D-BLOCK ELEMENTS

The elements that lie between S-block and P-block are the D-block elements. These elements are called
transition elements as they show transitional properties between S and P-block elements.
These elements contain partially filled d-orbitals and hence they are called d-block elements. The
general electronic configuration of d-block elements is (n-1)d1-10ns1-2.
Periodic Properties of Elements
As we know, the atomic number is the fundamental property of an atom. Most of the physical
and chemical properties of the elements change periodically with the atomic number as described
below.
Electronic Configuration
The elements in any group have similar electronic configuration. For example, the atoms of all
the elements of group 1 (alkali metals) have one electron in their valence shell while those of
group 2 (alkaline earth metals) have two electrons in their outermost shell. Thus, alkali metals
have ns1 configuration while alkaline earth metals have ns2 configuration. In the long form of the
periodic table, the elements are arranged in order of increasing atomic number.
Thus, an additional electron enters the principal shell at each step. Therefore, as we move across
a period, each element acquires a new electronic configuration as shown below in the case of
second period elements.
Element

Electronic configuration

Li

1s22s1

Be

1s22s2

1s22s22p1

1s22s22p2

1s22s22p3

1s22s22p4

1s22s22p5

Valency

Valency of an element is defined as the number of hydrogen atoms or the number of chlorine
atoms or double the number of oxygen atoms that combine with one atom of the element.
Elements having the valency of 1,2,3 and 4 are called monovalent, divalent, trivalent and
tetravalent respectively.
The valency of representative elements is usually equal to the number of electrons in the
outermost orbit or group number 10. For example, valency of S in SO3 = 2 x 3 = 6 (16 -10 = 6).
However, transition elements exhibit variable valency .

Variation in a Group
Due to the similarities of electronic configuration, the elements of a group have the same
valency. Thus, all the elements of group1 have valency one while of group 2 have valency two.
Variation in a Period
As we move across a period, the number of valence electrons increases. For example, sodium has
one valence electron (3s1), Magnesium has two valence electrons (3s2) while aluminum has three

valence electrons (3s23p1). As a consequence, the valency of the elements changes in a period
as we move from the left towards the right. The valency with respect to hydrogen increases from
1 to 4 and then decreases to zero. However, the valency with respect to oxygen increases from 1
to 7 and is 0 for inert gas.
Element
Hydride
Valency
Oxide

Na
NaH

MgH2
1

Na2O

Valency

Mg

2
MgO

Al
AlH3

SiH4
3

Al2O3
2

Si

P
PH3

H2S

SiO2

P2O5

2
SO3
6

Cl
HCl

Ar
--

1
Cl2O7

0
--

Atomic Volume
Atomic volume of an element is the volume in cm3, occupied by one gram atom of the
element in the solid state and hence it is also called gram atomic volume. It can be stated as the
ratio between gram atomic weight of the element and its density, i.e., Atomic volume = Atomic
weight/density.
Variation of atomic volume in a group: Atomic volume increases almost regularly in going
down a group due to the successive addition of new shells.
Variation of atomic volume in a period: Atomic volume decreases at first for some elements,
becomes minimum in the middle and then increases.
Atomic Radius
Atomic radius is the most probable distance from the centre of the nucleus to the outermost shell of
electrons.
The electron density around an atom is affected by the presence of neighboring atoms. Hence, the size of
the atom changes somewhat in going from one condition to another.
Covalent radius : Inter-nuclear distance between two covalently bonded atoms/2
Van der Waal's radius : Inter-nuclear distance between two non bonded nearest neighboring atoms/2
Metallic radius : Inter-nuclear distance between two nearest metal atoms in metallic lattice/2
Variation of atomic radius in a period: As we move from left to right in a period, the atomic radii goes on
decreasing. Across a period, the atomic number, i.e., nuclear charge is increasing. The electrons get
added in the same shell. The added electrons do not screen the nucleus appreciably. The attraction of the
nucleus for the outermost electrons goes on increasing. As a result atomic radius goes on decreasing.
It may be noted that in the case of noble gases, we measure van der Waal's radii instead of covalent radii
since these elements do not form covalent bonds. Therefore, at the end of each period, the radii show an
abrupt increase because van der Waal's radii give higher values of atomic radii than covalent radii.
Variation of atomic radii in a group: As we move, down a group in the periodic table, the atomic radii go
on increasing due to the addition of new shells.
Ionization enthalpy or Ionization energy or Ionization potential
It is defined as the amount of energy required to remove one valence electron from an isolated neutral
gaseous atom resulting in the formation of a monovalent positive ion. For example, the ionization energy
of Na is 496 KJ/mole. This means that 496 KJ of energy would remove an electron from each Na atom
in one mole of Na atoms.
Na(g) + I.E. Na+(g) + 1e- 496 KJ

Variation of Ionization energy in a group: As we move down a group the Ionization energy goes on
decreasing.
Variation of Ionization energy along a period: Ionization energy values go on increasing across a
period.

Electron Affinity or Electron Gain Enthalpy

Electron affinity is the amount of energy released when one electron is added to a neutral gaseous atom
to form a monovalent negative ion.
For example, electron affinity of chlorine is -349 KJ/mole. This means that 349 KJ of energy is released
when one mole of chlorine atoms change into Cl- ions.
Cl(g) + 1e- Cl- (g) + 349 KJ
Variation of electron affinity down a group: The electron affinity of elements decreases down the
group.
Variation of electron affinity along a period: The electron affinity increases across a period due to
increase in nuclear charge.
Electronegativity
The relative tendency or power of an element in a molecule to attract the shared pair of electrons
towards itself is known as its electronegativity.
Variation of electronegativity down a group: Down the group electronegativity decreases as atomic
size increases.
Variation of electronegativity along a period: While going from left to right in a period
electronegativity increases as the atomic size decreases.
Fluorine is the most electronegative element in periodic table.
List of D Block Elements
The d block elements are called transitional elements. This block contains elements lying between the
s and p blocks, i.e., between groups 2 and 13, starting from 4th period and onwards.
In the mentioned elements, the outermost shell contains one or may be two electrons in their s orbital
(ns) but the remaining electron enters the last but one d sub shell, i.e., (n-1)d.
The elements of this block have the general characteristic properties which are intermediate between the
elements of s block and p block.
The study of transition metals is important because the precious metals silver, gold and platinum and
industrially important metals like iron, zinc, palladium, copper, titanium, nickel, chromium, etc., are
transition elements.

Properties of Transition Metals

1. Nearly all transition elements have typical metallic properties such as high tensile strength,
ductility, malleability, high thermal and electrical conductivity and metallic luster.
2. They have high melting and boiling points and have higher heats of vaporization than non
transitional elements.
3. Transition elements have very high densities as compared to s block metals.
4. Most of them have colored compounds.
5. They have good tendencies to form complexes.
6. They exhibit several oxidation states.
7. They form alloys with other metals.
8. They form interstitial compounds with elements such as hydrogen, boron, carbon etc.
9. Most of the transition metals such as Mn, Ni, Cr, V, Pt, etc., and their compounds have been used
as good catalyst.
Transition Elements
All known elements can be arranged in the long form of the periodic table which is purposed by
Mendeleevs. It contains 18 groups and 7 periods with two series of 14 elements at the bottom of the
main table. The periodic table is based on the increasing order of atomic number of elements. We know
in an atom, the number of protons is equal to the total number of electrons.
In other words, an atom is neutral due to the presence of the same number of electrons and protons.
Hence the number of protons or atomic number is equal to the number of electrons. The atomic number
can be used to write the electronic configuration of elements. The long form of the periodic table can be
divided into four blocks; s, p, d and f-blocks. This classification is based on the position of valence
electrons in the elements. For example Na is a s-block element because the valence electronic
configuration of Na is 3s1.
In the periodic table, 1st and 2nd group is part of s-block whereas from 13th to 18th group, elements are
known p-block elements. Elements from 3rd to 12th group are commonly known as d-block elements or
transition elements whereas 2 series of 14 elements at the bottom of main table are called as f-block.
Lets discuss main characteristics of transition elements.
Transition Elements Definition
1. d-block elements are also known as transition elements.
2. They are located in between s and p block elements in the periodic table.
3. As s-block elements are metallic in nature and p-block elements are non-metallic, d-block
elements show a transition from metallic to non-metallic nature. In other words, they show a
transition from the most electropositive s-block elements to the least electropositive or most
electronegative p-block elements.
4. Because of their metallic nature, transition elements are also named as transition metals.
5. Another name for transition metals is d-block due to the presence of incomplete d-sub shell and
valence shell filled in (n-1)d orbital and their general electronic configuration is (n-1)d1-10, ns2.
6. The other reason for transition element name is variable oxidation state.

