Physics

BSCCH-
BSCCH 101
B. Sc. I YEAR
INORGANIC CHEMISTRY-I
CHEMISTRY
SCHOOL OF SCIENCES
DEPARTMENT OF CHEMISTRY
UTTARAKHAND OPEN UNIVERSITY
BSCCH-101
INORGANIC CHEMISTRY-I
SCHOOL OF SCIENCES
DEPARTMENT OF CHEMISTRY
UTTARAKHAND OPEN UNIVERSITY
Phone No. 05946-261122, 261123

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Board of Studies
Prof. Govind Singh Prof. B. S. Saraswat
Director, School of Sciences Professor Chemistry
Uttarakhand Open University Department of Chemistry
School of Sciences, IGNOU, New Delhi
Prof S.P. S. Mehta Prof. D. S. Rawat
Professor Chemistry Professor Chemistry
Department of Chemistry Department of Chemistry
DSB Campus, Kumaun University Delhi University, Delhi
Nainital
Dr. Charu C. Pant
Programme Coordinator
Department of Chemistry
School of Sciences,
Uttarakhand Open University
Haldwani, Nainital
Programme Coordinators
Dr. Charu C. Pant Dr. Shalini Singh
Department of Chemistry Department of Chemistry
School of Sciences, School of Sciences,
Uttarakhand Open University Uttarakhand Open University
Haldwani, Nainital Haldwani, Nainital
Unit Written By Unit No.

1. Dr. K. S. Dhami (Ret. Proff.) 01, 02, 03, 04, 05, 06, 07, 08, 09, 10 &11
D.S.B. Campus, Kumaun University
Nainital
2. Dr. Geeta Tiwari 12, 13 & 14
D.S.B. Campus, Kumaun University
Nainital
Course Editor
Dr. A. B. Melkani
Professor & Head
D.S.B. Campus Kumaun University, Nainital
Title : Inorganic Chemistry I

ISBN No. : 978-93-85740-53-4
Copyright : Uttarakhand Open University
Edition : 2017
Published by : Uttarakhand Open University, Haldwani, Nainital- 263139

INORGANIC CHEMISTRY-I BSCCH-101
UNIT 1: ATOMIC STRUCTURES
CONTENTS:
1.1 Objectives
1.2 Introduction
1.3 Idea of de Broglie matter wave
1.4 Heisenberg’s Uncertainty Principle
1.5 Schrodinger wave equation (No derivation)
1.5.1 Significance of ψ and ψ2
1.5.2. Radial and angular wave functions
1.5.3. Probability distribution curve
1.6. Shape of different orbitals
1.7. Quantum Numbers
1.8. Pauli’s Exclusion Principles
1.9. Hund’s rule of maximum multiplicity
1.10. Aufbau principle
1.11. Electronic configuration of the elements
1.12. Effective nuclear charge.
1.13. Summary
1.14. Terminal Questions
1.15. Answers
1.16. References
1.1. OBJECTIVES
The objective of the preparation of the text of this unit is to acquaint the readers with
the fascinating and exciting realm of the atoms. Accordingly, an attempt has been made to
through light on the arrangement of the internal constituents of the atoms (the subatomic
particles), their peculiarities and characteristics along with their behaviour towards their
neighbours, i.e. the arrangement of protons and neutrons in the nucleus and the rules
governing the arrangement of electrons in the extra nuclear region of an atom and filling of
UTTARAKHAND OPEN UNIVERSITY Page 1
orbitals belonging to higher energy shells prior to the entry of electrons in the orbitals of
lower energy shells. At the same time, the problem “what makes the electron cloud to acquire
different shapes in three dimensional space around the nucleus?” has been entertained and
various other interesting problems have also been taken into account.
1.2. INTRODUCTION
In the beginning of nineteenth century, John Dalton (1766-1844) put forward his
atomic theory, he regarded atom as hard and smallest indivisible particle of matter that takes
part in chemical reactions; the atoms of one particular element are all identical in mass and
atoms of defferent elements differ in mass and other properties.
Later on, various investigators around the end of nineteenth century and beginning of
twentieth centurydid several experiments and revealed the presence of much smaller
negatively charged particles, named electrons by J.J. Thomson (1897) and positively charged
particles, named protons by Rutherford (1911) within an atom. These tiny particles were
called subatomic particles. It was also established by Rutherford that the whole positive
charge and most of the mass of an atom lies at nucleus. The positive charge on the nucleus
was attributed to the presence of protons called the atomic number by Moseley (1912). The
electrons were said to be arranged around the nucleus in the extra nuclear region in certain
well defined orbits called energy shells and were said to be in constant motion (N. Bohr,
1913). Chadwick’s experiments (1932) also revealed the existence of yet another subatomic
particle in the nucleus which did not have any charge and named as neutrons. Further
investigations established that there were also present some other subatomic particles in the
nucleus in addition to electrons, protons and neutrons. These particles are positrons,
neutrinos, antineutrinos, pions (π-mesons) etc. The pions (Yukawa, 1935) are said to be
continuously consumed and released by proton-neutron exchange processes.
Thus, it is concluded that the atom no longer is an ultimate and indivisible particle of
matter and the outer or valence shell electrons are responsible for chemical activity of the
elements.

1.3. DE-BROGLIE’S MATTER WAVES: DUAL NATURE OF
MATTER
This is based on wave mechanical concept of an electron in an atom. Albert Einstein
proposed dual character of electromagnetic radiation in 1905, viz. wave character based on
Maxwell’s concept evidenced by diffraction, interference, polarisation kinds of phenomena
and particle character based on Planck’s quantum theory witnessed by quantization of energy
and hence photoelectric effect, i.e. the ejection of photoelectrons from metal surface on
striking electromagnetic radiation.
On the basis of above analogy, French Physicist Louis de Broglie (1924) postulated
that not only light but all material objects (both micro and macroscopic) in motion such as
electrons, protons, atoms, molecules etc. possess both, wave and the particle propertiesand
thus have dual character, i.e. the wave character and particle (corpuscular) character. He
called the waves associated with material particles as matter waves which are now named de
Broglie’s wave. These waves differ from electromagnetic or light waves in a sensethat these
are unable to travel through empty space and their speed is different form light waves.
de Broglie’s relation
de Broglie deduced a fundamental relation between the wave length of moving

particle and its momentum by making use of Einstein’s mass energy relationship and
Planck’s quantum theory. The material particle as a wave satisfies the Planck’s relation for a
photon, i.e.
E = hv ……….. (1.1)
where h is Planck’s constant and v is the frequency of the wave. The frequency for light

wave, v =
and for particle wave, v =
(c = speed of light wave and v = speed of particle
wave). At the same time, Einstein’s mass energy relationship is applicable to it, i.e.
E = mc2 (for a photon) ……….. (1.2)
or E = mv2 (for a particle where v ≠ c) ………...

(1.3)

where m is the mass and v the speed/velocity of the particle. From the equations 1.1 and 1.3,
we have
hv = mv 2 ……… (1.4)

or
= mv 2

or
= mv = p (momentum)

or ߣ = or () …… (1.5)
(momentum p = mv, mass x velocity)
Here, ߣ corresponds to the wave character of matter and p its particle character. This is
Known as de Broglie’s relation. From this relationship, it is concluded that “the momentum
of a moving particle is inversely proportional to the wavelength of the wave associated with
it”.
It is important to note here from above discussion that de Broglie’s relation is applicable to
material particles of all sizes and dimensions but the wave character is significant only for
micro objects like electrons and is negligible for macro objects hence cannot be measured
properly. This infers that de Broglies’s relation is more useful for smaller particles.
de Broglie’s relation has been applied to a moving electron around a nucleus in a circular
path in an atom to justify Bohr’s postulate which states that elections can move only in those

orbits for which the angular momentum is equal to an integral multiple of , i.e.

mvr = n ……….(1.6)
This moving electron is considered as a standing wave extended around the nucleus in
circular path and not as a mass particle. If the circumference of the orbit is an integral
multiple of the wave length, ߣ,
i.e. 2ߨ r = n ߣ ………(1.7)

where r is the radius of the orbit and n is the whole number, the wave remains continually in
phase, i.e. is a merging wave (Fig. 1.1 a)
From equation 1.5, we have

ߣ= =

Putting the value of ߣ in equation 1.7, we get

2ߨr = n
Fig 1.1 (a) merging waves, (b) Crossing waves

or mvr = n (on rearranging)

………(1.8)
which is the same as equation 1.6, i.e. Bohr’s postulate mentioned above. If the
circumference of the orbit is bigger or smaller than the value given above, the wave is out of
phase, i.e. a crossing wave (Fig. 1.1 b)
Fig. 1.1 a: in phase Fig. 1.1 b: out of phase
de Broglie’s concept has been experimentally verified by Davisson and Germer, G.P.
Thomson and later by Stern independently.
1.4. HEISENBERG’S UNCERTAINTY PRINCIPLE
According to classical mechanics, a moving electron behaves as a particle whose

position and momentum could be determined with accuracy. But according to de Broglie, a
moving electron has wave as well as particle character whose precise position cannot be
located because a wave is not located at a particular point rather, it extends in space. To

describe the character of a subatomic particle that behaves like a wave, Werner Heisenberg in
1927 formulated a principle known as Heisenberg’s Uncertainty Principle. According to the
principle “it is impossible to determine simultaneously both the position as well as the
momentum (or velocity) of a moving particle at the same time with certainty (or
accurately)”
He also proposed a mathematical relationship for the uncertainty principle by relating the
uncertainty in position with the uncertainty in momentum which is given below:

∆‫ݔ‬x∆‫
≥ ݌‬ ...............(1.9)

or ∆‫ ݔ‬x m (∆‫≥ )ݒ‬ (since p = m v and ∆‫ = ݌‬mx∆v)

……….(1.10)
where ∆‫ݔ‬is the uncertainty or error in the position of the particle, ∆‫ ݌‬and ∆‫ ݒ‬are the
uncertainties in it’s momentum and velocity and h is Planck’s constant.
This equation states that the product of ∆‫ ݔ‬and ∆‫ ݌‬can either be greater than or equal

to (≥) but never smaller than , a constant. If ∆‫ ݔ‬is measured more precisely (i.e. ∆‫ ݔ‬is

small) then there is large uncertainty or error in the measurement of momentum (∆‫ ݌‬is large)
and vice versa.
1.5. CONCEPT OF PROBABILITY AND SCHRODINGER’S

WAVE EQUATION
From the uncertainty principle, it has been concluded that the exact position and exact
momentum or velocity (related to kinetic energy) of a micro particle can be replaced by the
concept of probability. For an electron in an atom we can say that there is probability of
finding it in a particular region of space and in a particular direction (except for s-electron).
To describe the wave motion of electron in hydrogen atom, Schrodinger in 1927
combined the de Broglie’s relation for the wavelength of a particle wave with the well known
differential equation for standing waves and proposed a mathematical form called
Schrodinger’s wave equation. This equation is now widely used to explain the behaviour of

atomic and molecular systems. The equation for a single particle in three dimensional space,
i.e. along x, y and z directions is given as follows:
δ2ψ + δ2ψ + δ2ψ + 4π2 ψ = o ……….(1.11)

δx2δy2 δz2 λ2
In place of three partial differentials, symbol ‘∇’ (del) can be used, hence the above equation
becomes
∇2ψ + 4π2 ψ = 0
……….(1.12)
λ2
where ∇2 (del square) is equal to δ2 + δ2 + δ2 and is known as laplacian operator.
δx2δy2 δz2

Putting the value of λ from de Broglie’s relation (i.e. λ = ), the above equation becomes

మ మ
∇2 ψ + = 0
మ
……….(1.13)
Extracting the value of v from kinetic energy, potential energy and total energy terms i.e. E =

K.E+V where K.E. = ݉v and putting in the above equation, we get the final form of the
equation as:
మ
∇2 ψ + మ
(E -V) ψ = 0 ……….(1.14)
This equation is known as Schrodinger’s wave equation.

1.5.1. Significance of ψ and ψ 2
An electron, from the probability concept, is considered as a three dimensional wave
system extended around the nucleus and is represented by the symbol ψ which denotes the
wave function of the electron; ψ itself has no physical significance and simply represents the
amplitude of electron wave. Schrodinger’s equation has several solutions for ψ, both real and
imaginary. Some of the real values of ψ are appreciable while others are too small and hence

neglected. If the value of ψ obtained as above is continuous, finite, single valued and electron
probability in space related to ψ is equal to 1, then ψ is known as eigen function (meaning
characteristic), ψ2 gives the probability of finding an electron of a given energy, E from place
to place in a given region around the nucleus. Since, ψ often contains the imaginary quantity,
but the probability of an electron in a given volume must be a real quantity, therefore the
product ψ ψ* (ψ star) is used rather than ψ2 where ψ* is complex conjugate of ψ. This product
will always be real whereas ψ2 may be real or imaginary. If ψ is real quantity, then ψ and ψ*
both are same and hence ψ2 is also a real quantity and corresponds to probability density per
unit volume.
1.5.2. Radial and angular wave functions:
The radial wave function, R (r)
The value of ψ appearing in Schrodinger’s wave equation in polar coordinates, (r,θ,∅),
can be determined only when ψis written in the following form (mention of equation is not
required) :
Ψ (r,θ, ɸ) = R (r) Θ(θ) Ф(ɸ) …………..(1.15)
Where ψ (r,θ, ɸ), is known as total wave function, R (r) is the radial wave function and other
two are angular wave functions. The radial wave function, R (r) is dependent on r only where
r is the distance of electron from the nucleus and is independent of θ and ɸ. Therefore, R (r)
deals with the distribution of the electron charge density as a function of distance (r) from the
nucleus. R (r) depends on two quantum numbers n and l and can be denoted as Rn,l (r) or
simply Rn,l. Both Rn,l and R2n,l are significant only for drawing the probability curves for
various orbitals. The radial wave functions for all s-orbitals are spherically symmetrical.
The angular wave function, ψ (θ, ɸ).
The angular wave functions depend on the angles θ and ɸ and are independent of the
distance (r). As given above in equation 1.15, these are represented as Θ (θ) and ߆ (ɸ). Their
values depend on the quantum numbers l and m and can be written as Θ l,m and ߆m,
respectively. Therefore, the equation 1.15 can also be written as
Ψn,l,m = Rn,l Θ l,mФ m ………….(1.16)
This equation shows that the total wave function besides depending on r, θ, ɸ, also depends
on the quantum numbers viz., n, l and m. Each permitted combination of n, l and m gives a
distinct wave function and hence a distinct orbital.

The angular wave functions together are used to predict the shapes of the orbitals.
1.5.3. Probability distribution curves:
Before discussing the distribution curves, let us know about the electron probability
function. The probability or the chance of finding an electron in three dimensional space
round the nucleus is known as electron probability function, D. For an extremely small
spherical shell of radius r and thickness dr round the nucleus, the value of D can be given by
D = ψ2 x volume of shell = ψ2 x 4πr2 dr ………… (1.17)
and the electron probability between r = o and r = r would be equal to

‫ ׬‬ ψ2. 4πr2 dr. (ψ2 = R2 (r) or R2n,l)
Radial probability distribution curves
The square of the radial wave function multiplied by a volume element, dv, i.e. R2(r)
x dv measures the probability of locating an electron at a distance from the nucleus and
within a small radial space. This is same as electron probability function given above in
which ψ2 can be replaced by R2n,l, meaning radial distribution. When R2 (r). dv or R2n,l. 4πr2
dr where dv= 4πr2 dr, is plotted against r, the distance from nucleus, we get radial probability
distribution curves. The peak of the curve gives the distance from the nucleus where the
probability is maximum and at distances smaller or greater than this, value of probability is
less but not zero. Thus, it is observed that electron charge density decreases but volume of
shell increases with r. Various such curves are shown below:

Fig. 1.2 Radial Probability distribution curves for 1s,2s,2p,3s,3p and 3d-orbitals. Simple
sketches have been given in which the values of n and l have been shown and dr has been
omitted.
The important features of these curves are;
(i). Curves start from the origin and the areas covered by the envelopes of a particular curve
for a subshell (orbital) go on increasing from left to right so that the area of the last envelope
is maximum.
(ii). The number of minima where density of electronic charge is zero, appearing in a
particular curve gives the number of radial nodes or nodal points for the orbital (subshell).
The number of nodal points is equal to n-l-1. Thus for the electrons of 1s,2s,2p,3s,3p and 3d
orbitals, the number of nodal points is 0,1,0,2,1 and 0, respectively. This is also evident from
the curves of these orbitals. Evidently, 3s orbital (nodal points = 2) is bigger in size and more
diffused than 1s (nodal point = 0) and 2s orbitals (nodal point = 1) both due to greater number
of nodal points in it (see figure 1.2)
1.6. SHAPES OF ATOMIC ORBITALS AND ANGULAR PROBABILITY

DISTRIBUTION CURVES

The shapes of atomic orbitals depend θ and ɸ i.e. the product [Θ (θ) x Ф (ɸ)] or l,m x
Фm is related with the shapes of the orbitals. The values of ߆l,m x Ф m for s-orbital (l=0,m=0),
p-orbital (l = 1, m = 0, ±1), and d-orbitals (l = 2, m = 0, ±1, ±2) can be obtained and
correlated with the shapes of orbitals.
For s-orbitals (l = 0, m = 0), the angular wave function ߆o,o x Фo is independent of the angles
߆ and ɸ, i.e. there is no angular wave function and hence orbitals have only one orientation
and are spherically symmetrical over all the directions, hence have spherical shape as well as
are non-directional. Thus, s-orbitals are usually represented by circles. Greater the value of n
and higher the number of nodal points for s-orbital, larger is the size of orbital. The electron
density in s-orbitals could be shown by concentric shades as follows:
1s-orbital 2s-orbital 3s-orbital

(no nodal point) (1 nodal point) (2 nodal points)
Fig. 1.3 Electron charge density pictures for 1s, 2s and 3s-orbitals. Nucleus has been shown
by thick dot.
For p orbitals (l = 1, m = 0, ±1), there are three values of m and therefore, there are three
orientations of lobes of orbitals along cartesian coordinates viz. px, py and pz. The subscripts
x, y and z indicate the axes along which orbitals are oriented. The three p-orbitals are similar
in size, shape and energy but differ in orientation only. The angular wave function for these
orientations is the product߆,m x Фm. For l=1, m =0 orientation, the angular wave function ߆1,0
Ф0 is a real quantity and corresponds to pz orbital which is dumb-bell shaped curve along z-
axis in three dimensional space (Fig. 1.4 c).

For l = 1,m = +1 and l =1, m= -1 orientations, angular wave functions are ߆1,+1 x Ф+1 and ߆1,-1
x Ф-1 which have imaginary quantities and are avoided. The real values are obtained by the
normalised linear combinations (addition and subtraction) of angular angular wave functions.
Thus, addition process, i.e. ߆1,+1 x Ф+1 + ߆1,-1 x Ф-1 gives normalised wave function
corresponding to px orbital. In three dimensional space, this gives dumb-bell shaped curve
along x- axis (Fig.1.4a) The subtraction process, i.e. ߆1,+1 x Ф+1 - ߆1,-1 x Ф-1 gives normalised
wave function corresponding to py orbital which is again dumb-bell shaped curve in three –
dimensional space along y-axis (Fig. 1.4b).
Px orbital Py orbital pz orbital

(a) (b) (c)
Fig.1.4 The orientation of p- orbitals along x, y and z- axis.

The (+) and (–) signs are algebraic signs of angular wave function and not the charge. The
angular part of the wave function ψ (߆, Ф) has (+)sign on one lobe and (–)sign on the
opposite lobe although ψ2 (߆, Ф) will be positive on both the lobes. Thus, for p-orbitals, the
important points to be noted are:
(i) Since x, y and z axes are perpendicular to each other, the three p-orbitals are also
perpendicular to each other.
(ii) Each of the three p-orbitals has two lobes on each side of the nucleus which is at the origin of
the axes, hence the probability of finding the electron (s) in both lobes is equal. These lobes
are separated by nodal planes passing through the nucleus. The electron density on the nodal
plane is zero.

(iii) Greater the value of n (principal quantum number or the shell number), larger is the size of p
orbital i.e. 3p orbital is larger in size than 2p orbital though the shapes of both the orbitals are
the same.
(iv) The energy of the three p-orbitals with the same value of n is same i.e. all the three p-orbitals
are degenerate.
For d-orbitals (l = 2, m = 0, ±1, ±2), five orientations (or orbitals) are there corresponding to
five values of m for l = 2. Depending on the permitted combinations of l and m, values for
five d-orbitals, angular wave functions corresponding to different d-orbitals are as follows:
For l = 2 and m=0, the angular wave function ߆2,0 x Ф0 has a real value and corresponds to
dz2-orbital. For l =2 and m = ±1, we have two angular wave functions, ߆2,+1 x Ф+1 and ߆2,-1 x
Ф-1. The values of these angular wave functions contain imaginary quantity and hence, these
values are not accepted. The real and acceptable values are obtained from these by
normalised linear combinations (addition and subtraction) of above functions. The addition
process of above angular wave functions, i.e. ߆2,+1 x Ф+1 + ߆2,-1 x Ф-1 gives the wave function
for dzx (or dxz) orbital and subtraction process, i.e. ߆2,+1 x Ф+1 - ߆2,-1 x Ф-1, gives the wave
function for dyz, orbital, for l = 2 and m = ±2, we have two wave functions viz. ߆2,+2 x Ф +2
and ߆2,-2 x Ф-2. Again the values of these wave functions contain imaginary quantity and
hence are not accepted. Real and acceptable values are obtained by the nornalised linear
comlimation of the two angular wave functions. The addition process of above angular wave
functions, i.e., ߆2,+2 x Ф+2 + ߆2,-2 x Ф-2, gives the wave function for dx2-y2 orbital and
subtraction process i.e., Θ2,+2 x Ф +2 - Θ2,-2 x Ф-2, gives the wave subtraction for dxy orbital.
When these five angular wave functions for different orbitals obtained above are plotted in
three dimensional space, we get the solid curves which give the orientations along the axes or
in between the axes as shown below:
dxy orbital dyz (or dxz) orbital dzxorbital

dx2-y2 orbital dz2 orbital
Fig. 1.5 Angular dependence and shapes of d-orbitals.
The probability density is the square of the wave function and is positive everywhere. The
lobes on the positive or negative side of both the axes are assigned (+) sign and those on
positives side of one axis and negative side of the other or vice versa are assigned (–)sign.
The characteristics of the d-orbitals may be summarised as follows:
(i) dxy, dyz and dzx (or dxz) as well as dx2-y2 orbitals are double dumb-bell shaped and contain four
lobes. The lobes of the first three orbitals are concentrated between xy, yz and zx planes,
respectively and lie between their coordinate axes. The lobes of dx2-y2 orbital are concentrated
along x and y axes. dz2 orbital has a dumb-bell shape with two lobes along z-axis with (+)
sign and a concentric collar or ring around the nucleus in xy plane with (–)sign.
(ii) The d-orbitals belonging to same energy shell are degenerate, i.e. have the same energy in a
free atom.
(iii)The d-orbitals belonging to all main energy shells have similar shape but their size goes on
increasing as the value of n and number of nodal points increase. For example, the size of 5d-
orbital (number of nodal points = 5 – 2–1=2) is larger than that of 4d-orbital (number of
nodal points = 4 – 2 – 1=1).
N.B. The shapes of f, g etc. orbitals are beyond the scope of the text.
1.7. QUANTUM NUMBERS

These are the integral numbers and most of them (i.e. first three) have been derived
from the mathematical solution of Schrodinger’s wave equation for ψ. These numbers serve
as the address of the electrons in an atom and hence are also known as identification
numbers. These describe the energy of an electron in a shell, radius of that shell (i.e. distance
of electron from the nucleus), shape and orientation of the electron cloud (or orbital) and the
direction of the spinning of the electron on its own axis.
There are four quantum numbers viz. principal quantum number (n), azimuthal or subsidiary
quantum number (l), magnetic quantum number (m) and spin quantum number (s).
(i) Principal or Radial quantum number
This quantum number represents the number of shell or main energy level to which
the electron belongs round the nucleus. It is denoted by the letter n. It arises from the solution
of radial part of ψ. This quantum number can have integral values 1,2, 3, 4………..etc. which
are designated by the letters K,L,M,N……..etc. as follows (proposed by Bohr):
Value of n Designation
1 K
2 L
3 M
4 N
It can be concluded that the principal quantum number (n) gives an idea of:
(a) The shell or main energy level which the electron belongs to.
(b) The distance (r) of the electron from the nucleus, i.e. the radius of the shell.
(c) The energy associated with the electron.
(d) The maximum number of electrons that may be accommodated in a given shell.
According to Bohr-Berry scheme, the maximum number of electrons in nth shell = 2n2. Thus
the first shell (n = 1) can accommodate (2 x 12 = 2) two elections, second, third and fourth
shells with n = 2, 3 and 4 can accommodate eight (2x22 =8), eighteen (2x32 = 18) and thirty-
two (2x42 = 32) electrons, respectively.
(ii) Azimuthal or Subsidiary quantum number (l)

This quantum number is also known as orbital angular momentum quantum number.
It is denoted by the letter l and refers to the subshell which the electron belongsto. This
quantum number describes the motion of the electron and tells us about the shape of the
orbitals of a subshell. The values of l depend on the value of n (the principal quantum
number) and may have all possible values from 0 to (n-1), i.e. l = 0,1,2,3……….(n-1). Thus,
for a given value of n, total number of l values is equal to n, e.g. when n = 4, l = 0,1,2,3 (total
4 values of l). For each value of l, separate notation is used which represents a particular
subshell as shown below;
Azimuthal quantum number (l) 0 1 2 3 4 ……

Notation for the subshell s p d f g ……
These notations of subshells have been taken from the characteristics of the spectral lines in
atomic spectra. Thus, s stands for sharp, p for principal, d for diffuse and f for fundamental.
The subshells belonging to various shells are given below:
N L notation for the subshell
1 0 1s
2 0 2s
1 2p
3 0 3s
1 3p
2 3d
4 0 4s
1 4p
2 4d
3 4f
The main points to be noted for azimuthal quantum number are;
(a) This gives an idea of the subshell which the electron belongs to.

(b) Total number of subshells in a given shell is equal to the numerical value of n (main shell).
(c) This quantum number corresponds to the orbital angular momentum of the electron.
(d) This gives an idea of the shape of the orbitals of the subshell.
(e) The maximum number of electrons that can be accommodated in a given subshell is equal to
2(2l+1). Thus s, p, d and f- subshells with l = 0, 1, 2 and 3 can have a maximum of 2, 6,10
and 14 electrons, respectively, i.e. s2,p6, d10 and f14
(iii) Magnetic quantum number (m)
This quantum number determines the direction of angular momentum of the electrons
thereby describing the orientation of orbitals of a subshell in space. The value of m depends
on the value of l thus showing that each subshell consists of one or more regions in space
with maximum probability of finding the electron (i.e. orbitals). The number of such orbitals
(or regions) is equal to the number of ways the electrons can orient themselves in space. This
number is equal to (2l + 1) and values of m are represented as (+) l to (–) l through 0. Thus,
each value of m represents a particular orbital within a subshell and total number of m values
gives total number of orbitals in that subshell. For example, for s-subshell, m =0
corresponding to l=0, i.e. m has only one value indicating that s-subshell has only one orbital
or one possible orientation of electrons which is spherically symmetrical around the nucleus.
When l=1, (i.e. p-subshell), m has three values viz. +1, 0,-1 implying that p-subshell has three
orbitals or orientations which are perpendicular to each other and point towards x, y, and z-
axes. These are designated as px, py, and pz. For l = 2 i.e. d-subshell, m=+2,+1,0,-1,-2,i.e. five
values meaning thereby that this subshell has five orbitals or orientations viz., dxy, dyz, dzx, dx2-
y2 and dz2. On the same grounds it can be shown for f-subshell (l=3) that it has seven orbitals
or orientations corresponding to seven values of m viz., +3,+2, +1,0,-1, -2 and -3. For p, d,
and f subshells (l=1, 2 and 3) various m values may be summarised as follows:
Subshell Value of l Values of m Total m values
p - subshell 1 +1, 0, -1 3
d – subshell 2 +2,+1,0,-1,-2. 5

f – subshell 3 +3,+2,+1,0,-1, -2, -3 7
The main point to be noted for magnetic quantum number is that it determines the total
number of orbitals present in any subshell belonging to preferred orientations of electrons in
space.
(iv) Spin quantum number (s)
This quantum number arises from the direction of spinning of electron about its own

axis. It is denoted by the letter s which can have only two values shown as (+) and (-)

representing clockwise spin(α-spin) or anticlockwise spin (β-spin). These values i.e. (+) and

(-) are also represented as ↑ (upward arrow) and ↓ (downward arrow). Being a charged
particle, a spinning electron generates a so called spin magnetic moment which can be
oriented either up or downward. The value of s for an electron in an orbital does not affect the
energy, shape, size or orientation of an orbital but shows only how the electrons are arranged
in that orbital.
1.8. PAULI’S EXCLUSION PRINCIPLE
This principle was proposed by Pauli in 1924 and as an important rule, governs the
quantum numbers allowed for an electron in an atom and determines the electronic
configuration of poly electron atoms. In a general form, this principal states that “In an atom,
any two electrons cannot have the same values of four quantum numbers”. Alternatively,
this can be put in the form “any two electrons in an atom cannot exist in the same
quantum state”. Consequently, it can be said that any two electrons in an atom can have
same values of any three quantum numbers but the fourth (may be n or l or m or s) will
definitely have different values for them. This can be shown as follows;
Values of quantum numbers

n l m s
For any two electrons in an atom same same same different

or same same different same
or same different same same
or different same same same
Thus the values of all the four quantum numbers for any two electrons residing in the
same orbital like s, px, py, pz, dxy etc. cannot be the same. For example, in case of 2 electrons
in 1s-orbital (i.e. 1s2), the values of n, l and m are same for both the electrons but s has
different values as shown below:
n l m s

1st electron 1 0 0 +
For 1s2 electrons

2nd electron 1 0 0 -
The values of s may also be written in the reverse order but by convention the given order is
preferred. The important conclusion drawn from this discussion is that “an orbital can
accommodate only two electrons with opposite spins”
Application of Pauli’s Exclusion Principle
This principle has been used to calculate the maximum number of electrons that can be
accommodated in an orbital, a subshell and in a main shell. For example, for K-shell, n=1,

l=0 and m=0 and s can have a value equal to either (+) or (-). These values of n, l, m and s
give two sets of values of four quantum numbers as gives above. It is concluded that in K-
shell,there shall be only one subshellwith one orbital i.e. the s-orbital is present which can

contain only two electrons with s = (+) and (-).
For L-shell, n=2, l=0 and 1. The corresponding values of m are 0 (for l=0) and +1, 0, -1 (for

l=1). For each value of m, s will have two values, (+) and (-) . This leads to eight sets of
quantum numbers belonging to eight different electrons. These are shown below:

n = 2, l = 0, m = 0, s = + These values correspond to two

n = 2, l = 0, m = 0, s = - elections in 2s – orbital.



n = 2, l = 1, m = +1, s = + These values correspond to two

n = 2, l = 1, m = +1, s = - elections in 2px – orbital.

n = 2, l = 1, m = 0, s = + These values correspond to two

n = 2, l = 1, m = 0, s = - elections in 2py – orbital.

n = 2, l = 1, m = -1, s = + These values correspond to two

n = 2, l = 1, m = -1, s = - elections in 2pz – orbital.
By convention, the first p-orbital is denoted as px, second as py and third as pz-orbital as given
above.Therefore, we can say that an orbital can accommodate maximum two electrons.
Further, since same values of 1 for a particular value of n corresponds to a particular subshell,
total number of electrons in a subshell can be calculated, e.g., s-subshell contains two and p-
subshell (l=1) will accommodate six electrons, respectively. Thus total number of electrons in
L-shell will be eight (2 in s and 6 in p-subshell). Likewise, one can calculate total number of
electrons in M-shell (18) and N- shell (32) etc. as well as d (10) and f (14) subshells.
1.9. HUND’S RULE OF MAXIMUM MULTIPLICITY
This rule states that “electron pairing in the orbitals of a subshell will not take
place until each orbital is filled with single electron” (due to same energy of orbitals of a
subshell). This is because it is easier for an electron to enter an empty orbital than an orbital
which already possesses an electron.
If an atom has three electrons in p-subshell, these can be arranged in three p-orbitals as
follows:
↓↑ ↑ ↑ ↓ ↑ ↑ ↑ ↑
(a) (b) (c)

Among these arrangements, the option(c) is the correct arrangement because this rule can be
stated alternatively as “the most stable arrangement of electrons in the orbitals of a
subshell is that with greatest number of parallel spins”. It implies that before pairing
starts, all the electrons of the subshell have the same spins (parallel).
This rule serves as a guideline for filling of multi orbital p, d and f subshells, e.g., the electron
pairing in p, d and f-subshells will not start until each orbital of the given subshell contains
one electron. Thus pairing starts in the three orbitals of p-subshell at fourth electron, in five
orbitals of d-subshell at sixth electron and in seven orbitals of f-subshell at eighth electron,
respectively. The electronic arrangements (or configurations) for p4, d6 and f8 systems have
been illustrated here along with p3, d5 and f7:
P3 : ↑ ↑ ↑ d5 : ↑ ↑ ↑ ↑ ↑ f7 : ↑ ↑ ↑ ↑ ↑ ↑ ↑
P4 : ↑↓ ↑ ↑ d6 : ↑↓ ↑ ↑ ↑ ↑ f8 : ↑↓ ↑ ↑ ↑ ↑ ↑ ↑
Here p3, d5 and f7 provide the examples of maximum multiplicity in the respective subshells
and p4, d6 and f8 provide the examples where pairing of electrons in these subshells starts.
1.10. THE AUFBAU PRINCIPLE
Aufbau is a German word which means building up or construction. The building up

of orbitals implies the filling of orbitals with electrons. This principle gives us the sequence
in which various orbitals are filled with electrons. The principle can be stated as “in the
ground state of poly electronic atoms, the electrons are filled in various subshells in the
increasing order of their energy”. This means the electrons are filled in the subshell of the
lowest energy first followed by the higher energy subshells.
There are certain rules which constitute the Aufbau principle:
(i) In general, the subshells with lower n values are filled first followed by those with higher n-
values (called lower n rule).

(ii) For any given principal quantum number n, the order of filling up of subshells is s, p, d and f.
(iii) (n +l) Rule; sometime lower (n + l) rule is violated. In such cases (n+l) rule is applicable
according to which the subshells are filled in order of increasing (n+l) values, e.g., 4s-
subshell [(n+l) = 4+0 equal to 4] is filled before 3d subshell [(n+l) =3+ 2 equal to 5) due to
lower (n+l) values. Keeping in mind the above discussion, various subshells can be arranged
in the order of increasing energy as follows:
Energy sequence of subshells for electron filling
This relative order of energy of various subshells of an atom may also be given as follows:
1s<2s<2p<3s<3p<4s<3d<4p<5s<4d<5p<6s<4f<5d<6p<7s<5f<6d…
The electrons are filled according to this order only in polyelectron atoms. Configurations of
lanthanum (La, Z = 57) and actinium (Ac, Z = 89) are the exceptions where the last electron
enters 5d and 6d-subshells instead of 4f and 5f-subshells against the Aufbau’s lower (n + l)
rule though (n+l) values are same for 4f and 5d as well as 5f and 6d-subshells.

