Brijesh Dabhi

 because they form a series between the transition metal series.
 The filling of 4f and 5f-obitals takes place in f-block elements. This is the basis of
classification of f-block elements as lanthanides and actinides.
 Lanthanides are the elements in which the last electron enters the 4f-orbital.
Lanthanides constitutes the first inner transition series. These elements are called
lanthanides or lanthanum since series starts from the element lanthanum.
 The elements in which the last electron enters the 5f-orbital constitute the second
inner transition series. They are also called actinides or actinons because the series
starts from the element actinium.
 The members of two series with their electronic configuration are given in the table
below:
Electronic Configuration of Lanthanides

Name of the Symbol Atomic Electronic Oxidation

element number configuration states
Lanthanum La 57 5d16s2 +3
Cerium Ce 58 4f1 5d1 6s2 +3, +4
Praseodymium Pr 59 4f3 5d0 6s2 +3, (+4)
Neodymium Nd 60 4f4 5d10 6s2 (+2), +3
Promethium Pm 61 4f5 5d0 6s2 (+2), +3
Samarium Sm 62 4f6 5d0 6s2 (+2), +3
Europium Eu 63 4f7 5d0 6s2 +2, +3
Gadolinium Gd 64 4f7 5d1 6s2 +3
Terbium Tb 65 4f9 5d0 6s2 +3, (+4)
Dysprosium Dy 66 4f10 5d0 6s2 +3, (+4)
Holmium Ho 67 4f11 5d0 6s2 +3
Erbium Er 68 4f12 5d0 6s2 +3
Thulium Tm 69 4f13 5d0 6s2 (+2), +3
Ytterbium Yb 70 4f14 5d0 6s2 +2, +3
Lutetium Lu 71 4f14 5d1 6s2 +3

Electronic Configuration of actinides

Name of the Symbol Atomic Electronic Oxidation states

element number configuration
Actinium Ac 89 6d1 7s2 +3
Thorium Th 90 6d2 7s2 +3, +4
Protactinium Pa 91 5f2 6d1 7s2 +3, +4, +5
Uranium U 92 5f3 6d1 7s2 +3, +4, +5, +6
Neptunium Np 93 5f4 6d1 7s2 +3, +4, +5, +6, +7
Plutonium Pu 94 5f6 6d0 7s2 +3, +4, +5, +6, +7
Americium Am 95 5f7 6d0 7s2 +2, +3, +4, +5
Curium Cm 96 5f7 6d1 7s2 +3, +4
Berkelium Bk 97 5f8 6d1 7s2 +3, +4
Californium Cf 98 5f10 6d0 7s2 +2, +3
Einsteinium Es 99 5f11 6d0 7s2 +2, +3
Fermium Fm 100 5f12 6d0 7s2 +2, +3

Dr. Brijesh Dabhi

Mendelevium Md 101 5f13 6d0 7s2 +2, +3
14 0 2
Nobelium No 102 5f 6d 7s +2, +3
Lawrencium Lr 103 5f14 6d1 7s2 +3
 From the electronic configuration of lanthanides and actinides following remarkable
points can be seen.
(i) The electronic configuration of cerium (Z = 58) is 4f4 5d1 6s2 and that of the next
element praseodymium (Z = 59) is 4f3 5d0 6s2.
(ii) Europium (Z = 63) and gadolinium (Z = 64) have electronic configuration 4f 7 5d0 6s2
and 4f7 5d1 6s2 and thus is explained on the basis of extra stability of the half-filled
orbitals in their cores.
(iii) Similarly, the effect on stability due to completely filled orbitals is seen in electronic
configuration of ytterbium (4f14 5d0 6s2) and lutetium (4f14 5d1 6s2)

General Properties of Lanthanides and Actinides

 The elements of lanthanide and actinide series are highly dense metals with high
boiling points. These metals form alloys with other metals especially with iron. These
alloys are used extensively since the presence of rare earth elements is found to
improve the work ability of steel at high temperatures. Two important alloys of rare
earth elements are
(i) Misch metal: Misch metal consists of rare earth elements (94 – 95%), iron (upto 5%)
and traces of sulphur, carbon, calcium and aluminium.
(ii) Pyrophoric alloys: Pyrophroic alloys consist of following elements:
Cerium 40.5%
Lanthanum and neodymium 44%
Iron 4.5%
Aluminium 0.5%
Calcium, silicon and carbon 10.5%

Some characteristic properties of lanthanides:

(i) The typical oxidation state of lanthanide elements is +3. Some of the element also
exhibit +2 and +4 oxidation states but these oxidation states are not as stable as +3.
Thus, the elements in +2 and +4 oxidation states tend to become stable by attaining
+3 oxidation state.
Hence, Sm2+, Eu2+ and Yb2+ ions in solution act as good reducing agents since
they tend to oxidize to more stable +3 oxidation states. Similarly, Ce 4+ acts as a good
oxidizing agent in solution due to its ability to get reduced to Ce3+ easily.
(ii) The ionic radii of trivalent lanthanides decrease steadily as the atomic number of the
lanthanide element increases as is normally expected. But after the middle of the
series, the number of electrons added to (n–2) f-subshell increases and it is expected
that these electrons should shield the outermost electrons from the nuclear charge.
Thus, the screening offered by f-electrons would counterbalance the effect of
increased nuclear charge. But since f-orbitals are too diffused, shielding of the
outermost electrons is not perfect. This imperfect shielding is unable to
counterbalance the effect of increased nuclear charge leading to a steady contraction
in ionic radii. The regular contraction is size is called lanthanide construction.
Consequences of lanthanide contraction:
Dr. Brijesh Dabhi
(i) Similar chemical properties: The ionic radii of lanthanides are very similar and thus
separation of lanthanides in pure state is difficult. But, due to lanthanide contraction
there are some differences in chemical properties of these elements which enable the
separation of individual lanthanide elements by fractional crystallization or ion-
exchange methods.
(ii) Basic strength of hydroxides: As the size of the lanthanide ion decreases from Ce 3+
to Lu3+, the covalent character of M-OH bond increases and hence the basic strength
decreases. Thus, Ce(OH)3 is most basic while Lu(OH)3 is least basic.
(iii) Similarity of second and third transition series: The effect of lanthanide
contraction is also seen in the transition series elements. The ionic radii of Zr (160
pm) and Hf (159 pm) of the second and third transition series are almost same
because of the lanthanide contraction.

Some characteristic properties of actinides:

(i) The dominant oxidation state of these elements is +3. Actinides also exhibit an
oxidation state of +4. Some actinides such as uranium, neptunium and plutonium also
show an oxidation state of +6.
(ii) The actinides show actinide contraction (like lanthanide contraction) due to poor
shielding effect of the nuclear charge by 5f electrons.
(iii) All the actinides are radioactive. Actinides are radioactive in nature so the study of
their chemistry is difficult in the laboratory. Their chemistry is studied using tracer
techniques.

Comparison of lanthanides and actinides:

Similarities:
Lanthanides and actinides involve filling of f-orbitals and thus are similar in many respects.
(i) The most common oxidation state is +3 for both lanthanides and actinides.
(ii) Both are electropositive in nature and thus very reactive.
(iii) Magnetic and spectral properties are exhibited by both lanthanides and actinides.
(iv) Actinides exhibit actinide contraction just like lanthanides

Difference:
Lanthanides and actinides differ in some of their characteristics as follows:
(i) Besides +3, lanthanides also show oxidation states of +2 and +4 while actinides
show higher oxidation states of +4, +5, +6 and +7 as well.
(ii) Lanthanide ions are colourless while most of the actinide ions are coloured.
(iii) Actinides have a greater tendency towards complex formation as compared to
lanthanides.
(iv) Lanthanide compounds are less basic while actinide compounds have appreciable
basicity.
2+ 2+
(v) Actinides form few important oxocations such as UO 2 , PuO 2 , etc, while such
oxocations are not known for lanthanides.
(vi) Almost all actinides are radioactive while lanthanides, except promethium, are
non-radioactive.
(vii) The magnetic properties of actinides can be easily explained while it is difficult to

Dr. Brijesh Dabhi

 do so in the case of lanthanides.
Uses of Lanthanides and Actinides
 Inner transition elements and their compounds, find applications in variety of fields.
Some important applications of these elements and their compounds are listed below:
(i) Misch metal: An alloy of rare earth elements is used in the production of different
brands of steel like heat resistant, stainless and instrumental steels.
(ii) Pyrophoric alloys: Find their uses in the preparation of ignition devices such as
tracer bullet shells and flints for lighters.
(iii) Lanthanide oxides: Can absorb ultraviolet rays. Some such oxides are used as
additives in glasses for special purposes like
 Sunglasses (by adding Nd2O3)
 Goggles for glass blowing and welding work (by adding Nd2O3 and Pr2O3)
 Glasses protecting eyes from neutron radiation (by adding Ce2O3 + Sm2O3)
(iv) Lanthanide oxides are also used as abrasives for polishing glasses.
(v) Lanthanide compounds are used in manufacture of dyes and paints. For example,
cerium molybdate is used in yellow dyes and salts of Nd are used for red colour
(vi) Certain compounds of lanthanides are used as catalyst for reactions like
hydrogenation, dehydrogenation, oxidation of organic compounds and petroleum
cracking.
(vii) Lanthanide elements and compounds find uses in nuclear fuel control, shielding and
fluxing devices.
(viii) Actinides like uranium and plutonium are used as a nuclear fuel in nuclear reactors.
(ix) Aqueous solution of Ce +4 is used as an oxidizing agent while those of Sm 2+ , Eu 2+ and
Yb 2+ are used as reducing agents.
(x) Many radioactive actinides are used in radiotracer techniques for detection of cancer
and many metabolic pathways. Thorium salts are also used in treatment of cancer.

Dr. Brijesh Dabhi