A transition element may be defined as "the element whose atom in the ground state or ion in one of
the common oxidation state , has incomplete d-sub shell means having electrons 1 to 9".
Transition Elements on the Periodic Table
In the periodic table, all the elements are arranged in increasing order of their atomic number. The whole
periodic table contains 18 vertical columns called groups and 7 horizontal rows called periods.

Periodic table can be studied by using some common properties of elements like atomic radius,
ionization potential, electron affinity and electronegativity, metallic nature. Atomic radius and metallic
nature increases in a group from top to bottom and decreases from left to right in a period.
All the other properties decreases in a column from top to bottom and increases from left to right in
period. On the basis of chemical and physical properties of elements, the periodic table can be divided in
to four blocks. Each block has a characteristic property and shows a regular trend in the group as well as
in the period.
Elements which belong to the same group show the same type of properties. The four blocks are
1. s-block element
2. p-block element
3. d-block element
4. f-block element

s-block element: It involves all highly electropositive metals located in the 1st and 2nd group
also known as alkali and alkaline earth metals.

p-block element: It consists of metals, non-metals and metalloids from 13th to 18th group.

d-block element: This block formed from 3rd to 12th group contains only metal.

f-block element: It consists of two series of 14th elements. This block contains radioactive and
artificial element, commonly known as actinoids and Lanthanoides.

Inner Transition Elements

The elements in which the valence electron enters in anti penultimate energy level i.e., (n - 2) f are
known as f - block elements.This name is because of the position of the valence electron is in the f orbital.Since the last electron enters into (n - 2)f - orbital which is inner to the penultimate shell (For dblock elements), they are also called inner transition elements. Hence, the general electronic
configuration for these elements is
(n-2)f 1-14, (n-1)d0-1, ns2
There are a total of 14 elements in the inner transition elements which are arranged in two series of
fourteen elements. The first series is known as lanthanoides and another one as actinoids.
Lanthanoides
In these elements the valence electron filled in 4f orbital, hence they are also known as 4f-block
elements or first inner transition element. This series started from Cerium (Ce : Z = 58) ended at
lutetium (Lu: Z = 71). Lanthanoides are also known as "rare earth metals".
Chemical
Element

La

Ce

Pr

Nd

Pm

Sm Eu Gd

Tb Dy

Ho Er Tm Yb Lu

Prom Sam
Praseo Neo
Lanthanu Ceriu
e
a
dymiu dymiu
m
m
thiu riu
m
m
m
m

Eur
o
piu
m

Gad
Dys
Ter
Hol
Thu
ol
pr
Erb
b
miu
l
iniu
osiu
ium
ium
m
ium
m
m

Atomic
Number

57

58

59

60

61

62

63 64

Melting
Point(C)

920

795

935

1024

1042

107
135
146 152 154
826 1312
1407
824 1652
2
6
1
9 5

Atomic
electron
5d1
configurati
on

4f15d1 4f3

4f4

4f5

4f6 4f7

Ln3+
electron
4f0
configurati
on

4f1

4f2

4f3

4f4

4f5 4f6 4f7

Ln3+
radius
(pm)

102

99

98.3

97

95.8

103

65 66

67

Ytte
r
Lute
biu tium
m

68 69 70 71

4f75
4f145d
4f9 4f10 4f11 4f12 4f13 4f14 1
1
d

4f8 4f9

4f10 4f11 4f12 4f13 4f14

94.
92.
86.
93.8
91.2 90.1 89 88
86.1
7
3
8

Properties of Lanthanide
1. Lanthanoides are silvery-white color metals which can get tarnished due to exposure to air and
form their oxides.
2. They are relatively soft metals compared to d-block elements but the hardness increases with
higher atomic number.
3. All Lanthanoides show +3 oxidation states. Beside they can show +2 and +4 oxidation state also.

4. From left to right across the period the radius of each lanthanide (Ln 3+)ion decreases due to less
screening effect of f-electrons. This is referred to as 'lanthanide contraction'.
5. They show high melting points and boiling points and high reactivity.
6. Like other metals, Lanthanoides also react with water to form hydrogen (H2)gas in cold/quickly
upon heating.
7. In the same way they can react with acidic solution to form hydrogen gas at room temperature.
8. All Lanthanoides are strong reducing agents with paramagnetic nature and form ionic
compounds.
9. They can easily react with most non-metals to form binary compounds on heating.
10. Lanthanoides also form coordination complexes with ligand but coordination numbers of
lanthanides are high generally greater than 6; usually 8 or 9 or as high as 12 compare to
transition element.
Actinoids
1. These elements are located after actinium, hence are collectively termed as actinoids.
2. In these elements, the valence electron filled in 5f orbitals.
3. Most of these elements are radioactive and their study in a laboratory is difficult.
4. The earlier members of the series have a long half life, but later elements are very unstable with
short half lives.
5. The last element of actinoids, that is Lawrencium (103), has only 3 minute of half life.
Element

Ac

Th Pa

Np

Pu

Am Cm Bk

Cf

Es

Fm

M
No Lr
d

Atomic
number

89

90

92

93

94

95

98

99

100

10 10
103
1 2

91

Electronic
6d1
configurati
7s2
on

5f26d17
s2
5f36d
6d2
1
or
7s2
1
2
5f 6d 7 7s2
s2

Oxidation
state

3, 4 3, 4, 5

Metallic
radius,nm

0.20 0.18
0.162
3
0

96

5f46d17
5f76d
s2
5f67s 5f77s 1
2
2
or
7s2
5
2
5f 7s

97

5f97s2
5f1 5f1 5f14
or
5f10 5f11 5f12 3 4
7s27p
5f86d17 7s2 7s2 7s2
2
2 1
7s 7s
s2

3, 4,
3, 4, 3, 4, 5,
2, 3,
5, 6,
3, 4 3, 4
5, 6 6, 7
4
7

2,3 2,3 2,3 2,3 2,3 3

0.15
0.150
3

0.16 0.17 0.17

0.170
2
3
4

0.18 0.18
6
6

Temperatur
105 175
e,
1572
0
0
C: melting

1130 640

640 1176 1340 1050

900 860

Density,
g/cm3

19.0
20.25
6

19.8
13.5
11.7
14.78
4
1

10.0 11.7
15.37
7
8

All actinoids are radioactive in nature with high electro positivity.

153 83 83
1630
0
0 0

Like other metals, they also react with air and tarnish. They are very dense metals with certain
crystal structures.

One of the unique properties of actinoids is their numerous allotropes.

Actinoids also react with boiling water or dilute acid and release hydrogen gas.

Beside +3 oxidation state, they show higher oxidation states of +4, +5, +6, and +7 also.

They have a greater tendency to form complexes.

Actinoids compounds are more basic and they can form oxocations also like; UO22+.

Their magnetic properties are quite complex and cannot be explained easily.

They are very dense metals with certain crystal structures.

Transition Elements List

Period 4 after [Ar]
3 Scandium 21 4s2 3d1

Period 5 after [Kr]

Yttrium

Period 6 after [Xe]

39 5s2 4d1 Lutetium 71

6s 4f
5d1

14

Period 7 after [Rn]

Lawrencium 103 7s2 4f14 7p1

4 Titanium 22 4s2 3d2 Zirconium 40 5s2 4d2 Hafnium 72

6s2 4f14
Rutherfordium 104 7s2 4f14 6d2
5d2

5 Vanadium 23 4s2 3d3

6s2 4f14
5d3

Niobium 41 5s1 4d4 Tantalum 73

Dubnium

105 (unknown)

Chromiu
Molybdenu
6s2 4f14
24 4s1 3d5
42 5s1 4d5 Tungsten 74
m
m
5d4

Manganes
6s2 4f14
25 4s2 3d5 Technetium 43 5s2 4d5 Rhenium 75
e
5d5

Bohrium

107 (unknown)

26 4s2 3d6 Ruthenium 44 5s1 4d7 Osmium 76

6s2 4f14
5d6

Hassium

108 (unknown)

27 4s2 3d7

6s2 4f14
5d7

Iron

Cobalt

1
0

Nickel

Rhodium 45 5s1 4d8 Iridium 77

4s2 3d8
28 1or 9 Palladium 46 4d10
4s 3d

11 Copper

29 4s1 3d10

1
2

30 4s2 3d10 Cadmium 48 5s2 4d10 Mercury 80

Zinc

Silver

47 5s14d10

Platinum 78

Gold

79

Seaborgium 106 (unknown)

Meitnerium 109 (unknown)

6s1 4f14
Darmstadtium 110 (unknown)
5d9
6s1 4f14
Roentgenium 111 (unknown)
5d10
6s2 4f14
5d10

Copernicium 112 (unknown)

General properties of transition elements

1. There are a total of four series in d-block elements. The first three series contains ten elements in
each one, while the last series is incomplete.
2. First transition series or 3d series corresponding to filling of 3d-subshell with ten elements from
scandium to zinc.