1.11. ELECTRONIC CONFIGURATION OF ELEMENTS
Based on the Pauli’s exclusion principle, Hund’s maximum multiplicity rule and
Aufbau principle, we can formulate a system for electron distribution in atoms and electronic
configuration of the elements can be worked out. By electron distribution, we mean
arrangement of electrons in various atomic orbitals and subshells.
Looking at the relative energy sequence of subshells of atoms in the elements, it can be
concluded that we can work out and write down the electronic configuration of the elements
straightaway up to argon (Ar, Z = 18) as follows:
Name of the element Symbol with atomic number Electronic configuration
Hydrogen H (Z = 1) 1s1
Helium He (Z = 2) 1s2
Lithium Li (Z = 3) [He] 2s1
Beryllium Be (Z = 4) [He] 2s2
Boron B (Z = 5) [He] 2s2 2p1
Carbon C (Z = 6) [He] 2s2 2p2
Nitrogen N (Z = 7) [He] 2s2 2p3
Oxygen O (Z = 8) [He] 2s2 2p4
Fluorine F (Z = 9) [He] 2s2 2p5
Neon Ne (Z = 10) [He] 2s2 2P6
Sodium (Natrium) Na (Z = 11) [Ne] 3s1
Magnesium Mg (Z = 12) [Ne] 3s2
Aluminium Al (Z = 13) [Ne] 3s2 3p1
Silicon Si (Z = 14) [Ne] 3s2 3p2

Phosphorus P (Z = 15) [Ne] 3s2 3p3
Sulphur S (Z =16) [Ne] 3s2 3p4
Chlorine Cl (Z = 17) [Ne] 3s2 3p5
Argon Ar (Z = 18) [Ne] 3s2 3p6
If we try to write down the electronic configuration of potassium (Kalium) (K, Z=19)
according to above trend, the last electron must go to the 3d subshell, i.e. K19 = [Ne] 3s2 3p6
3d1 or [Ar] 3d1, but this electron is said to enter the 4s–subshell according to lower(n+l)rule
of Aufbau principle. This may also be explained on the basis of effective nuclear charge
given at the end of this topic. The (n + l) value for 4s = 4+0 is equal to 4 and for 3d, it is 3+2
is equal to5. Hence the electronic configuration of potassium (K, Z =19) is [Ar18] 4s1 and that
for calcium (Ca, Z = 20), the next higher element, is [Ar] 4s2. Again, the last electron in the
atom of the next element, Sc, (Z = 21) has the opportunity to occupy either 3d or 4p-subshell
because both are available to it. The (n+l) values for 3d (3+2=5) and 4p (4+l = 5) are same
and electron prefers to enter that subshell which has lower n value, i.e. 3d-subshell according
to lower n rule of Aufbau principle. The filling of 3d-subshell goes on up to zinc (Z = 30).
The electronic configurations of the elements with Z = 21 to 30 are given below:
Name of the Electronic
Symbol with atomic number Configuration
Sc (Z = 21) [Ar] 4s2 3d1
Ti (Z = 22) [Ar] 4s2 3d2
V (Z = 23) [Ar] 4s2 3d3
Cr (Z = 24) [Ar] 4s1 3d5
Mn (Z = 25) [Ar] 4s2 3d5
Fe (Z = 26) [Ar] 4s2 3d6

Co (Z = 27) [Ar] 4s2 3d7
Ni (Z = 28) [Ar] 4s2 3d8
Cu (Z = 29) [Ar] 4s2 3d10
Zn (Z = 30) [Ar] 4s23d10
The next six elements, viz. Ga31, to Kr36 belong to p-block and the last electron, as is evident,
enters the 4p – subshell of the atoms of these elements. The electronic configurations of these
elements are as follows:
Gallium Ga (Z = 31) [Ar] 4s2 3d10 4p1
Germanium Ge (Z = 32) [Ar] 4s2 3d10 4p2
Arsenic As (Z = 33) [Ar] 4s2 3d10 4p3
Selenium Se (Z = 34) [Ar] 4s2 3d10 4p4
Bromine Br (Z = 35) [Ar] 4s2 3d10 4p5
Krypton Kr (Z = 36) [Ar] 4s2 3d10 4p6 or 1s2 2s2 2p6 3s2 3p63d104s2 4p6
In next two elements of 5th period, the last electron goes to 5s- subshell. (s-block):
Rubedium Rb (Z = 37) [Kr] 5s1
Strontium Sr (Z = 38) [Kr] 5s2
Filling of 4d – subshell begins in the next element, yttrium, Y (Z = 39) and ends at cadmium,
Cd (Z = 48) {Y: [Kr] 5s2 4d1 to Cd: [Kr] 5s2 4d10} with anomalies in the configurations of
42 46 47
Mo, Pd and Ag as shown below. In the next six elements of p-block, electron filling
occurs in 5p – subshell, i.e. Indium 49In: [Kr] 5s2 4d105p1 to Xenon, 54Xe : [Kr] 5s2 4d10 5p6 or
1s2 2s2 2p6 3s2 3p63d104s2 4p6 4d10 5s25p6. Next two elements caesium 55Cs and barium, 56Ba
are s-block elements and the last electron in these elements enters the 6s-subshell. 55Cs: [Xe]
6s1 and 56Ba: [Xe] 6s2. Next element lanthanum 57La, belongs to d-block: [Xe] 6s2 5d1 and is
58 71
followed by 14 lanthanides: cerium, Ce to lutetium, Lu in which electron filling takes

place in f-subshell except 64Gd and 72Lu in which the last electron enters d-subshell due to f7
and f14 stable configuration but these show close resemblance with other f-block elements
and have been placed with them in the periodic table.
It is observed that in case of chromium (Cr, Z = 24) and copper (Cu, Z = 29), the
electronic configurations are against the trend. These configurations have been obtained
experimentally by spectroscopic studies. Simple explanation to these anomalies can be given
as under. For Cr and Cu, d-electrons being higher in number contribute more towards the
stability of the atoms. Because d5 (just half filled) and d10 (completely filled) configurations
are more stable compared to d4 and d9 configurations, electronic transition occurs from s to d-
subshells in these elements (due to exchange energy effect and symmetry of orbitals), i.e. Cr:
4s23d4 → 4s13d5 and Cu : 4s2 3d9 → 4s1 3d10. s- electrons being less in number have little
effect in this pursuit.
Similar anomalies have also been observed in the higher homologues of these
elements, viz. ,molybdenum (Mo, Z = 42) : [Kr] 5s1 4d5 and silver (Ag, Z = 47) : [Kr] 5s1
4d10. Palladium (Pd, Z = 46) contains another typical configuration: [Kr] 5s0 4d10. Also there
are anomalies in the configurations of lanthanides and actinides.
The important point to be noted here is that during the filling of electrons, these enter
first in ns-subshell and then (n-1) d or (n-2) f-subshell. But during the removal of electron (s),
it is first removed from nths orbital rather than (n-1) d or (n-2) f-subshell though Ens <En-1d<
En-2f and removal of the electron must occur from higher energy subshell. For example, in
case of first transition series (3d-series) elements filling and removal of 4-s-electrons occurs
first followed by 3d-electrons. This is, perhaps, because after filling of d-subshell, it becomes
of lower energy than 4s-subshell.
1.12. EFFECTIVE NUCLEAR CHARGE (ZEFF.)
This term is related with shielding or screening effect. The electrons residing in the
innermost shell experience the attraction of full charge of the nucleus (actual charge) but this
is not true for the electrons contained in the outer shells. Actually the electrons in the inner
shells called intervening electrons, act as a shield or screen between the nucleus and outer

shell electrons and thus reduce the force of attraction between them. This is called screening
or shielding effect. This effect of inner electrons causes a decrease in the actual charge of the
nucleus (atomic number, Z) acting on the outer electrons by a quantity σ (sigma) known as
screening or shielding constant. The decreased nuclear charge (Z- σ) is called effective
nuclear charge denoted by Zeff.
It is to be noted that only inner electrons cause the shielding of nucleus from outer
electrons and outer electrons do not produce any shielding effect on any of the inner electrons
in question.
The shielding constant is greater than zero and less than Zactual and is a measure of the degree
to which the intervening electrons shield the outer shell electrons from the nuclear pull.
The effective nuclear charge (Zeff.) is defined as “the difference between actual nuclear
charge (Zactual) and the screening constant (σ) produced by the intervening electrons”.
The shielding effect caused by inner electrons varies with the type of subshells to which these
electrons belong, e.g. s > p > d > f. This shows that s-electrons cause maximum shielding
effect followed by p, d and f-electrons which produce minimum shielding effect due to their
arrangement around nucleus. There are certain factors which influence the magnitude of σ
and Zeff.
(i) Number of intervening electrons: Greater is the number of intervening electrons, more will be
the magnitude of σ and less is the value of Zeff. Down in a group, number of intervening
electrons in elements increases and hence value of σ also increases. Consequently, Zeff value
goes on decreasing.
(ii) Size of atom: As the size of atoms increases, value of Zeff decreases, e.g. down in a group.
Along a period, atomic size decreases and hence Zeff goes on increasing.
Slater’s Rules for calculating σ and Zeff.
Slater gave illustrative rules for calculating σ and Zeff. These have been discussed here with
illustrations:

(i) The screening constant (σ) for an electron contained in ns or any of np orbitals of nth shell of
an atom/ion = 0.35 x [number of remaining electrons in nth shell] + 0.85 x [number of
electrons in (n-1th shell)] + 1.0 x [number of electrons in farther inner shells].
From this formula, we conclude that;
(a) Each of the remaining electrons in the nth shell contributes 0.35 to the value of σ.
(b) Each of the electrons in (n- l)th shell makes a contribution of 0.85 to the value of σ.
(c) Each of the electrons in the next inner shells makes a contribution of 1.0 to it.
(d) There is no contribution of electrons to the value of σ which are residing in the orbitals
having higher value of the principal quantum number than the shell number of the electron in
question.
(e) For an s-electron of first shell (n=1), there will be a contribution of 0.30 from other single
electron in 1s-orbital.
Some examples may be cited to make the rule clear:
Example 1. Calculate σ and Zeff. values for 4s electron in
(i) cu (Zn = 29) and (ii) Mn (Z = 25) atom.
Solution: (i) for cu (Z = 29), 29Cu = 1s2 2s2 2p63s23p63d104s1
(10) (18) (01)
σ for 4s1 electron in Cu atom = 0.35x0+0.85x18+1.0x10 = 25.30

∴ Zeff. for 4s1 electron in Cu atom = Zact.– σ = 29 – 25.30 = 3.70
(ii) For Mn (Z = 25), 25Mn = 1s2 2s2 2p6 3s23p63d5 4s2

(10) (18) (1)
σ for 4s1 electron in Mn-atom = 0.35 x 1+ 85 x 13 + 1.0 x 10 = 21.40
∴ Zeff experienced by a 4s – electron in Mn atom = Z act.– σ = 25 – 21.40 = 3.60
Example 2. Calculate Zefffor (i) the last electron in Cl atom (Z=17) and
(ii) 1s electron in N atom (Z = 7).

Solution: (i) for Cl (Z = 17), 17Cl = 1s2 2s2 2p6 3s23p5

(2) (8) (7)
∴ Last shell contains 7 electrons, hence remaining electrons in this shell for the last electron
= 7-1 =6
σ for the last electron of Cl-atom = 0.35 x 6 + 0.85 x 8+ 1.0 x 2 = 10.90
∴ Zeff for the last electron of Cl atom = 17-10.90 = 6.10
(ii) For N (Z = 7), 7N = 1s2 2s2 2p3

(2) (5)
There will be no contribution of valence shell electrons towards σ of 1s1 electron.
∴σ of 1s1 electron of N atom = 0x5+0.30x1 = 0.30
and Zeff for this electron = Zact.- σ = 6.70
(ii) σ for an electron contained in (n-1) d-orbitals of (n-1)th shell of an atom/ion
= 0.35 x [number of electrons in (n-1)d-orbitals]+ 1.0 x [Number of electrons in (n-1)s, (n-
1)p-orbitals and inner shells]
From this formula, it is inferred that
(a) These is no contribution of the electrons of ns-orbital to the value of σ.
(b) Each of the remaining electrons in the (n-1)d-orbitals contributes 0.35 to σ.
(c) Each of the electrons in (n-1) s and (n-1)p-orbitals as well as inner shells i.e. n=1 to n (n-2)th
shell makes a contribution of 1.0 to the value of σ.
Let us discuss few examples:
Examples 3. Calculate σ and Zeff for 3d-electron in (i) Cr (Z = 24) and (ii) Ni (Z = 28).
Solution. (i) for Cr (Z = 24), 24Cr = 1s2 2s2 2p6 3s2 3p6 3d5 4s1
(18) (5) (1)
(on arranging the configuration according to Slater’s rule)

Here 4s1 electron does not contribute towards the value of σ.
σ for a 3d-electron in Cr atom = 0.35 x 4+1.0 x 18 = 19.40
(remaining electrons in 3d orbitals = 5-1 = 4)
∴Zeff experienced by a 3d electron in Cr atom = Zact.– σ = 24 – 19.40 = 4.60
(ii) For Ni (Z = 28), 28Ni = 1s2 2s2 2p6 3s23p6 3d8 4s2
(18) (8) (2)
4s2 electrons do not contribute to the value of σ. Remaining electrons in 3d orbitals = 8-1 = 7.
σ for a 3d-elctron in Ni atom = 0.35x7+1.0x18 = 20.45
∴Zefffor a 3d-electron in this atom= Z – σ = 28-20.45 = 7.55
(iii) To calculate the Zeff experienced at the periphery of an atom/ion.
This is calculated by subtracting the shielding constant (σ) for all the electrons present in the
electronic configuration of the atom/ion from its actual nuclear charge.
For example, suppose we have to calculate the Zeff. at the periphery of Ti (Z = 22) atom,
then 22Ti= 1s2 2s2 2p6 3s23p63d2 4s2
(10) (10) (2)
σ for all the electrons of Ti atom = 0.35x2+0.85x10+1.0+10 = 19.20
∴ Zeff at the periphery of this atom = Zact.– σ = 22- 19.20 = 2.80
Applications of effective nuclear charge and Slater’s Rules
The concept of effective nuclear charge in the light of slater’s rule has been used to explain;
why is 4s-orbital filled in preference to 3d-orbitals in potassium atom (Z =19)?
Argon (Z = 18) with electronic configuration: 1s2 2s2 2p6 3s23p6, is the last element of third
period in which the 3d-orbitals remain vacant and the last electron goes to 3p-subshell. For
the 19th electron of potassium atom, two subshells are theoretically available, viz. 3d and 4s.
Under these two possibilities, the electronic configurations of potassium atom are:
K (Z = 19) = 1s2 2s2 2p6 3s2 3p63d1
(18) (1)
and K (Z = 19) = 1s2 2s2 2p6 3s23p64s1

(10) (8) (1)
The σ (shielding constant) for 4s-electron of K atom

= 0.35x0+0.85x8+1.0x10 = 16.80
∴ Zeff for 4s1 electron of K atom = Zact.– σ = 19-16.80 = 2.20
Similarly, the Zeffexperienced by 3d1 electron of K-atom is

19- [0.35x0+1.0x18] = 1.0

Since Zeff for 4s1 electron is greater than 3d1 electron of K atom, the attractive force between
4s1 electron and nuclear charge is greater than that of between 3d1 electron and the nucleus of
this atom. Hence the configuration, 1s2 2s2 2p6 3s2 3p64s1, would be more stable than that
having 3d1 electron. This infers that 4s-orbital is filled in preference to 3d-orbitals in K atom.
Other applications of the concept will be given in the next units of the text as and when
required.
1.13. SUMMARY
This unit contains the text related with the dual nature of matter, the uncertainty
principle, probability concept, the wave equation, significance of ψ and ψ2 and related wave
functions as well as probability distribution curves and shapes of atomic orbitals in the simple
way. A brief and informative discussion of quantum numbers, the rules governing the filling
of atomic orbitals such as Pauli’s exclusion principle, Hund’s rule and Aufbau principle has
been given. The electronic configuration of elements has effectively been discussed with
examples and the limitations are also given. At the last, Slater’s rules for calculating the
effective nuclear charge with examples and applications have been given briefly.
1.14. TERMINAL QUESTIONS

(only some samples have been given)
i) What do you mean by dual nature of matter?
ii) Discuss the meaning and significance of ψ and ψ2 with reference to the wave equation.
iii) Write a note on radial wave function.
iv) Discuss the angular wave function and correlation between this wave function
and shape of p-orbitals.
v) Discuss azimuthal quantum number with suitable examples.
vi) What possible values of n, l, m and s quantum numbers can an electron in a 4f- orbital have?
vii) How many electrons can be contained in fourth hell of an atom and why?
viii) How are the quantum numbersn, l and m related to one another?
ix) What is meant by shielding effect?
x) What quantum numbers would you assign to the last electron of Rb-atom(Z = 37) as well as
its 30th electron?
xi) Calculate σ and Zeff for 3d electron in Mn (Z = 25) atom.

xii) Write down the electronic configurations of the elements with Z = 46, and 71.
1.15. ANSWERS
i) Please see de Broglie’s matter waves.
ii) Please see significance of ψ and ψ2.
iii) Please see radial wave function.
iv) Please refer to angular wave function and shapes of orbitals.
v) Please see quantum numbers.
vi) An electron in a 4f orbital will have the values: n = 4, l = 3 (n-1 = 4-1),

m = any one of +3,+2,+1,0,-1,-2,-3,s = + or - .
vii) According to Bohr – Burry scheme, the maximum number of electrons in nth shall = 2n2.
∴ In fourth shell, maximum number of electrons = 2x42 = 32.
viii) n, l and m are inter related as follows:
l = 0 to n-1, m = +l to – l through 0, n is independent of both l and m.
ix) Please refer to effective nuclear charge and shielding effect.
x) The electronic configuration of Rb (Z = 37) atom is 37Rb = [Kr] 5s1 i.e. 1s2 2s2 2p6 3s2 3p6
4s2 3d10 4p65s1 (Aufbau principle) The last electron is 5s1 electron. Its quantum numbers

are n=5, l= 0, m = 0, s = +
The 30th electron is the last electron in 3d subshell i.e. the 10th electron.

Its quantum number are: n=3, l= 2, m= -2, s = -
25
xi) Mn = 1s2 2s2 2p6 3s2 3p6 3d154s2
(18) (5) (2)
4s2 electrons do not contribute to the value of σ for 3d electrons.

σ for a 3d-electron in Mn atom = 0.35 x [number of remaining electrons in 3d-orbitals]+ 1.0 x
[number of all the electrons in1s ,2s, 2p, 3s,and 3p, orbitals ] = 0.35 x 4+ 1.0x 18 = 19.40
∴ Zeff = Z – σ = 25- 19.40 = 5-60
xii) For this answer, please refer to Aufbau principle:
Z = 46 : 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s0 4d10 (observed config.)
Z = 71 : 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d10 5p6 6s2 4f14 5d1

1.16. REFERENCES
1. Principles of Inorganic Chemistry: B. R. Puri, L.R. Sharma & K. C. Kalia,
Milestone Publishers and Distributers, Daryaganj, Delhi (2013).
2. Selected topics in Inorganic Chemistry: W.U. Malik, G.D. Tuli & R.D. Madan, S. Chand &
Co. Ltd., New Delhi (1993).
3. Comprehensive Inorganic Chemistry: Sulekh Chandra, New Age International (Pvt.) Ltd.,
New Delhi (2004).
4. The Nature of the Chemical Bond: Linus Pauling, 3rd Edn., Cornell University Press, New
York (1960).
5. A Simple Guide to Modern Valency Theory: G.I. Brown, Revised Edn., Longmans Green,
London (1967).
6. Advanced Inorganic Chemistry: Satya Prakash, G.D. Tuli, S.K. Basu and R.d. Madan, Vol. I,
7th Edn., S. Chand & Co. Ltd, New Delhi (1998).
7. Shriver and Atkins’ Inorganic Chemistry: Peter Atkins et. al., 5th Edn., Oxford University
Press, New York (2010).

UNIT 2: THE PERIODIC TABLE
CONTENTS:
2.1 Objectives
2.2 Introduction
2.3 History of Periodic Table
2.4 Laws of Periodic Table
2.5 Summary
2.6 Terminal Question
2.7 Answers
2.8 References
2.1 OBJECTIVE
The objective of writing the text of this unit is to give the readers an information about how
the elements whose number increased with time, were organised in the tabular form.The
systematic classification of these elements with respect to their physical/chemical properties
made the readers and the scientists comfortable and predictable in their further study. Till
date, this number has gone up to 112 to whom symbols have been assigned and some more
elements have been predicted and evidenced by laboratory studies.
2.2 INTRODUCTION
With the rapid advance of chemistry with time, the number of discovered elements increased
continuously. These elements exhibited marked difference in their properties. Hence it
became more and more difficult and tedious job for the scientists to study each and every
element individually for its physical and chemical behaviour. Therefore, many attempts were
made to arrange the elements with similar physical and chemical bhaviour, at one place to
make their study systematic and easier. This attempt was named the periodic classification
of elements which means, the ideal arrangement of those elements which are alike in their
behavior. It was thought, in the process, that there might be some relation between some
fundamental characteristic of an element and its properties. Originally, this characteristic
taken into account was the atomic weight, later called atomic mass. Eventually, the atomic

mass was replaced by more appropriate basis, the atomic number. At the same time the
periodicity in properties of the elements was also taken care of.
2.3 HISTORY OF PERIODIC TABLE
The first important attempt for the arrangement of elements, i.e. their classification, was
made by Dobereiner in the beginning of nineteenth century by proposing what is now known
as “Dobereiner’s law of triads”.According to him when various triads (i.e. containing three)
of elements with similar properties were arranged in increasing order of their atomic weights,
the atomic weight of the middle element of the triad was found approximately equal to the
arithmetic mean of the remaining two corner elements. For example:
Li Na K
7 23 39
S Se Te
32 79 127.6
Cl Br I
35.5 80 127
This law of triads was not found useful because triads of all the known elements at that time
could not be formed.
In the middle of nineteenth century, scientist Duma put forward his idea called “Duma’s
homologous series” in an attempt to classify the elements. He proposed that “the atomic
weights of certain elements could be placed in homologous series like organic compounds”.
For example, the elements of nitrogen family were arranged as follows:
Element Atomic Weight Homologous series
N 14 A
P 31 (14+17) A+B
As 75 (14+17+44) A+B+C
Sb 119 (14+17+2x44) A+B+2C
Bi 207 (14+17+4x44) A+B+4C
(Here A = 14, B = 17 and C = 44).
This scheme of Duma was also not found useful in the classification of elements.

Further step in this field was takenin 1864 by John Newlands, an English chemist. He tried to
correlate the chemical properties of elements with their atomic weights and proposed a law,
now known as “Newlands’ law of octaves”. According to this law “if the elements were
arranged in increasing order of their atomic weights, every eighth element was found to
have similar properties”. For example, as given below, the eighth element starting from Li
is Na which have similar properties. Similarly, Mg is the eighth element from Be and both of
them also have similar properties.
Li Be B C N O F
7 9 11 12 14 16 19
Na Mg Al Si P S Cl
23 24 27 28 31 32 35.5
However, this classification proposed by Newlands was limited to 14 elements only (given
above) and his work was not accepted by scientific community.
2.4 LAWS OF PERIODIC TABLE

(A) Mendeleev’s Periodic law:
Dmitri Mendeleev, a Russian chemist, in 1869 observed that “when the elements were
arranged in the increasing order of their atomic weights, the elements with similar
properties recurred (or reappeared) at regular intervals (or periods)”. From this
observation, he put forward a law known as Mendeleev’s periodic law. This law states:
“The physical and chemical properties of elements are periodic functions of their atomic
weights”.
Working on this law, he arranged the elements, known at his time, in the increasing order of
atomic weights and presented them in the form of a table. That was known as Mendeleev’s
periodic table (please see table 2.1).

Table 2.1: Mendeleev’s original Periodic Table

In that table, the elements were arranged in columns (called groups) and rows (called
periods). The original periodic table formed by Mendeleev had following characteristics:
(i) The elements were arranged in the increasing order of their atomic weights.
(ii) The table contained eight vertical columns and seven horizontal rows.
(iii) Every column (group) contained two sub groups (subgroup A and subgroup B) except, the
eighthcolumn which contained three series of three elements (triads).
(iv) The columns contained the elements of similar physical and chemicalproperties.
(v) First period (horizontal row) was called very short period, second and third periods were
named as short periods, fourth and fifth periods were called long periods and sixth period was
named very long period. Seventh period contained only a few elements (and is still
incomplete). The elements of 2nd and 3rd periods were called the typical elements by
Mendeleev because, these were truely the representatives of their respective groups.
(vi) Mendeleev had left empty spaces for elements unknown at his time, e.g. Sc, Ga, Ge etc.
but had predicted their properties. At his time, around 65 elements were known.
Merits of Mendeleev’s Periodic Table:
(i) It helped in the study of elements and compounds which has become easy and systematic.
(ii) The empty spaces in the Mendeleev’s periodic table encouraged the scientists to work in the
field of discovery of new elements since he had predicted the properties of the probable
elements.

Defects of the Mendeleev’s Periodic Table:

Although Mendeleev’s periodic table helped a lot to study the properties of elements and
correlate the elements with one another, yet there were some anomalies which existed
unanswered in the Mendeleev’s table. These were:
(i) The position of hydrogen remained inappropriate because some of its properties resembled
with alkali metals and some others with halogens. Hence it might be placed in group I or
group VII.
(ii) Dissimilar elements of sub groups were placed together in groups, i.e. alkali metals and
coinage metals of 1st group have altogether different properties. Similar is the case with
halogens and elements of manganese family in group VII (sub groupA and B elements).
(iii)Certain elements with higher atomic weights were placed before those with lower atomic
weights, e.g.
Cobalt Nickel (elements of group VIII, triad I)

58.93 58.69
Tellurium Iodine (elements of group VI and VII)

127.60 126.90
(iv) The Table did not show any correlation between chemical properties and electronic
configuration of elements.
(v) No information regarding the position of isotopes and isobars was available from the
table.
Modified form of Mendeleev’s Periodic Table:
Mendeleev did not imagine the discovery of inert elements, therefore no place was left by
him in his periodic table for these elements. After the discovery of inert gases (later called the
noble gases),a new group was added to accommodate these elements to his Periodic Table
which is called zero group. Similarly, the lanthanides and actinides could not find the proper
place in his periodic table. Later including these and other elements which were discovered
after Mendeleeff, a modified table was prepared which has been given (Table 2.2).

Table 2.2 Modified form of the Mendeleev periodic table bassed on atomic weight.
This table has following characteristics:
(i) This table contains nine vertical columns or groups including the zero group.
(ii) Except the elements of zero group and eighth group, all the groups have been divided into A
and B sub groups. The elements of subgroup A have been kept on left side and those of B on
the right side of the group. Elements of a subgroup have more similarities than those placed
in the other sub group of the same group. For example, elements of subgroup I A (viz., Li,
Na, K, Rb, Cs, etc.) have almost similar properties but differ from subgroup IB elements (viz.,
Cu, Ag, Au).
(iii)The atomic weights of the elements increase regularly on moving from top to bottom in a
column and, in general, in a period with few exceptions.
(iv) The number of horizontal rows has been kept the same but the nomenclature of periods
(given in point v of Mendeleev’s original periodic table) has been changed in the modified
table. The first three periods, in this case, are known as short periods containing 2,8 and 8
elements and the last four are called the long periods though the number of elements is 18 in
the fourth and fifth periods and 32 in the sixth period. Seventh period is still incomplete. It
may be noted here that there is regular variation in the properties of elements from left to
right in a period.
(v) By the year 1900, some 30 more elements had been added to the list of elements. These
along with those discovered later have been given in the table.

(B) Lothar Meyer’s arrangement:

German chemist Lothar Meger, in 1870 proposed independently a more extensive tabulation
of the elements based on regular periodic recurrence of properties. He calculated the atomic
volumes of the known elements i.e. volume occupied by one mole of the elements (in cm3) in
the solid state. Thus

Atomic volume =

When he plotted these atomic volumes against the corresponding atomic masses, a curve with
sharp peaks and broad minima was obtained. This idea could not get wide acceptance and
was not taken for further work by scientific community.
(C) Modern Periodic law (Moseley’s Periodic Law).
This is also called Moseley’s periodic law. Henry Moseley, a British physicist, in 1911-12,
discovered a new property of the elements called atomic number which is equal to the total
number of protons in the nucleus of the atom of an element (this is also equal to the number
of electrons in the atom). He correlated this property with the physical and chemical
properties of the elements. This led Moseley to predict that most of the defects of
Mendeleeff’s periodic table could be removed if the classification of the elements is done on
the basis of atomic number rather than the atomic weight. He, thus, modified the periodic law
and stated that “the properties of the elements are the periodic functions of their atomic
numbers”. Meanig thereby, if the elements are arranged in the increasing order of their
atomic numbers, the recurrence of properties of the elements takes place at regular intervals.
The elements with similar properties fall in the same vertical columns (or groups) and are
called elements of that family.
Modern or Long form of Periodic Table:
This table is also known as Bohr’s periodic table and is based on the atomic number, which is
a fundamental property of the elements, and Moseley’s periodic law. This table helps us to
understand the cause of periodicity of properties, i.e. recurrence of similar properties at
certain regular intervals viz., 2,8,18, and 32 which are referred to as magic numbers. This is
because the atomic number of elements in a group increases by magic numbers at various
steps. This is said to be attributed to the electronic arrangement in the atoms of elements.
The modern periodic table has 18 vertical columns called groups or families and 7 horizontal
rows called periods. This has been given in (table 2.3).

Table 2.3 Modern or long form of the periodic table.

The detailed discussion of the modern periodic table is given below:
Groups:
In terms of the electronic configuration/arrangement in atoms of the elements, a group
consists of elements whose atoms have the same outer most shell electronic configuration
(except some of the higher homologues of iron triad). According to IUPAC (International
Union of Pure and Applied Chemistry), the groups are numbered as 1,2,3……17,18. Also
there is yet another system in practice among the authors in chemistry according to which
groups are named as IA, IB, IIA, IIB, IIIA, IIIB. ………..VIIA, VIIB, VIII and zero group in
place of numbering the groups from 1 to 18. In the table 2.3, both the systems of numbering
the groups have been given. At the same time, the elements have been allocated the blocks in
the table viz., groups 1 or (IA) and 2 or (IIA) have been placed in s-block, the groups 13 or
(IIIA), 14 or (IVA)……….17 or (VIIA) and 18 or (zero group) have been included in p-
block. These elements of s and p-block (total 8 columns) are collectively called main group
elements. The elements placed in s-block and p-block except the elements of groups 18 (zero
group) are also known as representative elements and zero group elements are called inert
or noble gases. The elements of the groups 3 or (IIIB), 4 or (IVB),……..7 or (VIIB), 8 to 10
or (VIII),11 or (IB) and 12 or (IIB) (total ten vertical columns) have been placed in d-block
(also called transition elements). There are 28 elements arranged separately in two horizontal
rows at the bottom of the main body of the periodic table, each row containing 14 elements.
These have been included in f-block also known as innertransition elements or rare earth

metals. First row of the elements is called 4f-block elements or lanthanides because they all
are having almost similar properties and follow the element lanthanum. The second row is the
5f-block elements or actinides as they fall after actinium and also have almost similar
properties.
The transition elements have been placed between s-and p-block elements and inner
transition elements within transition elements.
Periods:
The modern periodic table has seven periods. Each period begins with alkali metal (except
first one) and ends at a noble gas. The elements in the periods have also been arranged in the
increasing order of their atomic numbers and it increases by one unit at each step. The first
three periods are known as short periods:
The elements of first period are H1 and He2 only (2 elements) The second period contains the
elements from Li3 to Ne10 (8 elements) and the third period includes the from Na11 to Ar18(8
elements). The next three periods are collectively called long periods and include the
elements as follows:
Fourth period: potassium (K, Z= 19) to krypton (Kr, Z = 36) (18 elements)
Fifth period: rubidium (Rb, Z = 37) to xenon (Xe, Z = 54) (18 elements)
Sixth period: caesium (Cs, Z = 55) to radon (Rn, Z = 86) (32 elements).
Seventh period: francium (Fr, Z = 87) to copernicium (Cn, Z = 112) (26elements,
incomplete)
The seventh period will be completed at Z = 118 (a noble gas) but at present it is in complete.
All the elements of this period are radioactive.
The elements of third period except Ar (Na11 - Cl17) are called typical elements.
The typical feature of the long form of periodic table is that the elements of 4th, 5th and 6th
periods which fall under main group elements are sometimes called the “normal elements”
because they resemble the elements of 2nd and 3rd periods below which they are placed. The
6th period also includes 14 elements (Z = 58 to 71) which follow lanthanum (La57) and hence
are known as lanthanones or lanthanides. The 7th Period contains another series of 14
elements (Z = 90 to 103) following actinium (Ac89), therefore these elements are called
actinones or actinides. The elements beyond uranium (U, Z = 92) viz., Z = 93 to 103
(neptunium to lawrencium) are known as trans- uranic elements and have been prepared
artificially in the laboratory.
Lanthanides: Ce58 14 elements Lu71
Actinides: Th90 14 elements Lr103

In general, all the elements of the long form of periodic table have been divided into four
categories:
(i) Representative elements:
These are the main group elements including the groups 1,2,13…….17 which have either ns1
or ns2 and ns2 px (x = 1-5) outer shell electronic configuration where n is the highest value of
principal quantum number. All these elements have been placed in subgroups A of the
periodic table.
(ii) Noble gases:
These also fall within main group elements and include group 18 (or zero) elements. These
all have completely filled s- or s- and p-subshells of outer most or ultimate shell with highest
n value, i.e. ns2 or ns2p6 (ns2 for He). These have also been placed in subgroup A of periodic
table.
(iii)Transition metals:
These are the elements of groups 3 to 12 and in general have incomplete d-subshell of the
penultimate shell and filled s-subshell of ultimate shell with highest n-value. But the elements
of some of the groups also have incompletely filled s-subshell of the ultimate shell in addition
to incompletely filled d-subshell of the penultimate shell. All these elements have been
placed in subgroups B of the periodic table.
(iv) Innertransition elements:
These elements are said to belong to group 3 or (IIIB) due to close similarity in their
chemical properties with those placed in group 3. These elements genrally have incompletely
filled (n-1) d and (n-2) f-subshells.
According to their electronic configuration and the type of subshell to which the last of
differentiating electron enters in the atom of the elements, the elements in the modern
periodic table have been classified into four blocks i.e. s, p,d and f-block elements.
(i) s-Block elements:
All these elements are metals and solid except H and He which are gases. These are the
elements in which the last electron enters the s-subshell. The elements of group 1 (alkali
metals, viz., Li, Na, K, Rb, Cs, Fr) and group 2 (alkaline earth metals, viz., Be, Mg, Ca, Sr,
Ba, Ra) belong to this block in addition to hydrogen (H) and helium (He). The general
valence shell electronic configuration of these elements is nsx (x = 1 or 2) where n is the
number of valence shell or number of period which the element belongs to.
(ii) p-Block elements:

These elements in which the differentiating electron enters the orbitals of p-subshell of the
valence or outer most shell are called p-block elements. The elements of groups 13 to 18
(except He with configuration 1s2) belong to this block. The group number and the elements
contained in them are shown here:
Group 13 : B, Al, Ga, In, Tl
Group 14 : C, Si, Ge, Sn, Pb
Group 15 : N, P, As, Sb, Bi
Group 16 : O, S, Se, Te, Po
Group 17 : F, Cl, Br, I, At
Group 18 : Ne, Ar, Kr, Xe, Rn
The general valence shell electronic configuration of these elements in ns2 npx (x=1 to 6) and
n is the number of shell. The elements of this block exist in all the three states of matter viz.
solid, liquid and gas. Most of them are non- metals and the rest are metals and metalloids (or
semimetals).
(iii) d-Block elements:
The elements in which the last electron enters the orbitals of (n-1) d subshell, (i.e. the
subshell of penultimate shell) and d-orbitals are, thus, being progressively filled are known as
d-block elements. These elements are also termed as transition elements and have been
placed in the middle between s-block and p-block elements in the periodic table. Thus, these
elements serve as a bridge or transition between highly electropositive s-block and highly
electronegative p-block elements thereby being responsible for gradual change in the
properties along a period. Hence the name, transition elements has been given to them. These
include the elements of group 3 to group 12 (ten columns). These have further been
categorised into 3d, 4d, 5d and 6d series depending on the shell number whose d-orbitals are
being filled. Each of these series contains ten elements as given below:
3d series: scandium (Sc, Z = 21) to zinc (Zn, Z = 30)
4d series: yttrium (Y, Z = 39) to cadmium (Cd, Z = 48)
5d series: lanthanum (La, Z = 57), hafnium (Hf, Z = 72) to mercury (Hg, Z = 80)
6d series: actinium (Ac, Z = 89), rutherfordium (Rf, Z = 104) to
copernicium (Cn, Z = 112 )
The general valence shell electronic configuration of these elements is (n-1) dx ns1or2 (x = 1 to
10). All these elements are metalsand solid except Hg (a liquid).
(iv) f-Block elements:

In these elements, the last or differentiating electron, in general, enters the orbitals of (n-2) f-
subshell, i.e. the subshell of antipenultimate shell. All these elements are metals and solids.
These elements are also called inner transition elements because they have incomplete f-
subshell as well as incomplete d-subshell and fall within d-block elements. These elements
have been divided into two series of 14 elements each, as follows:
4f-series elements (lanthanides): cerium (Ce, Z = 58) to lutetium (Lu, Z = 71)
5f- series elements (actinides): thorium (Th, Z = 90) to lawrencium (Lr, Z = 103)
The general valence shell electronic configuration of these elements is (n-2) f0-14 (n-1)d0-2ns2.
It has been noticed that for s and p-block elements, the outermost shell itself is the valence
shell. For d-block elements, two subshells viz.,(n- 1)d and n-s subshells taken together form
the valence shell. For f-block elements, three subshells viz., (n-2)f (n-1)d and n-s subshells
jointly form the valence shell. This is due to nearly similar energy of these subshells. A
valence shell is that shell of the atoms of the elements, from which the electrons are used for
bond formation or chemical combination.
For long form of the periodic table, it may be noted that the s-block elements (group 1and2)
have been placed in the extreme left portion of the table and the p-block elements arekept in
the extreme right portion. The middle portion includes d-block elements. At the bottom, f-
block elements have been placed separately in two series/rows.
Merits and demerits of modern periodic table
By taking the atomic number as the basis for the classification of the elements in the modern
periodic table, most of the demerits of Mendeleeff’s periodic table have been removed.
(i) The main characteristic of the modern or long form of the periodic table is that the
classification of the elements has been made on the basis of their atomic number which gives
an information regarding the valence shell electronic configurations of the elements. If we
know theelectronic configurationor the atomic number of an element, we can find out its
position in the periodic table, i.e. to which group and period that element belongs. For
example, for an element the valence-shell electronic configuration is 3s23p5. This gives us the
information that 3 is the value of n, i.e. the period and there are 7 electrons in the valence
shell, means the elements belongs to VIIA group. Therefore, the element is a member of
VIIA group (group 17) and 3rd period.
(ii) The subgroups have been placed separately in the modern periodic table thereby making it
easy to have the information regarding the properties of the elements.
(iii)The modern periodic table still has the drawback regarding the position of hydrogen which
shows some properties similar to those of the group 1 elements (i.e. alkali metals) and some

with the group 17 elements (i.e. halogens). Also the lanthanides and the actinides have not yet
been included in the main body of the periodic table.
Nomenclature of the elements with Z = 104 and beyond
A systematic naming scheme was approved by IUPAC in 1977 for the new elments
discovered around that period or would be discovered thereafterhaving Z ≥ 104. It was
decided that a three-letter symbol derived directly from the atomic number would be used by
using following numerical roots:
0 1 2 3 4 5 6 7 8 9
nil un bi tri quadpent hex sept oct enn
These names and symbols can be used for elements with Z = 104 and beyond.These trivial
names have been internationally accepted. Hence, the element with Z = 104 is un-nil-
quadium (Unq), that with Z = 106 is un-nil-hexium….. and the elements with Z = 109 is un-
nil–ennium (Une) etc.
The general names of the elements from Rf (Z = 104) to Cn (Z = 112) are given here:
Symbol Atomic Number Name

Rf 104 Rutherforduim
Db 105 Dubnium
Sg 106 Seaborgium
Bh 107 Bohrium
Hs 108 Hassium
Mt 109 Meitnerium
Ds 110 Darmstadtium
Rg 111 Roentgenium
Cn 112 Copernicium.
Earlier, the elements with Z = 104 was named as kurchatovium (Ku) and Z = 105 as
hahnium (Ha)
Periodicity of properties
In the modern periodic table, the term periodicity of properties implies that the elements of
similar properties reappear at a certain regular intervals of atomic numbers. On examining the
properties of elements, it has been found that the elements of the same group have similar
properties. These numbers at which this repetition occurs, are 2,8,18 and 32, i.e. we have to

pass these numbers to come across an element of similar properties in a group. These
numbers are referred to as magic numbers as stated earlier.
Cause of periodicity
When we look into the electronic configuration of the elements, we find that all the elements
belonging to a particular group have similar outer or valence shell electronic configuration.
For example, elements of group 1 (IA) have ns1, those of group 3(IIIB) have (n-1)d1ns2, the
elements of group 13 (IIIA) have ns2p1 and those of group 17 (VIIA) have ns2p5 valence
shell electronic configuration. Because of similar valence shell electronic
configuration/arrangement, the elements of a particular group have similar properties.
2.5 SUMMARY
This unit contains a comprehensive text on the history of the periodic table i.e. how the
historical attempts were taken to develop a classification of elements system in a manner
which could facilitate their study, during the time of Dobereiner, Duma and Newlands. The
laws of periodic table and on the basis of these laws, the attempts to classify elements have
also been exhaustively discussed. In the light of these laws, the elements, arranged in the
tabular form, have been given, viz. Mendeleeff’s pefiodic table, Modified form of
Mendeleeff’s periodic table (both on the basis of atomic weights) and modern periodic table
on the basis of atomic number. In addition to this, the elements have also been classified in
the blocks (with general characteristics of each block). A concise description of the
periodicity of properties and its cause have been discussed.
2.6 TERMINAL QUESTIONS

i) Write a concise note on Dobereiner’s law of triads.
ii) Discuss in short, the Newland’s law of octaves.
iii) State the Mendeleeff’s periodic law.
iv) Give a brief discussion of Mendeleeff’s periodic table.
v) State and explain the merits and demerits of Mendeleff’s periodic talbe.
vi) Give a brief account of modern periodic law.
vii) Discuss the main features of modern periodic table.
viii) What are the transition elements and why are they called so?
ix) Write a brief note on inner transition elements.
x) What is the cause of periodicity of properties in the elements in periodic table?
xi) What are the p-block elements?

xii) “The group and the period assigned to the element with 3d14s2 valence shell
configuration are:
(a) IIIB & 3 (b) IIIB & 4 (c) IIIA & 3 (d) IIIA & 4
xiii) Nepturium (Z = 93) is an elements of
(a) 4f- series (b) 4d- series (c) 5f -series (d) 5d -series.
xiv) Seaborgium (Z = 106) is a member of
(a) 6d- series (b) 5d-series (c) 4d-series (d) 3d-series.
2.7 ANSWERS
i) Please refer to history of periodic table.
ii) Please see the history of periodic table.
iii) Please refer to the laws of periodic table. (A)
iv) Please refer to Mendeleeff’s periodic table.
v) Please see the merits and defects of Mendeleeff’s periodic table.
vi) Please refer to the modern periodic table.
vii) Please refer to the modern or long form of periodic table.
viii) Please refer to the d-block or transition elements.
ix) Please refer to the f block or inner transition elements.
x) Please see the cause of periodicity of properties
xi) Please refer to the p-block elements.
xii) b
xiii) c
xiv) a
2.8 REFERENCES
1. Principles of Inorganic Chemistry: B. R. Puri, L.R. Sharma & K. C. Kalia, Milestone
Publishers and Distributers, Daryaganj, Delhi (2013).
2. Selected topics in Inorganic Chemistry: W.U. Malik, G.D. Tuli & R.D. Madan, S. Chand
& Co. Ltd., New Delhi (1993).
3. Comprehensive Inorganic chemistry: Sulekh Chandra, New Age International (Pvt.) Ltd.,
New Delhi (2004).
York (1960).
London (1967).

6. Advanced Inorganic Chemistry: Satya Prakash, G.D. Tuli, S.K. Basu and R.d. Madan, Vol.
I, 7th ed., S. Chand & Co. Ltd, New Delhi (1998).

UNIT 3: PERIODIC PROPERTIES
CONTENTS:
3.1 Objectives
3.2 Introduction
3.3 Periodic Properties
3.3.1 Atomic and ionic radii
3.3.2 Ionization energy
3.3.3 Electron affinity
3.3.4 Electronegativity
3.4 Trends in periodic table
3.5 Summary
3.7 Answers
3.8 References
3.1. OBJECTIVE
The objective of writing the subject matter of this unit is to provide the readers an adequate
knowledge of the properties of atoms of the elements which are called atomic or periodic
properties. A sincere attempt has been made to provide the information regarding the size of
the atoms/ions and their determination, effect of energy supplied to an atom of the elements,
the behavior of the atoms towards the electrons trying to enter the region of their influence as
well as those lying between the atoms as bonding pairs, variation of atomic properties of
elements alongthe periods (horizontal rows) anddown in groups (vertical columns) and some
other interesting facts related to these properties.
3.2. INTRODUCTION
According to modern Periodic law, the atomic properties of the elements, viz. atomic and
ionic radii, atomic volume, ionization potential (or energy), electron affinity or affinity
energy and electronegativity and properties associated with them, viz. oxidizing and reducing
properties, metallic (or electropositive) and non-metallic (or electronegative) properties are
the periodic functions of their atomic number. Hence the term periodic means the recurrence
of similar properties of elements after certain regular intervals, also called the periodicity.
These properties have been found to depend on the electronic configuration of the elements.
It means the cause of periodicity in properties of elements appears to lie in the recurrence of
similar valence shell configuration of their atoms at certain regular intervals. Though, these
properties apply up to some extent to all the elements of the periodic table, yet special
emphasis will be laid down on the main group elements while taking the examples of the
applications of the properties.
3.3. PERIODIC PROPERTIES
3.3.1 Atomic and Ionic Radii:
These terms correspond to the size of the atoms and ions which are represented by the
magnitude of their radii. Atomic radii, in general, are used for the distance between the
nucleus and electron cloud of the outer most shell of the atoms. Since it is impossible to
isolated an individual atom or ion and at the same time, the electron cloud, according to wave
mechanical concept, is said to come closer to the nucleus at one moment and to go away from
it at the other moment, i.e. it does not remain at constant distance from the nucleus, hence it is
rather impossible to measure this distance by any means. These quantities are, however,
generally derived indirectly from the measured distance between the nuclei of two bonded
atoms in a gaseous molecule, generally known as inter nuclear distance (or bond distance) or
between the nuclei of two neighbouring ions in crystalline solids called inter ionic distance.
The experimental techniques like Infrared or microwave spectroscopy, X-ray diffraction,

electron diffraction etc. are used to determine the internuclear distance in covalent molecules
and interionic distance in ionic substances. These determinations become essential to
correlate certain physical properties of elements with them because density, melting point,
boiling point etc. are related to the size of atoms.
Classification of Atomic Radii
For the purpose of feasibility, the atomic radii of the elements have been explained in three
operational categories, as follows:
Atomic redii:
A. Covalent radii

B. Metallic or crystal radii

C. van der Waals’ radii
A. Covalent radii
Covalent molecules may be formed by two similar (A2 type) or two dissimilar atoms (AB
type). Hence, covalent radius of an atom is conveniently defined as “half of the distance
between the nuclei of two atoms of the same element bonded together in a molecule by a
single covalent bond”. Thus, for the atom A in A2 type molecule in which two A atoms are
linked by a single bond, covalent radius, denoted by rA, is given as:
dA-A = rA+ rA = 2rA …………..(3.1)

or rA =
………… (3.2)
where dA-A is the internuclear distance between two A atoms in A2 molecules; rA in equation
3.2 is known as single bond covalent radius of atom A and is used for a gaseous diatomic
molecule. For example, internuclear distance (dH-H) in H2 molecule is 0.74 Å. The covalent

radius of H – atom, rH = = pm = 0.37Å. Similarly, the internuclear distance (dCl-Cl)

atom (rCl) may be calculated as:

(Å = 10-8 cm)
.!
rCl = = pm = 0.99Å.

For atoms bonded together to form and extensive three dimensional network, atomic radius in
simply “half of the distance between the nuclei of two neighbouring atoms” i.e.
" #$" $
rcov =
Fig. 3.1 Diatomic molecule Fig. 3.2 Bulk of atoms

(covlalent radius) (internuclear distance)
In hetero nuclear molecules (e.g. AB type), the single bond covalent radius can be calculated
as given below;

(a) When the atoms A and B bonded together by purely covalent bond and the electronegativities
of these two atoms are almost same, the internuclear distance is equal to the sum of radii of A
and B;
dA-B = rA + rB (when χA = χB) ………………….(3.3)
The internuclear distance, dA-B, can be measured by experimental method and if rA or rB (any
one) is known, the other unknown term (rA or rB) can be calculated by using the equation 3.3.
% %
The value of rA or rB may be obtained from rA =
or rB =
.
(b) If the electronegativities of the two combining atoms are not the same (χA ≠ χB), then the
experimental value of dA-B has been found less than the calculated value obtained as a sum of
covalent radii rA and rB of the heteroatomic molecule. For example,
(i) in (CH3)3 N molecule,
(dN-C) exp = 1.47 Å
and (dN-C)cal. = rN + rC = 0.75+0.77 = 1.52 Å
(ii) In HF molecule,
(dH-F)exp = 0.92 Å
and (dH-F)cal. = rH + rF = 0.37+0.72 = 1.09 Å
This shortening of dA-B bond length may be due to the following factor:
(a) The higher ionic character of the bond between A and B atoms with larger difference in
electronegativities of the hetero atoms. In such a case more electronegative atom attracts the
shared pair of electrons towards itself thereby developing slight negative charge on that atom
due to accumulation of electrons closer to it and positive charge of equal magnitude on the
other atom. This development of opposite charges brings the atoms closer to each other. That
is why the experimental value of dA-B is less than the calculated value. Some correction
measures have been suggested in such cases.
In order to compensate this, the following correction has been suggested:
dA-B = rA + rB – 0.09 (χB - χA) …….(3.4)
(schoemaker and Stevenson)
Still, if the discrepancy remains, another correction measure may be applied (Porterfield):
dA-B = rA + rB – 0.07 (χB - χA)2 …….(3.5)
(b) The other factors in some cases, may be multiplicity of bonds and effective nuclear charge
which cause reduction in the length of covalent bonds and as a consequence in covalent radii.
For example, it has been found that single bond covalent radius> double bond covalent

radius> triple bond covalent radius. This is because the formation of multiple bonds brings
the combining atoms closer to each other and the bond length is reduced.
Table 3.1: Covalent radii (single bond radii) for hydrogen and some p-block (non- metallic
and metalloid) elements except noble gases (in Å)
s-block p-block
Group number 1 2 13 14 15 16 17
Elements with H - B C N O F
covalent radii 0.37 - 0.82 0.77 0.75 0.73 0.72
- - - Si P S Cl
- 1.11 1.06 1.02 0.99
Ge As Se Br
1.22 1.20 1.16 1.14
- Sb Te I
1.40 1.36 1.33
Among the s-and p-block elements, only the non-metallic elements and metalloids have been
taken to tabulate the covalent radii because the formation of covalent bond, in general, is the
exclusive property of the non-metals and metalloids. Noble gases have also been excluded
from the table because these, except a few, do not participate in covalent bond formation.
Factors affecting the magnitude of covalent radii
There are many factors which influence the magnitude of covalent radii. Some of them are:
(i) Effective nuclear charge (Zeff.)
As the value of Zeff increases, the force of attraction between the nucleus and outermost shell

electrons also increases thereby decreasing the covalent radii of the elements, i.e. rcov. α &'((
(ii) Principal quantum number (n)

This gives the number of shells present in the atoms of the elements. As the value of principal
quantum number increases the outermost electrons get farther away from the nucleus and
covalent radius also increases provided other factors remain the same, i.e. rcov. α n
(iii) Multiplicity of Bonds

With the increase in the number of bonds between the atoms, these come closer to each other

thereby decreasing the covalent radii i.e. rcov. α
)*+,*,-,+. /( 0/123
B. Metallic or Crystal Radii

These terms are taken synonymous to covalent radii of metal atoms, though metals generally
do not form covalent compounds except hydrides and organometallic compounds. Further,
metals are assumed to be closely packed spheres in the crystals in which their outer
boundaries touch one another. Thus metallic or crystal radius may be theoretically defined as
“half of the distance between the nuclei of any two adjacent metal atoms in close-packed
metallic crystal” For example, the internuclear distance between any two adjacent sodium
atoms in a crystal of sodium metal in 3.80 Å. Hence crystal or metallic radius of sodium
4.
metal is
= 1.90 Å
Fig. 3.3 Metallic radius
In practice, in the metallic phase, atomic volumes of metal atoms can be determined from

their atomic masses and respective densities. Thus, atomic volume = 2'13,+.. From these data,
metallic radii can be obtained. It has been found that the covalent radii of metal atoms
determined in metal hydrides and organimatallic compounds and metallic radii determined
from atomic volumes in metallic phase have almost similar values though not exactly equal.
Hence,the term metallic covalent radii can be used. The metallic radii have slightly higher
(10%) value than metallic covalent radii because individual bond in metals is weaker and
longer than the covalent bond.

Group number 1 2 13 14 15 16
Elements with Li Be - - - -
metallic radii 1.55 1.12 - - - -
Na Mg Al - - -
1.90 1.60 1.43 - - -
K Ca Ga - - -
2.35 1.97 1.41 - - -
Rb Sr In Sn - -
2.48 2.15 1.66 1.62 - -
Cs Ba Tl Pb Bi Po
2.67 2.22 1.71 1.75 1.70 1.76
Table 3.2 Metallic radii of main group metals (in Å)

C. van der Waals’ radii
In solid state, the nonmetallic elements usually exist as aggregations of molecules. Although
the bonding within a nonmetal molecule is more or less covalent in character yet the binding
force between the molecules is van der Waals’force. Thus each molecule assumes
equilibrium position within the crystalline solid. It is to be noted that these forces are absent
if the substances are in the gaseous state. van der Waals’ radius can be defined as” half of the
distance between the nuclei of two non-bonded but adjacent atoms belonging to two
neighbouring molecules”. These radii have higher values by 90-100% in lighter elements
and 70-80% in heavier elements than covalent radii because of non-bonded type of binding
force between the molecules. The values of van der Waals’ radii are obtained from X-ray
studies of various non-metallic elements in the solid state. On comparing the covalent radii
and van der Waals’ radii of the nonmetallic elements, it is noted that the van der Waals’ radii
have higher values. Please refer to table 3.2 and table
Group number 1 15 16 17 18

INORGANIC CHEMISTRY
CHEMISTRY-I BSCCH
BSCCH-101
Elements with van der Waal’s H He

radii
1.20 1.20
N O F Ne
1.50 1.40 1.35 1.60
P S Cl Ar
1.90 1.85 1.80 1.91
As Se Br Kr
2.00 2.00 1.95 2.00
Sb Te I Xe
2.20 2.20 2.15 2.00
Table 3.3
Fig. 3.3 van der Waals’ radii
Periodic trends of atomic radii

(a) Variation in a period
The atomic radii (viz.. covalent radii, metallic radii and van der Waals’ radii) and hence the
atomic size, in general, decrease on moving from left to right in a period. This is because the
atomic number in a period increases by one unit at each step but the electrons in all the
t
elements in a period enter the same outer or valence shell. Hence
Hence, there operates an increased
force for attraction between these outer electrons and the nuclear charge. As a result, the
atomic radius or atomic size decreases regularly except the noble gases. For example, we can
take the elements of second period and hydrogen. The term covalent radius does not apply to

the noble gases. van der Waals’ radii are applicable to all nonmetallic elements including
noble gases but the values for noble gases are exceptionally high due to larger repulsion
among the monoatomic species with large number of electron.
One Å unit is equal to 10-10m
Elements H C N O F Ne
Covalent radii 0.37 0.77 0.75 0.73 0.72 -
(in Å)
van der 1.20 - 1.50 1.40 1.35 1.60

Waals’ radii
(in Å)
(b) Variation in a group

On going down a group, the atomic sizes of elements increase continuously both in metals
and non metals as is evident from the table of covalent radii, metallic radii and van der
Waals’ radii except the metals of third transition series whose atomic sizes are almost similar
to those of second transition series metals. At the same time lanthanide series and actinide
series of metals have deceasing trend in their metallic radii.
The regular increasing trend in atomic sizes among the main group elements is due to the
introduction of new shell at each step in a group which produces larger effect than that
produced by the increase in effective nuclear charge.
Ionic radii
Though, it is very difficult to define ionic radius, yet an approximate definition can be given
as “the effective distance between the nucleus of an ion and the point up to which the
nucleus exerts its attractive influence on the electron cloud of the ion”. Because it is
rather impossible to determine the outer boundary of an ion, therefore if the ions in an ionic
crystal are taken as spheres whose outer boundaries are touching one another, the interionic
distance (or internuclear distance) may be supposed to be the sum of the radii of the two ions
(an additive property).

Fig. 3.4 The ionic radius
X-ray analysis of ionic crystals is used for measuring the eqiulibrium distance between the
nuclei of the two adjacent ions called interionic distance in taking the ions as spheres. This
distance in taken as the sum of the ionic radii of the two ions. e.g.
dC+ - A-= rC+ + rA- …….(3.6)
This equation can be used to find out the ionic radius of a cation or an anion. The interionic
distance dC+A- can be measured by experimental method and if the radius of any one ion is
calculated by some other method, the radius of antother ion can be obtained by using the
above equation. For example, the inter nuclear distance between sodium and chloride ions
(dNa+Cl-) in NaCl crystal is 2.76Å and radius of sodium ion (rNa+) is 0.95 Å. From these
values we can calculate the radius of chloride ion (rCl) as follows:
dNa+Cl- = rNa+ rCl-
Putting the values of dNa+Cl- and rNa+, we get 2.75 Å = 0.95 Å + rCl-
∴ rCl- = 2.76 – 0.95Å= 1.81Å
Periodic trends of ionic radii
Periodic variation of ionic radii can be easily visualised in main group elements though it is,
in general, applied for transition elements.
(a) Variation in a period

Since atomic size decreases along a period from left to right, the cationic or anionic size also
decreases in the same direction. For transition elements this trend is observed if they are in
the same oxidation state.
(b) Variation in a group
As we move down a group of main group elements, the cationic or anionic size increases
regularly provided the elements are in the same oxidation state. Similar trend, in general, is

observed for transition elements though the change in cationic size is very small or negligible
between second and third transition series elements. Reverse trend has been observed in case
of lanthanides and actinides where ionic size decreases in the series.
Some important facts regarding ionic radii are given below:
(i) Ionic radii of isoelectronic species
The isoelectronic species are the cations, anions and atoms of different elements having same
number of electrons and same electronic configuration. For example, a common isoelectronic
series with ten electrons, i.e. 1s2 2s2 2p6 configuration is given here with their radii;
Ion/atom C4- N3- O2- F- Ne Na+ Mg2+ Al3+ Si4+
Atomic 6 7 8 9 10 11 12 13 14
numbers
Radius 2.60 1.71 1.42 1.36 - 0.95 0.65 0.50 0.41
(Å units)
It is evident from this table that, as the atomic number (or nuclear charge) of the parent atoms
from which the ions have been derived, increases the ionic radius decreases. This is because
with the increase in the nuclear charge, the attractive force between the nucleus and the outer
electrons also increases thereby the electrons come closer to the nucleus and consequently the
size of the ions decreases.
(ii) A cation is smaller in size than its parent atom because a cation is formed by the removal of
electron (s) from the neutral atom; hence the number of electrons becomes less than the
number of protons (nuclear charge). As a result, the electrons are strongly pulled by the
nucleus thereby causing a contraction in the size of the cation. Therefore, the cation is smaller
in size than its parent atom.
(iii)An anion is larger is size than its parent atom. This is because, an anion is formed by the
addition of extra electron (s) in a neutral atom. Thus the number of electrons becomes greater
than that of protons (nuclear charge) and the electrons are loosely held by the nucleus. As a
result, the anionic size becomes larger than the size of the parent atom.
(iv) For the cations or the anions of the same element in different oxidation states, the cationic
size decreases but the anionic size increases with the increasing oxidation states, i.e. for
anions: rA-<rA2-< rA3- <rA4- …….etc. and for cations rC+> rC2+ >rC3+ >……etc. (C = cation,
A = anion)
Factors affecting ionic radii
The main factors that affect ionic radii are as follows:

(a) Crystal coordination number (CCN)

With the increase in the crystal coordination number, the interionic distance also increases
thereby increasing the ionic radii, For example, the radius of Cl- ion (rCl-) in CsCl crystal
(C.C.N. = 8) is slightly higher than its radius in NaCl Crystal (CCN =6). This is because with
the higher CCN, the number of ions surrounding a particular ion is greater, causing less
attraction between the oppositely charged ions than that with lower CCN i.e. rion α CCN
(b) Radius ratio (Rr)
- శ
Radius ratio (Rr = 5ష
) also affects the magnitude of ionic radius. If the Rr is larger due to
large cation and small anion, the anion-anion repulsion is less and the interionic distance
becomes shorter than the sum of the ionic radii (i,e. dC+A- <rC+rA-) but if Rr is smaller due to
small cation and large anion, the anion-anion repulsion is more and interionic distance is
greater than the sum of the ionic radii (i.e. . dC+A- > rC+ rA-)
(c) Covalent character of Ionic Bond

6
Ionic radii decrease as the covalent character in ionic bond increases. rion α 789:;<=> 7?:@:7><@ .
3.3.2 Ionization energy (IE):

This term is related with the removal of electron (s) from the neutral atom and converting it
into a positive ion (or cation). If the energy is supplied to an atom, its electron (s) may be
promoted to a higher energy level and if this energy is sufficient enough, the electron (s) may
completely be removed from it giving a cation. Thus “the minimum amount of energy
required to remove a loosely bound electron from an isolated gaseous atom of an
element in its ground state is called its ionization energy”. In the definition, gaseous atoms
are specified because an atom in gas phase is uninfluenced by its neighbours and there is no
intermolecular forces to take into account while measuring ionization energy. This can be
shown as follows:
C(g) + (IE)1 C+ (g) + e ( energy absorbed, endothermic process)
In this process, if one electron is removed, it is termed as the first ionization energy, (IE)1.
For many electron atom, if more electrons are removed from an atom, the ejection of
electrons occurs one by one in steps depending on the amount of energy absorbed/supplied.
Thus corresponding to the removal of second electron, the energy is known as second
ionization energy, (IE)2 and if third electron is removed, the corresponding energy which has
to be supplied is called third ionization energy, (IE)3 and so on. Alternatively, these are also

known as successive ionization energies. The sequence of ionization energies in their

increasing order may be given as:
(IE)1 ≪(IE)2≪(IE)3 …………..(IE)n.
This is because when an electron is removed from a neutral atom to give a cation, the number
of the remaining electrons of the cation becomes less than the nuclear charge and greater
attractive force operates between these electrons and nucleus causing contraction in the size
of cation. Therefore, more energy is required to remove another electron from the cation, i.e.
(IE)1 ≪(IE)2. Due to the similar reason, still higher amount of energy is required to remove yet
another electron, i.e. (IE)2≪(IE)3 and so on.
An alternative explanation for this observation may be given. Since, the magnitude of
ionization energy is a measure of tightness with which an electron is held in the atom, hence
higher the ionization energy, more tightly the electron is held in the atom and more difficult it
is to remove it. The ionization energy is expressed in the units of kilojoules per mole
(kJ/mole) or kilo calories per mole (k Cal/mole)
It has been observed that among the elements of the periodic table, the alkali metals have the
least and the noble gases have the highest ionization energy values in the respective periods.
Helium has the highest value and caesium possesses the lowest value of first ionization
energy among all the main group elements.
Atomic Element (IE)1 (IE)2 (IE)3 ……
Number (Z)
1 H 1312 - -
2 He 2373 5251 -
3 Li 520 7300 11850
4 Be 899 1757 14850
5 B 801 2430 3660
6 C 1086 2350 4620
7 N 1400 2860 4580
8 O 1314 3390 5300

9 F 1680 3370 6050
10 Ne 2080 3950 6120
Table 3.4: The successive ionization energy values (in kJ/ mole) of the first ten element
Factors affecting the magnitude of ionization energy
(i) Atomic Size (or The Principal Quantum Number)
As the principal quantum number for the outer electrons increases, the atomic size also
increases and the ionization energy of the elements decreases and vice versa, i.e. IE α

. This can be seen in a group.
1 / A+/
(ii) Nuclear charge

As the nuclear charge increases, other factors remaining the same, more and more attractive
force operates between the nucleus and outer electron(s). Thus more energy is required for
the removal of electron(s) and as a consequence, the ionization energy goes on increasing.
This is observed along the periods, in general, IE α nuclear charge.
(iii) Penetrating power of valence electrons
In a given shell, the penetrating power of the electrons decreases in the order s > p > d >f,
therefore, ns electrons are more firmly held by the nucleus (due to highest penetrating power)
than np – electrons followed by d and f electrons (due to their scattered orientation).
Accordingly, the ionization energy decreases as follows: ns >np >nd >nf i.e. IE α
penetrating power.
(iv) Shielding effect of inner electrons
In poly electron atom, the valence electrons are attracted by the nucleus and at the same time
repelled by the inner shell electrons. As a result, the outer most electron experiences less
attraction from the nucleus because inner electrons act as screen or shield between outer
electrons and nucleus. This effect produced by inner electrons is called the shielding effect.
Within a given shell, this effect decreases in the order: s>p>d>f. Thus, an increase in the
number of inner or intervening electrons causes more shielding effect thereby decreasing the
attractive force between the nucleus and outer electrons. Consequently the ionization energy

also decreases, i.e. IE α 3B,'*2,1C '(('-+
(v) Stable electronic configuration

According to Hund’s rule, half filled (viz.ns1, np3, nd5 etc.) or completely filled
orbitals (viz.ns2, np6, nd10 etc.) are more stable than the partially filled orbitals. Hence more
energy is required to remove the electron (s) from such orbitals. This means that the

ionization energy of an atom having half filled or completely filled orbitals in its ground state
is relatively higher than expected normally from its position in the periodic table. The relative
stablility order of such orbitals has been found as d5< p3< d10 ≪ p6. For example, the
ionization energies for Be (2s2) and N (2s2 2p3) in the second period and Mg and P, the higher
homologues of Be an N, in the third period are slighty higher than expected values. This is
becauseof the extra stability of the electronic configuration of these elements, High values of
ionization energy for noble gas elements is also due to stable ns2 np6 (He - ns2) configuration
in the vacance shell, i.e. IE∝ stable configuration.
To gain the necessary energy for the removal of electrons from an atom, a potential
difference has to be applied across the sample of element. This potential difference giving the
necessary energy is called the ionization potential.
Priodic trends
i) Variation along a period
On going from left to right in a period, there is, in general, an increase in the ionization
energy values of the elements due to the effect of reduction in the atomic radii and increase in
the nuclear charge by one unit at each step but the outer shell remaining the same (n is
constant for the elements of a period). Thus, the electrons in these elements are being
successively filled to the same shell. Such electrons shield each other poorly from the
increasing nuclear charge. As a result, Zeff increases which cause an increase in ionization
energy.
There are some exceptions to this trend. Let us consider the elements of secound period i.e.
Li3 to Ne10 for which the expected order of ionization energy is Li< Be < B < C< N< O< F
< Ne. The experimental values, however, show that Be and N have higher IEvalues than
those of the nextelements, i.e. B and O. This anomaly can be explained on the basis of their
stable electronic configurations, i.e. Be (ns2)> B (ns2 np1) and N (ns2 np3) > O (ns2 np4)
(please refer to the IE table of elements). This is evident from the ionization energy values of
the above elements that it is easier to remove the last and loosely bound electron from B or
O-atoms as compared to that from Be or N-atom and thus elements (B and O) have lower
first ionization energy values than Be and N.
The elements of the transition series show irregular trends of ionization energies along their
periods due to shielding effects and electronic configurations.
ii) Variation in a group
On going from top to bottom in a group of elements, the nuclear charge increases regularly.
This must cause an increase in the IEvalues of the elements. At the same time, the atomic size
also increases due to the introduction of a new shell at every next element in the group. This
causes a decrease in the IE values of the elements. The effect of increased size is more than
that due to increased nuclear charge. The net result is the continuous fall in the values of
ionization energy down the group.
Alternatively, this trend may also be explained by the fact given here. As we move down a
group, the number of inner shell electrons called intervening electrons increases. As a result
there in more shielding effect caused by the inner electrons on the outer electrons. This
decreases the ionization energy values of the elements in a group.
There are some exceptions also. The first ionization energy of Ga31, an element of fourth
period is slightly higher than that of Al13, the element of third period [(IE)1 of Al = 577.6
kJ/mole and (IE)1 of Ga= 578.8 kJ/mole]This is perhaps due to the poor shielding effect of
3d10 electrons.
Also, the third row of transition elements shows higher value of ionization energy as
compared to second row elements. This is due to the decrease in size of these elements as a
result of insertion of lanthanides in 6th period (Lanthenide contraction).
Application of ionization energy
(i) Prediction of electropositive character
The electropositive character of the elements is related to the ease with which the electron (s)
could be removed from the atom of the elements. More electropositive is the elements, more
easily the electron (s) can be removed. As we move down a group, the ionization energy of
the elements decreases regularly and hence the electropositive character also increases
accordingly. Across a period, the ionization energy of the elements, in general, increases
means the electropositive character decreases from left to right. Alkali metals placed at the
extreme left portion of the periodic table, are the most electropositive elements with low
values of ionization energy.
(ii) Prediction of metallic and non-metallic character
The elements with low ionization energy are more metallic in nature because they can lose
electrons easily. Hence metallic character increases from top tobottom in the groups and
decreases along the period from left to right. The elements showing the opposite trend in
ionization energy and periodic variation to that of metals are called the non-metals.
(iii)Prediction of reducing power of an element
Lower the value of ionization energy of an element, greater is its reducing power. The alkali
metals with the lowest ionization energy values are the strongest reducing agents among all
the elements.

3.3.3 Electron affinity (or affinity energy) (EA).

This term is related with the formation of an anion from a neutral atom of an element by the
addition of electron (s). Thus, this is the tendency of the atom to gain the additional electron
(s). The electron affinity (EA) of an element can be defined as the “amount of energy
released when an electron is added to the outer shell of an isolated gaseous atom of the
element to produce the gaseous anion”. This can be shown as: A (g) + e → A-(g) – (EA)1
(electron affinity energy released). Evidently, this is an exothermic process. The expression
actually shows the first electron affinity. Once the uninegative anion has been formed by
accepting one electron by the neutral atom, addition of another electron (s) in this ion
becomes more difficult due to repulsive force operating between the anion and the incoming
electron. To overcome this repulsive force, extra energy has to be supplied to the electron
which must actually be more than the energy released during the addition of electron, i.e. the
energy supplied to electron > energy released during the addition of electron. The net energy
change is the energy absorbed (supplied) by the electron, hence the addition of second or
third etc. electron to the anion is an endothermic process:
A- (g) + e → A2 - (g) + (EA)2 (energy supplied)
2- 3-
A (g) + e → A (g) + (EA)3 (energy supplied)
The electron affinity values for the elements of second period are given below:
Element Li Be B C N O F
(EA)1 in kJ/mole 60 ≤0 27 122 ≤0 141 328
The electron affinity values of Be and N are shown zero because it is very difficult to add an
extra electron to the outer shells of these elements due to extra stability of the electronic
configuration.
The electron affinity values of halogens are very high because of the ns2 np5 outer shell
electronic configuration and very strong tendency to accept the incoming electron thereby
getting converted into the negative ions with noble gas configuration, i.e. ns2 np6. Though the
first element of halogen group, is expected to have the highest value of EA,but its EAvalue is
less than that of Cl. This is due to the smaller size and greater electron-electron repulsion in
F-atom which opposes the entry of the incoming electron. The EA values of the noble gases
are almost zero due to no tendency of accepting the additional electron because of stable ns2

np6 configuration. EA values of halogens and noble gas elements are given below (in k
J/mole):
Element F Cl Br I At He Ne Ar Kr Xe Rn
(EA)1 value 328 349 325 295 280 ≤0 ≤0 ≤0 ≤0 ≤0 ≤0
Factors affecting the electron affinity

All the factors which affect the ionization energy also affect the electron affinity. The main
factors among them are discussed here:
(i) Atomic size
Smaller the atomic size, stronger is the attraction of nucleus for the incoming electron and

hence greater is its electron affinity and vice versa, i. e. EA∝A+/,- 3,D' (as is seen along a
period)
(ii) Effective nuclear charge (Zeff)
Greater is the effective nuclear change of the elements, stronger is the attraction between it
and the electron to be added to the atom. Thus with the increase in Zeff, other factors
remaining the same, electron affinity of the elements also increases, i.e. EA∝ Zeff (as is seen
along a period).
(iii)Stable electronic configuration
The atoms of the elements with stable electronic configuration do not show any tendency to
accommodate the incoming electron (s). Hence the EA values for such elements is almost
zero. For example, the elements of 2nd group with ns2 outer electronic configuration have zero
EA values. The elements of 15th group with ns2np3 outer electronic configuration have zero or
very low EA values. The noble gases with ns2np6 stable configuration in the outer shell also
have zero EA values i.e. do not have any affinity for the electron (s) to be added to them.
The electron affinity of an element can be determined by using the Born-Haber cycle.
Periodic trends of electron affinity
(i) Variation along the periods
In general, with few exceptions, the electron affinity values of the elements go on
increasing on moving from left to right in a period, i.e. from alkali metals to halogens. This is
because atomic size decreases and the effective nuclear charge increases along a period. Both
these factors increase the force of attraction between the nucleus and the incoming electron

which is added easily to the outer shell of the host atom. Exceptions are the elements of 2nd,
15th and 18th groups.
(ii) Variation in the groups
The electron affinity values go on decreasing when we move from top to bottom down in a
group. On descending a group, the atomic size and the nuclear charge both increase regularly.
The increasing atomic size tends to decrease the EAvalues while increasing nuclear charge
causes an increase in these values. The net result is that the effect produced by the
progressive increase in size more than compensates the effect produced by progressive
increase in nuclear charge and hence EA values decrease regularly down the group.
3.3.4 Electronegativity (૏, chi)
In a homoatomic molecule, the bonding pair of electrons lies at the middle of internuclear
space. But this is not true for a hetroatomic molecule. As a result polarity is developed on the
hetero atoms of the molecule due to the shifting of the bonding pair of electrons towards one
particular atom. For example, in H2 or Cl2 molecules, the bonded pair of electrons lies at the
middle of two nuclei, i.e. is equally attracted by both the atoms. But in HF or like
molecules, the bonded pair of electrons is attracted with stronger force by F atom (in HF) and
thus, is shifted towards it from its expected middle position. This causes the development of
slight negative change on F and equal positive change on H atom, therefore HF is a polar
molecule.
This means an atom in a heteroatomic molecule with stronger affinity for bonding electrons is
able to pull them towards itself and takes them away from the atom with weaker affinity for
them. In the above example (viz. HF) F is said to have stronger affinity for bonded electrons
as compared to that of hydrogen atom.To explain this tendency in heteroatomic molecules,
Linus Pauling, in 1932, introduced the concept of electronegativity. According to him
“electronegativity is the relative tendency or power of an atom of an element in the
heteroatomic molecules to attract the shared pair of electrons towards itself”.
Methods of evaluating electronegativity

Various chemists have defined and proposed the methods for evaluating electronegativity.
These are known as electronegativity scales.
(i) Pauling’s Scale
Pauling’s definition of electronegativity has been given in the beginning. He used
thermodynamic data to calculate the electronegativity of different elements. He considered
the formation of AB molecule by the combination of A2 and B2 molecules.
A2 + B2 = 2 AB

Or A2 + B2 = AB ……… (3.8)

This reaction may also be written as

(A-A) + (B –B) = A - B because A2, B2 and AB are covalent molecules. This is an

exothermic reaction, means the formation of A-B molecules is accompanied by the release of
energy, i.e. the bond dissociation energy of A-B covalent bond (EA-B) is always higher than
the mean of the bond dissociation energy of

A-A (EA-A) and B-B (EB-B) covalent bonds and EA-B> (EA-A+ EB-B)
Pauling proposed that the difference in the EA-B and mean of EA-A and EB-B is related to the
difference in electro negativities of A (χA) and B (χB)

∴ ∆ = E A-B- (EA-A+ EB-B) = 23 (χB - χA)2 (where χB> χA, ) …….(3.9)
Thus, ∆ = 23 (χB - χA)2
Or χB -χA = 0.208 √∆ ……………(3.10)
In place of arithmetic mean, he later used the geometric mean of EA-A and EB-B and expressed
the equation as:
∆’ = EA – B- (EA-A x EB-B)1/2 = 30(χB - χA)2 ………(3.11)
∴ ∆’ = 30 (χB - χA) 2
∴ χB - χA = 0.182 √∆’ ………….(3.12)
Here χA and χB are the electronegativities of the atoms A and B. The factors 0.208 and 0.182
arise from the conversion of ∆ measured in kCal/ mole into electron volts.
s-block p-block elements

1 2 13 14 15 16 17 18
H He
2.1 0
Li Be B C N O F Ne

1.0 1.5 2.0 2.5 3.0 3.5 4.0 0
Na Mg Al Si P S Cl Ar
0.9 1.2 1.5 1.8 2.1 2.5 3.0 0
K Ca Ga Ge As Se Br Kr
0.8 1.2 1.6 1.8 2.0 2.4 2.8 0
Rb Sr In Sn Sb Te I Xe
0.8 1.0 1.7 1.8 1.9 2.1 2.5 0
Cs Ba Tl Pb Bi Po At Rn
0.7 1.9 1.8 1.8 1.9 2.0 2.2 0
Fr Ra
0.7 1.9
Table 3.5: Electronegativity values of s and p-block elements as determined by Pauling (on F
= 4.0 scale)
From this table it can be noted that the variation in the values of electronegativity is more
pronounced among the non-metals.
(ii) Allred and Rochow’s Scale
Allred and Rochow proposed that the electronegativity of an element (say A) can be
calculated by using the following equation:
.4E! F&'((
(χA)AR = మ
+ 0.744 …………(3.13)
where (߯A)AR = electronegativity of the element A on Allred and Rochow’s scale, Zeff =
effective nuclear charge (Z – σ) at the periphery of the element A,
r is radius of the atom of element A in Å.
Putting the value of Zeff, the equation can be rewritten as

.4E! FG&HI
(χA)AR = + 0.744 …………(3.14)
మ
The electronegativity values obtained by this method agree closely to those obtained by
Pauling’s approach. These values for the elements of first three periods are given below:
Table 3.6: Electrongativity values of s and p-block elements belonging to first three periods
on Allred and Rochow’s scale
Group 1 2 13 14 15 16 17 18
H He
2.20 3.2
Li Be B C N O F NA
0.97 1.47 2.01 2.50 3.07 3.50 4.10 5.1
Na Mg Al Si P S Cl Ar
1.01 1.23 1.47 1.74 2.06 2.44 2.83 3.3
K Ca Ca Ge As Se Br Kr
0.91 1.04 1.82 2.02 2.20 2.48 2.74 3.1
Rb Sr In Sn Sb Te D Xe
0.89 0.99 1.78 1.72 1.82 2.01 2.21 2.4
Cs Ba Tl Pb Bi Po At Rn
0.86 0.97 1.44 1.55 1.67 1.76 1.90 -
According to this scale, the inert elements also possess electronegativity. As per the
definition given by Pauling, this scale seems to be arbitrary but it has its own importance.
(iii) Mulliken’s scale

It is based on the ionization energy and electron affinity of an atom of an element. According
to Mulliken “the average of ionization energy (IE) and electron affinity (EA) of the atom
of an element is a measure of its electronegaivity”.