3. Second series or 4d series located in the 5th period contains ten elements from Ytterbium to
cadmium.
4. Third series or 5d series located in 6th period with ten elements from lanthanum to mercury. After
lanthanum (57) there is a gap of 14 elements of lanthanide than next element Hafnium (72) again
a part of d-block element.
5. Last series of transition started from actinium (89) after that 14 elements will be part of actinoids
than next element kurchatovium (104) will place in this series. The rest of the elements in this
series are artificial and radioactive in nature.
6. Transition elements contain an incomplete d-subshell, so they show a variable oxidation state.
For example; Osmium (Os) shows a maximum +8 oxidation number and Manganese (Mn) shows
+7 oxidation number in potassium per magnate (KMnO4).
7. The atomic radius follows the general trend of the periodic table. When we move in a series from
left to right, the atomic radius first decreases than becomes stable and increases at the end of
series. This trend is due to the screening effect of inner d-electrons.

Except for mercury, all transition metals are solid in nature with typical metallic crystal structure. As the
number of unpaired electrons increases in an element, the strength of the metallic bond increases. But
half filled orbitals decrease the metallic bond strength. All transition elements have a high melting point
directly related to the metallic bond strength. Tungsten (W) has the highest melting point of all the
transition elements. They show high ionization potential compared to s-block elements but lesser than pblock elements.
Because of the presence of unpaired electrons in the inner d-orbital, they can form coordination
complexes with appropriate ligand. The unpaired electrons are responsible for the magnetic properties of
elements. The second and third series elements show almost the same atomic radius and other properties
due to Lanthanides contraction.

Oxidation States
Lets take an example of an atom that is made up of one proton and one electron, is called hydrogen. The
proton and electron stay together because just like two magnets attracted from opposite poles. Have you
ever thought why these two particles not colloid? The electron in an atom is constantly spinning in a
certain energy level around the centre of the atom, called the nucleus. Electrons are placed in fixed
energy levels, known as orbitals. A compound is a pure substance consisting of two or more different
elements.

Do you know, why elements combined to form element? We know that each element has a certain value
of valency; means combining capacity of element with another element which is due to electrons present
in the outermost shell of the element. These electrons are known as valence electrons. An atom always
tries to make eight electrons in its outermost shell; that is called Octet rule. Hence, the valency of an
element depends on valence electrons. The atoms of elements, having a completely filled outermost
shell show little chemical activity. Or we could also say that their combining capacity or valency is zero.
Like inert elements, the helium atom has two electrons in its outermost shell and all other elements have
atoms with eight electrons in the outermost shell. They all commonly termed as inert elements.
An atom having an incomplete outer shell converts in octet configuration by:
It can gain electrons from another atom.
It can lose electrons to another atom.
It can share one or more electron pairs with another atom.
Lets discuss about oxidation state of the elements.

Oxidation State Definition

Oxidation state of any atom shows the ability of an atom to oxidize (to lose electrons) or to reduce (to
gain electrons) other atoms or species in a chemical compound. It is related to the number of electrons
which an atom loses, gains, or appears to use when bonding with another atom in a compound. Its a
difference between the number of electrons of the same atom in a compound, as compared with the
number of electrons in an atom of the element. The oxidation state is the ionic charge on ions and the
formal charge in the case of covalent compounds. For example, in NaCl the oxidation states of Na and
Cl are +1 and -1 respectively and in CCl4 the oxidation state of Carbon is (+4) and (-1) for each chlorine.
Oxidation State of Transition Metals
All the transition elements, except the first and last members of the series, exhibit a number of oxidation
states. They show variable valency in their compounds. Some basic oxidation states of the first, second
and third transition series elements are given below in tables.
Oxidation states of 3d series
Elements

Outer electronic
configuration

Oxidation states

Sc

3d14s2

+2, +3

Ti

3d34s2

+2, +3, +4

3d34s2

+2, +3, +4, +5

Cr

3d54s1

+2, +3, +4, +5, +6

Mn

3d54s2

+2, +3, +4, +5, +6, +7

Fe

3d64s2

+2, +3, +4, +5, +6

Co

3d74s2

+2, +3, +4

Ni

3d84s2

+2, +3, +4

Cu

3d104s1

+1, +2

Zn

3d104s2

+2

Oxidation states of 4d series

Elements

Oxidation states

+3

Zr

+3, +4

Nb

+2, +3, +4, +5

Mo

+2, +3, +4, +5, +6

Tc

+2, +4, +5, +7

Ru

+2, +3, +4, +5, +6, +7, +8

Rh

+2, +3, +4, +6

Pd

+2, +3, +4

Ag

+1, +2, +3

Cd

+2

Oxidation states of 5d series

Elements

Oxidation states

La

+3

Hf

+3, +4

Ta

+2, +3, +4, +5

+2, +3, +4, +5, +6

Re

+1, +2, +4, +5, +7

Os

+2, +3, +4, +6, +8

Ir

+2, +3, +4, +6

Pt

+2, +3, +4, +5, +6

Au

+1, +3

Hg

+1, +2

Cause for variable oxidation states

The valence electrons of the transition elements are in (n-1) d and ns orbitals which have little difference
in energies. Both energy levels can be used in bond formation.
They show the +2 oxidation state due to the 2 electrons in ns orbitals when the electrons of (n-1) d
remain unaffected.
The higher oxidation state from +3 to +7 is due to the use of all 4s and 3d electrons in the transition
series of elements. In the excited state, the (n-1) d electrons become bonding and give the variable states
to the atom. Thus the variable oxidation state is due to the participation of both ns and (n-1) d orbitals in
bonding.
Some important features of oxidation state of transition metals are,
1. The most common oxidation state of 3d series is +2 except scandium, due to the loss of two ns
electrons. This shows that d orbitals are more stable than s orbitals after scandium.
2. The ionic bonds are generally formed in +2 and +3 state while the covalent bonds are formed in
higher oxidation states. Covalent bonds are formed by the sharing of d-electrons. For examplepermanganate ion MnO4, all bonds formed between manganese and oxygen are covalent.
3. The highest oxidation state increases with increasing atomic number of element, reaches
maximum in the middle and then starts decreasing as shown in the table. For example, iron
shows the common oxidation state of + 2 and + 3, but ruthenium and osmium in the same group
form compounds in the +4, + 6 and + 8 oxidation states.
4. The elements in the beginning of the series exhibit less oxidation state because of having small
number of electrons to lose or contribute. The elements in the middle of the series show the
greatest number of oxidation. For example; Mn shows all the oxidation states from +2 to +7.
The highest oxidation state shown by any transition metal is eight which is shown by Ru and Os.
5. The maximum oxidation state of reasonable stability in 3d series is equal to the sum of s and d
electrons up to Mn followed by decrease in the stability of higher oxidation states.
6. The variability of oxidation states arises in such a way that successive states differ in unity.
7. The higher oxidation states are more stable in heavier elements. Like in Mo (VI), W (VI) are
more stable than Cr (VI).