Jಶ KLಲ
Thus, the electronegativity =
…………(3.15)
He proposed two relations for obtaining the electronegativity:
(a) When the energies are measured in electron volts (eV), then
(Jಶ KLಲ )
χA = 0.374
+ 0.17
(Jಶ KLಲ )
= 0.187
+ 0.17 ………(3.16)
(b) When the energies are expressed in kJ/mole, then
Jಶ KLಲ
χA = E

………..(3.17)
All these terms χA, IEand EA are for the atom A.
Factors affecting the magnitude of electronegativity
Various factors which affect the magnitude of the electronegativity of an element

qualitatively are as follows:
(i) Atomic size

It has been observed that the smaller atom has greater tendency to attract the shared pair of
electrons towards itself and hence has greater electronegativity. Thus electronegativity α

5+/,-3,D'
(ii) Charge on the atom (or oxidation state of the element)

Higher the amount of positive charge on the atom of an element means higher positive
oxidation state, smaller is the size and more is the electronegativity, i.e. electronegativity α
positive oxidation state (or charge).
(iii) Effective nuclear charge (Zeff)
With the increase in the magnitude of Zeff of an element, the electronegativity of that element
also increases. This factor may effectively be used to explain the variation of
electronegativity in a group or along a period. Thus, electronegativity α Zeff.
(iv) Ionization energy and electron affinity
According to Mulliken’s scale, electronegativity of an element depends on its ionizations
energy and electron affinity, Thus, the atoms of the elements which have higher values of
ionization energy and electron affinity also have higher values of electronegativity, i.e.
electronegativity α IEand EA.
(v) Type of hybridization of the central atom in a molecule

It has been observed that electronegativity of an atom having hybrid orbital with greater s-
character is high because the electronic charge in hybrid orbitals of an atom in a molecule
which has greater s-character remains closer to the nucleus of that atom. For example, the s-
character in sp3, sp2, and sp hybrid orbitals of CH4, C2H4 andC2H2 is 25%, 33% and 50%,
respectively. Accordingly, the s-character of hybrid orbitals gives more electronegativity to C
atom. Hence the electronegativity of carbon atom in these molecules is in the following
increasing order:
CH4< C2 H4 < C2 H2
Periodic trends of electronegativity
(i) Variation in the groups of main group elements
On going down a group of main group elements, the electronegativity values go on
decreasing due to increasing atomic size and decreasing Zeff of the elements. At the same
time, the electropositive character of the elements also increases causing a reduction in
electronegativity values of the elements as well as their ionization energies and electron
affinities.
(ii) Variation along a period
On moving from left to right across a period of main group elements i.e. from alkali metals to
halogens, electronegativity values increase with increasing atomic number. This happens
secause Zeff increases, electropositive character decreases, atomic size of the elements also
decreases thereby increasing electronegativity. Ionization energy and electron affinity, in
general, also increase along a period.
Applications of Electronegativity
On the basis of electronegativity, certain facts in chemistry can be explained which are given
below:
(i) To predict the nature of bonds
With the help of the electronegativity difference χB – χA (where χB<χA) between two atoms A
and B, we can predict whether A-B bond would be non-polar covalent bond, polar covalent
bond or ionic bond. If χB – χA = 0, i.e. either the atoms A and B are same or if different have
almost similar electronegativity values, the bond is non- polar covalent bond. When χB – χA is
relatively small, e.g. O- H, Cl-H etc. the bond formed between the atoms is polar covalent
bond. When χB – χA is very large, complete transfer of an electron from atom A to atom B
takes place and the resulting bond between the atoms is purely ionic.

The percent ionic character present in the polar covalent bond can be calculated. For a polar
covalent molecule AS+-BS-, Pauling has correlated the percent ionic character of a covalent
bond with the electronegativity difference between the combining atoms as is given below:
(χB – χA) 0.6 1.0 1.7 2 3
Percent ionic character 9 22 51 63 91
He used the equation:

Amount of ionic character in A-B bond = [1-e0.25(χB – χA) ] % ………(3.18)
Further, Hannay and Smith gave the following equation to calculate the ionic character.
Ionic Character in A - B bond = [ 16 (χB – χA ) + 3.5 (χB – χA )2] % (χB>χA )….(3.19)
(ii) To calculate the bond length

In a heterodiatomic molecule of AB type, the bond length dA-B can be calculated provided the
molecule has ionic character and the values of atomic radii rA and rB as well as the
electronegatitvities χA and χB are known. This can be done by using the Schoemaker and
Stevenson equation, viz.
dA- B = rA + rB – 9 (χB – χA ) (χB>χA ) …………..(3.20)
(iii) To predict the trends in acid-base character
(a) The acidic character of the oxides has been bound to increase from left to right along a period
because of decreasing χ0 – χB values (χ0 and χB are electronegativities of oxygen and other
atom), e.g.
Oxide Na2O MgO Al2O3 SiO2 P4O10 SO2 Cl2O7
χB 0.9 1.2 1.5 1.8 2.1 2.5 3
χ0 – χB 2.6 2.3 2.0 1.7 1.4 1.0 0.5
Nature strongly basic ampoteric weakly acidic strongly strongly
basic acidic acidic acidic
(χo = 3.5)
(b) The acidic character of hydrides of the elements of the same period goes on increasing from
left to right across a period. For example, the acidic nature of CH4, NH3, H2O and HF
molecules, the hydrides of the elements of second period, increases in the order: CH4, < NH3,
< H2O < HF because of the increasing electronegativity of the central atom and increasing
elelctronegativity difference between the central atom and hydreogen atom i.e.

χcentral atom – χH
(c) The acidic character of oxyacids of the elements of the same group and in the same oxidation
state, e.g. HClO4, HBrO4 and HIO4 decreases as the electronegativity of central halogen atom
decreases as we move down the group form Cl to I (χCl = 3.0) and χI = 2.5 on Pauling’s scale).
(iv) To explain the diagonal relationship
It has been found that the elements of second period of the periodic table show similarities in
properties with the elements lying diagonally opposite on right hand side in the third period
This property is called diagonal relationship. These elements are shown below:
Elements of 2nd period Li Be B C N O F
Elements of 3rd period Na Mg Al Si P S Cl

This similarity in properties can be explained by various facts and one of them is the concept
of electronegativity. The electronegativites of the diagonally opposite elements are almost the
same and hence show similar properties.
3.4 TRENDS IN PERIODIC TABLE

All the periodic properties, i.e. atomic and ionic radii, ionization energy, electron affinity and
electronegativity show variation along the period and down a group. The trends for various
properties have been discussed in the respective sections.
3.5 SUMMARY
The text of this unit contains a concise and comprehensive discussion of various periodic
properties such as atomic and ionic radii, ionization energy, electron affinity and
electronegativity, factors affecting these properties, periodic trends (or variation) of the
properties, the methods of their determinations and their applications wherever necessary and
available. The periodic properties are the basis of the physical and chemical properties of the
elements which can be predicted keeping in view the above propert
3.6 Terminal questions.

i) Arrange the following ions in the increasing of their size
a. Na+, Mg2+, Al3+, F-, O2-, N3-
b. C4-, N3- ,O2-, F-
ii) Which atom or ion in the following pairs has smaller size and why ?
a. Na, Na +

b. Be, Mg
c. Fe2,Fe3
iii) Explain giving appropriate reasons:
a. The Cl— ion is larger in size than Cl atom.
b. The atomic radius decreases with the increasing atomic numbers in a period.
iv) Arrange the following in the decreasing order of their ionization energy: Be, B, N, O and F.
v) Arrange the Be, B, N, O and F in the increasing order of their electron affinities.
vi) EA values of the halogens are the highest in each period. Explain.
vii) The noble gases have very high values of ionization energy but their electron affinity values
are almost zero. Why?
viii) Which of the following elements has the highest values of electronaffinity and why?
a. Na, Cl, Si, Ar
b. (i)1s2, 2s2, 2p1 (ii) 1s2, 2s2, 2p6, 3s1 (iii) 1s2, 2s2, 2p5 (iv) 1s2, 2s2, 2p3
ix) Distinguish between electron affinity and electronegativity.
x) Which element among the following has the highest value of electro negativity and the
highest value of electron affinity? F, Cl, O, Br, and I.
xi) Which one of the following oxides is basic, amphoteric, and acidic in nature?
a. MgO
b. Al2O3
c. P4O10
xii) How does electron affinity depend on effective nuclear charge?
3.7 . ANSWERS
i) a. Al3+ < Mg2+< Na+< F-<O2-<N3-
d. F-< O2-<N3-< C4-
All of the above are isoelectronic ions whose ionic size decreases with increasing nuclear
charge (atomic number) of the parent atom.
ii) a. Na+ has smaller size because this has been derived from Na atom by removing its
outermost electron. This causes greater attraction between the nucleus and the remaining
electrons and contraction in the size occurs.
b. Be has smaller size because both Be and Mg belong to the same group. Down a group the
size of the atom of the elements increases.
c. Fe3+ ion has smaller size because both Fe2+ and Fe3+ are the ions of Fe. As the oxidation
state increases, the ionic size decreases (for the ions of the same element).

iii) a. Please see some important facts regarding ionic radii no. 3.
b. Please see variation of atomic radius in a period.
iv) The decreasing order of the ionization energy is
F > N > O > Be > B.
v) The increasing order of the electron affinity is
Be < N < B < O < F
vi) Please refer to the electron affinity.
vii) Due to the most stable electron configuration, it is very difficult to remove the electron(s)
from the noble gases and hence have very high values of ionization energy. Due to the same
reason, they do not have the tendency to accommodate the electron(s) in their outer shell,
therefore have almost zero electron affinity.
viii) a. Among the given elements Cl with 3s2 3p5 outer shell configuration has the greatest
tendency to accept the incoming electron and hence has the highest value of electron affinity.
b. (iii) With 2s2 2p5 configuration in the outer shell has the highest value of electron affinity
among the given elements,
ix) Please refer to the definitions of electron affinity and electornnegativity.
x) Among the given elements F has the highest values of electronegativity. (Pauling’s scale) and
Cl has the highest value of electron affinity.
xi) Basic oxide: MgO
Amphoteric oxide: Al2O3
Acidic oxide: P4O10
xii) Please refer to the factors affecting the electron affinity.
3.8 . REFERENCES
For references please see at the end of Unit 5

UNIT 4: CHEMICAL BONDING- I
CONTENTS:
4.1 Objectives
4.2 Introduction
4.3 Covalent bond
4.3.1 Valence bond theory and its limitation
4.3.2 Directional characteristics of covalent bond
4.3.3 Sigma and pi covalent bond
4.4 Hybridization of atomic orbitals
4.4.1 Types of hybridization
4.4.2 Shape of simple inorganic molecules and ions
4.5 Valence shell electron pair repulsion theory (VSEPR) theory
4.6 Molecular Orbital theory
4.6.1 Homonuclear diatomic molecules
4.6.2 Heteronuclear (CO and MO) diatomic molecules
4.7 Multicenter bonding in electron deficient molecules
4.8 Bond strength
4.8.1 Bond energy
4.8.2 Measurement of bond energy
4.9 Percent ionic character
4.10 Summary
4.12 Answers
4.1 OBJECTIVES
The objective of writing the text of this unit is to enable the readers to understand various
facts regarding the driving force that makes the isolated atoms to combine to form the
polyatomic molecules or ions as well as to find the answers of certain interesting questions
such as: What is a chemical bond? What happens to the energy of the atoms and the
molecules? What happens in terms of electronic structure, while bond formation takes place?

Why do the group 18 elements, i.e. the noble gases, generally not participate in bond
formation and suffer from lack of reactivity while almost all other elements do so? etc.
4.2 INTRODUCTION
The atoms are said to combine together because of the following two main
reasons:
(i) Concept of lowering of energy

It has been observed that the aggregate (or the molecules) are lower in energy than the
individual atoms from which they have been formed. This means when the individual atoms
combine to form molecules through a bond, the potential energy of the combining atoms
decreases and the resulting molecules are more stable than the free atoms. This energy
difference between the free atoms and bonded atoms (or molecules) is generally 40kJ mol-1 or
more. It follows from this that the process of bond formationbetween the atoms decreases the
energy of the molecule formed from these atoms and forms a system of lower energy and
greater stability.
(ii) Electronic theory of valence (the octet rule)
The atoms of the noble gases-helium to radon- do not, except a few cases, react
with any other atoms to form the compounds and also they do not react with
themselves. Hence they stay in atomic form. These atoms are said to have low energy
and cannot be further lowered by forming compounds. This low energy of noble gas atoms is
associated with their outer shell electronic configuration, i.e. the stable arrangement of eight
electrons (called octet). It has also been established that the two electrons in
case of helium atom (called doublet) is as stable as an octet present in other noble gas atoms.
The chemical stability of the octet of noble gases led chemists to assume that when atoms of
other elements combine to form a molecule, the electrons in their outer shells are arranged
between themselves in such a way that they achieve a stable octet of electrons (noble
gas configuration) and thus a chemical bond is established between the atoms.
This tendency of the atoms to attain the noble gas configuration of eight electrons in their
outer shell is known as octet rule or rule of eight and when the atoms attain the helium
configuration, it is called doublet rule or rule of two. This octet rule was later called
“Electronic Theory of Valence”.
It may be noted here that in the formation of a chemical bond, atoms interact with each
other by losing, gaining or sharing of electrons so as to acquire a stable outer shell

configuration of eight electrons. This means, an atom with less than eight electrons in the
outer shell is chemically active and has a tendency to combine with other atoms.
Accordingly, three different types of bonds may exist in the molecules/aggregates.
4.3. COVALENT BOND

A covalent bond is formed between the two combining atoms, generally of the
electronegative non-metallic elements by the mutual sharing of one or more electron pairs
(from their valence shell). Each of the two combining atoms attains stable noble gas
electronic configuration, thereby enhancing the stability of the molecule. If one electron pair
is shared between the two atoms, each atom contributes one electron towards the electron pair
forming the bond. This electron pair is responsible for the stability of both the atoms. A
covalent bond is denoted by the solid line (-) between the atoms. Depending on the number of
shared electron pairs i.e. one, two, three etc. electron pairs between the combining atoms,
the bond is known as a single, double, triple etc. covalent bond. For example,
H:H H-H
single bond
Cl:Cl Cl-Cl
H:Cl H-Cl
O::O O=O double bond
multiple bond
N:::N N≡N triple bond
In the molecules, the bond strength and bond length has been found in the following
order:
Bond strength: triple bond > double bond > single bond
Bond length: triple bond < double bond < single bond
It may be noted that the covalent bond formation between multielectron atoms involves
only the valence shell electrons that too, the unpaired electrons. Thus O-atom has two
unpaired electrons in its valence shell and N-atom has three unpaired electrons thereby
forming two and three bonds with themselves or other atoms.
Polar and non-polar covalent bond
In the examples given above, most of the bonds viz. single, double and triple covalent
bonds, have been shown to be formed between the like atoms such as H-H, Cl-Cl, O=O
and
N≡N in H2, Cl2, O2 and N2, respectively. The bonded atoms in these molecules attract the
bonding or shared pair of electrons by equal forces towards themselves due to equal

INORGANIC CHEMISTRY
CHEMISTRY-I BSCCH
BSCCH-101
electronegativity of the atoms. Hence the bonding pair of electron lies at the mid point
of the internuclear
ear distance ( or bond distance). This type of bond is known as the
non-polar
polar covalent bond.
But if the covalent bond is formed between two unlike atoms of different elements, e.g.
HCl, H2O, NH3 etc., the shared pair of electrons will not be equally at
attracted
tracted by the bonded
atoms due to electronegativity difference. It shifts towards more electronegative atom and
hence moves away from less electronegative atom. This develops small negative charge on
more electronegative atom and equal positive charge on less electronegative atom. Such
a molecule is called a polar molecule (this is different from ionic bond) and the bond present
in such molecules is known as polar covalent bond. For example,
4.3.1. Valence Bond Theory

heory (VBT) and its llimitations:
This theory was put forward by Heitler and London in 1927 to explain the nature of
covalent bond. They gave a theoretical treatment of the formation of the bond in H2
molecule and the energy changes taking place therein. Later,
Later it was extended by Pauli
Pauling and
Slater in 1931 to account for the directional characteristics of the covalent bond.
The main points called the postulates of this theory are given below:
(i) The atoms involved in the bond formation maintain their individuality(identity)
individuality(identity) even
after the bond is formed i.e. in the molecule.
(ii) The bond is formed due to the overlapping of half filled atomic orbitals (or the
interaction of electron waves) belonging to the valence shell of the combining
atoms as these approach each other. Thus the spins of thee two electrons get mutually
neutralised. The electrons in the oorbitals of inner shells remain undisturbed.
(iii) The filled orbitals (i.e. containing two electrons)
electrons) of the valence shell do not take part
in the bond formation. However, if the paired electrons can be unpaired without using much

energy, they are first unpaired by promoting to the orbitals of slightly higher energy and
then can take part in bonding. For example, N can form NCl3 only retaining a lone pair while
P can form both PCl3 and PCl5.
(iv) The electrons forming the bond undergo exchange between the atoms and
thus stabilize the bond.
(v) The strength of the covalent bond depends on the extent to which the two atomic
orbital overlap in space.
This theory is based on two main theorems which are:
(a) If ΨA(1) and ΨB(2) are the wave functions of the orbitals containing electrons in
two isolated independent atoms A and B with energies EA and EB, respectively then the total
wave function Ψ of the system can be given as a product of wave functions of two atoms,
i.e.
Ψ= ΨA(1). ΨB(2) ……(4.1)
and the energy of the system by
E=EA+EB …….(4.2)
Where (1) and (2) indicate two electrons belonging to atoms A and B.
(b) If a system can be represented by a number of wave functions such as Ψ1, Ψ2, Ψ3
……, then the true wave function Ψ can be obtained by the process of linear combination of
all these wave functions as:
Ψ= N(C1Ψ1+C2Ψ2+C3Ψ3+……) …..(4.3)
Where N is normalization constant and C1, C2, C3…are the coefficients indicating the
weight of each of Ψs. They are so adjusted as to give a state of lowest energy. The squares of
the coefficients may be taken as the measure of the weight of each wave function to total
wave function.
The valance bond theory was first applied to the formation of H2 molecule. If the
two H-atoms, viz. HA and HB are infinitely apart from each other, there is no interaction
at all but if these are brought close together, HA- HB covalent bond is formed and the
energy of the system is decreased. Now if the orbitals of the two H-atoms are
represented in terms of wave functions ΨA and ΨB, then the wave function for the
system HA.HB can be written as
Ψ=ΨA(1). ΨB(2) ……(4.1 as given above)
Where electrons belonging to HA and HB are 1 and 2.
But once the bond is formed, the electrons 1 and 2 have equal freedom to get associated
with either of the H-atoms. Thus due to the exchange of electrons between H-atoms,

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two possible covalent structures of H2 molecule may shown as HA(1).HB(2) and

HA(2).HB(1). The wave functions of these structures are ΨA(1). ΨB(2) and ΨA(2). ΨB(1)
respectively. Now the true wave function for H2 molecules can be obtained by linear
combination of the wave functions for the two covalent structures. This can be done in two
ways:
(i) When the combination of these wave functions takes place in a symmetric
way, i.e. by addition process, symmetric wave function Ψs is obtained:
Ψs= ΨA(1). ΨB(2) + ΨA(2). ΨB(1) ……..(4.4)
This is also known as covalent wave function, Ψ cov.
(ii) When the combination of the above wave functions takes place in a asymmetric way
i.e. by subtraction process, asymmetric wave function, Ψa, is obtained: Ψa= ΨA(1).
ΨB(2) - ΨA(2). ΨB(1) …….(4.5)
The value of Ψs does not change by exchange of electrons

electrons 1 and 2 but that of Ψa
changes in this process. The two situations are presented graphically as follows: (Fig 4.1)
The curve s is for addition process and curve a is for subtraction process of the
wave functions. The calculated value of ro for the minimum energy state i.e. the bonding state
is 87 pm against the experimental value of 74 pm.
Fig 4.1
Pauling has suggested that the bond between two H
H-atoms in H2 molecule is not
absolutely covalent, it rather has partial ionic character. He proposed two ionic structures for
H2

molecule in which both the electrons 1and 2 are either attached to HA or HB as given
below,
HA(1,2). H+B H+A.HB(1,2)
If the above wave functions for these structures are Ψ(1) and Ψ(2),
then Ψ(1)= ΨA(1). ΨA(2) …..(4.6)
And Ψ(2)= ΨB(1). ΨB(2) ……(4.7)
The consideration of ionic structures as given above of H2 molecule converts the equation 4.4
to
Ψs=[ΨA(1). ΨB(2) + ΨA(2). ΨB(1)] +λ [Ψ(1)+Ψ(2)]
or Ψs=[ΨA(1). ΨB(2)+ ΨA(2). ΨA(1)] + λ[ΨA(1). ΨA(2)+ ΨB(1). ΨB(2)]
..(4.8)
or Ψs =Ψcov. + Ψionic …..(4.9)
the coefficient λis used in equation 4.8 is a measure of the degree to which the ionic forms
contribute to the bonding. Thus three important contributions to covalent bonding may be
summarized as follows:
(i) Delocalization of electrons over two or more nuclei
(ii) Mutual screening
(iii) Partial ionic character.
Limitations of Valence Bond theory:

i) The formation of coordinate covalent bond (also known as dative bond) cannot be
explained on the basis of this theory because according to this theory a covalent bond is
formed as a result of overlapping of half filled orbitals of the combining atoms and the
paired orbitals of the atoms do not take part in normal covalent bond formation.
ii) The odd electron bond formation between the atoms cannot be explained by this theory
because a covalent bond is an electron pair bond means two electrons are required for a bond.
iii) This theory is unable to explain the paramagnetic behaviour of oxygen molecule because
paramagnetism is a property caused by the presence of unpaired electrons and in an oxygen
molecule, according to VBT, two electron pair bonds are present between the oxygen atoms
and hence it should be diamagnetic.
iv) In some molecules, the properties like bond length and bond angles could not be
explained by assuming simple overlapping of atomic orbitals of the atoms.
4.3.2 Directional characteristics of covalent bond:

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The covalent bonds are directed in space. This fact is evidenced by the stereoisomerism and a
wide variety of geometrical shapes shown by the covalent compounds. It is also possible to
measure the actual bond angles between cova
covalent
lent bonds in the molecules because of the
directional nature of bonds. An important fact about the covalent bonds is that these are
formed by the overlapping of pure as well as hybridised atomic orbitals. All these atomic
orbitals except the pure s-orbitals
ls, are oriented in the particular directions which determine
the direction of covalent bonds i.e. the direction in which the overlapping orbitals have the
greatest electron density. From this discussion we can conclude that it is the directional
nature of p, d and f orbitals which accounts for the directional nature of the covalent bond.
For example, the three p-orbitals
orbitals are directed along the three axes x,y and z and the bonds
formed by their overlapping are also directed towards the three axes. Thoug
Thoughh the s-orbitals
s
are spherically symmetrical around the nucleus, their overlapping along the molecular axis
gives a bond in that direction.
Let us discuss the modes of overlapping of pure and some of the hybridised atomic orbitals:
(i) s-s overlapping
This type of overlapping occurs between the ss-orbitals

orbitals of the combining atoms thereby giving
the s-ss covalent bond. This type of overlapping always occurs in the direction of molecular or
internuclear axis.
Fig 4.2 ovrelapping of two s-orbitals

orbitals along molecular
molecula axis
(ii) s-p overlapping
The overlapping taking place between the s-orbital

s of one atom and p-orbital
orbital of another atom
is called s-pp overlapping. The resulting bond is the ss-p
p covalent bond formed in the direction
of the orientation of p-orbital
orbital taking part in
i overlapping.

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Fig 4.3 overlapping of s and p orbitals along molecular axis

(iii) p-p overlapping
When the p-orbital

orbital of one atom overlaps with the pp-orbital
orbital of another atom, this process is
called p-pp overlapping and the bond so formed is known as p-p
p covalent bond. The necessary
condition for this type of overlapping is that the pp-orbitals
orbitals must be of the same type, i.e. px
and px, py and py and pz and pz. The px-py or px-pz type of overlapping does not occur.
Fig 4.4 overlapping of two p-orbitals

orbitals along molecular axis
If an atom possesses two or three half filled orbitals, they can simultaneously overlap with
another similar atom (or other atoms as well) thereby forming multiple bonds (both σ and π),
for example oxygen molecule.
Similarly bonding in N2 cann be explained
Fig 4.5 overlapping of orbitals forming σ and πbonds

(iv) Overlapping of the hybrid orbitals
itals with pure atomic orbitals
The s and p-orbitals

orbitals may overlap with hybrid orbitals to give the directional covalent bonds
such as s-sp(BeH2), s-sp2(BH3 ,C2H4), s-sp3 (CH4 and higher alkanes), p-sp
sp (BeCl2), p-sp2
(BCl3), p-sp3 (CCl4), p-sp3d (PCl5), p-sp3d2 (SF6) p-sp3d3(IF7) etc. bonds in the directions of
hybrid orbitals. d and f - orbitals in non
non-metallic
metallic elements (which mostly form covalent
compounds) do not generally take part in overlapping as such to form covalent bonds but d-
d
orbitals may participate in hybridisation, e.g. in PCl5, SF6, higher intehalogens etc. and form
covalent bonds by the overlapping of hybrid orbitals with atomic orbitalss in the directions of
hybrid orbitals.

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(v) Overlapping of the hybrid orbitals among themselves. This type of overlapping mainly
sp-sp(C2H2), sp2-sp2(C2H4), sp3-sp
occurs among the organic compounds, e.g. sp sp3(C2H6) etc.
Here only the overlapping of hybrid orbitals with
wit themselves has been given.
4.3.3 Sigma (σ) and pi (π)) covalent bonds:

bonds
σ Covalent bonds
The covalent bond formed between the two atoms by axial or head on overlapping
overlapping of pure or
hybrid atomic orbitalss belonging to valence shells of the atoms is called a σ bond. Pure s-
s
orbitals of the atoms on overlapping w
with s or p atomic orbitalss or hybrid orbitals of other
atoms always form σ bonds. Pure p-orbitals
p of the atom when overlap with s and p-orbitals
(of the same symmetry) or hybrid orbitals of other atoms al
also form σ bonds. d and ff- orbitals
by themselves seldom take part in σ bond formation through the d-orbitals
orbitals are sometimes
involved in hybridisation and thus form a σ bonds, e.g. PCl5, SF6, IF7 etc. The overlapping of
hybrid orbitals between two atoms always gives σ bond.
(i) Pure atomic orbital – pure atomic orbital overlapping
Fig 4.6(a) formation of σbond

bond by atomic orbitals
(ii) Hybrid atomic orbital – hybrid atomic orbital overlapping
Fig 4.6(b) formation of σbond

bond by hybrid orbitals
In this case only partial overlapping has been shown though other hybrid orbitals will also
form σ bonds, generally with atomic orbitals of other atoms.
Similarly sp3-sp3σ bond formation may also be shown.
π (pi) Covalent bond
A covalent bond formed between two atoms by side to side or lateral (perpendicular to the
molecularr axis) overlapping of only p-atomic
atomic orbitals or sometimes p and d-
d orbitals
belonging to the valence shell of the atoms is called a π bond. If in a molecule, a particular
atom uses one of its p-orbitals
orbitals for σbond formation then rest of the two p-orbitals
orbitals are used to
form the πbonds
bonds by lateral overlapping. For example, if x axis is taken as the molecular axis,

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then πbond is formed by py - py or pz-pz overlapping as happens in the oxygen and nitrogen
molecules.
Fig 4.7 formation of πbond by lateral overlapping of atomic orbitals

Forσ and πbonds,
bonds, the following points are important:
(i) A σbond
bond is formed by axial overlapping
overlapp of either pure or hybrid atomic orbitals
orbital of the two
combining atoms while a πbond
bond results from the lateral
lateral overlapping of the pure atomic
orbitals.
(ii) A σbond is stronger than a πbond
bond due to greater extent of overlapping of orbitals along the
inter nuclear axis than in lateral overla
overlapping.
(iii) A σbonds
bonds determine the direction of th
the covalent bond and bond length, πbonds
bonds have no
effect on the direction of the bond. However, their presence shortens the bond length.
(iv) There is free rotation of the atoms about a σbond
bond because the electron cloud overlaps
symmetrically along the internuclear axis while this is not possible about a πbond
bond because the
electron clouds overlap above and below the plane of the atoms.
(v) A σbond
bond has its free existence between any two atoms in a molecule while πbond
bond is formed
between the atoms only when σbond
bond already exists.
The shapes of covalent molecules and ions can be explained by employing (a) the concept
of hybridisation and (b) VSEPR Theory.
4.4. HYBRIDISATION OF ATOMIC ORBITALS

It iss the theoretical model used to explain the covalent bonding in the molecules and is
applied to an atom in the molecule. To explain the anomaly of expected mode of bonding
(according to VBT) shown by Be, B and C in their compounds where these elements should
shou
be zerovalent, monovalent and bivalent due to the presence of 0,1 and 2 unpaired electrons in
their valence shells and the observed bonding exhibited by them, i.e. these are bivalent,
trivalent and tetravalent due to the availability of 2,3 and 4 unpaired
red electrons in their
valence shells in those compounds, a hypothetical concept of hybridisation was put forward.
According to this concept, before the bonding occurs in the compounds of Be, B and C, one

of the 2s electrons gets promoted to the vacant 2p orbital due to the energy available from the
heat of reaction when covalent bonds are formed or perhaps due to the field created by the
approaching atoms, thereby making 2,3 and 4 unpaired electrons available in the valence
shell of the atoms of these elements.
These orbitals having unpaired electrons then mix up together or redistribute their energy to
give rise a new set of orbitals equivalent in energy, identical in shape and equal to the
number of atomic orbitals mixed together. This process is known as hybridisation, the atomic
orbitals are said to be hybridised and the new orbitals formed are called the hybrid orbitals.
The hybrid orbitals so formed then overlap with the half filled orbitals of the approaching
atoms and form covalent bonds.
Salient features (or the Rules) of hybridisation
i) The atomic orbitals belonging to the valence shell of the central atom/ion of a
molecule/ion with almost similar energies mix up together or hybridise to give the
hybrid obitals. But the atomic orbitals of the central atom participating in the πbond
formation are excluded from the hybridisation process.
ii) The number of hybrid orbitals produced is equal to the number of atomic orbitals undergoing
hybridisation. The hybrid orbitals like pure atomic orbitals can accommodate a maximum
of two electrons of opposite spins.
iii) If required, electron(s) may be promoted from an orbital in ground state of the central atom to
the next empty higher energy orbital provided the value of n does not change as happens in
the central atom of BeCl2, BCl3, CH4, PCl5, SF6etc.
iv) Most of the hybrid orbitals are equivalent in energy, shape and size but may not be identical.
They differ from one another in their orientation in space.
v) From the type of hybridisation, the geometry and bond angles of a molecule can be predicted.
vi) In a few cases empty atomic orbitals or those with lone pairs of electrons (i.e. filled
atomic orbitals) are also involved in the hybridisation process but in such cases normal
covalent bond is not formed rather this process leads to the formation of coordinate covalent
bond. Sometimes these filled hybrid orbitals do not form the bonds and the electron pair
remains as lone pair on central atom.
vi. The hybrid orbitals are involved in the σbond formation only and π bond is not formed by
them at all.
4.4.1. Types of hybridization:

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Following are the important types of hybridisatio

hybridisation. The central atom in a given
molecule/ion
ule/ion can undergo any of the following possible hybridisations.
(i) Sp hybridization:
When one s and one p (oriented along molecular axis) atomic orbitals belonging to the
valence shell of the central atom in a given molecule/ion mix up together to give rise two
hybrid orbitals,
als, the process is known as sp
s hybridisation and the new orbitals
orbit formed
are called sp hybrid orbitals. This process can be shown diagrammatically as follows:
Fig 4.8 (a) Formation of two collinear sp hybrid orbitals from the mixing of
one s and one p atomic orbitals
Characteristics:
i) These hybrid orbitals are equivalent in energy, shape (oval shaped) and are oriented in
0
the opposite directions at an angle of 180 from each other, leading to linear geometry.
ii) Each hybrid orbital has one large lobe and oone
ne small lobe. The larger lobe takes part in
overlapping process.
iii) These hybrid orbitals possess 50% characte
character of s-orbital (spherical) and 50% that of p-
p
orbital (pear shaped) and hence are oval shaped.
Examples: BeX2 (X=H,F, Cl). Let us take BeF2 molecule for illustration.
Beg: 2s2p0 Beex: 2s1p1
sp
Fig 4.8 (b) formation of two σcovalent

covalent bonds by the overlapping of sp-hybrid
sp hybrid orbitals of Be
and 2p-orbitals of F-atoms
(ii) Sp2 hybridisation:
On mixing together one s and any two pp-orbitals
orbitals belonging to the valence shell of the central
atom of a given molecule/ion, a set of three hybrid orbitals is obtained. This process is known
as sp2 hybridisation and the new orbitals formed are termed as sp2 hybrid orbitals. The
process can be shown as given below:

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Fig 4.9(a) Formation of three trigonal planar sp2 hybrid orbitals from the mixing of one s
and two p atomic orbitals
Characteristics:
i) The sp2 hybrid orbitals are equivalent in energy and shape and are oriented towards
the corners of an equilateral triangle, hence inclined at an angle of 1200with one another,
leading to trigonal planar geometry.
ii) They all lie in one plane (i.e. planar).
iii) They possess 33% s- character and 66% pp- character and therefore are less oval than
sp- hybrid orbitals.
Examples: BX3(X=H, F,Cl) Let us take BF3 molecule for discussion.
Bg :2s2 2px1 Bex: 2s1px1py1
sp2
Fig 4.9(b) formation of three σ covalent bonds by the overlapping of sp2 hybrid orbitals of B-
atoms and 2p-orbitals of 3F-atoms
atoms
(iii) Sp3 hybridisation:

In this hybridisation, one s and three pp-atomic
atomic orbitals belonging to the valence shell of the
central atom of a given molecule/ion mix up together and form a set of four hybrid orbitals.
This mixing process is known as sp3 hybridisation and the new orbitals formed are called sp3
hybrid orbitals. This process has been shown below:
Fig 4.10(a) formation of four tetrahedral sp3 hybrid orbitals from the mixing of 1s and
3p atomic orbitals

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Characteristics:
i) These sp3 hybrid orbitals are equivalent
equivale in energy and shape and are oriented along the four
corners of a regular tetrahedron. The bond angle between each pair of these orbitals is 109.50,
called tetrahedral angle.
ii) Each sp3 hybrid orbital has 25% s-
s character and 75% p- character, hence their shape is
closer to that of p- orbitals i.e. are pear shaped.
Examples: AX4 where A = C, Si and X = H, F, Cl,, Br, I, simplest of these is CH4. In
atom is the central atom which undergoes sp3
this molecule, C-atom hybridisation
isation as follows:
Cg:2s2 px1py1pz0 Cex: 2s1px1py1pz1
sp3
covalent bonds by the overlapping of sp3 hybrid

Fig 4.10 (b) formation of four σcovalent
orbitals of C-atom and 1s orbitals of four H
H-atoms
(iv) Sp3d hybridization:
When one s, three p and one d (generally dz2) atomic orbitals of the valence shell of the
central atom of a given molecule/ion mix up together and give rise to the formation of a set of
five hybrid orbitals, the process is known as sp3d hybridisation and the new orbitals formed
are called sp3d hybrid orbitals. The process of this type of hybridisation has been shown
here:
Fig 4.11 (a) formation of five trigonal tripyramidal sp3d hybrid orbitals from the mixing of
one s, three p and one d (dz2) atomic orbitals
Characteristics:
i) The sp3d hybrid orbitals are equivalent in energy and shape and are oriented
iented towards the
five corners of a regular trigonal bipyramid i.e. their spatial arrangement is trigonal
bipyramidal.

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ii) They do not lie in one plane. Three of the ffive hybrid orbitals called the basal or equatorial
hybrid orbitals are oriented towards th
the corners of an equilateral triangle forming a triangular
plane while the remaining two called axial hybrid orbitals lie above and below the plane on
the axis passing through the centre of plane. The angle between each adjacent pair of
basal hybrid orbitals is 1200, that between two axial hybrid orbitals is 1800 and that between
the axial and basal hybrid orbitals is 900.
Examples: AX5 molecule (A = P, As, Sb and X = F, Cl, Br). Let
et us discuss the hybridisation
and bonding in PCl5 molecule.
pg: 3s2 px1py1 pz1 pex: 3s1 px1py1pz1 dz21
sp3d
Fig 4.11(b) Formation of five covalent bonds by the overlapping of sp3d hybrid
fiveσcovalent
orbitals of P central atom and p-orbitals of five Cl-atoms
(v) Sp3d2 hybridisation:

On mixing one s-orbital,
orbital, three p-orbitals
p and two d (generally dx2-y2 and dz2) orbitals of the
valence shell of central atom of the given molecule/ion, a set of six hybrid orbitals is formed.
This process is known as sp3d2 hybridisation and the new orbitals formed are called sp3d2
hybrid orbitals. The formation of these orbitals is shown below:
Fig 4.12(a) Formation of six sp3d2 hybrid orbitals from the mixing of one s, th
three p and
two d-atomic orbitals
Characteristics:
i) All the six hybrid orbitals formed are equivalen
equivalent in energy and shape and are oriented along
the six corners of a regular octahedron i.e. their arrangement in space is octahedral.

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ii) All the orbitals do not lie in a plane. Four hyb

hybrid orbitals of the six
ix called basal or
equatorial hybrid orbitals are lying in square
squ plane while the remaining two called
axial hybrid orbitals lie above and below the plane on the axis passing through the centre
of the square base. The angles between any adjacent pairs of hybrid orbitals (basal or
0
axial) is 90 .
Examples: AF6 type molecule (A=S, Se, Te). Let us see the process of bond formation
in SF6 molecule.
Sg: 3s2px2py1pz1 Sex: s1px1py1pz1 d1z2d1x2-y2
sp3d2
covalent bonds by the overlapping of sp3d2 hybrid

Fig 4.12 (b) Formation of six σcovalent
orbitals of S central atom with p-orbitals
p of six F atoms
(vi) Sp3d3 hybridisation:
When one s, three p and three d (generally dxy, dyz, dzx) orbitals of the valence shell of the
central atom in a given molecule/ion mix up together, a set of seven new orbitals is formed.
This process of mixing is called sp3d3 hybridisation and the new orbitals formed are known as
sp3d3hybrid orbitals. Their formation occurs as follows:
Fig 4.13 (a) Formation of seven sp3d3 hybrid orbitals from the mixing of one s, three
p and three d-orbitals
orbitals of the central atom
Characteristics:
i) All the seven hybrid orbitals are equivalent
equivale in energy and shape and are oriented towards
the seven corners of a regular
ular pentagonal bipyramid i.e. their spatial arrangement is
pentagonal bipyramidal.

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ii) All of them do not lie in one plane. Five of th

them
em lie in the pentagonal plane and are called
basal or equatorial hybrid orbitals
als while remaining two cal
called axial hybrid orbitals lie above
and below the plane on the axis passing through the centre of the pentagonal plane.
iii) The angle between any adjacent pair of basal hybrid orbitals is of 720 and that between an
equal to 900.
axial and a basal hybrid orbital is eq
Example: IF7 (an interhalogen compound)
Ig : 5s2px2py2pz1 Iex : 5s1px1py1pz1dxy1dyz1dzx1
sp3d3
The whole act of hybridisation and bond formation
for in this molecule can be shows as given
below:
Fig 4.13(b) Formation of seven covalent bonds from the overlapping of sp3d3 hybrid
orbitals of central I-atom
atom and p-orbitals of seven F-atom
4.4.2 Shape of simple
le inorganic molecules and ions:
i
In all the above examples, the central atom uses all of its valence electrons for the bond
formation i.e. the hybrid orbitals of the central atom and atomic orbitals (s or p) of the
attached atoms are half filled, and after overlapping of the appropriate oorbitals,
rbitals, form the
normal σcovalent
covalent bonds. The molecules so formed have regular geometrical shape i.e. there
is no distortion in the shape of the molecule.
However, there are examples in which the central atom of the molecule/ion undergoes a
particular type of hybridisation which involves orbital/s with paired electrons as such along
with orbitals having unpaired electrons. These hybrid orbitals (with both paired an unpaired
electrons)) overlap with the orbitals of approaching atoms to give the
the normal as well as dative
σbonds or sometimes the hybrid orbitals with paired electrons do not overlap with the orbitals
of approaching atoms and remain attached as such with the central atom in the
molecules as lone pairs. The presence of these lone pairs causes distortion in the sh
shape of the
molecule/ion. This leads to irregular geometry of the molecule/ion.
The geometrical shapes, and process of hybridisation involved, of some inorganic
molecule/ions along with those given uunder
nder VSEPR Theory in the syllabus will be discussed
after the discussion of VSEPR Theory.

4.5. VALENCE SHELL ELECTRON PAIR REPULSION (VSEPR)

THEORY
The valance bond theory also called the atomic orbital theory can explain the geometrical
shape of many molecules/ions of both transition and non-transition elements by employing
the concept of hybridisation. But many molecules/ions remain unexplained in terms of their
geometry by this method. To overcome this shortcoming, a modification of VBT was
developed by Gillespie and Nyholm which can predict the shapes of many species which are
left uncovered by the concept of simple hybridisation. According to this theory “The shape or
the geometry of a polyatomic molecule/ion of non-transition (mostly non-metallic) element
depends upon the number and nature of the electron pairs contained in the valence shell of the
central atom.” Thus the electrons already present in the valence shell plus the additional
electrons acquired by the central atom as a result of bonding with other atoms are called its
valence shell electrons. These electrons may be present as bonding or non-bonding electron
pairs in the central atom which arrange themselves in such a way that there is a minimum
repulsion between them and the molecule has minimum energy and maximum stability. Since
there can be only one orientation of orbitals corresponding to minimum energy, hence the
molecule attains a definite shape/geometry.
The following rules have been proposed by Gillespie and Nyholm to explain the shape of
some inorganic molecule/ions-
i)If the central atom of a molecule/ion contains only the bond pairs of electron in the valence
shell, the geometrical shape of the molecule/ion is said to be regular (or undistorted) e.g.
linear, trigonal planar, tetrahedral, octahedral etc., respectively. This fact is evidenced by
the examples given above in the chapter of hybridisation.
ii)When the valence shell of the central atom in a molecule/ion contains the bonding electron
pairs and non-bonded electron pairs (called lone pairs), the molecule/ion has distorted or
irregular geometrical shape due to the alteration in bond angles which is caused by the
presence of lone pairs on the central atom.
This happens because of the following fact. Since the lone pair of electrons is under the
influence of only one nucleus (of central atom), i.e. mono centric, these electrons occupy a
broader orbital with a greater electron density radially distributed closer to that nucleus than
bonding pair of electrons which is under the influence of two nuclei of bonded atoms i.e.
bicentric. Its location between the atoms depends on the electronegativities of the
combining atoms. Thus lone pairs experience more freedom than the bonded pairs and hence

exert more repulsion on any adjacent electron pair than a bond pair does on the same
adjacent electron pair. The repulsion among the electron pairs follows the sequence as:
l.p.-l.p. repulsion>l.p.-b.p. repulsion>b.p.-b.p. repulsion
maximum intermediate minimum

Because of this fact, if the central atom in a molecule/ion contains both lone pairs
(l.ps.) and bonded pairs (b.ps.), there occurs a contraction in the bond angle (which is formed
between two adjacent b.ps.). More the number of l.ps. on the central atom, greater is the
contraction caused in the bond angle. This statement is supported by the bond angles
observed in CH4, NH3 and H2O:
molecules CH4 NH3 H2 O
3 3
Type of hybridisation involved sp sp sp3
No. of l.ps. on the central atom 0 1 2
Bond angle 109.50 107.30 104.50
Contraction in the bond angle - ≈20 ≈50
iii) ∠BAB in AB2 type molecules decreases with increasing electronegativity of the atom
B where A is a central atom. This is because as the electronegativity of the attached atom B
increases, the b.p. of electrons moves away from the central atom and experiences less
repulsion from its l.ps. and enhanced distance between two bond pairs also causes less
repulsion between them resulting in the contraction in bond angle.
For example, (i) PI3(≈1020)>PBr3(≈101.50)>PCl3(≈1000)
(ii) AsI3(≈1010)>As Br3(≈100.50)> AsCl3(≈98.50)
iv)The repulsion between the electron pairs in filled shells is larger than that between electron
pairs in incompletely filled shells. As an example, let us compare ∠HOH and ∠HSH in H2O
and H2S molecules. It has been observed that∠HOH (104.50)>>∠HSH (92.20). In both the
molecules, the central atoms O and S contain eight electrons in their valence shells, six of
their own and two from H-atoms. Thus the valence shell of O-atom (with 2s and 2p orbitals
only) is completely filled but that of S-atom is incompletely filled due to the availability of
3d-orbitals (which remain vacant) in addition to 3s and 3p-orbitals. The total capacity of the
valence shell of S-atom is to accommodate a maximum of 18 electrons (from 2n2 rule).
v)The bond angle involving the multiple bonds are generally larger than those involving only
single bonds. However, the geometrical shape of the molecule is not affected by multiple
bonds.
Limitations:
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The VSEPR Theory suffers from certain limitations which are as follows:
(i) This theory cannot
ot explain the shapes of very polar molecules and those having an
inert pair of electrons.
(ii) The shapes of the molecules which have extensive delocalised πelectron
electron systems are
not explained by this theory.
(iii) This theory does not cover certain transition metal complexes.
The VSEPR Theory in combination

ombination with the concept of hybridisation has been successfully
used to discuss and explain the geometrical shapes of most of the covalent inorganic
molecules/ions. Here we shall discuss the type of hybridisation and mode of bonding in
certain inorganic molecule/ions in addition to those given in the syllabus of VSEPR theory.
A. Shape of SnCl2 molecule (sp2 hybridisation)

The central atom, Sn, has the ground state valence shell configuration as given below:
Sng: 5s25px1py1pz0 → sp2 hybridization
This atom undergoes partial hybridisation mixing up together the paired 5s and unpaird 5px
orbitals, leaving behind the empty pz -orbital, to form three sp2 hybrid orbitals one of
and 5py -orbitals,
which is occupied by the electron pair coming from the 5s-orbital.
orbital. The process of
hybridisation and overlapping
ping of hybrid orbitals with atomic orbitals
orbital of Cl-atoms
atoms have been
shown below:
Fig 4.14 Formation of hybrid orbitals and their overlapping with 3p-orbitals
3p orbitals of Cl atoms to
give SnCl2 molecule
Two unpaired hybrid orbitals of Sn atom overlap with unpaired pp-orbitals
orbitals of approaching Cl-
Cl
atoms and give SnCl2molecule which contains one lone pair of electrons on Sn
Sn-atom.
Because of the greater repulsion of lone pair on bond pairs, the ∠Cl SnCl is less than 1200,
the expected angle in case of sp2 hybridisation. The molecule thus attains angular or bent
shape.
B. Shape of NH3 Molecule ( sp3 hybridisation)
In NH3 molecule, the central atom N has following ground state valence shell configuration:
Ng : 2s2px1py1pz1 → sp3 hybridization

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All these atomic orbitals participate in hybridisation and give four equivalent sp3 hybrid
orbitals. One of them contains an electron pair (lone pair)
pair) and three half filled hybrid orbitals
then overlap with 1s orbitals
rbitals of three H-atoms
H to form σcovalent bonds (N-H
H bond).
Fig 4.15 Formation of hybrid orbitals and their overlapping with 1s orbitals of 3H atoms to
give NH3 molecule
From the figure,
re, it is evident that one lone pair of electrons is present in NH3 molecule which
exerts more repulsion on bonded pairs than that operating between the bonding pairs of
electrons. The net result is that the NH3 molecule attains trigonal pyramidal shape with the
bond angle of 107.30, a deviation of about 20 from the tetrahedral angle of 109.50.
C. Shape of H2O Molecule (sp3 hybridisation)
The ground state valence shell configuration of the central atom O of H2O molecule is:
Og: 2s2px2py1pz1 → sp3 hybridization
All these atomic orbitals undergo hybridisation and give rise to four equivalent sp3 hybrid
orbitals. Two of these hybrid orbitals are half filled and remaining two contain lone pairs of
electrons. The unpaired hybrid orbitals than overlap with 1s orbitals of two H
H-atoms
atoms to form
σcovalent bonds (O-H bonds).
Fig 4.16 Formation of hybrid orbitals and their overlapping with 1s orbitals of two H-atoms
H
to give H2O molecule
There are two lone pairs of electrons present in H2O molecule which exert strong repulsion
on each other and move away towards the bonded pairs of electrons. This brings the bonded
pairs closer to each other thereby causing contraction in the bond angle. H2O molecule thus
shaped geometry with the bond angle of 104.50, a deviation of a bond 50 from the
attains a V-shaped
tetrahedral angle of 109.50
D. Shape of H3O+ Ion (sp3 hybridisation)

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Hydronium ion (H3O+) is formed by the combination of H2O molecule and H+ ion in which
olecule donates one of its lone pairs of electrons to H+ ion and it accepts that lone pair
H2O molecule
of electrons
ctrons in its vacant 1s orbital.
Actually, filled sp3 hybrid orbital of O
O-atom in H2O molecule overlaps with empty s-orbital
s
of H+ ion as follows thereby forming a coordinate covalent bond:
Fig 4.17 Overlapping of filled sp3 hybrid orbital of O-atom in H2O and empty 1s orbital of
H+ ion to form H3O+ ion
This ion has trigonal pyramidal shape like that of NH3 molecule with one lone pair of
electrons on O-atom.
E. Shape of SF4 molecule (sp3d hybridisation)
In this molecule the central S--atom
atom is in its first excitation state in which one of its px
electrons is promoted to the next empty dz2 orbital. The electronic configuration in the
ground and first excited state has been shown below:
Sg: 3s2px2py1pz1 S1ex : 3s2px1py1pz1 (dz2)1 sp3d
All these atomic orbitals of Sex central atom get hybridised to give five sp3d hybrid orbitals
directed toward the corners of a trigonal bipyramid, one of these hybrid orbitls contains an
electron pair (b.p.) and the next four orbitals have unpaired electrons which overlap with the
p-orbitals of four F-atom
atom to form SF4 molecule.
Fig 4.18 Formation of five hybrid orbitals of Sex atom and their overlapping with pp-orbitals
of four F-atom to give SF4 molecule

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This molecule attains a see-saw

saw shape bec
because
ause of the presence of one lone pair of electron
(sometimes also called distorted tetrahedral) and
a lone pair lies at one of the basal positions
po
(the molecule has 1 lone pair and 4 bonded pairs)
pairs
F. Shape of ClF3 molecule (sp3d hybridisation)
Cl is the central atom in this molecule with valence shell electronic configuration in ground
and first excited state as given below wherein one electron from a filled pp-orbital
orbital say py is
viz. dz2) of the same shell:
promoted to a vacant d-orbital (viz
Clg: 3s2px2py2pz1 Cl1stex : 3s2px2py1pz1 (dz2)1 sp3d

All the orbitals of the valence shell of Clstex atom are mixed up together to produce five sp3d
hybrid orbitals. Two off the hybrid orbitals have lone pairs of electrons and three have
unpaired electrons which then overlap with unpaired pp-orbitals of three F-atoms
atoms to form σ
covalent bonds. The lone pairs are said to occupy the equilateral positions and the molecule
shaped structure with the bond aangle of 87.60 instead of 900 due too the distortion
attains T-shaped
caused by lone pairs The T-shaped
shaped structure has been confirmed by the experimental
evidences. The whole act of hybridisation, overlapping and bond formation can be shown as
below (molecule has 2 lone pairs
rs and 3 bonded pairs):
pairs
Cllstex atom and their overlapping with pp-

Fig 4.19 Formation of five hybrid orbitals of C
orbitals of three F
F-atoms to give ClF3 molecule
The mode of hybridisation shape and bonding in BrF3 and ICl3 molecules can also be
explained on the similar grounds as in the case of ClF3.
G. Shape of ICl2- Ion (sp3d hybridisation)
In ICl-2 ion, the central atom I (iodine) has the ground state electronic configuration in its
valence shell as shown below:
Ig: 5s2px2py2pz1 (dz2)0

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All these atomic orbitals including a vacant dz2 orbital participate in hybridisation to produce
five sp3d hybrid orbitals of which
ich three orbitals contain lone pairs
pairs,, one hybrid orbital is half
filled which overlaps with half filled pp-orbitals of Cl-atom to give normal σbond
bond and one
hybrid orbital remains vacant and overlaps with the filled orbital of Cl- ion to give a
coordinate covalent σbond
bond (dative bond). The lon
lone pairs occupy the equatorial
uatorial positions and
the bonded pairs are situated in axia
axiall positions. The ion has 3 lone pairs and 2 bonded pairs as
shown below and has almost linear shape:
Fig 4.20 Formation of five sp3d hybrid orbitals ofcentral

of atom, I and overlapping of one of
orbital of Cl atom and that of filled pp-orbital of Cl-ion with
these hybrid orbitals with p-orbital
vacant hybrid orbital of I atom
H. Shape of NO3- ion (sp2 hybridisation)
atom in this ion is sp2 hybridised leaving a pure pz orbital behind. These
The central N-atom
sp2hybridised orbitals then overlap with the orbitals of one O atom and one O-ion to form two
normal σbonds and one dative σ bond as follows:
Fig 4.21 Formation of two normalσbonds,

normal one dative σ bond and one π bond between N
central
ntral atom and oxygen atoms/ion
I. Shape of SO42- ion (sp3 hybridisation)
S atom has 6 electron its valence shell and in this ion all the valence electrons of S are present
in unpaired state i.e. S2ex state. Out of six, four orbitals are hybridised as follows:
Sg : 3s2px2py1pz1 S2ndex : 3s1px1py1pz1 (dx2-y2)1(dz2)1 sp3

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The SO42- ion can be shown as follows:

For details please refer to sp3 hybridization & CH4 molecule.
It has tetradedral shape like CH4 molecule but has two single and two double bonds (σand
( π).
On the similar grounds the type oof hybridisation and shape of XeF2, XeF4, XeOF4 and XeF6
molecules can be discussed. It is to be kept in mind that F
F-atom
atom is monovalent, O-atom
O is
bivalent (forms one σand one π--bond
bond with central atom) and central atom requires only that
number of hybrid orbitals which can form σbonds
bonds with approaching atoms and these hybrid
orbitals are generally unpaired or half filled. Hence in the above molecules partial
hybridisation may take place.
XeF : sp3d 3 lone pairs + 2 bonded pairs and linear in shape
XeF4: sp3d2 2 lone pairs + 4 bonded paires and square planar
XeOF4 : sp3d2 1 lone pair + 5 bonded pairs +1 πbond and is square pyramidal
XeF6 : sp3d3 1 lone pair
air + 6 bonded pairs and pentagonal pyramidal
Fig 4.22 Shapes of XeF2, XeF4, XeOF4 and XeF6 molecules
4.6 MOLECULAR ORBITAL THEORY (MOT)

To explain the formation of the covalent bond in molecules/ions and their behaviour like
relative bond strength, magnetic property etc., a new approach was developed by Hund and
Mulliken in 1932 and later by Lennard Jones and Coulson. This approach is know
known as
Molecular Orbital Theory.. This theory treats the covalent bonds in terms of Molecular

Orbitals (MOs) which are associated with the entire molecule and result from the linear
combination of atomic orbitals (LCAOs) of constituent atoms of the molecule/ion. Thus the
molecules are supposed to have their own orbitals of varying energy in the same way as the
isolated atoms have. The difference between an atomic orbital and a MO is that an electron in
an atomic orbital is influenced by one nucleus only i.e. an atomic orbital is monocentric while
an electron in a M.O. is under the influence of all the nuclei contained in the molecule/ion,
i.e. a M.O. is polycentric.
The atomic orbitals combining linearly to form the MOs must be of the similar energy and
same symmetry and may be of the two similar atoms of a homonuclear diatomic molecule/ion
(e.g. H2, H2+, N2, O2, O22- etc.) or may be of two different atoms of a heterodiatomic
molecule/ion (e.g. CO, NO, CN-, NO+ etc.).
The main characteristics of MOT are as follows:
(i) The atomic orbitals (AOs) combining linearly together to form the moleculer orbitals (MOs)
lose their identity and the number of atomic orbitals is equal to the number of moleculer
orbitals formed.
(ii) MOs are the energy states of the molecules/ions in which the electrons are filled just like in
AOs of the atoms.
(iii) The linear combination of the AOs may occur in two different ways, i.e. the additive
combination gives bonding molecular orbitals (BMOs) and the subtractive combination gives
antibonding molecular orbitals (ABMOs).
(iv) The bonding MO has lower energy and hence greater stability than the antibonding MO
obtained from two AOs.
(v) The bonding MOs are denoted by σ,π,δ,Ψetc. symbols while the antibonding MOs by
σ*,π*,δ*,Ψ* etc. symbols.
(vi) The shapes of MOs formed depend on the type of combining AOs and mode of combination
and their filling takes place according to the rules which are applicable for AOs, viz.
Aufbau principle, Pauli’s exclusion principle and Hund’s rule of maximum multiplicity.
Formation of MOs LCAO approximation
Suppose ΨA and ΨB represent the wave function of the electrons in the A.Os. of the atoms A
and B respectively. Then linear combination of these A.Os. may be done in two ways:
i) Ψb = ΨA+ΨB (++ combination) ……… (4.10)
This additive combination of AOs gives bonding molecular orbital for which the wave
function is denoted by Ψb. This is also called constructive interaction. Further, from the
above equation, we have

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(Ψb)2 = (ΨA+ΨB)2 = ΨA2+ΨB2+2ΨAΨB -………. (4.11)

Or (Ψb)2>ΨA2+ΨB2 by a factor 2Ψ
ΨAΨB where squares of respective Ψs give the probability of
locating the electrons in the different orbitals. From this we infer that
th electrons prefer to
reside
de in the BMO rather than the AOs and placing electrons in BMO yields a stable covalent
bond. In this MO the electron density is greater between the nuclei of bonding atoms.
ii) Ψ* (or Ψa) = ΨA-ΨB ( +- (plus minus combination) ….. (4.12)
This
is subtractive combination of AOs gives the antibonding molecular
ular orbital, the wave
function for which is represented by Ψ* ( psi star). This is also called destructive interaction.
From this equation, we have
(Ψ*)2 = (ΨA-ΨB)2 = ΨA2+ΨB2 - 2Ψ
ΨAΨB … (4.13)
* 2
Or (Ψ ) < ΨA2+ΨB2 by a factor 2Ψ
2 AΨB.From this relation it can be concluded that eelectrons
prefer to occupy the AOs rather than the ABMO and placing electrons in this MO opposes
the bond formation.
rmation. The electron density in this MO,
MO, decreases to zero between the nuclei.
The pictorial representation of the for
formation of BMOs and ABMOs form AOs is shown
below:
s-orbitals: combination of s-orbitals
orbitals gives only σMOs (both bonding and antibonding)
s and p-orbitals: This combination also gives only σM.Os.

M.Os. This is possible only along
molecular axis i.e. orientation of p-orbital is along molecular axis.
p-orbitals: The linear combination of pp-orbitals may give σas well as π MOs (b and * both).

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It is to be noted that the interaction of AOs occurs to form the MOs only if the symmetry
consideration are taken care of
of, e.g. s-px combination is allowed but s-py and s-Thepz
combination is disallowed if px lies along the molecular axis. Similarly
Similarly, px-py, px-pz and py-pz
combinations are disallowed. py-p
- y and pz-pz combination will produce πM.Os.
M.Os. if X-
X axis is
the molecular axis. Theπbpy and πbpz as well as πpy* and πpz* MOs have the same energy, i.e.
these are degenerate orbitals.
Energy level diagrams of the molecules/ions
The MOs of the molecules/ions if arranged in the increasing order of their energy, we get the
so called energy level diagrams
iagrams for them in which the MOs are taken as energy levels.
The electron are filled
illed in these energy levels (MOs) from the lowest energy MO to higher
h
energy MOs
Os according to Aufbau principle
principle. The degenerate MOs are filled according to
Hund’s rule, i.e. first singly and then in pairs. This condition is applicable to both
homonuclear and heteronuclear diatomic molecules/ions.
At the same time if these MOs are written is a sequence using their symbols along with the
number of electrons contained in them, then we get the molecular electronic configuration in
the same way as the electronic configuration of atoms. This sequence according to increasing
energy is:
This sequence has been found to hold for O2, F2 etc. but for hypothetical B2, C2, N2 etc. σb2px
is of slightly higher energy than πb2py/z MOs due to certain well established reasons and
hence the sequence becomes (taking x axis as the molecular axis).
Bond order: The

he bond order is the number of bonds in the molecular species and is given as:
Bond Order = (Na – Nb)/2, Na= number of antibonding electrons, Nb=number of bonding electrons

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4.6.1. Homonuclear
nuclear diatomic molecules/ions
molecules/ions:
i) H2 molecule ( i.e. 1+1=2 valence shell electrons) It is simplest case with 1s1 configuration in
each H-atom. Molecular electronic configuration:
(σb1s)2< (σ*1s)0. Also denoted as KK in the higher molecules.
Bond Order = (2–0)/2=1
.: There is single bond between H-atoms

H in H2 molecule (H-H).
Fig 4.23) Energy level diagram of H2

ii) N2 molecule (5+5=10 valence shell electrons)
Each N-atom has 2s22p3 electronic configuration in the valence shell. Thus Molecular
electronic configuration of N2 is:
Fig 4.24 Energy level diagram of N2

Bond order= 8-2=6/2=3.
2=6/2=3. Hence there is a triple bond between N atoms in N2 molecule. KK
are non bonding orbitals.
iii) O2 molecule (6 + 6 = 12 valence shell electrons)
Each O-atom has 2s22p4 valence shell electronic configuration. 1s2 electrons of both O atoms
belonging to KK MOs. are non-bonding.
bonding.

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.: Electronic configuration of O2 molecule is:
Fig 4.25 eneregy level diagrm of O2
Because of the presence of two unpaired electrons

in ABMOs, O2 molecule is paramagnetic in nature.
Bond order = (8-4)/2 = 2, There is a double bond between O-atoms
O in O2 molecule (O=O)
Similarly we can write down the electronic configuration and draw the energy level diagrams
for O2+, O2- (super oxide ion), O22- (peroxide ion) and F2 molecule.O2+ (oxygenyl ion) has
one electron less than O2 molecule. O2- ion will have one electron more than O2 molecule.
Both are paramagnetic. O22- ion and F2 molecule will have two electrons more than O2 which
go to π2py* and π2pz* MOs thereby making them diamagnetic.
4.6.2. Heteronuclear
onuclear diatomic molecules/ions
molecules/ions:
i) CO molecule ( 4+6=10 valence shell electron).
This molecule is isoelectronic with N2 molecule and has similar molecular electronic
configuration and energy level diagram to that of N2 molecule. There is only a minor
difference in electronic distribution in A.Os. as given below:
C : 2s22p2 ; O : 2s2 2p4
Electronic configuration of CO molecule
molecule is (the M.O. energy level sequence is like that of
N2):

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Fig 4.26 Energy level diagram of CO

Bond order =8-2/2=3
2/2=3 (triple bond)
ii) NO molecule (5+6=11 valence shell electron)
N: 2s22p3 and O: 2s22p4
The electronic configuration of NO molecule is (the M.O. energy level sequence is like that
of O2) but electron distribution is slightly different.
It is paramagnetic due to the presence of one unpaired electron. The bond between N and O is
2½ times as strong as a normal covalent bond.
Similarly, we can write down the electronic configuration and draw energy level
diagram for NO+ (one electron less than NO) ion which is diamagnetic and has only paired
electrons upto πbzpx M.Os. and πzp*y M.O. is vacant.

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Fig. 4.27 Energy level diagram of NO
4.7. MULTICENTRE BONDING IN ELECTRON DEFICIENT

MOLECULES
In the covalent compounds, in general, an electron pair bond holds two atoms together but
there are a number of compounds in which an electron pair holds severa
severall atoms together. In
these cases, it is said that multicentre or delocalized bond exists. The best known molecule
which displays multicentre bonding is B2H6, diborane.
A number of evidences showthat the B2H6 molecule has hydrogen bridged structure in which
four H-atoms
atoms are terminal hydrogen atoms (Ht) and the remaining two H-atom
atoms are the
bridging hydrogen atoms (Hb). The four Ht atoms are bonded with B-atoms
atoms by the normal
electron pair bonds (two H-atoms
atoms are attached to each B
B-atom) and Hb-atoms
atoms form a
multicentre (3c-2e)
2e) bond with each B-atom.
B
Boron has valence shell configuration: Bg: 2s2p1 Bex: s1px1py1pz0 sp3 hybridization
Thus a maximum of three unpair
unpaired orbitals are available in B-atom
atom to form three electron
pair bonds with H-atoms
atoms to give BH3. But the given molecule
is B2H6, it means H3B?BH3 type situation must be there and
there are no electrons available to form the B
B-B bond in this
molecule. This anomaly has been explained as follows:
Each B-atom undergoes sp3 hybridisation. Two of the hybrid
orbitals (half filled) form two σbonds
bonds with two Ht atoms in each B- atom. Now one half filled
(shaded) orbital of say B1and empty hybrid orbital of B2 overlap jointly with half filled 1s
orbital of Hb atom to give B1HbB2 type multicentre bond. Similarly, another 3c
3c-2e bond is
formed by the overlapping of empty hybrid orbital of B1, half filled hybrid orbital (shaded)
( of
B2 and half filled 1s-orbital
orbital of another Hb-atom. These 3c-2e
2e bonds are banana shaped.
Therefore, this structure of B2H6 is also known as banana structure. Thus the Hb atoms in this

molecule may be said to show bivalence which is possible only when the two Hb atoms are
bonded with both the B-atoms forming two BHB bridging or 3c-2e bonds.
Another example of multicentre bonding is H2+ (hydrogen molecule ion) which contains a 2c-
1e bond.
4.8. BOND STRENGTH
By bond strength we mean how strong is the bond between the atoms in a molecule. Bond
length, bond multiplicity and extent of overlapping of atomic orbitals in addition to bond
energy are the factors which determine the bond strength.
It has been observed that as the bond multiplicity increases, the bond length decreases
thereby increasing the bond strength. Similarly, as the extent of overlapping between the
atomic orbitals increases, the bond formed becomes stronger. That is why a σbond is stronger
than a πbond. Another important factor influencing the bond strength is the bond energy(bond
strength ά bond energy).
4.8.1 Bond energy:
The bond energy can be explained in two ways:
(i) Bond formation energy (ii) bond dissociation energy

(i) Bond Formation Energy:
The bond formation energy of a covalent bond A-A or A-B in a diatomic molecule A2 or AB
is the amount of energy released during the formation of these molecules from the atoms A
and B.
A+A A-A + Energy released, -EA-A these are the exothermic

atoms molecule processes, hence the
A+B A-B + Energy released,- EA-B energy is shown with
atoms molecule negative sign
This can be defined as “the amount of energy released when one mole (Avogadro’s
number) of bonds are formed between the constituent atoms in gaseous state of a
molecule of A2 or AB type”. This energy is expressed in kJ mol-1.

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(ii) Bond dissociation energy

It is the energy required to break the A
A-A bond in A2 or A-B bond in A-B
B molecule into the
constituent atoms, i.e.
A-A + Energy required, + EA-A A+A these are the endothermic
molecule atoms processes and hence the
A-B + Energy required, + EA-BB A+B energy is shown with
molecule atoms positive sign
This can be defined as “the

the amount of energy required to break one mole of bonds in
gaseous state of a molecule of A2 or AB type into the constituent atoms.”
Evidently both the bond formation energy and bond dissociation energy for A-A or A-B
bonds in A2 or AB diatomic molecule are equal in magnitude but are associated with
opposite processes.
In polyatomic molecules of ABn type, n numbers of A-B
B covalent bonds are present e.g. H2O
etc. molecules have two,
three and four bonds respectively and equal number of bond dissociation energies are there.
Each bond requires 1/n bond dissociation energy in these molecules to break up that bond.
In such cases the bond energy is actually an average bond energy. For example, there are two
bonds in H2O molecule:
H2 O OH+H, DHO-H = 496 KJ Total bond dissociation energy
and OH O+H, DO-HH = 426.5 KJ of two covalent bond in H2O
molecule
= 496+426.5 =922.5 J mol-1
H bond in water is 461.2 kJ mol-1. Thus, it can be generalized
The average bond energy for O-H
as:
Average bond dissociation energy of A-B

A bond in ABn gaseous
molecule
= sum of successive A-B

B bond dissociation energires
Total number of A-B
B bonds in ABn molecule (n)
4.8.2 Measurement of bond energy:

e
i) In diatomic molecules

The determination of bond energy in a diatomic molecule containing a covalent bond
involves the measurement of heat of formation of the molecule from its free atoms. But
normally this cannot be measured directly because a compound is formed from molecules
and not from free atom as well as a compound on dissociation splits up into molecules and
not into free atoms of its component elements. Further, a molecule cannot be completely
dissociated into its free atoms merely by heating. This can, however, be obtained from heat of
reaction which, in turn, is measured from the change in the degree of dissociation with
temperature and from heat of sublimation.
ii) In polyatomic molecule
The average bond energy in a polyatomic molecule can be obtained from measured heats of
formation and heats of atomisation. For example, to obtain the average bond energy for the
C-H bond in methane, it require measurement of the heats of combustion of methane,
graphite and hydrogen gas together with the heats of atomization of graphite and hydrogen
gas.
4.9. PERCENTAGE OF IONIC CHARACTER
The percentage of ionic character of a polar covalent bond (also called polarity) depends on
two factors: (i) dipole moment and (ii) electronegativity difference between the combining
atoms. Accordingly, various methods are employed to calculate the percentage of ionic
character of a covalent bond.
i) Dipole moment (dpm) method
A polar molecule acts as a dipole i.e. Aδ+ - Bδ- (χ A<χB) because of the electronegativity
difference between the combining atoms. The degree of polarity in the molecule is given by
the dipole moment (µ) which is the product of the magnitude of the charge at each centre

(this is equal and of opposite in nature at the two centres) and the distance separating the two
centres, i.e. positive and negative.
Thus, µ = qxd, where q is magnitude of change at each centre and d is distance between the
two poles. The measured (or experimental) dipole moment (µ exp) of a molecule can be used to
evaluate the ionic character in a bond.
% ionic character = Experimental or measured dipole moment

x 100
calculated dipole moment (assuming 100% ionic character
µ exp
= x100
µ cal
= µ exp
x100
dA-B x electronic charge
where dA-B is internuclear distance between A and B atoms in AB molecule. For example,
the experimental or observed dpm of HF is 1.98D and the internuclear distance (dH-F) is
0.91Å. If the bond is taken 100% ionic in the molecule, then calculated dpm (µ cal) is
electronic charge X internuclear distance = 4.8x10-10 esu x 0.91x10-8 cm = 4.37 x 10-18 esu
cm = 4.37 D (Å=10-8cm and D stands for Debye)
.: % ionic character = 1.98/4.37 x100=45.3%
ii) Electronegativity difference method
In the polar molecule AB, polar covalent bond is present, the polarity or % ionic character
which depends on the electronegativity difference between the linked atoms and can be
evaluated by using various empirical equations.
(a) Pauling’s equation
According to Pauling, the amount of ionic character in the A-B bond is:

% ionic character = 1- e1/4(χB-χA) (χB>χA)
With the help of this equation Pauling established the following relation:
χB-χA 1.0 1.7 2.0 3.0
% ionic character ҄ 22 ҄ 51 ҄ 63 ҄ 91
This shows that when χB-χA=1.7, A-B bond has 50% ionic character and 50% covalent
character. When χB-χA>1.7, the bond has more ionic character than the covalent character
and when χB-χA<1.7, the bond has more covalent character than ionic character.
(b) Hannay and Smith equation
These two workers proposed a more simplified equation for calculation the % ionic character
in a polar covalent bond.
% ionic character = [16 (χB-χA)+3.5(χB-χA)2] (χB>χA)
Using the electronegativity values as calculated by using Pauling’s scale and this equation,
the percent ionic character of hydrogen halide (gaseous) molecules are as follows:
HF 43%, HCl 17%, HBr 13% and HI 12%
These values reveal that the hydrogen halide molecules in gaseous state, are only partially
ionic and mainly covalent.
4.10. SUMMARY
This unit of the study material consists of a concise discussion of covalent bond based on the
octet rule and deviation from the octet rule. A brief account of polar and non-polar nature of
covalent bond has been given. The valence bond theory and its limitations, directional nature
of covalent bond as well as pictorial representation along with the formation of sigma and pi
bonds have also been discussed. The concept of hybridisation has been fruitfully discussed
with examples as well as shapes of inorganic molecules and ions based on hybridisation and

valence shell electron pair repulsion theory have been given in the simple way.Molecular
orbital theory, the energy level diagrams of the molecules/ions, multicentre bond, bond
strength, bond energy and percentage of ionic character in polar covalent bonds have also
been discussed and explained.
i) The d-orbital involved in sp3d hybridisation is
(a) dz2 (b) dx2y2 (c) dxy (d) dzx
ii) Which of the following compounds contains covalent bond?
(a) NaOH (b) HCl (c) K2S(d) LiH
iii) Which of the following compounds has the least tendency to form hydrogen
bond?
(a) HF (b) NH3 (c) HCl (d) H2O
iv) Nitrogen atom in NH3 molecule is sp3 hybridised. NH3 contains a lone pair of
electron on N-atom. What is the shape of this molecule?
(a) Tetrahedral (b) square plannar
(c) Trigonal plannar (d) Trigonal pyramidal
v) Discuss the difference between a polar and a non-polar covalent bond with
examples.
vi) What do you understand by directional nature of covalent bond?
vii) What is a multicentre bond. Explain with example.
viii) Discuss the shape of H3O+.
ix) Write down theMOelectronic configuration of O2, O2+ and O-2and predict the bond order and
magnetic behaviour.

x) Write down Hannay and Smith equation for calculating the percent ionic character of a polar
covalent bond. With its help, evaluate percent ionic character present in HCl molecule (χH=
2.1, χCl=3.0).
xi) Draw molecular orbital energy level diagram for NO+ ion and predict its magnetic
behaviour.
xii) XeF2 molecule is linear though Xe atom in this molecule undergoes sp3d hybridisation.
Explain.
4.12. ANSWERS
i) (a)
ii) (b)
iii) (c )
iv) (d)
v) Please see polar and non-polar covalent bonds
vi) Please refer to directional characteristics of covalent bond
vii) Please refer to multicentre bonding
viii) Please see the VSEPR Theory
ix) Please see the MO theory
x) please refer to % ionic character of polar bond
xi) Please see the MO theory
xii) Please refer to shapes of inorganic molecules
4.13 . REFERENCES
For references and list of books consulted kindly see at the end of Unit 5.