8. They also form compounds in low oxidation states such as +1 and 0 having ligands like CO. For
example, nickel in nickel tetra carbonyl, Ni(CO)4 and Fe in Fe(CO)5 has zero oxidation state. Cu
is in +1 state in CuCl.
9. The oxidation state of a metal in solvent depends on the nature of the solvent. For example, Cu in
+1 state in water is unstable as it may undergo oxidation while Cu in +2 states is stable.
10. The oxidation state of transition metals depends on the nature of the combining atoms. So the
compounds of metal with fluorine and oxygen exhibit the highest oxidation state due to their
small size and the high electro negativity of fluorine and oxygen.
11. The relative stabilities of elements which exist in more than one oxidation state can be known
from the standard electrode potential.
Determining Oxidation States
The process of determining the oxidation states is based on knowing the elements which can have only
one oxidation state other than in the elemental state and which elements are able to exist in more than
one oxidation state other than in the elemental state. These are some of the "rules" for assigning the
oxidation states.
Rules for Assigning Oxidation States

The oxidation state of free elements is always zero. For example, Fe(s), O2(g), O3(g), H2(g),
Hg(l), Hg(g), S(s) etc.

The oxidation state of metals is taken as the charge of the ion. For example, Group IA, Group
IIA, Group IIIA (except Tl), Zn2+, Cd2+ forms only one ion.

In the case of monatomic ions, either anions or cations, the charge on the ion is considered as its
oxidation state. For example, Cl- (-1), Fe2+ (+2), Fe3+(+3), S2- (-2), H+ (+1) etc.

In the case of compounds having polyatomic ions, the overall charge of the polyatomic ion is
used to determine the charge of the ion.

Some elements have common oxidation states.

1. Alkali metals (Li+, Na+, K+) are always in +1 oxidation state while alkali earth metals (Mg2+,
Ca2+, Sr2+, Ba2+) are in +2 state.
2. Hydrogen is in +1 state (except in metal hydride compounds such as LiH).
3. Oxygen is in (-2) state (except in peroxides such as H2O2).
4. Halogens (F-, Cl-, Br-, I-) are generally in -1 state.

The total sum of the oxidation states in a molecule is always zero. For example; In CH2O, the
sum of the oxidation state is (0) + 2(+1) + (-2) = 0. Similarly, in CH3OH, sum of the oxidation
states= (+2) + 3(+1) + (-2) + (+1) = 0

For example, determining the oxidation states of the elements in the compound KMnO4. By applying
rule, the oxidation state of K = +1 and four oxygen is in -2 state.
Let the oxidation state of Mn = x as manganese can be in several oxidation states.
As the overall charge of the compound is zero. So the algebraic expression can be written as
1+x-8=0

So the oxidation state of manganese is x - 7 = 0 or x = +7.

Similarly the oxidation state of chromium in dichromate ion, (Cr2O72-).
Since the oxidation state for chromium is not known, so taken it as 2x for chromium Cr2O7 2- 2x 7(-2)
Since the overall charge of the ion is -2, so the algebraic equation for x 2x + 7(-2) = -2
After solving it for x: 2x - 14 = -2
2x = 12
x = +6, so each chromium is +6 oxidation state.
Iron Oxidation States
Iron has atomic number 26 and the electronic configuration is [Ar] 3d6 4s2.Iron has 4 unpaired electrons
in 3d orbital and 2 paired electrons in 4s. So the possible oxidation states are + 2, + 3, + 4, + 6 but
generally it shows +2 and +3 oxidation state.

1. Iron (II) (Ferrous ion) - Iron in the +2 oxidation state is known as the ferrous ion which is pale
green in color. Ferrous ion is easily oxidized to the ferric ion in the presence of a small amount of
oxygen. So the solutions of ferrous ion are sometimes used as reducing agents. The ferrous ion
complexes usually have octahedral geometry. For example, hexaaquo and hexacyano complexes
of Fe+2. These ions have a particular affinity for amine ligands.
2. Iron (III) (Ferric ion) - Iron in the +3 oxidation state is known as the ferric ion. The solutions
containing the ferric ion are usually yellow or yellow-brown and acidic in nature due to the
formation of species such as [Fe(H2O)5(OH)]2+. They form a blood-red complex ion with the
thiocyanate (SCN-) ion which is used for testing the presence of the ferric ion.
Oxidation State of Chromium
Chromium has atomic number 24 and electronic configuration is [Ar] 3d5 4s1 due to more stable half
filled orbitals. They show the oxidation state + 2, + 3, + 4, + 5, + 6. Generally Chromium forms
compounds with oxidation state +2, +3 and +6.
The +2 state of chromium is easily oxidized in aqueous solution to the +3 state. The +3 and +6 states are
more stable in chromium.

Chromium (III) They can be obtained by dissolving the element chromium in acids like HCl or
H2SO4. Generally they form the octahedral complexes. For example-the dark green complex
chromium(III) chloride hydrate [CrCl2(H2O)4]Cl, Chromium(III) hydroxide (Cr(OH)3),
chromium(III) oxide (Cr2O3), Anhydrous chromium(III) chloride (CrCl3) etc.

Chromium (VI)- These compounds are powerful oxidants at low or neutral pH. For examplechromate anion (CrO42-) and dichromate (Cr2O72-) anions. Their halides are also known like
hexafluoride CrF6, chromyl chloride (CrO2Cl2). Other examples are Chromic acid (H2CrO4),
chromium (VI) oxide CrO3 which is the acid anhydride of chromic acid.

Chromium (V) Only few compounds are known. For examples-peroxochromate (V),
chromium (V) fluoride (CrF5) etc.

Chromium (IV) - They are more common than Cr(V). For example- tetra halides like CrF4, CrCl4
and CrBr4 etc.

Chromium (II) For example- CrCl2, chromos acetate (Cr2(O2CCH3)4) etc.

Oxidation State of Silver

The electronic configuration of silver is [Kr] 4d10 5s1. The most common oxidation state of silver is +1
and +2 state. For example- AgNO3 silver(I) nitrate, Silver(II) fluoride (AgF2), potassium tetra fluoro
argentate K[AgF4] for +3 state of silver etc.
Catalysis
The word catalysis was first introduced by Berzelius in 1836 to describe a number of experimental
observations. Catalysis is defined as a phenomenon in which the presence of a foreign substance in a
reaction can accelerate its rate without being used up in that reaction. These foreign substances are
called as a catalyst. The catalyst can change the speed of a reaction without being used up in that
reaction.
What is Catalysis?
In a reaction, a catalyst reacts with one or more reactants and forms intermediates, which subsequently
gives the final reaction product and regenerates the catalyst. For example, in a chemical reaction, where
C represents the catalyst, A and B are reactants, and D is the product of the reaction between A and B.
A + C AC --------(1)
B + AC ABC ----------(2)
ABC CD ---------(3)
CD C + D ------- (4)
In the given mechanism, the catalyst is consumed in the first step of the reaction but subsequently
produced in the last step, hence the overall reaction will be
A + B D
The catalyst is regenerated in a reaction and often, only a small amount, is sufficient to increase the rate
of the reaction. A catalyst provides an alternate path for the reaction that has a lower energy of activation
Ea.

Characteristics of a Catalyst

The catalyst remains unchanged in mass and chemical composition at the end of the reaction.

Usually, a small amount of the catalyst is needed for a chemical transformation, i.e., because the
catalyst itself is not consumed in a reaction.

In heterogeneous catalysis, the rate of the reaction increases with the increasing surface area of
the catalyst.

In reversible reactions, the catalyst helps to attain equilibrium quickly but does not affect the
composition of the reaction mixture in equilibrium. The value of the equilibrium constant
remains unchanged due to the presence of the catalyst.

A catalyst can accelerate the rate of reaction but it cant initiate the reaction.

All catalysts are specific for the reactant. A certain catalyst can react with a particular reactant
only.

A catalyst increases the speed of the reaction but it cant change the nature and type of product.