UNIT 5 : CHEMICAL BONDING II
CONTENTS:
5.1 Objectives
5.2 Introduction
5.3 Ionic solids
5.3.1 Characteristics of ionic solids
5.3.2 Crystal coordination number
5.3.3 Radius ratio
5.3.4 Limitation of radius ratio rule
5.4 Lattice defects
5.5 Semiconductors
5.6 Lattice energy of ionic crystals
5.7 Born-Haber Cycle; experimental determination of lattice energy
5.8 Fajan’s Rule: polarization of ions
5.9 Weak interactions
5.9.1 Hydrogen bonding
5.9.2 van der Waals’Forces
5.10 Summary
5.11 Terminal questions
5.12 Answers
5.13 References
5.1. OBJECTIVE
The objective of writing the study material of this unit is to make the readers comfortable
with electrostatic attraction forces and to acquaint them with the exciting world of the ionic
crystals. An attempt has been made to through light on the type of force that holds an
extremely large number of ions together forming a bulk or cluster of ions which exists in
solid state only. At the same time the text gives an idea about why are the ions in an ionic
crystal arranged in a regular manner and have a definite ratio. It has also been tried to give a
brief account of lattice defects and semi conductors which are of immense importance

industrially. The readers must also have an idea of the covalent character of ionic bond and
weak interactions which has been taken care of.
5.2. INTRODUCTION
The solids have been classified in two different ways:
A. First kind of Classification
This classification gives two categories of solids, viz. true solids and pseudosolids.
(i) True solids-These have definite shape and volume which are retained even on long standing.
These are rigid and hence cannot be distorted. These solids have sharp melting points.
Examples are NaCl, KCl, Fe, Cu, S etc.
(ii) Pseudo solids-These do not have definite shape and volume and lose them on long standing.
These are less rigid and hence can easily be distorted. These solids melt over a range of
temperature. Examples are glass and pitch.
B. Second kind of classification
This classification is more appropriate and gives three categories of solids, viz. crystalline
solids, non-crystalline or amorphous solids and polycrystalline solids.
(i) Crystalline solids- The constituent particles (atoms, ions or molecules) of these solids are
arranged in a regular and definite manner in three dimensional space. These are said to have
long range order. They have sharp melting points and can be broken into pieces, e.g. NaCl,
sugar, diamond, graphite, sulphur etc.
(ii) Amorphous solids- The constituent particles of these solids are not arranged in a regular
manner and hence have short range order. These do not have sharp melting points, i.e. they
first soften and then change to liquid state on heating. Example are glass, rubber, plastics,
silica etc.
(iii)Polycrystalline solids- These solids occur as powder and resemble amorphous solids but their
individual particles have all the characteristics of crystalline solids.
Based on the nature of bonding forces existing between the constituent particles of crystalline
solids, these have further been categorised into five classes, viz. ionic crystals, covalent
crystals, molecular (van der Waals’) crystals, metallic crystals and hydrogen bonded crystals.
Lattice points and crystal lattice

It has been mentioned above that the constituent particles of a crystalline solid are arranged in
a regular order. The position of these particles relative to one another in the solid is
represented by points (·) which are called lattice points or lattice sites and the orderly
arrangement of these infinite lattice points is called a crystal lattice or space lattice.
Unit cell is a small unit of lattice points which on repeating infinitely in three dimensions
gives a crystal lattice. This small unit is called a unit cell of the lattice. This shows all the
properties of the crystal lattice.
5.3 IONIC SOLIDS
In these solids, the constituent particles are the ions, both positive and negative, which are
held together by strong electrostatic force of attraction. There operates a repulsive force
between the ions of same charge if these are adjacent to each other, therefore, the ions of
similar charge move away from one another and those of opposite charge come closer
together. These ions are arranged in the crystal lattice in regular pattern where the positive
ions are surrounded by a definite number of negative ions and the negative ions, in turn, are
surrounded by a certain number of positive ions. The attractive forces are maximum when
each ion is surrounded by the greatest possible number of the oppositely charged ions. The
positive and negative ions are present in the crystal lattice in a simple whole number ratio, i.e.
1:1, 1:2, 2:1 etc. The ionic solids along with other crystalline solids have been assigned seven
basic crystal systems. These systems along with types of space lattices present in the crystal
system and examples have been given below (Table 5.1):
Table. 5.1 The seven crystal systems
S. Name of the Type of space lattices Examples

No. crystal system present in the crystal
system
1 Cubic (i) Simple cubic (SC) NaCl, KCl, CaF2, NaClO2
(ii) Body-centred cubic ZnS, Cu2O, alums, diamond

(BCC)
Pb, Au, Ag, Hg
(iii) Face- centred cubic

(FCC)
2 Orthorhombic (i) Simple orthorhombic KNO3, K2SO4, BaSO4, MgSO4
(ii) Body centred Mg2SiO4

orthorhombic
Pb CO3, α–sulphur.
(iii) End – centred
orthorhombic
3 Tetragonal Simple tetragonal NiSO4, SnO2, TiO2

Body centred tetragonal
ZrSiO4, KH2PO4, PbWO4
4 Monoclinic Simple monoclinic Na2 SO4. 10 H2O

End-centred monoclinic
FeO4, CuSO4. 2H2O,
Na2B4O7. 10H2O
5 Triclinic Simple triclinic CuSO4.5H2O, K2Cr7O7, H3BO3
6 Hexagonal Simple hexagonal AgI, ZnO, CdS, HgS, PbI2,

quartz, Mg, Cd, Zn.
7 Rhombohedral Simple NaNO3, calcite, magnesite, Sb,

Bi.
The ions in a given ionic crystal are arranged (or packed) in different ways which are given
below:
(i) Hexagonal close-packed (hcp) structure, i.e. AB AB ………packing of spheres.

This structure has the packing sequence of different layers of spheres as AB AB….. In this
structure, each sphere is surrounded by 12 other nearest spheres and hence the coordination
number (CN) of each spheres is 12.
(ii) Cubic close-packed (ccp) or face-centred cubic (fcc) structure, i.e. ABC
ABC……packing of spheres.

This structure has the packing sequence of different layers of spheres is ABC
ABC………This structure has cubic symmetry. Each sphere is surrounded by 12 other
nearest spheres in this arrangement and hence the coordination number of each sphere is 12.
In both of the above structures, the coordination number of each sphere is 12 since each
sphere is surrounded by six nearest spheres lying in the same layer, three spheres lying in the
layer just above it and three spheres lying in the layer just below it. Both types of the above
structures have the same packing efficiency which is 74 %, i.e. 74 % of the total volume of
the unit cell is occupied by the spheres.
(iii)Body-centred cubic (bcc) structure-In this arrangement, there are 8 spheres at eight corners
of a cube and one sphere at the centre of the cube. Each sphere is in contact with 8 other
spheres in this structure and hence the coordination number of each sphere is 8.
Interstitial sites (holes or voids) in ionic crystals
In an ionic crystal, the bigger ions (i.e. anions) have close packed structure which may be
either hexagonal close packed or cubic close packed type. In this close-packed structure,
there is some vacant space between the anions which is called interstitial site (or hole or
void). These sites or voids are occupied by smaller ions, i.e. cations.
Depending on the number of anions and the pattern in which they surround a cation in a
given ionic crystal, there are four types of interstitial sites, viz. trigonal (C.N. = 3), tetrahedral
(C.N. =4), octahedral (C.N. =6) and cubic (C.N. =8), respectively.
5.3.1 Characteristics of ionic solids:
Following are the main characteristics of ionic solids:
(i) The constituent particles of these solids are the cations and the anions which are held together
by strong electrostatic force of attraction known as ionic bond and these exist as crystalline
solids.
(ii) The ionic bond in ionic crystals is not rigid and nondirectional, i.e. it extends equally in all
directions. Hence the ionic solids neither have any definite geometry nor show
stereoisomerism like covalent molecules.
(iii)Since the anions are generally larger in size than the cations, the anions have closest packing
arrangement in ionic solids in which there are left some empty spaces called interstitial sites
or voids. These sites may be tetrahedral, octahedral or cubic type which are occupied by the
cations.

(iv) Each ionic solid is formed from a small unit called a unit cell which contains a definite
number of cations and anions. This unit cell in electrically neutral.
(v) The ionic solids are poor or bad conductors of electricity because in solid state the ions are
fixed in their position and cannot move even if an external electric field is applied on them.
However, in fused state or in aqueous solution they conduct electricity because under these
conditions the ions are free to move. Also, the ionic solids having defects can conduct
electricity due to the movement of ions from the lattice sites to the vacancies or that of free
electrons present in them.
(vi) These solids are very hard and brittle due to the movement of one layer over the other along a
plane on applying external force.
(vii) These have lattice energy and high melting points and boiling points.
(viii) These solids are generally soluble in water or polar solvents due to ionization and undergo
ionic reactions in that medium.
5.3.2 Crystal coordination number (CCN):
We have learnt above that in ionic crystals the positive ions are surrounded by a definite
number of negative ions and vice versa. The number of ions of opposite charge surrounding
an ion in the ionic crystal is called the crystal coordination number or simply coordination
number (C.N.)
In case of ionic crystals of AB type (e.g. NaCl, CsCl, Zns etc.) in which the number of both
kind of ions is same, the C.N. of cation is equal to the C.N. of the negative ion, e.g. in NaCl
crystal each Na+ ion is surrounded by six equidistant Cl- ions and each Cl- ion, in turn, is
surrounded by six equidistant Na+ ions. Hence the coordination number of both Na+ and Cl-
ions is 6. In CsCl, the C.N. of Cs+ ion and Cl- ion, both is 8 (due to different type of packing
of ions than in NaCl).
In ionic crystals of the type AB2 or A2B (e.g. CaF2, Na2S etc.) in which the cation-anion ratio
is 1:2 or 2:1, the two types of ions have different coordination numbers. For example, in Ca
F2, the C.N. of F- ions is half to that of Ca2+ ions. The X-ray study has shown that C.N. of
Ca2+ ions is 8 and that of F- ions is 4.

5.3.3 Radius ratio (Rr):
In an ionic crystal, the arrangement of ions (packing) and their coordination number depend
on the relative size of ions or the ratio of radii of the ions which is known as radius ratio.
Thus the radius ratio (Rr) is defined as “the ratio of the radius of cation (rC+) to that of
anion (rA-) in an ionic crystal”. This can also be shown as

Rr = ಴శ Where rC+is the radiusof cation and rA-is the radius of anion, Rr is radius ratio.
ಲష
The radius ratio plays an important role in determining the structure of ionic solids
and predicting the coordination number of the cation or the anion.
Radius ratio effect
The effect of radius ratio in determining the coordination number and the arrangement
of ions (structure or packing) in an ionic crystal is known as radius ratio effect. As the cation
becomes larger with respect to the anion, i.e. Rr increases, higher number of anions can fit
around the cation and hence the coordination number of the cation increases. Which C.N. will
give the most stable arrangement of ions is dependent on radius ratio.
The relationship between the various ionic arrangements and the radius ratios is given below:
Limiting value of Coordination Arrangement of ions

೎శ
number
ಲష
< 0.155 2 Linear

0.155-0.225 3 Trigonal planar (B2O3)
0.225-0.414 4 Tetrahedral (ZnS)
0.414-0.732 4 Square planar
0.414-0.732 6 Octahedral (NaCl)
0.732-0.999 8 Body centred cubic (CsCl, CaF2)
The Rr value can be used for predicting the ionic arrangement and C.N. in the ionic crystals
as already mentioned. For example, the radius ratio for NaCl crystal is rNa+/rCl-= 0.95Å/1.81Å
= 0.525. This value lies between 0.414 and 0.732. Thus the C.N. should be either 4 or 6 and
the arrangement should be square planar or octahedral. The X- ray study of NaCl crystal has
revealed that the crystal has octahedral arrangement of ions, i.e. each Na+ ion is surrounded

by six equidistant Cl- ions and each Cl- ion has six equidistant Na+ ions. The cation-anion
stoichiometry is 1:1 and the C.N. is 6 for both the ions. Similarly, it can be shown for CsCl
(Rr = 169/181 = 0.93) that the C.N. is 8 for both the ions and arrangement of ions in the
crystal is cubic.
Let us now consider the effect of Rr on the C.N. of the ionic crystal:
(i) If the value of Rr decreases due to decreasing size of cation or increasing size of anion, the
crystal will become unstable. In this arrangement all the anions will not be able to touch the
outer surface of cation. To do so, anions will move closer to each other and repulsion
between them will increase. This repulsion pushes away one or more anions so that
remaining anions fit around the cation giving more stable arrangement and coordination
number may decrease from 8 to 6 or from 6 to 4.
(ii) It Rr increases either by increasing cationic size or decreasing anionic size, the arrangement
will not be stable. In such a case the outer surfaces of the anions will not touch each other.
On further increasing the Rr value, anions move far apart from each other and more anions
may be accommodated in the packing arrangement. As a result, the coordination number may
increase from 4 to 6 or from 6 to 8 This happens with Cl- ion in NaCl (C.N. 6) and CsCl
(C.N. 8).
5.3.4 Limitations of Rr rule:
Though the radius ratio rule is applicable to a majority number of ionic crystals, yet there are
exceptions also. Following are some limitations of this rule:
(i) The ionic radii measured are not accurate or reliable because the radius of an ion is not
constant but changes depending on its environment. It has been observed that the radius of an
ion increase about 3% when C.N. changes from 6 to 8 and decreases about 6% when C.N.
changes from 6 to 4. In such cases the radius ratio rule does not apply.
(ii) The Rr rule is valid to the packing of hard spheres of known size only. The anions are not
hard due to their large size and are polarisable under the influence of cations thereby forming
covalent bonds which are directional in nature and may prefer other orientations.
(iii) This rule does not explain the octahedral lattice arrangement of oxides of large divalent
cations such as Pb2+, Sr2+,Ba2+ etc. through they are expected to have this arrangement
(structure).

(iv) Rb halides (RbX,X = Cl, Br, I) show C.N. 6 at ordinary conditions but adopt the CsCl
structure at high pressure. Rr rule is unable to explain this observation.
(v) According to this rule, Li-halides should adopt 4-coordination structure but they crystallize in
octahedral lattice thus violating the Rr rule. It may be due to covalent character of halides of
lithium.
5.4 LATTICE DEFECTS
The packing of ions (or structure) in the ionic solids given above relate to ideal crystals. An
ideal crystal is that which has the same unit cells containing the same lattice points
throughout the whole of the crystal.
At absolute zero, most of the ionic crystals show well-ordered arrangement of ions and there
are no defects, if the crystals are ideal. With rise in temperature, however, there is a chance
that one or more of the lattice sites may remain unoccupied due to the migration of ions from
their positions to the interstitial sites or out of the surface of the crystal. This constitutes a
defect called lattice or point defect. The lattice defects in the ionic crystals are of three types:
(i) Stoichiometric defects

(ii) Non-stoichiometric defects
(iii)Impurity defects
(i) Stoichiometric defects
In the stoichiometric crystals of the compounds, the ratio of different atoms or ions is exactly
the same as indicated by the chemical formulae of the compounds. These compounds obey
the law of constant composition. If there is deviation from this ideal or perfect crystal
structure, the crystal is said to have the defect or imperfection which arises due to the
presence of cationic or anionic vacancies or dislocation of ions in the lattice structure.
Accordingly, these defects are of two types:
(A) Schottky defects
If equal number of cations and anions are missing from their lattice sites in an ionic crystal of
the type A+B- and the electrical neutrality of the crystal is maintained, the resulting defect is
called the Schottky defect. This consists of pair (s) of holes in the crystal lattice due to
missing cation (s) and anion (s).
This type of defect occurs mainly in the highly ionic compounds where
(i) The cations and anions are of similar sizes

(ii) C. N. of the ions is high, i.e. 6 or 8
Examples: NaCl, KCl, CsCl etc.
The presence of this defect decreases the density of the crystal due to missing ions.
Fig. 5.1 Schottky defect showing Fig. 5.2 Frenkel defect showing
one cation and one anion missing migration of cation to interstitial site
(B) Frenkel defects

This type of defect arises in the ionic crystals due to the departure (or migration) of an
ion, usually cation due to its smaller size, from its regular position in the lattice to the vacant
interstitial site between the lattice points. This creates a hole in the lattice. The electrical
neutrality and the stoichiometry of the crystal are maintained even after this defect is created.
This defect occurs mainly in the compounds where;
(i) There is large difference in the cationic and anionic sizes, i.e. an ions are much larger in size
than cations (Rr is low)
(ii) The C.N. of the ions is low, i.e. 4 or 6
Examples: ZnS, AgCl, AgBr, AgI etc.
Lattice vacancies (or holes) occur in almost all the ionic solids. However, Schotlky
defect occurs more often than Frenkel defect. The reason being much less energy required to
form a Schottky defect than needed to create a Frenkel defect. X-ray diffraction of Nacl
crystal has shown that at room temp., this substance has one defect for 1015 lattice sites but at
5000C 109 defects and at 8000C, 1011 defects have been observed for the same number of
lattice sites.
Consequences of the stoichiometric defects

(i) Crystalline solids having these defects are able to conduct electricity to a small extent when
an electric field is applied on them. This happens through an ionic mechanism, i.e. a nearby
ion under the influence of electric field moves from its lattice site to occupy the vacancy
present in the crystal and creates a new hole. Another nearby ion moves to occupy this
vacancy. The process in repeated many times thereby causing a hole to migrate across the
crystal which is equivalent to moving a charge in the opposite direction. In alkali halides, the
migration of cation only has been detected below 5000c but both ions migrate at higher
temperature thereby increasing the conduction.
(ii) The presence of holes lowers the lattice energy and hence the stability of the crystal. If too
many holes are present, then it may cause a partial collapse of the lattice.
(iii)The closeness of similar charges brought about by the Frenkel defect tends to increase the
dielectric constant of the crystals.
(ii) Non-stoichiomstric defects
In the non-stoichiometric crystals, the ratio of different atoms or ions present in the
compound differs from that which is required by ideal chemical formula of the compound.
These compounds do not obey the law of constant composition. In such cases, there is either
an excess of metal ions or deficiency of metal ions (or excess of anions) which creates non-
stoichiometric defect. The crystal as a whole is neutral but the crystal structure becomes
irregular. These defects can exist in a crystal in addition to the stoichiometric defects. These
defects are of two types:
(a) Metal excess defects
In these defects the positive ions are in excess. These may arise due to either the absence of
anions, i.e. the anions are missing from the lattice sites leaving the vacancies which are
occupied by extra electrons to maintain the electrical neutrality or due to the presence of extra
cations occupying the vacant interstitial sites in the lattice which are counter balanced by
extra electrons also present in interstitial space.

Fig. 5.3 (a) Metal excess defect Fig. 5.3 (b) Metal exess defect
due to missing of anion due to interstitial cation
The anion sites occupied by electrons are called F-centres which are responsible for the
colour of the compounds and their paramagnetic behaviour. The first type of metal excess
defect is produced by heating the compound with excess of metal vapours. Examples: NaCl,
KCl etc. The second type defect is observed in ZnO, CdO, Fe2O3, Cr2O3 etc.
(b) Metal deficiency defects
These defects occur in the compounds where the metal ion exhibits variable oxidation state,
i.e. the compounds of transition elements. The defect is caused either due to missing cations
from the regular positions in the lattice thus creating cation vacancies and to maintain the
electrical neutrality, the nearby cations acquire extra positive charge (examples FeS, FeO,
NiO etc.) or the defect may also be produced by the presence of extra anions in the interstitial
sites. The extra negative charge is balanced by extrapositive charge on some of the cations.
However, due to the larger size of anions, these can hardly be adjusted in the interstitial sites.
Therefore, the examples of this type of defect are rare and the defect remains merely a
theoretical possibility.
Fig. 5.4 (a) Metal deficiency defect Fig. 5.4 (b) Metal deficiency defect
due to missing cation due to an interstitial anion
Consequences of non-stoichiomtiric defects
Due to the metal excess defects the compounds show electrical conductivity because free
electrons present in the crystals can migrate easily under the electric field. Since the number
of defects and hence the number of electrons is small, so such compounds show lesser
conductance than metals, fused salts or dissolved salts. These compounds, therefore, are
termed as semiconductors. These electrons may also be excited to higher energy levels by

absorption of certain wavelengths from the white light (visible range) and are responsible for
colour of the compounds.
The crystals of the compounds with metal deficiency defects can also act as semiconductors
due to the movement of electrons from one ion of normal oxidation state to that of higher
oxidation state to create another higher oxidation at its position. This type of movement of
electrons between the ions appears as an apparent movement of positive holes thereby
making the crystal a semiconductor.
5.5 SEMICONDUCTORS (THERMAL DEFECTS AND

IMPURITY DEFECTS)
Semiconductors are the materials which have electrical conductivity at normal temperature
which isintermediate between a conductor (like metals) and an insulator. Thus, the
semiconductors allow only a portion of the applied electric field to flow through them.
According to the band theory which differentiates among conductors, semiconductors and
insulators, the semiconductors are the solids which have only a small difference of energy
between the filled valence band of electrons and an empty conduction band. This is called
band gap. If this band gap can be overcome by any means, viz. thermal energy or impurity
addition, the electrons from the filled band may go to higher energy empty conduction band
in a limited number thereby making the material to conduct electric current.
This is evident from the fact that there are some materials which may be insulators at low
temperature, (i.e. absolute zero) but become conductors at elevated temperatures (thermal
defects) or on adding certain impurities (impurity defects). These are called semiconductors,
e.g. crystals of silicon (Si) and germanium (Ge).
metal excess defects
ionic solids
In a general sense, metal deficiency defects
semiconductors may be thermal defects
nonmetals and metalloids
impurity defects
The conductivity of the semiconductors arises in the following two ways:

(i) Intrinsic semiconductors (thermal defects)

A semiconductor which is obtained by heating an insulator is called intrinsic semiconductor,
i.e. the defect in the crystal is produced by thermal energy. Pure silicon, pure germanium or
pure grey tin are some examples of materials which act as semiconductors. Actually at
elevated temperatures, sufficient amount of energy is available to break the covalent bonds in
the crystal to make some electrons free. These electrons can migrate through the crystal
leaving behind positive holes at the site of missing bonds. We can thus conclude that the heat
energy promotes some electrons from the filled band into the next higher energy conduction
band across the small energy gap and the material becomes conductor. With the rise in
temperature the conductivity of semiconductors, therefore, increases.
Fig. 5.5 Energy bands in semiconductor
(ii) Extrinsic semiconductors (impurity defects); n-type and p-type semiconductors

Certain defects in crystals arise from the presence of chemical impurities called impurity
defects. Thus the materials obtained by adding impurity atoms to the insulators and making
them conductors are called extrinsic semiconductors which are said to have impurity defects.
For example, the addition of phosphorus, arsenic, boron or gallium atoms to silicon or
germanium crystals makes them semiconductors. These are of two types:
(a) n- type semiconductors (n = normal)
If a very small amount of (say) arsenic, the element of group 15th,is added as impurity to the
pure crystal of silicon, the element of group 14, by a suitable means, the process is called
doping and we get the so called arsenic dopedsilicon. During the process of doping, a minute
proposition of Si atoms is randomly replaced by arsenic atoms with one extra electron in their
outer shell because only four outer electrons of As are required to form bonds with
neighbouring Si atoms in the lattice (Si, ns2p2& As: ns2p3, i.e. Si has 4 and As has 5 valence
electrons). At low temp., like absolute zero, these free electrons are located at the As atoms
but at normal or elevated temperatures, these free electrons migrate through the crystal lattice

to conduct the electricity in the normal way as happens in the metallic conductors. Hence this
is called n-type semiconduction and the material so obtained in known as n-type extrinsic
semiconductor. In these materials, the impurity atoms act as charge carriers.
(b) p-type semiconductors (p-positive hole)
Here the pure crystal of Si is doped with a minute quantity of gallium, an element of group 13
(Ga: ns2p1, i.e. 3 electrons in the valence shell) in which some of the Si atoms are substituted
by Ga atoms. Each Ga atom forms three electron pair bonds with neighbouring Si atoms.
Fourth neighbouring Si atom forms a weak one electron bond with Ga atom which behaves as
free electron at Si atom. This creates electron deficiency or positive hole in the lattice site
from where the electron is missing. There are as many positive holes as the number of Ga
atoms. At absolute zero, the positive hole is located at Ga atom and free electron at Si atom.
At elevated or normal temperature, these free electrons move through the crystal from one
vacancy site to another thereby leaving new vacancies or positive holes behind. Thus, it
appears that the positive holes are moving though actually it is the flow of electrons that takes
place to conduct electric current through the crystal on applying the electric field. The flow of
electrons and the movement of positive holes occurs in opposite directions. This process is,
therefore, called p-type semi conduction and the material so produced in known as p-type
extrinsic semiconductor.
5.6 LATTICE ENERGY OF IONIC CRYSTALS
An ionic crystal lattice consists of a large number of cations and anions which are considered
to be hard spheres. These ions arrange themselves in a regular pattern to attain a close packed
structure. The system gets stabilized by releasing energy during the packing process, i.e. the
potential energy of the system is decreased. This released energy is called the lattice energy
of the ionic crystal lattice. Similarly, if the ionic lattice has to be broken down into the
constituent ions, the energy required is also known as the lattice energy of the ionic crystal.
Thus, the lattice energy of an ionic crystal may be defined in two ways depending on the
process of packing of ions or their separation from the crystal-
(a) “The amount of energy released when one mole of gaseous cations and one mole of
gaseous anions are brought closer together to their equilibrium position in the stable
lattice, from an infinite distance, to form one mole of ionic crystal”. It is denoted by the
letter U.
e.g. C+ (g)+ A- (g) C+A-(s)+ Energy released (-U, exothermic process)

(s = ionic solid) ………… (5.1)

(b) “The amount of energy required to remove the constituent ions of one mole of a solid
ionic crystal from their equilibrium position in the crystal to infinite distance”.
e.g. C+A- (s) + Energy released (+ U, endothermic process) C+(g) + A- (g)
(s = ionic solid) ………… (5.2)
In both the processes, the magnitude of the energy is same, i.e., energy released = energy
required (absorbed) but the symbol of lattice energy is associated with opposite signs. The
lattice energy is a quantitative measure of the stability of any ionic solid.
Factors affecting the magnitude of lattice energy
The lattice energy of ionic crystals depends on the following factors:
(i) Charge on the two ions or the product of charges α lattice energy.Greater the charge on the
cation or the anion or greater the product of charges on the ions, greater is the magnitude of
lattice energy, U. Thus, the lattice energy of ionic crystals containing polyvalent ions is more
than those containing monovalent ions, e.g.
Ionic solids Na+F-< Mg2+F2< Mg2 O2-
lattice energy (kJ mol-). 914 2882 3895
and Li+Cl- (845 kJ mol-1) < Ca2+O2- (3460 kJ mol1)

(ii) Interionic distance (r) between the ions or ionic size α

Lattice energy is inversely proportional to the interionic distance (r) between the ions. Since r
= rC+ - rA-, smaller the size of ions, smaller will be the value of r and higher will be value of
lattice energy. For example, in case of alkali metal fluorides, the rM+ increases from Li+ to
Cs+ hence energy of these compounds decreases from LiF to CsF:
Ionic solid Li F > NaF > KF > RbF > CsF
-
Lattice energy (kJ mol ) 1034 914 812 780 744
(iii) Electronic configuration of the cation
Pure ionic crystals are generally formed by the cations having inert gas configuration in their
outershell, i.e. ns2p6 type. If the cation has non-inert gas/pseudo inert gas configuration in the
outer shell, i.e. ns2p6 d10 type, this involves covalent character in the ionic bond of the crystal
thereby increasing the lattice energy of the crystal. For example, AgCl(904kJ mol-1) has
larger value of lattice energy than that of NaCl (788kJ mol-1). AgCl has significant covalent
character while NaCl is essentially ionic because Ag+ has ns2p6d10 outer shell configuration
and Na+ has ns2p6 type configuration.

Effect of lattice energy on crystals
(i) Solubility- For an ionic solid to be dissolved in a solvent, the strong forces of attraction
between its ions (i.e. lattice energy) must over come by the ion-solvent interaction energy
called solvation energy (which is released during this interaction). For non-polar solvents,
solvation energy is small so ionic solids do not dissolve in them because lattice energy >
solvation energy. In a polar solvent like water, generally, ionic solids dissolve because the
solvation energy> lattice energy and thus ion-solvent interaction breaks the ionic solid into
constituent ions which are solvated and go into the solution.
There are some ionic solids which do not dissolve in polar solvents, viz. water. For example,
AgCl in insoluble in water. This is due to greater cohesive forces in AgCl resulting from
covalent character of ionic bond. BaSO4, SrSO4, PbSO4 etc. are also insoluble in water due to
very high lattice energy of these crystals.
(ii) Melting point - As the lattice energy increases, the melting point also increases.
5.7 BORN-HABER CYCLE: EXPERIMENTAL DETERMINATION

OF LATTICE ENERGY OF AN IONIC SOLID
Since direct experimental determination of lattice energies are not easy, there are determined
by indirect method using a thermo-chemical cyclic process known as Born-Haber cycle. To
illustrate this, we take example of formation of compound MX(s) from M(s) and X2(g). The
different steps involved in the formation of MX(s) in crystalline state are as given below;
(i) Sublimation of M (s) to M (g). In this step 1 mole of solid M absorbs energy equal to its
sublimation energy, (∆Hsub)M and is converted to gaseous state, M(g), this is an endothermic
process. (Energy is absorbed)
M (s) + (∆Hsub) M M (g) …..(5.3)

(1mole) (1mole)

(ii) Dissociation of X2 (g) to X (g). In this step half mole of X2 (g) absorbs energy equal to half

of the dissociation energy X2 (g), (∆Hdiss.)x2 and is converted to X (g). It is an endothermic
process. (Energy is absorbed):

X2 (g) + (∆ Hdiss.)x2 X (g) ………….(5.4)

(1mole)

(iii) Ionisation of M (g) to M+ (g). Each M (g) atom absorbs energy equal to its ionisation energy
(IE)M and loses its outermost electron to form M+(g). It is an endothermic process. (Energy is
absorbed):
M (g) + (IE)M M+ (g) + e- …………..(5.5)
(1mole) (1mole)
(iv) Conversion of X(g) into X- (g). The X (g) atom gains electron given by M(g) above to its
outer shell to form X- (g). In this process X(g) releases energy equal to its electron affinity or
affinity energy (EA)X. This is an exothermic process (Energy is released):
X (g) + e- X- (g) - (EA)X …………(5.6)

(1mole) (1mole)
(v) Combination of M+ (g) and X- (g) to form MX (solid). This is the final step in which M+ (g)
and X- (g) formed as above combine together to form MX(s). In this process energy equal to
lattice energy of MX, (U)MX is released. This is also an exothermic process and energy is
released:
M+ (g) + X- (g) MX (s) - (U)MX ………….(5.7)
(1mole) (1mole) (1mole)
The overall change as illustrated above may be represented in one direct step, as;

M (s) + X2 (g) MX (crystal) – (∆Hfor)MX (exothermic process) …..(5.8)
According to Hess’s Law, the heat of formation (total enthalpy change) of MX, (∆Hfor)MX
must be same irrespective of the fact weather it takes place directly in one step or through a
number of steps as illustrated above. Hence,

-(∆ Hfor)MX = (∆ Hsub)M + (∆ Hdiss)x2 + (IE)M – (EA)X – (U)MX ……….(5.9)
Here energy terms of endothermic processes are associated with positive sign and
those of exothermic processes with negative sign. With the help of the above final equation
we can determine the value of (U)MX if the quantitative values of other energy terms are
known and placing these values in the equation along with their algebraic signs. NaCl may be
taken as an example.
The whole act of above processes can also be given diagrammatically as shown below:

Applications of Born-Haber Cycle:
(i) Born-Haber cycle can be used to obtain any one of the six energy values for the six
appropriate equations given above. In particular, the value of electron affinity of the non-
metals which is most difficult to determine experimentally can be obtained by this method.
(ii) This cycle is useful in establishing the stability of ionic compounds. It is generally observed
that the lattice energy for a compound is known but standard enthalpy of formation is not. So
standard enthalpy of formation can be obtained with the help of Born-Haber cycle.
(iii) This cycle helps to understand the disproportionation reactions from lower to higher
oxidation states in metal salts, i.e. most metals fail to form stable ionic compounds in low
oxidation states such as MnCl, CaCl, AlO etc, If Born – Haber cycle is compared for MCl
and MCl2 (M = Mg, Ca etc). it can be shown that the formation of MCl2 in favoured over that
of MCl. The much higher lattice energy of MCl2 over that of MCl is the answer to this
question.
5.8 FAJAN’S RULES; POLARISATION OF IONS
In an ionic solid, both cation and anion are maintained at an equilibrium distance but when a
cation approaches an anion closely, the net positive charge on the cation attracts the electron
cloud of anion and at the same time the cation also repels the positive nucleus of anion. The
combined effect of these two forces, attractive and repulsive, is that the electron cloud of
anion (being larger in size) no longer remains symmetrical but is shifted towards the cation.

This is called distortion or polarization of the anion by the cation and anion is said to be
polarised. The ability of cation to polarise a nearby anion is called its polarising power.
Unpolarised Polarised
anion anion
Fig. 5.6 Polarisation of anion

The anion also polarises a cation but due to the larger size of anion, it polarises a cation to a
lesser extent (or almost negligible) while the polarisation of anion by a cation is appreciable,
i, e. the anions are more susceptible to get polarised. Thus, in general, the cations have high
polarising power and anions have more polarisability, i.e. the tendency to get polarised.
Due to the polarisation of anion by the cation, the electron cloud of anion is concentrated
between the nuclei of two ions and behaves as if it is being shared by the two ions. Because
of this tendency, the ionic bond in the compound passes to the covalent bond, i.e. has
covalent character. There are certain factors which affect the polarisation of the ions, These
are known as Fajan’s rules.
Fajan’s Rules: These rules are as follows:
(i) Charge on the cation or the anion
Generally the polarising power of a cation increases with increasing positive charge on it.
This is because a cation having higher charge can attract electrons effectively. This can be
seen in the anhydrous chlorides, viz. NaCl, MgCl2 and AlCl3. With increasing polarising
power of cation, the covalent character of the bond between the cation and the anion also
increases. Because the covalent compounds have lower melting points, therefore in the above
chlorides the polarising power increases in the order: Na+< Mg2+ < Al3+ and accordingly the
melting points decrease from NaCl to AlCl3 as given below:
Compound : Nacl <MgCl2< AlCl3 (covalent character increases)
Melting point (0C) : 800 > 712 > 575

Similarly, the polarisability of an anion increases with increasing negative charge on it

because the outer electron cloud is loosely held by the nucleus of the anion and also the anion
can repel its outer electrons more effectively. Thus the oxide ions, O2- in the oxides of metals
are more polarised than (say) F-ions in the fluorides of the same metals and hence the oxides
are more covalent than fluorides having lower melting points.
(ii) Size of the cation (cationic radii)
Smaller the cationic size, closer it can go to the anion and more is its polarising power. Thus,
with increasing cationic size, the power of cation to polarise an anion decreases which
decreases the covalent character of the bond between the ions. This increases the melting
points of the compounds. Let us take anhydrous chlorides of group 2nd elements, viz. Becl2,
MgCl2, CaCl2, SrCl2, BaCl2 and RaCl2. The cationic size and melting points of these
chlorides are given below:
Metal chloride BeCl2 MgCl2 CaCl2 SrCl2 BaCl2 RaCl2
Cation present Be2+ Mg2+Ca2+Sr2+ Ba2+ Ra2+
Cationic size (Å) 0.31 < 0.65 < 0.99 <1.13 < 1.35 < 1.40
Melting point (0C) 405 < 712 < 772 <872 < 960 < 1000
The covalent character decreases with increasing cationic size and melting point of the
compound and hence ionic character increases.
(iii)Size of the anion (anionic radii)
Larger the anionic size, more is its polarisalility, i.e. the tendency to get polarsed. With
increasing anionic size, the polarisalility also increases thereby increasing the covalent
character in the bond and consequently decreasing the melting point of the compounds.
Calcium halides may be taken as examples.
Calcium halide CaF2 CaCl2 CaBr2 CaI2 The covalent character of
Anion present F- Cl- Br- I- the halides increases.
Anionic size (Å) 1.36 <1.81 < 1.95 <2.16
Melting point (0C) 1392 > 772 > 730 > 575

(iv) Electronic configuration of the cation
A Cation with pseudo inert gas electronic configuration (i.e. ns2p6d10) in its outer most shell
(18 electrons) has greater polarising power, due to greater Zeff, to polorise an anion than a
cation with inert gas configuration (i.e. ns2p6) in its outer shell (8 electrons) even if both type
of cations have the same size and charge. Thus the first type of cation will polarise the anion
to a greater extent thereby resulting in a more covalent bond with lower melting point of the
compound. Let us look at two chlorides, viz. AgCl and KCl, Ag+ ion has 4s2p6d10 outer shell
electronic configuration and gives more covalent AgCl (m.p. 4550C) than KCl (m.p. 7760C)
which has K+ ion with 3s2p6 outer shell configuration.
5.9 WEAK INTERACTIONS
The force that holds the atoms together in a molecule is called a chemical bond. These
bonds viz. ionic bond, covalent bond and coordinate covalent bond are formed due to strong
attraction tendency between the species. The resulting products, i.e. the molecules or their
aggregates (sometimes) are stable species. But there are instances where only weak bonds
exist between/amongst different species, for example within molecules. In these cases, we
say that molecular forces are present between the molecules. Such species are said to have
formed by weak interactions. Hydrogen bonding and van der waals’ forces are common
examples of such molecular forces causing weak interactions.
5.9.1 Hydrogen Bonding:
This is a peculiar type of bonding which has been named after an element, hydrogen and
operates between the molecules containing hydrogen and an atom of the electronegative
elements. It is defined as “the electrostatic force of attraction between H-atom linked
covalently to an atom of highly electronegative element like F, O, N etc. in a molecule
and another atom of a highly electronegative elements of the same or different
molecule”. Thus hydrogen bond may be formed either between the molecules of same
substance or between the molecules of different substances. It is a weak bond formed by the
weak interaction and is represented by dotted line (……).
The common examples in which hydrogen bonding exists are:
H-------O H-------O H-------O H-------O

H H H H
(H2O)x Cluster
H H H H
H-------N H-------N H-------N H-------N
H H H H
(NH3)x cluster
(HF)x cluster
CH3
H C ≡≡ C ─ H --- O =C
CH3
Hydrogen bonding taking place between the molecules of same substance or different
substances.
Cause of hydrogen bond formation
When H-atom is linked with an atom of highly electronegative element (say) A atom (Amay
be F, O, N etc.) to form a polar covalent molecule HA, the molecule develops polarity like
Hδ+-Aδ- due to electronegativity difference between H and A-atoms. If this molecule comes
closer to another such molecule, e.g. Hδ+-Aδ- or Hδ+-Bδ- (B may also be F, O, N etc.), the two
dipoles will be linked together by a special type of bond through hydrogen atom, called
hydrogen bond: Aδ -Hδ+----- Bδ -Hδ+ Here H-atom acts as a bridge between electronegative
atoms A and B. This process may be repeated for several molecules to give a cluster of
molecules where H– bond is formed between any two adjacent molecules of the aggregate or
cluster.
Types of Hydrogen bonding

The hydrogen bonding in the compounds has been found of two types:
(i) Intermolecular hydrogen bonding (molecular association)
This type of H-bonding takes place between several molecules of the same substance or
different substances. The molecules get associated as a result of H-bonding to give a large
cluster. This process is known as association. The examples of this type of H-bonding are
H2O, NH3, HF etc. which have been shown above in the beginning of this topic where
association of similar type of molecules occurs. Association of C2H2 (acetylene)and
CH3COCH3(acetone) has also been shown above. Other examples of intermolecular H-
bonding are given below between the molecules of different substances:
H H CH3
H C H O H--------O H O H--------O =C
C H H H H CH3
Alcohol water Acetone
CH3
Cl H---O = C
HCl CH3
Acetone
(ii) Intramolecular hydrogen bonding (Chelating)
This type of hydrogen bond is formed between the two atoms of the same molecule, one of
the atoms being H-atom. It may lead to the linking of two groups of a molecule to form a ring
structure, the ring being generally, a five-membered or a six–membered chelate ring
(meaning claw). The examples in which intramolecular hydrogen bonding occurs are
aromatic organic molecules viz. o-nitrophenol, o-chlorophenol, salicylic acid, salicylaldehyde
etc.