Type of Catalysis Process

Catalysis can be divided into two main classes:
Homogenous catalysis
In homogenous catalysis, the catalyst and reactants are in the same phase or physical state. For example,
the formation of sulfur trioxide gas in the presence of nitric acid gas.
NO(g)
2SO2(g) + O2(g) 2SO3(g)
Here both reactants (SO2 + O2) and the catalyst (NO) are in a gaseous state. Another example of
homogenous catalysis is inversion of sugar, in which both the reactants and catalyst are in liquid state.
H+
C12H22O11 + H2O C6H12O6 + C6H12O6
The hydrolysis of ester is also an example of homogenous catalysis.
H+
CH3COOCH3 +H2O CH3COOH + CH3OH
In homogenous catalysis, the function of the catalyst is to bring about a reaction between molecules
which do not posses enough energy to enter into a chemical combination by providing an alternative
path in which lesser energy f or activation is required. For example ; for the given reaction
A + B AB in the presence of catalyst X,
the reaction mechanism will be;

AX+bk3AB+X

Here Ea1 is the activation energy leading to the formation of an intermediate complex. Ea2 is the
activation energy for the change of the intermediate complex into products. Ea3 is the activation energy
of the un-catalyzed reaction.
Heterogeneous catalysis
The phase or physical state of a catalyst and a reactant is different in heterogeneous catalysis. For
example, the decomposition of potassium chlorate in the presence of solid catalyst MnO2
2KClO3(s)M2(s)2KCl(s)+302(g)
Other examples of heterogeneous catalysis are
2H2O2(l)PtAu(s)2H2O+O2
SO2g+O2gPt(s)2SO3(g)
Following are the common steps in heterogeneous catalysis:
1. Adsorption: The Reactant gets adsorbed on the catalyst surface.
2. Recombination: Reactant are combined with the catalyst to form an intermediate reactantcatalyst complex.
3. Dissociation: Reactant converts into the product and the product gets dissociated from an
intermediate complex.
4. Diffusion: The product gets diffused from the catalyst surface and moves away from the reaction
site.
5. Desorption: The product gets desorbed from the metal surface and the catalyst surface gets free
for other reactants.
6. The best example of the heterogeneous catalysis is the hydrogenation of ethene on a solid metal
surface like nickel which acts as a catalyst and forms ethane.
Enzyme catalysis
Enzymes are the complex organic compounds which are produced by living plants and animals. They
act as a catalyst for biochemical reactions in living bodies. They disperse in water and form a colloidal
solution, hence they follow colloidal properties and heterogeneous catalysis.
Compared to inorganic catalysts, enzymes are very specific for reactants, temperature, pH of medium
and other reaction conditions. Some common examples of enzymes are,

Characteristics of enzymes

Enzymes are nitrogenous compounds, which get consumed during biochemical reactions. They
cant be synthesized in an artificial manner.

Certain inorganic substances like ammonium salts are required for the production of enzymes
and the presence of co enzyme are essential for enzymes.

The enzymes accelerate the biochemical reactions by decreasing the activation energy. They do
not alter the nature and amount of product.

A very small amount of catalyst is enough to accelerate the reaction.

They are specific in their action and catalyze reactions at lower temperature. At high
temperature, they lose their specific nature and get denatured.

Enzymes are very sensitive to the pH of the reaction medium. For each enzyme, there is an
optimum p value at which the rate of the reaction is at its maximum pH value and at which the
rate of the reaction is maximum.

Enzymes are very specific for reactants. There are some active sites on the enzyme surface,
known as the active site, in which only a certain reactant fits and forms a product. It is same as a
Lock and Key. There is always a certain key for a lock. This model of enzyme catalysis in also
called the Lock and Key model.

Enzyme catalysis can be explained by using the steady state theory. In enzyme catalysis, an
enzyme provides a catalytic surface to reactant molecules and forms a transition state. Since the
enzyme catalysis follows a steady state concept, the production and consumption of the transition
state proceed at the same rate and the concentration of transition state stays constant.

Mechanism of Catalysis
Acid- base catalysis
There are many homogenous catalytic reactions which are catalyzed by acid and bases. Such type of
reactions are called as acid-base catalyzed reactions. There are three kinds of acid-base catalysis;

Reactions catalyzed by hydrogen ion: For example, inversion of sugar.

Reactions catalyzed by hydroxyl ion: For example, dimerization of acetone.

Reaction catalyzed by both hydrogen and hydroxyl ion: for example, hydrolysis of ester to form acid
and alcohols. The Keto-enol tautomerism (conversion of keto form to enol form) is the best example of
acid-base catalysis.

Aldol condensation, hydrolysis of p-nitrophenylacetate with imidazole are some other examples of acid
base catalysis.

Covalent catalysis
In some catalytic reactions, the covalent bonds are formed between enzymes and subtract. Such type of
catalysis is known as covalent catalysis. For example, A-B reactants react with enzyme E-H to form an
intermediate E-A, which further reacts with water to form the final product A-OH.
H2O+ABslowAOH+BH
A-B + E-H > E-A + BH
EA+H2OFastAOH+EH
In a covalent catalysis, there are some steps,

Attack of the nucleophilic reactant on an enzyme

Withdrawal of electrons from the reactant

Removal of nucleophilic group and regenerate enzyme

Covalent catalys is generally found in enzymes like chymotrypsin and trypsin, and in this process an
acyl-enzyme intermediate is formed. The Covalent catalysis of acetylcholine esterase is as follows

Enzymes That Form Covalent Intermediates

Enzymes

Reacting
group

Covalent
intermediate

Chymotrypsin Elastase Esterases Subtilisin Thrombin Trypsin

Glyceraldehyde-3-phosphate dehydrogenase Papain

Alkaline phosphatase Phosphoglucomutase

Phosphoglycerate mutase Succinyl-CoA synthetase

Aldolase Decarboxylases Pyridoxal phosphate-dependent

enzymes
Phase Transfer Catalysis
It is a special form of heterogeneous catalysis. The phase transfer catalysis involves changes in the phase
of the reactant during the reaction between the reactant and the catalyst. Phase transfer catalysis is
mainly used for reactions between anions and organic substances. Since many anions are soluble in
water, but not in organic solvents, and organic reactants are not soluble in water, the phase transfer
catalyst acts as a shuttling agent between organic solvent and water.
Phase transfer catalyst bound with the anion carries it to the organic solvent so that it can easily react
with the organic reactant to form a product. This mechanism is called the extraction mechanism.

Oxidation Catalyst

Oxidation metals are catalytic metals like platinum or palladium because these metals convert exhaust
gas pollutants into harmless gases by chemical oxidation. These metals oxidize pollutants like carbon
monoxide, hydrocarbons and some organic compounds like aldehyde and ketones.
Carbon Monoxide

CO +

O2 CO2
Hydrocarbons
) O2 m CO2 + n2
H2O

CmHn + (m + n4

Aldehydes, Ketones, etc.

- 0.5) O2 m CO2 + n2
H2O

CmHnO + (m + n4

Hydrogen

H2 + 12

O2 H2O
These oxidation catalysts are present in a stainless steel canister which contains a honeycomb structure
known as a substrate or catalyst support. This canister contains a large amount of interior surface area
which is coated with catalytic metals. This canister is also known as the Catalytic Converter or the
OxyCat. It converts Hazardous Air Pollutants up to maximum percentage.
NO
Non-methane
CO
x
hydrocarbons (NMHC)
Nil

7099%

40-90%

Volatile organic
compounds (VOC)

Formaldehyde
(CH2O)

Hazardous Air
Pollutants (HAPs)

60-99%

60-99%

60-99%

Catalytic oxidation of ammonia

The catalytic oxidation of ammonia is the basic reaction of the Oswald process for the formation of
nitric acid. The oxidation of ammonia in the presence of platinum forms NO, a brown colored gas and
water vapour.
4NH3 (g) + 5O2 (g) 4NO (g) + 6H2O (g) (H = 950 kJ/mol)

The oxidation of ammonia is carried out in the presence of various catalysts like Pt/CuO/Al2O3 or
copper-cerium composite catalyst which is prepared by co-precipitation of copper nitrate and cerium
nitrate. The oxidation of ammonia is an exothermic reaction which is initiated by some catalyst. In the
Ostwald process a wire mesh consisting of platinum and rhodium is used as a catalyst.

Since the reaction is exothermic in nature, a high temperature is required to initiate the reaction. Hence
the percentage yield is very low due to the break down of products.
F Block Elements

The long form of the periodic table is a tabular representation of all known elements. Elements are
arranged in this table in the increasing order of their atomic number. We know that an atom is neutral
due to the same number of electrons and protons therefore the atomic number of element provides the
complete information about the electronic configuration of elements.
On the basis of the valence shell configuration and position of valence electron in the element, the long
form of the periodic table can be classified in 4 blocks. The s-block elements are placed in 1st and 2nd
group on the table and called as alkali metal and alkaline earth metal. The p-block elements are placed
from a 13th group to 18th in the periodic table. There are metals, metalloids and non-metals in this
block. The d-block elements are placed from the 3rd group to 12th group of the periodic tables. They are
also known as the transition elements.
There are only metals in this block which show variable oxidation states and widely used as catalyst for
several organic and inorganic reactions. There are two series of 14 elements, placed at the bottom of
main table which are commonly known as f-block elements. These elements show unique properties
compared to other elements therefore are placed at the bottom of the table. Lets discuss some chemical
and physical properties of f-block elements.
F-block Elements
F- block elements are also called Inner transition elements. The last electron of these elements enters
the 'f' sub shell. They are mostly radioactive elements. They are present beneath the main periodic table,
in the form of two rows, one row belonging to lanthanides and the other row belonging to actinides.
Lanthanides and Actinides
The first row of the f- block , the 4f series consists of the Lanthanides and the second row, the 5f series
are the Actinides.
Lanthanides Series
Lanthanides or Lanthanones as they are also called, belong to the 4f series, the first series of f- block
elements. In these elements, the differentiating electron enters the 4f- orbitals. This series has
Lanthanum( Z= 57) and the next fourteen elements (Z = 58 to 71). But, La, z = 58 has a completely
empty f- sub -shell. So, the elements from Ce to Lu (58 to 71) usually consists of the lanthanide series.
As the number of electrons in the outermost and the penultimate shell remains the same, the fourteen
elements resemble each other. The lanthanides are also called as rare-earths. The name lanthanides is
given because of the strong resemblance of these elements to lanthanum. The name rare earths was
given to these elements because they were originally extracted from oxides, which were called 'earths'
earlier and which were considered rare.
The 4f electrons of these elements are completely shielded and do not take part in the chemical bonding,
unlike the d- electrons of transition series. These are silvery white metals and are good conductors of
heat. Among all the elements only some elements have a fully filled and half-filled f-orbital. The
elements with these f-orbitals are more stable.
Example : Europium and gadolinium has half-filled f-orbital. Ytterbium and lutetium has fully filled forbital. The list of elements in this series, with atomic number and symbol are
Elements+symbol
Atomic number

Ce Pr Nd

Pm

Sm Eu Gd Tb Dy Ho Er

Tm

Yb Lu

58 59

61

62

69

70

60

63

64

65

66

67

Groups of lanthanides
Klemm has divided lanthanides into two groups of seven elements each. These are
1. From Cerium Ce(58) to Gadolinium - Gd ( 64)

68

71

2. From Terbium (Tb - 65) to Lutetium (Lu - 71)

In the case of the first group, the half filling of 4f orbitals takes place and in the case of second group,
the pairing of electrons in the 'f' sub-shell takes place.
Oxidation States
All the elements of this series exhibit an oxidation state of +3 (Ln3+ ). Some of these elements also
exhibit +2 and +4 states, but these states are not as stable as the +3 state. Only +3 state is exhibited by
La, Gd and Lu which is due to extract-ability of empty, completely half filled or completely filled 4f
orbitals. Along with +3, other two oxidation states, +2 and +4 are exhibited by some members of this
series.
Example: Eu and Yb can acquire +2 state as it provides them with extra stability.
The Ce4+ ion is stale and it can convert easily to Ce3+ thereby making the 4+ ion a very strong oxidizing
agent.
Chemical Reactivity
Lanthanides are chemically reactive. They react with carbon, hydrogen, oxygen and sulfur and form
carbides, hydrides, oxides and sulphides respectively. The oxides formed are M2O3 oxides. They react
with water and form insoluble hydroxides. The oxides and hydroxides react with CO2 and form
carbonates, M2(CO3)3.
Lanthanide Contraction
In moving along the lanthanide series from Ce(58) to Lu (71) a regular decrease in the size of the
atom/ion with increase in atomic number is observed. This decrease in size is called the Lanthanide
contraction. In this series the size of Lanthanum is maximum and that of Lu, lutetium is minimum. The
decrease is size, though continuous, is not regular.
Reason for Lanthanide Contraction
The cause of lanthanide contraction can be traced to the imperfect shielding of one 4f electron by
another in the same sub-shell. On moving along the lanthanide series the number of 4f electrons
increases by one unit at each step and the imperfect shielding increases, causing the contraction in
electron cloud of the 4f sub-shell. Ionic radii changes from 1.06 to 0.85A.
Important Consequences
The lanthanide contraction plays a significant role in the chemistry of lanthanides. The important
consequences of it are:
1. There is a steady decrease in ionic size.
2. There is a slight increase in electronegativity of the trivalent ions.
3. The Eo values for M3+ + 3e M(g) increases regularly from Lanthanum -252V to 2.25 V for
Lutetium.
4. Since there is a very small change in the size of ions in the lanthanide series and there is no
change in the outermost shell, there is a close resemblance in chemical properties.
5. Lanthanide contraction plays a significant role in the chemistry of lanthanides and heavier
transition elements.

6. The atomic radii of 5d transition elements are very close to those of the corresponding 4d
transition elements. Due to this the crystal structure and other properties of lanthanides are very
similar.
Applications of Lanthanides
1. Metallurgical applications: Some of the alloys of lanthanide elements find important
metallurgical applications as reducing agents. Example: Misch meals (Ce- 30 to 35%)
2. Ceramic applications: Ce(III) and Ce(IV) oxides find use in glass polishing powders whereas
Nd and Pr oxides are extensively used in coloring glass and in the production of standard light
filters.
3. Catalytic applications: Some lanthanide compounds are used as catalysts. Example: Cerium
phosphate is used in petroleum cracking as a catalyst.
4. Electronic applications: The ferromagnetic garnets of 3Ln2O3.5Fe2O3 type are used in
microwave devices.
5. Nuclear applications: These elements and some of their compounds are used in nuclear control
devices, shielding devices and fluxing devices. Sm - 140, Eu - 153, Gd- 155, Gd- 157 and Dy 164 are some of the important isotopes used in nuclear technology.
Actinides Elements
The 5f block elements are also called actinoids or actinones. This series includes 15 elements, from
Thorium(Z = 90) to Lawrencium (Z = 103). The name actinides is derived from actinium, the very first
member of the series.
F-block Periodic Table
F-block elements are present beneath the main periodic table, in the form of two rows.
1. First row makes up the Lanthanide series.
2. Second row makes up the Actinide series.
Actinide Series
The periodic table can be represented by using their valence shell configuration. Whole periodic table
classified in four blocks. The name of block represents the position of valence shell of an element. Like
an s-block elements has its valence electron in s-orbital. d- Block elements are also known as transition
element and f- block are also called and inner transition element. Lets take an example; you have an
element with atomic number 11, and electronic configuration 2, 8, 1 or 1s2
, 2s2, 2p6, 3s1
. Out of these 4 blocks, s-block is consisted of 1st and 2nd group whereas p-block contains group-13 to
group-18. From 3rd to 12th groups, elements are commonly known as d-block elements.
There are 2 series of 14 elements at the bottom of main table which are commonly known as f-block
elements. The first series is called as lanthanide and 2nd series is known as actinide series. Glenn
Seaborgs discovered many elements especially after uranium. Starting with plutonium in 1940, he
discovered elements from 94 to 102 and placed them in the periodic table as the lanthanide/actinide
series at the bottom of the table. The elements of this block show unique physical and chemical
properties. Almost all radioactive elements are placed in this block. Lets discuss actinide series with the
chemical and physical properties of elements.

Actinides
The elements in which the extra electron, also called the differentiating electron enters the (n-2) f
orbitals are called as 'f' block elements. Since the extra electron goes to (n-2) f-orbitals, these elements
have been given the name f-block elements. Since (n-2) f orbitals lie comparatively deep within the
kernel, (being the inner penultimate shell), these elements are called "Inner transition elements".
The (n-2) f orbitals may either be the 4f or 5f orbitals. Thus, f- block elements are classified into two,
namely.

4f- series elements: These elements are called Lanthanides or lanthanones.

5f- series elements: These elements are called actinides or actinones.

What are Actinides?