Strength of H-bond
As has been stated above that this bond is a weak bond since it is merely an electrostatic force
of attraction and not a chemical bond. The strength of H-bond increases with increasing
electronegativity of the atom attached with H-atom by a covalent bond, i.e. N, O, and F. This
bond is much stronger than van der Waals’ force but about ten times weaker than a covalent
bond. The order of the strength may be given as: van der Waals’ forces < H-bond < covalent
bond < ionicbond.
Consequences of hydreogen bonding
Hydrogen bonding largely affects a number of physical properties of H-bonded

compounds. Some of them are given below:
(i) Melting and boiling points of hydrides of group 15,16 and 17 elements; the hydrides of N, O
and F among those of other elements of these groups show abnormal melting and boiling
points. This is attribute to the association of molecules caused by the formation of hydrogen
bonds. Let us take hydrides of group 16 elements, viz. H2O, H2S, H2Se & H2Te. The melting
and boiling points of H2O are exceptionally high in comparison to those of other hydrides
which show the increasing trends in these properties, i.e. H2O >>H2S >H2Se > H2Te (both
m.p. and b.p.)
(ii) Density of ice and water; like every solid crystal, ice has definite lattice structure in which
water molecules are arranged in such a way that every water molecule is surrounded by four
other water molecules in tetrahedral fashion. The central H2O molecule is linked to four other
H2O molecules by hydrogen bonding (See Fig. 5.7). Because H-bonds are weaker and longer
than covalent bonds, this arrangement gives a three dimensional open cage like structure with
large empty space within the structure. This increases the volume and decreases the density
of ice. That is way ice floats on water surface.

In liquid form water molecules lie closer together hence the same mass of water has smaller
volume and its density is more than that of ice.
Fig. 5.7 Open cage like crystal structure of ice

(iii) Density of water is maximum a 40C; When ice melts, the cage like structure breaks down and
the molecules of water are packed closely together, thereby decreasing the volume. The
breaking of structure (i.e. hydrogen bonds) is not completed until the temperature reaches
40C. Above 40C, expansion commences thereby increasing the volume. Thus, the volume of

water is minimum and density is maximum (density = ) at 40c.
5.9.2 van der Waals’ Forces (or Intermolecular forces):

The weak attractive forces between the uncharged atoms or molecules of polar as well as
non-polar substances are collectively referred to as van der Waals’ forces. The magnitude of
these forces is maximum for solids and decreases for liquids and minimum for gases. The
crystals whose constituent particles are held together in position by these forces are called
molecular crystals. These forces arise from the electrostatic attraction of the nuclei of one
molecule for the electrons of a different molecule. The repulsions between the electrons of
the two molecules and the nuclei of the two molecules try to counter balance the electrostatic
attractions but there is always a small net attractive force. Van der Waals’ forces are short
range forces. These forces are due to different type of interactions which are given below:

Fig. 5.8 Dipole-dipole interaction (head to tail arrangement)
(i) Dipole-dipole interaction

These interactions are present in polar molecules like NH3, SO2, HCl etc. (all gases).
Although these molecules are neutral, they have permanent dipole moments and behave as
dipoles. Larger the dipole moment of a molecule, greater is the dipole-dipole attractive force
between the molecules. Actually in the dipoles, the van der Waals’ forces are due to the
electrostatic interactions between the positive end of one dipole and the negative end of the
other dipole.
(ii) Ion-dipole interaction

If a charged particle such as an ion is introduced into the neighbourhood of an uncharged
nonpolar molecule (e.g. an atom of a noble gas), it will distort the electron cloud of the atom
or molecule in the same way as a cation does on a large anion (polarisation). The polarisation
of neutral species depends on its inherent polarisability and polarising field afforded by the
charged ion (±). Such interactions occur only in solution of ionic compounds in non-polar
solvents.
(iii) Dipole- induced dipole interaction
A dipole can induce an uncharged non-polar species into a dipole as does an ion in ion dipole
interaction. Then there occurs dipole induced dipole interaction. These are important only in
solution of polar compounds in non-polar solvents.
(iv) London or dispersion forces (instantaneous dipole-induced dipole interactions)
These interactions are present in non-polar molecules like N2, O2, Cl2, CH4 etc. and mono
atomic molecules like He, Ne, Ar etc. These molecules do not have permanent dipole
moment. The average electronic distribution in a non-polar molecule is symmetric but
because of continuous motion of the electrons, at any given instant, the centres of negative
and positive charges may not coincide. This causes a momentary distortion of the electronic

charge cloud which results in an instantaneous temporary polarity. Then this instantaneous
dipole may induce polarity in another non-polar atom/molecule. These two dipoles attract
each other by electrostatic forces called London forces.
Since van der Waals’ forces are weak and may be easily overcome, the condensed gas readily
vapourises and molecular crystals are soft and have low melting points.
Fig. 5.9 Instantarery dipole dipole induced dipole interaction between non-polar
5.10 SUMMARY
This unit consists of a brief discussion of ionic solids, their characteristics, the interesting
topic of radius ratio and its effect, crystal coordination number and limitations of radius ratio
rule. The lattice defects have been fruitfully discussed and an elaborate account of
semiconductors has been given. A concise account of lattice energy, the factors affecting its
magnitude and its experimental determination has been discussed. The rules governing the
covalent character of ionic bond, a brief discussion of H-bond and van der Waals’ forces have
also been taken care offor the readers.

i. The coordiniation number of Cl- ion in NaCl crystal is:
(a) 4 (b) 6 (c) 8 (d) 12
ii. CsCl crystal has the packing pattern of ions:
(a) Cubic (b) Tetrahedral (c) Octahedral (d) Square planar
iii. If one cation and one anion are missing from their positions in a crystal lattice, the defect
produced is:
(a) Schottky defect (b) Frenkal defect (c) n-type defect (d) p-type defect
iv. Which one of the following will have covalent character?
(a) LiCl (b) NaCl (c) KCl (d) CsCl
v. How do the ionic crystals behave towards the electric field applied on them in solid state,
fused state and in solution?

vi. Give a brief account of n-type semi conductors.

vii. How is lattice energy of an ionic compound related with its solubility in polar solvent?
viii. What is polarization of ions?
ix. What is the cause of H-bonding in the compounds?
x. We have two cations. One of them has pseudo inert gas outer shell electronic configuration
and the other has inert gas configuration in the outer shell. Which of these will cause more
polarisation of an anion?
xi. Give a brief account of London forces.
5.12 ANSWERS
i. (b)
ii. (a)
iii. (a)
iv. (a)
v. Please refer to characteristics of ionic compounds.
vi. Please see semiconductors.
vii. Please refer to the effect of lattice energy on crystals.
viii. Please refer to polarisation and Fajan’s rules.
ix. Please see H-bonding.
x. Please refer to Fajan’s rules.
xi. Please see van der Waals’ forces.
5.13 REFERENCES: LIST OF BOOKS CONSULTED

8. Principles of Inorganic Chemistry: B. R. Puri, L.R. Sharma & K. C. Kalia,
Milestone Publishers and Distributers, Daryaganj, Delhi (2013).
9. Selected topics in Inorganic Chemistry: W.U. Malik, G.D. Tuli & R.D. Madan, S. Chand &
Co. Ltd., New Delhi (1993).
10. Comprehensive Inorganic chemistry: Sulekh Chandra, New Age International (Pvt.) Ltd.,
New Delhi (2004).
York (1960).
London (1967).

13. Advanced Inorganic Chemistry: Satya Prakash, G.D. Tuli, S.K. Basu and R.d. Madan, Vol. I,
7th Edn., S. Chand & Co. Ltd, New Delhi (1998).

UNIT6: HYDROGEN
CONTENTS:
6.1 Objective
6.2 Introduction
6.3 Protic and aprotic solvents
6.3.1 Isomers of hydrogen
6.4 Reactions in non-aqueous solvents
6.5 Summary
6.6 Terminal question
6.7 Answers
6.1. OBJECTIVE
The objective of writing the course material of this unit, i.e. on hydrogen, the first and the
lightest element of the periodic table, is to make it easy for the readers to understand its
various aspects such as its isotopes and their nature, its isomers, its oxides, viz. heavy water
and hydrogen peroxide and its compounds with various elements called hydrides etc.
6.2. INTRODUCTION
Cavendish in 1766 while studying the comparative effect of dilute acids on metals like zinc,
tin and iron discovered that a similar gas was liberated in each case and named that gas a
inflammable air because it burnt on ignition. This gas was given the name hydrogen (from
hydra, a Greek term meaning water forming) by Lavoisier who noticed that on burning in air,
the gas produced water. Hydrogen occurs free in nature only in traces, about 1part in1.5
million parts of air and in volcanic regions. The sun’s atmosphere is said to contain
appreciable amounts of hydrogen as revealed by solar spectra. It occurs most commonly in
combination with oxygen as water and to a much smaller extent in combination with carbon,
sulphur, nitrogen and halogens. All organic matter contains hydrogen combined with carbon,
nitrogen and oxygen.
Hydrogen shows the unique property of the existence of a typical bonding called after its
name, the hydrogen bonding present in the biomolecules (RNA, DNA etc.) or in other simple
molecules. Hydrogen also exhibits the prevalent nuclear spin isomerism (i.e. ortho and para

forms). Because of its dual behaviour, i.e. resemblance with alkali metals in some properties
and halogens in some other aspects, it can be placed in Group 1(of alkali metals) or Group17
(of halogens) of the periodic table.
6.3. ISOTOPES OF HYDROGEN
It has been established by mass spectrometry that hydrogen has three isotopes each with
atomic number 1 and mass numbers 1, 2 and 3, respectively. They differ to a great extent in
their physical properties as there is comparatively a large difference in their atomic masses.
Because of the similar electronic configuration, they have similar chemical properties. Their
names, symbols, mass numbers and relative abundance are summarized in Table 6.1.
Table 6.1 Isotopes of Hydrogen
Name Symbol Atomic Mass Number Percentage

Number abundance
Protium or ordinary 1 1 (1 proton only) 99.984
1
hydrogen 1H
2
Deuterium or heavy 1H 1 2 (1Proton+1 0.016
hydrogen neutron)
3
Tritium or Radioactive 1H 1 3 (1proton+ 2 10-15
hydrogen neutron)
(i) Protium or ordinary hydrogen (1H1):
It is the most common isotope of hydrogen and constitutes 99.984 percent of total hydrogen
available in nature. Its nucleus consists of one proton only, that is why its mass number is 1.
(ii) Deuterium or heavy hydrogen (1H2 or 1D2)
This isotope of hydrogen called deuterium occurs in nature only in traces, i.e. about 1 part in
6000 parts of hydrogen or about 0.016 percent. Its main source is heavy water (D2O) from
which it is separated mainly by electrolysis. Its nucleus consists of 1 proton and 1 neutron
(mass number 2). Generally, this isotope is represented by the symbol D and referred to as
heavy hydrogen.

(iii) Tritium or radioactive hydrogen (1H3 or 1T3):
Hydrogen’s this isotope is formed in the upper atmosphere only by certain nuclear reactions
induced by cosmic rays. It constitutes only 1x10-15 percent of total natural hydrogen i.e. 1
molecule in 1017 molecules of H2. Its nucleus consists of 1proton and 2 neutrons (mass
number 3 ). Unlike deuterium, it is radioactive with a half- life of 12.4 years and hence is
present in nature only in traces. Generally, this isotope is given by the symbol T and is
referred to as radioactive hydrogen.
It is to be noted that since the quantities of D2 and T2 present in natural hydrogen are
exceedingly small, the properties of natural hydrogen are substantially those of protium.
Isotope effect:
Because of similar electronic configuration (1s1) all the three isotopes are chemically
identical. But these isotopes show a quantitative difference in their reaction rates i.e. for
heavy isotopes reaction rates are slower and equilibrium constants, e.g. the dissociation
constant (K) for heavy water is significantly smaller than that for ordinary water:
H2 O ⇌ H+ + OH- ; K= 1 x 10-14
D2 O ⇌ D+ + OD- ; K= 0.3 x 10-14
The mass difference of isotopes of hydrogen has marked effect on the rates of
chemical reactions, e.g.
(i) A bond to a protium atom can be broken as much as 18 times faster than that to a deuterium
atom. Thus protium has been found to react with Cl2 about 13.5 times faster than deuterium
does.
(ii) The addition of H2 to ethylenic compounds takes place about two times faster than that of D2
at the same temperature.
(iii) Protium has been found to adsorb more rapidly over the solid surfaces than deuterium.
These examples show that reactions with deuterium are slower than those with protium.
Such differences in properties which arise due to the difference in masses of the isotopes
are termed as isotopic effect.

Now let us discuss the isotopes one by one
A. Protium or ordinary hydrogen (1H1):
This isotope does not need to be discussed in detail, hence discarded.
B. Deuterium or heavy hydrogen (1D2 or 1H2):
The presence of very small amount of heavy hydrogen with mass 2 in the ordinary hydrogen
was indicated by various workers. On the basis of these clues, Urey and coworkers worked
further and showed that a residue obtained by fractional evaporation of liquid hydrogen at
reduced pressure when examined spectroscopically, was found to contain an isotope of mass
number 2. This isotope was called heavy hydrogen and named deuterium by Urey. It was
assigned the symbol D.
Preparation:
Deuterium has been obtained either from ordinary hydrogen or from heavy water.
(i) From ordinary hydrogen (or Protium):
Ordinary hydrogen contains deuterium, though small (0.016 percent) and hence can be used
as the source of deuterium. From ordinary hydrogen deuterium has been separated by
employing various techniques which are discussed below:
(a) By diffusion process:
Deuterium can be isolated directly from ordinary hydrogen gas by taking the advantage of
different rates of diffusion of the two isotopes. The process is carried out in a series of porous
diffusion chambers called Hertz diffusion units, each unit consisting of porous membrane.
When ordinary hydrogen gas is led into diffusion units under reduced pressure with the help
of mercury diffusion units, protium being lighter, diffuses more readily than deuterium which
diffuses at slower rate and is left behind. The process is repeated several times till, protium is
collected in the reservoir on the right and deuterium is collected in the another reservoir on
the left side. The efficiency of the process is increased by carrying out the diffusion at
reduced pressure and increasing the number of units. The apparatus used for this process is
shown in Fig. 6.1

INORGANIC CHEMISTRY
CHEMISTRY-I BSCCH
BSCCH-101
Although this process is slow and tedious, yet it gives absolutely pure deuterium such that the
spectrum of deuterium so obtained shows no traces of ordinary hydrogen.
(b) By fractional distillation of liquid hydrogen

hydrogen:
Deuterium can also be separated from ordinary hydrogen by ye

yett another process, i.e.
fractional distillation of liquid hydrogen. The boiling point of protium is lower (-)252.80C
than that of deuterium (-249.50C
C).
). Hence the fractionation process results in the enrichment
of later fractions in deuterium. From the deuterium
deuterium enriched fractions, it can be recovered by
the diffusion process as given above.
(c) By adsorption on charcoal

charcoal:
It has been observed that charcoal has different adsorption power for the two isotopes of
hydrogen, i.e. 1H1 and 1H2. Protium is adsorbed more readily and strongly on its surface than
deuterium. The difference in adsorption of these isotopes can be used for their separation.
The mixture of two isotopes is passed over charcoal kept at liquid air temperature, when most
of the protium gets adsorbed while most of the deuterium passes out unadsorbed. By
repeating the process, a deuterium enriched fraction is obtained from which deuterium can be
isolated from protium by the usual diffusion process.
(ii) From heavy water:
Ordinary water contains

ntains 1 part in about 6000 parts of heavy water (D2O) and is the important
source of it. Heavy water can be separated from ordinary water by employing various
physical methods such as multi-- stage electrolysis, fractional distillation, fractional freezing,
freezin
preferential adsorption etc. as well as chemical methods such as exchange reactions etc. (The

details of these methods will be discussed ahead in the chapter under heavy water.). From
heavy water, deuterium can be obtained by any of the following methods:
(a) By decomposition of D2O:
This can be done with sodium metal, Mg – shavings at high temperature, red hot iron, heated
W – filament, heated zinc turnings or uranium.
(i) 2Na (metal) + D2O 2NaOD + D2 ↑
This method is used when small quantity of D2 has to be prepared.
(ii) Mg (savings) + D2O (vapours) MgO + D2 ↑
When a large quantity of D2O is required, this method is used.
(iii) 3Fe (red hot) + 4D2O (steam) Fe3O4 + 4D2 ↑
↑2W (heated) + D2O (vapors) W2O + D2 ↑
Zn (turnings) + D2O (vapour) ZnO + D2 ↑
(iv) U + 2 D2O UO2 + 2D2 ↑ (pure D2)
2U + 3D2 2UD3 2U + 3D2 ↑
The last method using uranium (U) gives pure D2. It can also be stored as UD3 for the
production of D2 when required.
(b) By electrolysis of D2O:
D2 can also be obtained from pure D2O by the electrolysis of acidified heavy water in an
evacuated all glass apparatus using Pt-electrodes when D2 is liberated at cathode.
2D2O electrolysis 2D2 ↑ + O2 ↑

Cathode Anode
D2 obtained by this method may contain O2 and D2O vapours. When it is heated over
platinised asbestos and dried at liquid air temperature, both O2 and D2O vapours are removed.
Physical Properties:

The properties of deuterium (D2) are slightly different from ordinary hydrogen (H2). It also
exists as a diatomic molecule and is insoluble in water and bad conductor of heat and
electricity. Its melting and boiling points are slightly higher than those of ordinary hydrogen
due to its higher mass number, e.g.
H2 D2
0
Melting point ( C) (-)259.2 (-)254.5
0
Boiling point ( C) (-)252.8 (-)249.3
Chemical properties:
The chemical properties of deuterium are similar to those of hydrogen, the only difference is
that deuterium reacts at slower rate than hydrogen.
i) Burning in oxygen:
It is combustible like hydrogen and burns in oxygen or air at elevated temperature to give its
oxide (heavy water).
2D2 + O2 2D2O
ii) Reaction with halogens:
It combines with halogens under suitable conditions to form deuterium halides, e.g.
D2 + Cl2 in light 2DCl
D2 + Br2 on heating 2DBr
D2 + F2 in dark and 2DF

cold
iii) Reaction with nitrogen:
In presence of a catalyst, it combines with nitrogen to form deutero – ammonia (or deuterium
nitride).
3D2 + N2 cata. 2ND3
iv) Reaction with metals:

It combines with alkali metals at high temperature to form deuterides which resemble with
alkali metal hydrides.
2Na + D2 2NaD
These deuterides are hydrolysed easily to give deutero hydrides
NaD + H2O NaOH + DH (or HD)
v) Addition reactions:
Like hydrogen, it gives addition reactions with unsaturated hydrocarbons in presence of

catalyst and at high temperature but at slower rate.
CH2 = CH2 + D2 Ni CH2D CH2D (deutero ethane)

2600C
vi) Exchange reactions:
Deuterium and hydrogen atoms undergo ready exchange under suitable conditions, e.g. at
high temperature it reacts with H2, NH3, CH4 etc. and slowly exchanges their hydrogen
partially or completely.
H2 + D2 ⇌ 2HD
2NH3 + 3D2 ⇌ 2ND3 + 3H2
CH4 + 2D2 ⇌ CD4 + 2H2
Some exchange reactions can be catalysed by finely divided nickel, chromium, palladium or
Pt- black, e.g.
C6H6 + 3D2 Pt-black C6D6 + 3H2

H2 O + D2 cata. D2 O + H2
Acetylene, acetone and acetyl acetone undergo ready xchange reactions in alkaline solution.
C2H2 + D2 C 2 D2 + H2
Deutero acetylene
This reaction is due to the weakly acidic character of C- H bond in acetylene.
vii) Reducing Property:

It reduces certain halides at high temperature, e.g. when D2 is passed through the suspension
of AgCl at very high temperature of about 7000C, AgCl is reduced to metallic Ag.
D2 + 2AgCl 2Ag + 2DCl
Uses of D2:
(i) Accelerated deuterons (deuterium nuclei) are employed for bombarding atoms in the
nuclear transformation of elements and artificial radioactivity.
(ii) Its oxide, D2O, known as heavy water, is used as a moderator in the nuclear reactors for
slowing down the speed of the fast moving neutrons.
(iii) Deuterium and its compounds are used as tracers in the study of mechanism of various
chemical and metabolic reactions taking place in the body because deuterium with higher
mass number increases the density of the compound.
C. Tritium or radioactive hydrogen (1H3 or 1T3):
Tritium is a rare isotope of hydrogen and its oxide, T2O, is present in water in extremely
minute quantities. Though this is present in atmosphere only in traces, yet is produced
continuously in upper atmosphere by the reaction of neutrons on atmospheric nitrogen. These
neutrons are generated by the action of cosmic radiations on the atmospheric gases.
1
Atmospheric gases + cosmic rays 0n
14 1 12
7N + 0n 6C + 1T3 (or 1H3)
Production of Tritium:
Tritium has been obtained, in small quantities, by the certain nuclear reactions given below:
(a) Bombardment of deuterium compounds viz. D3PO4, ND4Cl etc. with high energy
deuterons.
2
1D + 1D2 1T
3
+ 1H1
(b) Deuterium induced reactions, e.g.

9
4Be + 1D2 4Be
8
+ 1T3
7
3Li + 1 D2 3Li
6
+ 1T3
(c) Neutron induced reactions
10 1 11 3
5B + 0n 5B 1T + 2 2He4
6 1
3Li + 0n 1 T3 + 2He4
The last one is the best method of obtaining tritium.
Properties:
Because of the unfavourable neutron to proton ratio, tritium is radioactive (unstable) isotope
of hydrogen with a half life of 1̴ 2.4 years. It decays emitting low energy β- particles and is
transformed into a lighter isotope of helium, 2He3.
3 3
1T 2He + -1e0 (β- particle)
Because of this decay, traces of 2He3 are present in the atmosphere. Its melting point is
(-)252.40C and boiling point is (-)248.10C. Being an isotope of hydrogen, it shows similar
chemical properties to that of hydrogen and deuterium but reacts at much slower rate, even
slower than those of deuterium.
For example,
(i) On burning in O2 or air, it gives T2O

2T2 + O2 2T2O
(ii) It combines with H2, on heating to 300 to 4000C, forming tritium hydride.
H2 + T2 2HT (or TH)
HT reacts with HCl to give tritium chloride
HT + HCl TCl + H2
Uses:
(i) It is used as a radioactive tracer in chemistry, biology and medicine.

(ii) It is also used in nuclear fusion reactions such as
2
1D + 1T3 4 1
2He + On + Energy
In the fusion reaction huge amount of energy is released which is used in hydrogen bomb
(Thermonuclear process).
(iii) It is used as the source of tritons which are employed in several nuclear transformations.
(iv) TH is an important compound for the preparation of a number of organic compounds

containing this radioactive isotope.
6.3.1 Isomers of hydrogen:
Hydrogen exists in two isomeric forms, first revealed in 1929 by Bonhoeffer and Harteck
from spectral studies, known as ortho and para hydrogen. These two forms are isomeric and
differ apparently only in their nuclear spins. That is why hydrogen is said to exhibit nuclear
spin isomerism and the two forms are called nuclear spin isomers.
It has been observed that the nucleus of hydrogen atom spins about its own axis like a top as
does an electron. Because the hydrogen molecule is composed of two hydrogen atoms
containing, as is well known, a proton in the nucleus and an electron revolving around it.
When two hydrogen atoms combine to form the molecule, two types of hydrogen molecules
should be formed, one having the spins of the two nuclei parallel or aligned (i.e. in the same
direction) and the other having the nuclear spins antiparallel or opposed (i.e. in the opposite
direction). The former variety is known as ortho hydrogen and the latter as para hydrogen,
respectively.
The two types of hydrogen molecules have been discussed below:
(i) Ortho hydrogen molecule:

The hydrogen molecule in which the nuclei (protons) of both the combining hydrogen atoms
spin in the same (i.e. parallel) direction is termed as ortho hydrogen (Fig 6.2a). In this form

the resultant nuclear spin is one (i.e.+ + + = 1).

(ii) Para hydrogen molecule:

The hydrogen molecule in which the nuclei (protons) of both the constituent hydrogen atoms
spin in the opposite (antiparallel) direction is called para hydrogen. (Fig 6.2b). In this form

the resultant nuclear spin is zero (i.e. + + - = 0).

It is to be noted that the two electrons in both the ortho and para forms of hydrogen molecules
always spin in the opposite directions to result in the stable molecular structure.
Difference between ortho and para hydrogen molecules
(i) Internal molecular energy:

The two forms of hydrogen differ in their internal molecular energy which is attributed to the
fact that in case of ortho hydrogen molecule, the spins of the two nuclei (protons), being in
the same direction, increase the molecular energy of this form.
On the other hand, in para hydrogen molecule, the spins of the two nuclei (protons) being in
the opposite direction, neutralise (or cancel) each other. The neutralisation of spins decreases
the molecular energy of para hydrogen molecule. Thus the para form has lower internal
energy than the ortho form.
(ii) Physical properties:

The physical properties such as melting point, boiling point, thermal conductivity and
specific heat of both the forms are different from each other. Some physical constants of para
form are given below whereas those of ortho form have been left blank because the ortho
from is difficult to be obtained in a pure state.
Ortho form Para form

Melting point (0C) - (-)259.170C

Boiling point (0C) - (-)252.740C

(at 760 mm)
Vapour pressure(mm) at 751 737
0
(-)253 to (-)243 C
The magnetic moment of parahydrogen is zero because of the neutralisation of nuclear spins
while that of ortho form obtained from the data for known ortho-para mixture is
approximately twice the moment of a proton.
The appreciable difference in the thermal conductivities of the two forms is used to estimate
the percentage of ortho and para forms in a given sample of hydrogen.
(iii) The ortho form is more stable than the para form and hence the latter ( i.e. para form) has a
tendency to change into the ortho form.
(iv) Effect of temperature on the relative proportions of the two forms in ordinary
hydrogen.
Ordinary hydrogen gas (H2) is an equilibrium mixture of ortho and para hydrogens,
Ortho H2 ⇌ Para H2 and their relative proportion (i.e. ortho-para ratio) in the gas is
dependent on temperature. It has been shown that at absolute zero molecular hydrogen
consists mainly of the para form and the ratio of para to ortho forms is 1:0 (approximately).
As the temperature increases, the proportion of ortho form gets increased and that of para
form decreases. At the temp. of liquefaction of air, the ratio of ortho to para forms has been
found ot be 1:1 and at room temperature, 270C, this ratio is 3:1 and remains constant
thereafter. This means that it is rather impossible to get pure ortho hydrogen at any
temperature, i.e. the above equilibrium cannot be shifted entirely in favour of ortho H2.
However, this equilibrium shifts towards the right, i.e. para H2, on decreasing the temperature
up to near absolute zero when the sample of molecular hydrogen has mainly para hydrogen.
This situation has been shown by graphical representation as below in Fig 6.3.

(v) Both the forms have different band spectra and this fact was used to demonstrate the
existence of ortho and para hydrogens.
Separation of pure para form of H2 from ordinary hydrogen:
In order to separate almost pure para form from ordinary hydrogen, the latter is passed
through a tube packed with activated charcoal and cooled in liquid air or liquid hydrogen for
about four hours. The para form thus obtained is pumped off and is about 99.5% pure. The
para hydrogen can be stored in glass vessels at room temperature for about a week with
appreciable change into ortho form.
Conversion of para hydrogen into ortho form:
Since ortho form of hydrogen is more stable, it can be easily transformed into the para form.
However, the process P O hydrogen is accelerated by the following methods:
(i) by passing an electric discharge through it
(ii) by heating it to high temperature of about 8000C and above.
(iii) with the help of catalysts like platinised asbestos.
(iv) by mixing it with paramagnetic molecules, viz. O2, NO2, NO in gas phase or ions like Mn2+,
Co2+, Ni2+ etc. in solution.
6.4 HYDRIDES
The binary compounds of hydrogen with other elements whose electronegativity is lower
than that of hydrogen (i.e. 2.1 on Pauling’s scale) are generally called hydrides. This
definition excludes the binary compounds of hydrogen with non-metallic elements like H2O,
NH3, PH3, H2S, HF, HCl, HBr, HI etc. But on the basis of type and nature of bonding in the
compounds of hydrogen, Gibb (1941) has classified them into the following types:
(a) Ionic or salt like hydrides

(b) Covalent or molecular hydrides
(c) Metallic or interstitial (alloy type) hydrides
(d) Complex hydrides
(e) Borderline hydrides
(a) Ionic or salt like hydrides

The hydrides of the elements of groups IA, IIA (e.g. LiH, CaH2 etc.) and some highly
electropositive lanthanides and actinides are called ionic hydrides (Fr of group IA and Be and
Mg of group IIA are the exceptions).
Preparation
These hydrides can be prepared by any of the following methods:
(i) By heating the metals in a current of H2

Alkali and alkaline earth metals when heated at different temperatures in a current of H2 give
ionic hydrides.
2M + H2 4000C 2MH (M= Na, K etc.)

M+ H2 152-3000C MH2 (M= Ca, Sr, Ba)
Li kept in a hard glass tube in an iron boat combines with H2 at 6000C to give LiH
2Li + H2 2LiH
(ii) By heating carbonates in a current of H2
Certain alkali metal carbonates when heated in a current of H2 at high temperature of about
620 - 6500C and in the presence of Mg give hydrides, e.g. RbH, CsH etc.
Rb2CO3 + 2H2 2RbH +CO2 + H2O
Mg
(iii) By heating metal nitride with H2 gas.
LiH is prepared by this method.
2Li3N + 3H2 6LiH + N2
(iv) CaH2 may be prepared by heating CaO with metallic Mg in a current of H2 at high temp. and
optimum pressure:
CaO + Mg + H2 2500C Ca H2 + MgO
~ 50 cm
This is a quick method and the yield is high (99.2%).