The elements with atomic numbers 89-103, in which the 5f orbitals are being filled up, constitute the
actinides series. Just as in the lanthanides, where the anti penultimate 4f orbital is filled successively by
the addition of one electron at a time, in actinides the anti-penultimate 5f orbital is successively filled by
the addition of one electron at each step. Thus, lanthanides constitute the first inner transition series and
the actinides constitute the second inner transition series.
In the atoms of 5f-block elements the extra electron enters the 5f-orbital. The elements of this series are
also called as actinides or actinones, since these elements follow actinium, Ac(Z= 89) in the periodic
table and show close similarities with Ac.
Although, the fourteen elements from Thorium (Th- 90) to Lawrencium (Lw- 103) are called actinides,
due to the similarities in properties among the 15 elements, from Ac -89 to Lw-103, all these 15
elements are considered to be members of the actinides series. Thus, Ac-89 is also studied under
actinides. The actinides constitute the second inner transition series.
Actinides Properties
1. Occurrence
Excepting Ac, Th , Pa and U, which occur in nature in Uranium minerals, all the remaining actinides are
unstable and made artificially by nuclear transmutations. The actinides elements lying beyond Uranium,
are called trans-uranium or trans-Uranic elements All the actinides are radioactive.
2. Electronic configuration
There is some uncertainty about the electronic configuration of these elements. There is doubt whether
thorium, protactinium and uranium contains the differentiating electron in the 5f or 6d orbital. The
uncertainty is due to the entry of electrons in the 5f or 6d orbital, which are of almost same energy. Thus
there are two views regarding the electronic configuration of these elements. According to one(Seaborg
view) the 5f orbital starts filling at thorium while according to other(Dawson view) the 5f orbital starts
filling at neptunium
Example: Thorium 5f1 6d1 7s2 (Seaborg view) and 6d2 7s2 (Dawson view).
3. Oxidation state
Unlike lanthanides, actinides show a variety of oxidation states, viz. uranium shows all the oxidation
states from +3 to +6,Np and Pu shows +3 to +7. However the principle oxidation states are +3 and +4.
It may be seen from these oxidation states that the +2 oxidation state is shown by two elements namely,
Am and Th in a few compounds like ThBr2, ThI2, ThS etc. +3 oxidation state is shown by all actinides.

+3 state becomes more stable as the atomic number increases. +4 oxidation state is shown by Th, Pa, U,
Np, Pu, Am and Cm, while +5 state is shown by Th, Pu, U, Np, Pu and Am.
4. Ionic radius
The ionic radius of actinides decreases regularly along the series. The decrease in ionic radius of
actinides is called actinides contraction, and is due to the poor screening effect of the nuclear charge by
the f electrons.
5. Color
Actinides ions are usually colored. The color depends upon the number of 5f electrons, ions with 5f 0
electrons and 5f 7 electrons are colorless. The color is due to f-f electronic transitions. Most of the tri
positive and tetra positive (3+ and 4+) ions are colored.
Example: Ac3+-colorless , U3+ - Red, Np3+ - Purple, Pu3+ - Violet, Am3+ - pink, Cm3+ - colorless, U4+ Green, Np4+ - Yellow-green.
6. Complex formation
The actinides have a greater tendency to form complexes than lanthanides because their ions have high
charge and are smaller ions.
The degree of complex formation decreases in the following order:
M4+>MO22+>M3+>MO2+
The complexing power of different singly charged and doubly charged anions following order.
F->NO3->ClCO32->C2O42->SO42Actinides will also form complexes with a large number of organic substances.
Actinides Series
Actinides lie in the 7th period (Incomplete period with n=7) and III B group of the periodic table.
The following flow chart shows the Actinide series :

Actinides Periodic Table

Prior to the discovery of trans-Uranium elements, (Trans-uranium elements are the elements lying
beyond Uranium in the periodic table), the naturally occurring heaviest known elements namely, Th- 90,
Pa- 91 and U - 92 were placed below Hf-72, Ta- 73 and W-74 in IV B, V B and VI B groups of the
periodic table, because these elements showed +4, +5 and +6 oxidation states and resembled Hf, Ta and

W respectively in many of their properties. The then undiscovered trans-uranium elements with atomic
numbers 93 to 100 were thus expected to occupy the positions in the periodic table below Re- 75, Os76, Ir- 77 , Pt- 78, etc.
The discovery of Neptunium (Np - 93) came in 1940 and this discovery was followed shortly by the
discovery of Plutonium, Pu- 94 in 1941. The tracer elements Np- 93 and Pu - 96 showed that the
chemical properties of these two elements very much resemble Uranium - 92 and not at all those of Re75 and Os- 76.
On this basis, all the three elements, U, Np and Pu were placed under W- 74 in group VI B in a column.
But later, this was also proved wrong, since many other elements discovered did not follow this pattern.
In 1944, Seaborg suggested that all the elements with atomic number greater than 89 constitute a second
series of inner-transition elements, similar to the lanthanide series.
Thus, they were placed below the lanthanides and named as Actinides series. So, the actinides form a
second row below lanthanides and these two series are separated and placed below the main periodic
table.
Lanthanides and Actinides

In the atoms of the elements of both series, the extra electron enters (n-2) f orbitals.

The elements of both the series show +3 oxidation states.

Like lanthanide contraction seen in lanthanides, actinides also have actinides contraction.

Elements of both the series have low electronegativity and are very reactive.

Most of the lanthanide and actinides cations are paramagnetic.

Lanthanides and Actinides

All known elements are arranged in the long form of the periodic table. It was proposed by Mendeleevs
and also called as a Modern periodic table. The long form of the periodic table was based on the
increasing order of atomic number of elements. It is a tabular form in which elements are arranged in
columns and rows. The columns of the periodic table are called as groups whereas the horizontal rows
are known as periods. The entire table is composed of 18 groups and 7 periods. There are two series are
the bottom of main table which consist of 14 elements in each series.
Complete table can be classified as s, p, d and f-block elements. First and 2nd group belong to s-block of
the periodic table as their valence electrons are filled in the s-orbital of the atom. Similarly from 3rd to
12th group, elements are related to d-block and also known as the transition elements. The p-block of the
periodic table is comprised from 13th to 18th group of the periodic table.
All metals are placed at the left side of the periodic table. Around 75% of elements are metallic in nature
and belong to s, d and f-blocks. The non-metals and metalloids are placed in p-block with few metals.
The elements of f-block are also called as Lanthanides and Actinides. These names come from the
Lanthanum and Actium after which, both series of f-block are started.
Lanthanide and Actinide Series
The f-block elements in which the last electron or the differentiating electron enters in (n-2) f-orbitals
and the general electronic configuration is (n-2)f1-14 (n-1)d0-1 ns2 consists of two series of inner transition
elementsLanthanides (the fourteen element following lanthanum)

The elements in which the last electron enters one of the 4f-orbitals are called 4f-block elements or first
inner transition series. They are also called Lanthanides (or) lanthanones because they come
immediately after lanthanum.
Actinides (the fourteen element following actinium)
The elements in which the last electron enters one of the 5f-orbitals are called 4f-block elements or
second inner transition series. They are also called Actinides because they come immediately after
actinium. The general electronic configuration is [Rn]5f1-14 6d0-1 7s2

Lanthanides (58Ce- 71Lu) - This series starts from Lanthanum ( atomic numbe r= 57) and continues up
to Lu (Lutetium) as shown in the table above. All the elements of the lanthanide series resemble each
other very closely due to the presence of the same number of electrons in the outermost and the
penultimate shells. They are also called rare earth elements. Though Lanthanum is a d-block element it
is included in the lanthanides series as it resembles them.
General Characteristics
Some important characteristics are given below1. Electronic Configuration of Lanthanides: The general electronic configuration is. All have
electronic configuration with 6s2 is common but variable occupancy of 4f and 5d-subshells due
to the closeness in energy of 4f and 5d electrons. So it is considered that the 5d orbital remains
vacant and the electrons enter into the 4f orbital. Exception are in the case of gadolinium, Gd (Z
= 64) where the electron enters the 5d orbital due to the presence of half filled d-orbital and in
Ytterbium (z = 70) in which all the 4f orbital's are completely filled and the differentiating
electron of the next element that is lutetium (z = 71) enters the 5d orbital. The complete
electronic configuration of Lanthanides can be given as 1s2 2s2 p6 3s2p6d104s2p6d10f0-14 5s2p6 d0-1
6s2.
2. Oxidation States: Lanthanides show variable oxidation states. The most stable oxidation state of
Lanthanides is +3. They also show +2 and +4 oxidation states due to the presence of either half
filled or completely filled or empty 4f sub shell.
3. Color: Many of lanthanide metals are silver white. The lanthanide ions with +3 oxidation state
are colored both in solid state and in aqueous solution. The color of a cation depends on the
number of unpaired f electrons.
4. Magnetic Properties: The lanthanide ions other than f0 and f14 type are paramagnetic in nature
due to unpaired electrons in f-orbitals.
5. Melting and boiling point: They have fairly high melting point but there is no definite trend in
the melting and boiling point of lanthanides.
6. Density: They have high density ranging between 6.77 to 9.74 g cm-3. Its increases with
increasing atomic number.
7. Ionization enthalpies: They have low ionization enthalpy.

8. Complex formation: They don't have much tendency to form complexes because of low charge
density. The order of complex formation can be best represented as Ln4+ > Ln3+ > Ln2+.
9. Reactivity: All the lanthanides show the same electronic configuration and the +3 oxidation
states, they show similarity in the reactivity which is greater than the transition elements. This is
due to shielding of the unpaired electrons of the inner 4f-orbital by the outer 5s, 5p, and 5d
orbital's. Due to the small change in the size of the ions, they show great similarity in their
chemical properties. The first few members are quite reactive. A few properties are given below.

All lanthanides react rapidly upon exposure to air.

They dissolve in hot water and react with acid, liberating hydrogen.

They act as a strong reducing agent because of the strong electro positive nature

They form the nitrides and hydrides after reacting with nitrogen and hydrogen respectively.

They also react with non-metals like halogens, sulfur, phosphorus, carbon and silicon and form
their corresponding compounds.

Lanthanide Contraction
The atomic size or ionic radii of tri positive lanthanide ions show a steady and gradual decrease with the
increase in atomic number from La to Lu. Although they show some irregularities, the ionic radii
decrease steadily from La to Lu. This gradual decrease in the size with increasing atomic number is
called lanthanide contraction.
Cause of lanthanide contraction
The major cause for lanthanide contraction is due to the inappropriate shielding of the 4f electrons due
to the improper shape of the f-orbitals. As the atomic number increases in the lanthanide series, for every
proton in the nucleus the extra electron goes to fill the 4f-orbitals.
The 4f-electrons constitute inner shells and are rather ineffective in screening the nuclear charge. Thus,
there is a gradual increase in the effective nuclear charge experienced by the outer electrons. So the
attraction of the nucleus for the electrons in the outermost shell increases as the atomic number increases
and the electron cloud shrinks.

This results in gradual decrease in the size of lanthanides with increasing atomic number. The decrease
in size is not regular throughout the lanthanides. A rapid decrease is seen only in the first six elements

compared to the rest of the elements.

Consequences of lanthanide contraction
1. Similarity of second and third transition series- Generally the size of atoms increases down a
group. So the size of the atoms of an element of second transition series is larger than any atom
of the first transition series but the size of the atom of third transition series is nearly same as that
of the atom of the second transition series. The similarity in the size of atoms of the elements
belonging to the same group of the second and third transition series is due to the effect of
lanthanide contraction. For example- radius of Zr radius of Hf & radius of Nb radius of Ta etc.
2. Difficulty in the separation of lanthanides- As there is small change in the ionic radii of
lanthanides so their chemical properties are similar. This makes the separation of elements in the
pure state difficult. This contraction makes the slight difference in size so the properties like
solubility, complex formation, hydration etc shows some differences and its possible to separate
them by ion exchange methods.
3. Effect on the basic strength of hydroxides- As the size of lanthanides decreases from La to Lu,
the covalent character of the hydroxides increases and hence their basic strength decreases. Thus,
La(OH)3 is more basic and Lu(OH)3 is least basic.
Actinides
Actinides are termed as the second inner transition series. This series is named after actinium, the first
element of the series. Only the first four elements occur in nature. The other elements are made by
nuclear bombardment because most of these are radioactive.
General characteristics of Actinides
Some general characteristic of actinides are given below.
1. Electronic Configuration: All the actinides have common 7s2 configuration and variable
occupancy of 5f and 6d sub shells. The general electronic configuration of actinium is [Rn] 5f014
6d0-2 7s2 where, Rn is the electronic configuration of the element Radium. The irregularities in
the electronic configuration are related to the stabilities of half filled or full filled orbitals (f0, f7,
f14 ).

2. Oxidation States: Unlike lanthanides, actinides show a variety of oxidation states from +3 to +6
due to the very small energy gap between 5f, 6d and 7s sub shells. The principal oxidation states
are +3 and +4. The +3 oxidation state is the most stable. The +4 oxidation state is the most stable
in Th and Pu. +5 in Pa and Np and +6 is seen in U. In actinides, the distributions of oxidation
states are uneven.
3. Complex formation: The degree of complex formation decreases in the order. M4+ > MO2+2 >
MO+2 where, M is an element of the actinide series. There is a high concentration of charge on
the metal atom.
4. Melting and boiling point: They have high melting and boiling points like lanthanides but dont
show any regular trend with increasing atomic number.
5. Density: All actinides except thorium and amercium have high density.
6. Electropositive character: These metals are highly electropositive in nature like lanthanides.
7. Ionization enthalpies: The actinides have lower ionization enthalpies than lanthanides because
5f is more effectively shielded from nuclear charge than 4f.
8. Magnetic behavior: All actinides are paramagnetic in nature which depends on the presence of
unpaired electrons.
9. Radioactivity: All are radioactive in nature. First few members have relatively long half lives
but the remaining have half-lives from a few days to a few minutes.
10. Color of the ions: Actinides ions are generally colored due to f f transitions. It depends upon
the number of electrons in 5f orbitals.
11. Chemical behavior: They are highly reactive metals in fine state and a strong reducing agent. A
few properties are given below.

They react with boiling water to give oxide and hydride.

They combine with most of the non-metals at moderate temperature.

All these metals are attacked by HCl acid but the effect of nitric acid is very small.

Actinide Contraction
The size of atoms or M+3 ions decrease regularly along the actinides series with increase in atomic
number from Th to Lr. The steady decrease in ionic radii with increase in atomic number is referred to as
actinide contraction just like lanthanide contraction.
The reason of this contraction is the poor shielding effect of 5f electron by another in the same shell
which increases the effective nuclear charge and thus contraction in size of the electron cloud. This is
because 5f orbitals extend in space beyond 6s and 6p orbitals whereas, 4f orbitals are buried deep inside
the atom.
Similarities Between Lanthanides and Actinides
1. Both lanthanides and actinides involve the filling of f-orbitals.
2. Both exhibit a common oxidation state of +3.
3. Both are electropositive and very reactive.

4. Both exhibit magnetic and spectral properties.

5. Lanthanides exhibit lanthanide contraction and actinides exhibit actinide contraction.
Difference Between Lanthanides and Actinides
Lanthanides

Actinides

They have the ability to show a maximum

oxidation state of + 4

Actinides show variable oxidation states of + 3, + 4, + 5,

+ 6 and + 7.

They have smaller tendency to form

complexes.

They have a good tendency to form complexes with

ligands such as thio-ethers.

All lanthanides are non-radioactive except

promethium.

They are radioactive in nature.

They do not form oxo-ions

Actinides form oxo-ions such as UO+, NpO2+.

They are non radioactive in nature.

Actinides are radioactive.

Uses of Lanthanides and Actinides

The important uses of lanthanides are given below.
1. They dont find any use in their pure state. They are used in the production of alloys of steel to
improve the strength and workability of steel. A well known alloy is mischmetal which is used in
making magnesium based alloy (Mg mixed with 3% of mischmetal). This is a pyrophoric alloy
which is used in making bullets, shells and lighter flints.
2. Their oxides are used in the glass industry for polishing glass and making colored glass for
goggles and television screens.
3. Mixed oxides of lanthanides are used in petroleum cracking.
4. Due to their paramagnetic and ferromagnetic nature, they are used in magnetic and electronic
devices.
5. Ceric sulphate is a well known oxidizing agent which is used in volumetric analysis.
Uses of Actinides
The most useful actinides are thorium, uranium and plutonium.
1. Thorium is used in the atomic reactors and in the treatment of cancer. Their salts are used in
making incandescent gas mantles.
2. Uranium is used as nuclear fuel. Their salts are used in the glass industry for imparting green
color, ceramic industry, textile industry and in medicines too.
3. Plutonium is also used as nuclear fuel and for making atomic bombs.