Properties
These hydrides are crystalline compounds with ionic lattices, hydrogen acting as
electronegative element. These have high melting and boiling points and conduct electricity
when fused. The crystals of hydrides are somewhat denser than the parent metal itself

because of strong polar bonds existing in the lattice. Except LiH, they decompose on fusion.
All these hydrides are stoichiometric compounds.
(i) Thermal stability and order of reactivity
The hydrides of Li, Ca and Sr are stable while others decompose above 4000C. In a particular
group their thermal stability decreases with increasing size of the cation, i.e. down the group:
LiH > NaH > KH > RbH > CsH

CaH2 > SrH2 > BaH2
This has been supported by the decreasing values of heats of formation of these hydrides.
Hence the relative order of the reactivity is as: LiH < NaH < KH < RbH < CsH.
(ii) Electrolysis: Presence of hydride ion

When these hydrides are electrolysed in their fused states, they liberate hydrogen at the anode
showing the presence of H- ions in them.
(iii) Action of protonic solvents
They all react vigorously with protonic solvents such as H2O, NH3, C2H5OH etc. forming a
base and liberating hydrogen.
MH M + + H-
H- + H2 O OH- + H2
H- + NH3 NH2- + H2
H- + C2H5OH C2H5O- + H2
(iv) Reducing property
All these hydrides show reducing property at high temperature which is attributed to the
formation of atomic hydrogen. They reduce refractory metal oxides to free metal, chlorides of
some semimetals to hydrides, sulphates to sulphides etc.
4NaH + Fe3O4 3Fe + 4NaOH
4NaH+ SiCl4 SiH4 + 4NaCl
2CaH2 + PbSO4 PbS + 2Ca(OH)2
(v) The alkali metal hydrides possess face-centred cubic lattice while alkaline earth metal
hydrides have orthorhombic lattice.
(vi) Reaction with Nitrogen
The hydrides are converted to the nitrides on treating with Nitrogen
6LiH + N2 2Li3N + 3H2

3CaH2 + N2 Ca3N2 + 3H2

(vii) Complex hydride formation
Only LiH reacts with AlCl3 in ether forming LiAlH4 which is an important reducing agent.
4LiH + AlCl3 (in ether) LiAlH4 + 3 LiCl
Uses
These hydrides are used as condensing agents in organic chemistry. Because these are
hydrolysed by water giving large quantities of H2, they are used as reducing agents. LiH and
CaH2 are used as the source of hydrogen for balloons. LiH, NaH and CaH2 are the important
members of such hydrides.
(b) Covalent or molecular hydrides
These hydrides are formed by most of the p-block elements, may these be metals, metalloids
or non-metals. The binary compounds with non-metals are excluded from the class of
hydrides and those of metalloids and metals (both p-block) are included. The elements, e.g.
Sn, Pb, Sb, Bi, Te, Po etc, give only mononuclear hydrides while the elements like B, Al, Ga,
In, Si etc. give mono nuclear as well as polynuclear (or polymeric) hydrides as follows:
B B2H6, B4H10, B5H9 etc
Al AlH3, (AlH3)n
Ga Ga2H6, Ga3H8 etc.
In (In H3)n
Si SiH4, Si2H6, Si3H8 etc.
Preparation
(i) By the hydrolysis of compounds
Mg3B2 + 6HCl 3MgCl2 + B2H6
Mg2Si + 4HCl 2MgCl2 + SiH4
Zn3As2 + 6HCl 3 ZnCl2 + 2AsH3
(iii) By the reducition of anhydrous chlorides with LiAlH4
MCl4 + Li AlH4 MH4 + LiCl + AlCl3

Properties
In these hydrides H-atom forms covalent bond with central atoms. They exist as discrete
molecules held together (in polymeric compounds) by weak van der Waals’ forces or
hydrogen bonds. Hence these are gases, liquids or solids (with low melting and boiling
points).
(i) Thermal stability
In a group, thermal stability decreases with increasing atomic number or metallic character of
the elements forming hydride, e.g. AsH3 > SbH3 > BiH3. Thus the hydrides of predominantly
metallic elements (e.g. PbH2 and BiH3) are unstable.
(ii) Property of behaving as Lewis base or Lewis acid
Electron rich hydrides show this property which decreases down a particular group, e.g.
AsH3>SbH3. Some hydrides, viz. B2H6, (AlH3)n are electron deficient and hence behave as
Lewis acids.
B2H6 + 2 : PF3 2[BH3 : PF3]
(AlH3)n + n:NR3 n[AlH3 : NR3]
(iii) Formation of complex hydrides
Some covalent hydrides react with ionic hydrides to form complex hydrides, e.g.
B2H6 + 2MH 2M [BH4] (M=Li or Na)
Borohydride
AlH3 + LiH Li (AlH4)

Li- Al hydride
Uses
Boron hydrides are used as fuels and fuel additives. Silane (SiH4) is used as a source of pure
Si employed in transistors.
Hydrides of Boron: Boranes
These will be discussed in Unit 9 ahead.
Hydrides of Silicon: Silanes
These are represented by the general formula SinH2n+2 like alkanes. Members of this series up
to n = 6 are definitely known. In addition, silico ethylene, (Si2H4)n and silico acelyline,
(Si2H2)2 are also known.
Preparations
When Mg2Si (obtained by heating a mixture of Mg and SiO2 in absence of air) is treated with
20% HCl in an atmosphere of H2, a mixture of silanes is obtained containing varying
proportions of different members. These can be separated by fractional distillation of the
mixture obtained in liquid form by cooling at liquid N2 temperature.
Mg2Si + 4HCl MgCl2 + SiH4↑ + other silanes
2 Mg2Si + 8HCl 4MgCl2 + Si2H6↑ + H2↑
Properties

These hydrides are analogous to alkanes. Their thermal stability decreases with increasing
molecular weight SiH4 and Si2H6 are colourless gases at room temperature and higher
members are liquids. These are poisonous. Chemically these are very reactive and burn
spontaneously in oxygen to give SiO2.
SiH4 + 2O2 SiO2 + 2H2O
Si4H10 + 13/2 O2 4SiO2 + 5H2O
They form silicates in alkaline water:
SiH4 + 2NaOH + H2O Na2SiO3 + 4H2↑
Si2H6 +4NaOH + 2H2O 2Na2SiO3 + 7H2↑
Structure
As these are analogous to alkanes, hence have the structures similar to those of alkanes.
(c) Metallic or interstitial hydrides
Many of the d-block elements like Ti, Zr, V, Nb, Pd etc., lanthanides and actinides, e.g. La,
Ce, Pr etc. absorb hydrogen into the holes or the interstices existing between the atoms in the
metallic lattice at elevated temperature without changing the original crystal structure of the
metal and thus give the metallic hydrides. The interstitial combination of hydrogen and metal
atoms takes place during the process, hence these are also called interstitial hydrides. These
may or may not be stoichiometric e.g.
Non – stoichiometric : Ti H1.73, Pd H0.6, NbH0.86 etc.
Stoichiometric : NiH2, CoH2, FeH2, CrH3 etc. (typical metallic hydrides)
Mostly these are non-stoichiometric with lower densities than the parent metals (due to
expansion of lattice).
(d) Complex hydrides

These hydrides may be regarded as the combined hydrides of the elements, e.g. LiBH4,
NaBH4, Be(BH4)2, LiAlH4 etc. Here hydrogen is covalently linked with trivalent element to
form a complex anion which is bonded to the monovalent metal ion through ionic bond, i.e.
LiAlH4 ionises to Li+ and AlH4- ions. Such hydrides can be obtained by the action of an
excess of alkali metal hydride on an appropriate halide, e.g.
4Na H + BF4 Ethers NaBH4 + 3NaF
4LiH + AlCl3 Ethers LiAlH4 + 3LiCl

LiAlH4
It is an import complex hydride. It is best prepared by the above reaction from LiH and
AlCl3. LiAlH4 remains in solution. On evaporating ether, LiAlH4 is obtained.
(i) It is decomposed by water liberating H2

LiAlH4 + 4H2O LiOH + Al(OH)3 + 4H2
(ii) It is an import reducing agent and reduces many halides and other
compounds to hydrides, e.g.
3Li AlH4 + 4BCl3 Ether 2B2H6 + 3AlCl3 + 3LiCl

LiAlH4 + SiCl4 Ether SiH4 + LiCl + AlCl3
LiAl H4 + SnCl4 Ether SnH4 + LiCl + AlCl3
LiAlH4 + Zn(CH3)2 ZnH2 +Li[AlH2 (CH3)2]
4H O
4RCHO + LiAlH4 [R-CH2O)4 LiAl 2 4RCH2OH + LiOH +Al(OH)3
Uses
(i) It is used for reducing almost all the compounds containing a carbonyl group, >c=0 like
ketones, aldehydes, carboxylic acids etc. to alcohols.
(ii) It is also used for the preparation of hydrides of Si, B, Al etc. from their chlorides.
Structure
The complex ion, [AlH4]- like other [M III H4]- ions, is tetrahedral involving sp3 hybridisation
in the central atom. Three of these sp3 hybrid orbitals of Al or MIII atom overlap with three
unpaired orbitals of H-atoms to form 3 normal σ bonds and fourth vacant sp3 hybrid orbital
overlaps with filled orbital of H- ion to give coordinate σ bond as follows:
Li H Li+ + H-
H- + AlH3 [AlH4] -
Al atom in ground state 3s23p1
Al atom in excited state 3s13px13py1 3pz0

sp3
(e) Borderline hydrides

These hydrides do not belong to any type given above and are not easily formed from the
elements, e.g. BeH2, MgH2, ZnH2, CdH2 etc. These are prepared by special methods.
Generally these have the properties of both ionic and covalent hydrides or sometimes of
metallic hydrides also. These are less known hydrides.
6.5 Oxides of hydrogen

Hydrogen forms four oxides, viz. H2O, D2O, T2O and H2O2. H2O and T2O have not been
discussed here. Only D2O and H2O2 will be discussed in detail.
6.5.1 Heavy water, D2O
It is an oxide of heavy hydrogen, discovered by Urey in 1932 and is an important compound.
Preparation of D2O.
It occurs in ordinary water in traces which is the chief source of D2O. Heavy water is
prepared by the following methods:
(A) Prolonged (or multistage) electrolysis of ordinary water
Heavy water is largely prepared by the continuous electrolysis of ordinary water in presence
of small quantity of NaOH (~3%). The electrolysis is carried out in a steel cell (shown in Fig.
6.4) which itself acts as a cathode and a perforated cylindrical sheet of nickel acts as anode.
In actual practice, a large number of such cells are used for each stage and the electrolysis is
carried out in many stages usually five to seven. The gases H2 and D2, obtained from each
stage (second onwards) are burnt and water so formed is returned to the previous stage. Thus
by continuous and prolonged electrolysis of ordinary water in several stages, the
concentration of heavy water goes on increasing gradually in the residual water left behind at
the end of each stage which is taken to the next stage cells. At the end about 99% pure D2O is
obtained which is distilled and the distillate so obtained is again electrolysed to get pure

deuterium. This deuterium is burnt in oxygen to get 100% pure D2O. This technique is used
in heavy water plant at Nangal (Punjab) for manufacturing D2O used in the atomic plants in
the country.
(B) Fractional distillation of ordinary water

Taking the advantage of the difference in the boiling points of H2O (1000C) and heavy water
(101.420C), latter can be separated from ordinary water using long fractionating column and
repeating the process several times. The lighter fraction (i.e. H2O) having lower boiling point
is distilled first while the heavier fraction (i.e. D2O) with higher boiling point is left behind at
the end of the repeated process.
(C) Fractional freezing of water

Since the freezing point of ordinary water 00C and that of D2O is 3.820C, the two oxides of
the isotopes of hydrogen can be separated which is completed in several cycles.
(D) Preferential adsorption
The vapours of D2O are adsorbed more rapidly on charcoal than H2O vapours and can be
separated by preferential adsorption.
(E) Preparation of pure D2O
Pure D2O can be prepared by the action of D2 gas on O2 gas
2D2 + O2 2D2O
Properties
Some of the physical properties of H2O and D2O are similar like odour, colour, taste etc. but
many properties, e.g., density, melting and boiling points etc. are different.
i) Action on metals and their oxides
Like H2O, D2O reacts with alkali and alkaline earth metals to liberate D2 and with basic oxide
to give heavy alkalies.

2Na + 2D2O 2NaOD + D2↑

Ca + 2D2O Ca (OD)2 + D2↑
Na2O + D2O 2NaOD
CaO + D2O Ca(OD)2
Heavy alkalies
ii) Action on non-metallic oxides
With non-metallic oxides (acidic), it gives deutero acids.
N2O5 + D2O 2DNO3 (Deutero nitric acid)
P2O5 + 3D2O 2D3PO4 (Deutero phosphoric acid)
SO3 + D2O 2D2SO4 (Deutero sulphuric acid)
iii) Action on nitrides, phosphides etc.
D2O, like water, decomposes metallic nitrides, phosphides, arsenides and carbides etc. to give
deutero compounds.
Mg3N2 + 6D2O 3Mg(OD)2 + 2ND3 (deutero ammonia)
Ca3P2 + 6D2O 3Ca(OD)2 + 2PD3 (deutero phosphine)
CaC2 + 2D2O Ca(OD)2 + C2D2 (deutero acetylene)
Al4C3 + 12D2O 4Al(OD)3 + 2CD4 (deutero methane)
iv) Formation of deuterates
Heavy water also gets associated with salts like water to form deuterates or deutero-hydrates,
e.g.
CuSO4 .5H2O + 5D2O CuSO4. 5D2O + 5H2O
Other examples are: BeCl2.4D2O, CoCl2.6D2O, NiCl2. 6D2O, MgSO4 7 D2O etc.
v) Exchange reactions
With a number of compounds containing labile hydrogen atoms, it undergoes exchange
reactions in which H-atoms are partially or completely replaced by D-atoms.
NaOH + D2O ⇌ NaOD + HOD
HCl + D2O ⇌ DCl +HOD
NH4Cl + D2O ⇌ ND4Cl + 4HOD
The last exchange reaction occurs in steps replacing H-atoms one by one in each step.
C6H6 + 3D2O ⇌ C6D6 + 3H2O
deutero benzene
vi) Deutrolysis

These reactions are similar to hydrolysis reactions in which certain inorganic chlorides and
other salts are involved. The process is called deutorolysis.
AlCl3 + 3D2O Al(OD)3 + 3DCl
BiCl3 + D2O BiOCl + 2DCl
SiCl4 + 4D2O D4SiO4 + 4DCl
Uses
(i) It is used as a moderator of neutrons in nuclear reactors.
(ii) It is also used for the preparation of D2 either by electrolysis or by the action of Na-metal on
it.
(iii) It is sometimes used as a tracer compound particularly in organic chemistry.
6.5.2 Hydrogen Peroxide (H2O2)

(a) Laboratory preparation of H2O2
(i) H2O2 is generally prepared in the laboratory by the action of cold dilute sulphuric acid on
hydrated barium peroxide which is readily decomposed to give H2O2 solution while
anhydrous barium peroxide gets a protective coating of BaSO4 hence not used.
BaO2.8H2O + H2SO4 (cold dilute) BaSO4 + H2O2 + 8H2O
BaSO4 is filtered off to get the solution of H2O2.
Hydrated BaO2 is obtained by slowly adding anhyd.BaO2 to a cold conc.HCl (1 part HCl + 1
part H2O) until it is neutralised.
BaO2 + 2HCl BaCl2 + H2O2
After filtering the impurities, if present, the filtrate is treated with saturated Ba(OH)2 solution
and precipitate of BaO2.8H2O is filtered off.
H2O2 + Ba(OH)2 + 6 H2O BaO2.8H2O (precipitate)
.
(ii) It may also be prepared in the laboratory by adding small quantities of sodium peroxide
to ice-cold water.
Na2O2 + 2H2O 2NaOH + H2O2
(b) Manufacture of H2O2
(i) Electrolytic process
On a large scale, H2O2 is prepared either by the electrolysis of 50% sulphuric acid followed
by distillation in vacuum. Perdisulphuric acid so obtained reacts with water during distillation
to give H2O2.

INORGANIC CHEMISTRY
CHEMISTRY-I BSCCH
BSCCH-101
2H2SO4 2H+ + 2HSO4- (anode)

2HSO4- H2S2O8 + 2e- (at anode)
H2S2O8 + 2H2O 2H2SO4 + H2O2
Or an aq. solution of ammonium sulphate and sulphuric acid in molecular proportion
proportion, at low
temperature, using pt-anode
anode and graphite cathode separated by a porous diaphram.
(NH4)2SO4 + H2SO4 2NH4HSO4

NH4HSO4 ⇌ H+ + NH4SO4- (anode)
2[NH4SO4]- -2e- (NH4)2S2O8
(NH4)2 S2O8 is distilled with H2SO4 under reduced pressure and H2S2O8 obtained is
converted to H2O2.
(NH4)2 S2O8 + H2SO4 H2S2O8 + (NH4)2SO4

H2S2O8 + 2H2O 2H2SO4 + H2O2
(c) Auto-oxidation process

This is a recent process in which ethyl anthraquinone is reduced to ethyl anthraquinol by
passing H2 through its solution in an organic solvent in presence of Pd
Pd-catalyst.
catalyst. On frothing
the product with air, about 20% solution of H2O2 is obtained and ethyl anthraquinone is
regenerated.
Concentration of H2O2 solution

H2O2 obtained by above methods is always in the form of dilute solutions. It can be
concentrated as follows:
ful evaporation of the solution
Careful
Dilute solution of H2O2 is carefully heated on a water bath preferably under reduced pressure
at 60-700C using a fractionating column. Water being more volatile distils over to increase
the concentration of H2O2 to 20-25%.
25%.

The above solution is heated in a distillation flask upto 450C at low pressure (15mm).
Initially, water distils over and at ~700C H2O2 begins to distil over. For most commercial
purposes, concentration is carried out upto 55-60% only.
Further concentration of H2O2 is possible by using H2O2 along with solid CO2 and ether. The
whole mass of CO2 and ether freezes and if little of frozen solid is dropped in a conc. solution
of H2O2, needle-shaped crystals of almost 100% pure H2O2 separate out.
Properties
Anhyd. H2O2 is a colourless syrupy liquid, produces blisters in skin, boils at 1120C (at 68 mm
pressure) and freezes at ∼(-)2710C.
(i) Decomposition
Pure H2O2 is unstable and decomposes by itself to give O2 on standing or on heating.
2H2O2 2H2O + O2
The decomposition is accelerated in the presence of alkalies, MnO2, finely divided metals,
e.g. Pt, Ag, Cu, Co, Fe etc.
The addition of small quantities of alcohol, acetanilide or glycerol inhibits the decomposition.
H2O2 is stored in paraffin wax coated bottles and not in glass bottles to avoid its
decomposition by alkali oxides present in glass.
(ii) Oxidising and bleaching properties

H2O2 is a strong oxidising agent in acidic as well as alkaline solutions because of its tendency
to lose oxygen.
H2O2 H2 O + O
It oxidises Fe2+ to Fe3+ ions, I- ions to I2, sulphides and sulphites to sulphates, nitrite ions to
nitrate, arsenites to arsenates, ferrocyanides to ferricyanides, formaldehyde to formic acid etc.
Some of these reactions are given here:
2Fe2+ + 2H+ + H2O2 2Fe3+ + 2H2O
2I- + 2H+ + H2O2 I2 + 2H2O
S2- + 4H2O2 SO42- + 4H2O
SO32- +H2O2 SO42- + H2O
NO2- + H2O2 NO3- + H2O
AsO33- + H2O2 AsO43- + H2O
2[Fe(CN)6]4- + H2O2 2[Fe(CN)6]3- + 2OH-
HCHO + H2O2 HCOOH + H2O

INORGANIC CHEMISTRY
CHEMISTRY-I BSCCH
BSCCH-101
The bleaching of silk, hair, ivory and wool is carried out with H2O2. This is because of
oxidising properties of H2O2.
(iii) Reducing properties
H2O2 also acts as reducing agent in presence of strong oxidising agents. It reduces MnO4- ion
to Mn2+ ion, X2 to HX, Ag-oxide
oxide to Ag metal, MnO2 to Mn2+ ion etc.
2MnO4- + 5 H2O2 + 6H+ 2Mn2+ + 8H2O + 5O2
X2 + H2O2 2HX + O2 (X=halogen)
Ag2O + H2O2 2Ag + H2O + O2
MnO2 + 2H+ + H2O2 Mn2+ + 2H2O +O2
It is noted that in all its reducing reactions O2 gas is liberated.
(iv) Addition reaction
It is capable of adding itself to ethylenic linkages:
CH2=CH2 + H2O2 CH2OH – CH2OH (ethylene glycol)
Strength (or concentration) of H2O2 solution
The strength (or concentration) of H2O2 solution may be expressed in terms of
(i) Volume of O2 gas
(ii) Weight of pure H2O2 in a given solution of H2O2
(iii) Normality
Let us discuss the first type: The volume of O2 gas obtained at N.T.P. by heating one
volume of H2O2 solution is called the concentration of H2O2 solution, e.g. 1 ml. of a 10
volume of H2O2 solution, on heating, will give 10 ml. of O2 gas.
Uses
(i) It is used in medicine as antiseptic for washing wounds, teeth and ears.
(ii) It finds use as an oxidising agent in the laboratory.
(iii) Used for bleaching materials.
(iv) For restoring the colour of blackened lead paints,
PbS+ 4H2O2 PbSO4 + 4H2O
Black white
(v) As a propellent or fuel in submarines and rockets.
ro
Structure
re of hydrogen peroxide
The empirical formula of H2O2 has been proposed as HO and molecular formula H2O2. Thus

two formulae were suggested for it as:
Structure I is supported by its unstable nature giving oxygen.

H2O2 H2 O + O
and structure II is evidenced by the formation of two-series of salts, e.g. Na-O-O-H and Na-
O-O-Na as well as by its reaction with diethyl sulphate and subsequent reduction of the
product to ethyl alcohol:
H-O-O-H + (C2H5)2SO4 C2H5O-O C2H5 + H2SO4
C2H5O-O C2H5 + 2H Zn/CH3COOH 2C2H5OH
Similar reaction with structure I would have given diethyl ether. But actually ethyl alcohol is
obtained. This is in favour of structure II which is further supported by X-ray analysis of
K2S2O8 crystals obtained from H2O2 and chlorosulphonic acid and subsequent treatment with
potassium salts.
Non- planner and non-linear structure
Its dipole moment value (2.1D) indicates its non-planner and non-linear structure confirmed
by X-ray analysis of solid H2O2 molecule in which the two O-H bonds are asymmetrically
distributed and all the four atoms are not lying in the same plane. The position of the atoms,
bond angles and bond lengths as determined by experimental methods are shown in the figure
(Fig 6.5).
6.6. SUMMARY
This unit on hydrogen and its compounds contains a detailed discussion on isotopes of
hydrogen and its isomeric forms, hydrides and oxides along with their preparation, properties
and uses wherever necessary. The structure of H2O2 has also been given.


i. Heavy hydrogen has in its nucleus
(a) 1 neutron
(b) 2 neutrons
(c) 3 neutrons
(d) no neutrons
ii. At 300K, the ratio of O to PH2 is
(a) 1:1
(b) 1:2
(c) 3:1
(d) 3:2
iii. Silicon hydrides are
(a) Ionic hydrides
(b) Covalent hydrides
(c) Metallic hydrides
(d) complex hydrides.
iv. The boiling point of heavy water is
(a) Higher
(b) Lower
(c) Equal
(d) Much lower than that of ordinary water.

6.8 ANSWERS
i. (a)
ii. (c)
iii. (b)
iv. (a)

UNIT 7: THE ALKALI METALS
CONTENTS:
7.1 Objectives
7.2 Introduction
7.3 General characteristics and use (Flame Colouration)
7.4 Oxides and Hydroxides
7.5 Solubility and hydration
7.6 Complexation of alkali metal ions
7.7 Anomalous Behavior of Lithium.
7.8 Summary
7.10 Answers
7.1. OBJECTIVE
The objective of preparing the course material of this unit, i.e. on the alkali metals (the
elements of Group 1) is to give a summary of the general properties and their trends in the
group. That is to acquaint the readers with general characteristics of these metals along with
their flame colouration and their uses, the nature and behaviour of their oxides and
hydroxides, solubility behaviour of their salts and hydration, and complexation of alkali metal
ions. The anomalous behaviour of lithium, its dissimilarity with other alkali metals and
similarity with Mg, the element of next group and next period, called diagonal relationship
shall be discussed.
7.2. INTRODUCTION
The six elements of Group 1(or IA) of the periodic table, viz. lithium (Li3), sodium (Na11),
potassium (K19), rubedium (Rb37), caesium (Cs55) and francium (Fr87) are collectively called
the alkali metals. This name alkali has been derived from arabic which means ash because the
ashes of plants contain the compounds of Na and K in large quantities. In addition to this,
these elements form strongly alkaline oxides and hydroxides. The individual elements were
named on the basis of their use, origin in plants and spectral characteristics, i.e. colours of
spectral lines. The last but radioactive element francium was named after the name of the

country where M. Curie worked (France) on her persistence, though she was born in Warsaw
(Poland).
All these elements belong to s-block of theperiodic table because in the atoms of these
elements the last or differentiating electron enters the s-subshell of the valence shell. These
occupy their position at the extreme left portion of the periodic table. Every period of the
periodic table commences with an alkali metal.
The alkali metals, due to their reducing nature and their oxides being too reactive to occur in
nature, are generally found as cations combined with anions of the most electronegative
elements. The less electropositive element (viz. Li) is present in nature as silicate minerals
and more electropositive elements are found as chlorides. The elements are obtained from the
minerals/ores by the electrolysis of their fused salts.
All these elements are metals and have less gradation in their characteristic properties.
7.3. GENERAL CHARACTERISTICS OF ALKALI METALS AND

THEIR USES
(i) Electronic configuration
The valence (or ultimate) shell electronic configuration of these elements is invariably ns1
where n denotes the principal quantum number of the valence or outer shell and s is the
subshell that receives the solitary differentiating electron while the penultimate shell contains,
in general, eight [(n-1)s2P6] electrons (Li is an exception with two electrons in its penultimate
shell). On losing the solitary valence electron, the alkali metal atoms are converted into M+
ions having inert gas configuration in the outer shell. These ions are colourless and
diamagnetic in nature. The similarity in the electronic configuration of these elements is
responsible for their similar physical and chemical properties. These are all monovalent
elements and give colourless ionic salts.
(ii) Physical state, hardness and density
The alkali metals, except lithium, are extremely soft solids to be cut by knife and can be
readily fused. This is because of the weak metallic bonding among the atoms of the metallic
crystals. They are also highly malleable and ductile, freshly cut metals have a bright lustre

which is quickly tarnished as soon as the metal comes in contact with atmospheric air. In
general, these metals have high density due to the close packing of atoms in the metallic
crystals but lithium has low density due to low atomic weight. The density increases down
the group because atomic weight increases.
(iii) Atomic and ionic radii (atomic volume)
Both the atomic and ionic radii (of M+ ions) increase from the first (i.e. Li) to the last (i.e. Fr)
element on moving down the group due to the inclusion of an extra shell of electrons at each
step, i.e. in the next element. But the ionic radii are smaller than the atomic radii of the
corresponding elements due to the elimination of the outer shell and greater attractive pull of
nuclear charge on the outer electrons of the ions. The above statement is evidenced by the
values of atomic and ionic radii for the alkali metals given below:
Elements Li Na K Rb Cs
Atomic (i.e. metallic radii (Å) 1.55 1.90 2.35 2.48 2.67
Ionic (or Crystal) radii (Å) 0.60 0.95 1.33 1.48 1.69
(for M+ ions)
The group trend of the atomic volume is the same as that for atomic radius due to the similar
reason as given above. These elements have the largest atomic radii, ionic radii and atomic
volumes among the elements of the respective periods.
(iv) Melting points, boiling points and heats of atomization
Alkali metals have low melting and boiling points because of weak inter- atomic bonds in the
crystal lattice which decrease further down the group due to increasing atomic size.
These metals also have low heats of atomization and have the same trends as the melting and
boiling points due to the same reason as discussed above though the change is sharp at the
beginning and a small change is observed in the higher members.
(v) Ionization energies, electron affinities and electronegativities

Alkali metal atoms can lose their solitary electrons from the respective outer shells (i.e. ns1)
with relative ease because the electron in each atom in held weakly with nucleus due to the
larger size of the atom. These metals, therefore, have low ionization energies. Further, the
ionization energy values decrease on moving down the group from Li to Fr as shown below:
Elements Li Na K Rb Cs
Ionisation energy
520 496 419 403 376
(kJmol-1)
The electron affinity and electronegativity values are also very low for these metals as these
have no or very low tendency to attract or accommodate the electrons. The values of these
properties decrease down the group though the change is small.
(vi) Electropositive (or Metallic) character and reducing properties
The electropositive character of the elements depends on the ease with which the atoms of the
elements lose their outermost electrons. Because of their low ionization energy values, the
alkali metals have the highest electropositive character among all the elements of the periodic
table. With decreasing ionization energy values, the electropositive character also increases
down the group for alkali metals, i.e. Li metal is the least electropositive due to highest
ionization energy and Cs, the most electropositive with the least ionization energy value
among the alkali metals. The last element, Fr has been excluded because all its isotopes are
radioactive with very short half life periods to be available for their detailed study.
According to the trend of electropositive character of alkali metals, their reducing property
must also increase down the group, i.e. from Li to Cs but the reverse trend is observed in the
reducing properties though the basic nature of their oxides increases from the first to the last
element in accordance with the electropositive character. Li has maximum reducing power
and Cs has minimum reducing tendency. The anomalous trend in the reducing properties can
be explained as follows:
The standard electrode potential is taken as the measure of the reducing properties of these
elements. More negative is the standard reduction potential or more positive is the standard
oxidation potential of the metal, greater is its tendency to lose electron (s) and stronger is its
reducing power.

It has been found that Li has the highest standard oxidation potential (+3.05V) or highest
negative standard reduction potential value (-3.05V) thereby making it the strongest reducing
agent among all the alkali metals as it can lose the ns1 electron most readily in aqueous
condition.
Actually the conversion of an alkali metal in the solid state, M (s), in contact with water into
M+ (aq.) represents the reducing power of M in aqueous medium which takes place in three
steps, i.e. sublimation, M (s) ---- →M (g) requiring sublimation energy, S, which is slightly
higher for Li metal than for others, ionization, M (g) M+ (g), absorbing ionization
energy, I, again which is maximum for Li atom and hydration of the cation, M+(g) + nH2O
M+ (aq), liberating hydration energy, H. Anhydrous Li+ ion, being the smallest in size, gets
hydrated to the maximum extent releasing the highest hydration energy content.
The standard oxidation potential (E0ox) and other energy terms are related as E0 = H – I – S
The hydration energy of lithium being very high, enough to compensates the values of I and
S and consequently results in high electrode potential value making it the strongest reducing
agent in contact with water though the reducing power of alkali metals in the dry or
anhydrous conditions depends on their ionization energy values.
(vii) Photoelectric effect (effect of light)
The outermost ns1 electron in the atoms of alkali metals is so loosely held with the nucleus
that even the low energy photons (i.e. light) can eject this electron from the surface of these
metals. This property of emitting the electron from the metal surface even on the exposure of
light is called Photoelectric effect and permits the application of these metals (especially K
and Cs) in the photoelectric cells which are sensitive particularly to blue light. Li metal with
the highest ionization energy does not show this effect.
(viii) Flame colouration and use
The alkali metals give characteristic colour in Bunsen flame, i.e. Li- crimson red, Na- yellow,
K-violet, Rb and Cs – also violet.
The reason for this flame colouration being when an alkali metal or its any compound is
heated in the flame, the outer electron can be excited to higher energy levels by absorbing
some energy from the flame. When the excited electron returns back to the ground or original

level, the absorbed excitation energy is released in the form of light in the visible region of
the electromagnetic spectrum and colour is imparted by the metal to the flame. Since for the
same excitation energy, the electrons of the atoms of different alkali metals are excited to
different higher energy levels depending on the tightness with which the nuclear charge holds
the outer electron (s) with itself. Thus in Li, electrons are excited up to lower levels and in
other metals up to higher levels and the released energy as a consequence goes on increasing
from Li to Cs and accordingly the colours are observed for them, i.e. for Li crimson- red(due
to lower energy) and for Cs, violet(due to higher released energy).
This property of alkali metals to impart colouration in the Bunsen flame has been used to
detect their presence in the salts by the so called flame test and to estimate Na and K
quantitatively in plant samples.
(ix) Polarizing power of alkali metal ions
On approaching nearer to an anion, the alkali metal cations attract the anionic charge and
repel the nuclei of anions thereby distorting or polarizing the anion. This results in the
passage of ionic bond in the compound to covalent bond. This effect has been found to be
more pronounced in smaller alkali metal cations, i.e. Li+ ion (all alkali metal cations have the
same charge). That is why Li salts are covalent in nature and insoluble in water but soluble in
organic solvents. While others form ionic compounds which are freely soluble in water.
(x) Action of liquid ammonia
The alkali metals dissolve in liq. NH3 without the evolution of H2 to give blue colour in dilute
solutions. This is due to the excitation of free electrons to higher energy level to give an
absorption band in visible range of the spectrum and therefore, the solution looks blue due to
transmitted light. The concentrated solutions are good conductors of electricity due to the
presence of ammoniated electrons, [e(NH3)]- and are bronze coloured.
Uses of alkali metals
(a) The most important use of lithium is in making alloys, e.g. on adding to the alloys of
magnesium, it improves their tensile strength and resistance to corrosion.
(b) Lithium is also used as deoxidizer in the purification of nickel and copper.

(c) It is an ingredient of high energy fuels employed for the propulsion of intercontinental
rockets (i.e. thermonuclear energy).
(d) Compounds of lithium are used in glass and pottery industry to increase the strength and
resistance of glass and to prevent the surface cracking of pottery.
(e) Li-citrate and salicylate are used in medicine for gout.
(f) LiOH is used in making high quality lubricating greases which can withstand extreme
temperature variations.
(g) Sodium is used in the laboratory as a reducing agent in the form of sodium amalgam and it is
also used for detecting N, S and halogens (Cl, Br, I) in organic compounds.
(h) In metallurgy, this metal is employed for the extraction of many elements like Si, B, Mg etc.
(i) It is largely used in industry for the production of artificial rubber, dyes and drugs.
(j) Its compound, Na2 CO3, is used as a laboratory reagent, for laundry works and as domestic
cleansing agent as well as in softening of hard water.
(k) NaHCO3, another compound of Na, is used in medicine (as soda bicarb) to neutralize the
acidity in the stomach and as baking soda.
(l) Potassium and caesium metals are used in photoelectric cells.
(m) The sodium-potassium alloy is used in the special thermometers employed for measuring
high temperature.
(n) KClO3, an important compound of potassium is used as oxidizing agent in the laboratory in
fireworks as well as match industry.
7.4. OXIDES AND HYDROXIDES OF ALKALI METALS
Oxides:
Alkali metals react with oxygen or air rapidly and get tarnished due to the formation of their
oxides on the surface of the metals. That is why alkali metals are stored in kerosene or
paraffin oil.
When these metals are burnt in oxygen or air, they yield either of the three types of oxides:
monoxide (M2O) or peroxide (M2O2) (Na, K, Rb, Cs) or super oxide MO2 (K, Rb, Cs)
depending on the nature of the metal. The oxides of these metals can also be obtained by
dissolving the metal in ammonia and treating the solution with the required amount of
oxygen. Lithium does not form higher oxides because Li+ ion is too small and has much
stronger positive field around it than other alkali metal ions. This strong positive field near

one oxygen anion restricts the spread of negative charge towards another oxygen atom
making the formation of higher oxide difficult.
Generally under normal conditions, following oxides of different metals can be obtained:
4Li + O2 2Li2O (Monoxide only)
4Na + O2 2 Na2O and
2Na + O2 Na2O2 (monoxide and peroxide both)
M + O2 MO2 (M = K, Rb, Cs; superoxide, generally)
Since the normal oxide of alkali metals other than that of Li are not formed by the direct
reaction between the metal and O2 or air, they are obtained by indirect methods, e.g.
2Na2O2 + 4Na 4 Na2 O (reversible reaction)
2NaNO2 + 6Na 4Na2O + N2
The normal monoxides are strongly basic and highly soluble in water giving alkaline
solutions by proton exchange O2-+ H2O OH- + OH- (hydrolysis of oxide ion to
hydroxide) and disproportionate to peroxide and metal vapours when heated
∆
2Na2O Na2O2 + 2Na (vapours)
The peroxide of sodium yields H2O2 on treatment with dilute acids in cold and superoxide
(NaO2) by heating with O2.
Na2O2 + 2H+ H2O2 + 2Na+
Na2O2 + O2 2NaO2
In general alkali metal peroxides and super oxides are strongly oxidizing agents and react
with water and dilute acids to H2O2 and O2 :
O22- + 2H2O 2OH- + H2O2
O22- + H2SO4 SO2-4+ H2O2

` 2O2- + 2H2O 2OH- + H2O2 +O2
4O2- + 2H2SO4 2SO42-+ 2H2O + 3O2
Hydroxides:
All alkali metals form ionic hydroxides with the general formula MOH and can be prepared
by treating the monoxides or metals with water:
2M + 2H2O 2MOH + H2
M2O + H2O 2MOH (M = alkali metals)
The reaction between water and the metal, except Li, is highly explosive hence this method is
not generally used for the preparation of hydroxides. These are obtained by the electrolysis of
aqueous solutions of the chlorides.
These hydroxides are highly soluble in water and alcohol and ionize to yield OH- ions and
thus behave as strong bases or alkalies in solution. The solubility increases and the
hydroxides become more and more basic on moving down the group, i.e. from Li to Cs due to
an increasing trend in electropositive character. LiOH is less basic and less soluble in water.
The hydroxides other than LiOH are thermally stable even at very high temperature:
7800C
2 LiOH Li2O + H2O↑
13000C
2NaOH stable but sublimes
The alkali metal hydroxides are strong bases and react with acids, acidic oxides and
amphoteric oxides to form salts:
2MOH + H2SO4 M2SO4 + 2H2O
2MOH + CO2 M2CO3+ H2O
2MOH + Al2O3 2MAlO2+ H2O
The hydroxides absorb CO2, even in traces, from the air to form carbonates:
2NaOH + CO2 Na2CO3+H2O

7.5. SOLUBILITY AND HYDRATION OF ALKALI METAL

COMPOUNDS (IONIC HYDRATION)
The terms, solubility and hydration of compounds are related with the lattice energies and
hydration energies of the compounds. The lattice energy is a direct and quantitative measure
of ionic bond strength of any compound. When an ionic compound is placed in water (or any
polar solvent), the ionic charges of the compound attract the polar molecules (called dipoles).
The ions of the compound after separation combine with water (solvent) molecules. This
process is called hydration (solvation). For example, when NaCl is placed in water the
positively charged Na+ ions attact the partially negatively charged oxygen atoms (O∂-) and the
negatively charged Cl- ions attract the partially positively charged hydrogen atoms (H∂+) of
water molecules. Energy is released in this process which is known as hydration energy. If
the hydration energy is more than the lattice energy of the compound, the ionic bonds will be
broken and the solid compound dissolves, i.e. the ions go into solution as hydrated ions. But
if the hydration energy is less than the lattice energy of the compound, the ionic compounds
remain insoluble. It may be concluded that the solubility of ionic compounds depends on the
difference between their lattice energies and hydration energies. The large lattice energy of
LiF makes it insoluble in water. Thus it can be said that lattice energy and ionic hydration are
intimately related with each other. The alkali metal ions are hydrated to different extents, e.g.
anhydrous Li+ ion being smallest in size is hydrated to the maximum extent and anhydrous
Cs+ ion is hydrated to the minimum extent due to its largest size among these ions. After
hydration Li (aq)+ ion is the largest and Cs (aq)+ ion is the smallest in size.
7.6. COMPLEXATION OF ALKALI METAL IONS
The alkali metal ions have the least tendency of complexation with normal ligands among the
elements of the periodic table. This is mainly due to:
(i) Relatively larger ionic size of the alkali metal ions

(ii) Low charge densities (charge/size) of the ions
(iii) Non-availability of the vacant d-orbitals of right energy to accept lone pairs from the ligands
(iv) Very high basicity of the metals and
(v) Non-availability of variable oxidation states in the ions.
However, a few complexes of these elements have been formed but the complex forming
ability decreases down the group from lithium to caesium. Alkali metals form complexes
with oxygen containing multidentate chelating ligands such as salicylaldehyde, acetylacetone

etc. (Fig. 7.1) given below:
Figure 7.1
An important class of complexing agent, the crown ether, has been synthesized known as
dibenzo-18-crown-6 containing two benzene rings and 18 atoms making a crown-shaped
ring, six of them being oxygen atoms. These six oxygens may form complexes with a metal
ion, even with a large alkali metal ion. The bonding of the metal ion to the polyether is
largely electrostatic. Polyethers having different sizes are known. The size of the metal ion
and that of the hole in the centre of Polyethers must be comparable for close fitting of the
metal ion in the ring.
Benzo-12-crown-4 has a ring of 12 atoms, four of which are oxygens. A crown-4 polyether
forms stable complex with Li+ or Na+ ion where as a crown-6 polyether prefers K+ ion with
unusual coordination number.
The polyethers act as ion carriers inside living cells to transport ions across cell membranes
and thus maintain the balance between Na+ and K+ ions inside and outside cells.
The crown ethers also form some unusual complexes called electrides. These are
paramagnetic such as Cs+ (crown ether)e-. Because of very large size and hydrophobic
character of the complexed cation, crown ether complexing can lead to salts becoming
soluble in organic solvents containing no donor atoms, e.g. [K(crown-6)]OH and K (crown-
6)]MnO4 in benzene and toluene, respectively.
Three dimensional equivalents of crown ethers contain nitrogen atoms to obtain branching
and to provide extra donor sites. They are called cryptands as they hide the cation. A typical

cryptand-222 has been shown in (Fig.7.2) below. All the N and O atoms of this compound
act as donors, the conformations at the nitrogen atoms being the ends, i.e. the lone pairs
inwards cryptands shield the cations such that they are complexed more effectively than
crown ethers. The cryptands-221 and -222 form their more stable alkali metal complexes with
Li+, Na+ and K+ respectively in terms of enthalpy.
Fig. 7.2 . Cryptand-222
The action of cryptand-222 on sodium in ethylamine solution produces [Na (cryptand-222)]+

Na-, a golden yellow solid. This shows the striking application of cryptand-222 in shifting the
disproportionation equilibrium to the right hand side:
2Na Na+ + Na-
Also the salts containing the ions K-, Rb- and Cs- have also been prepared.
7.7 ANOMALOUS BEHAVIOUR OF LITHIUM
Lithium, the first element of the alkali metal series, though shows most of the characteristic
properties of the alkali metals (Group IA) as has been discussed above yet it also differs from
them in many respects. This anomalous behaviour of lithium may be attributed to the
following points:
(i) Very small size of Li and Li+ ion as compared to those of others.
(ii) High charge density (charge/size) and high polarizing power of Li+ ion.
(iii) Higher electronegativity and ionization energy of Li than other alkali metals and less
electropositive character.
The main points of difference are summarized below:
i. Lithium is harder and more ductile metal than the other alkali metals with higher melting and
boiling points.

ii. Chemically it is less reactive than other alkali metals. Thus it is attacked by water only slowly
even at 270C while other metals react instantly and vigorously even at lower temperature.
Also, Li is not attacked by air easily and does not lose its lustre even on melting.
iii. Li is the only alkali metal which forms nitride (Li3N) by the reaction with nitrogen. Other
alkali metals do not react with N2.
iv. On burning with O2 or air, Li gives only monoxide (Li2O) while other alkali metals generally
give peroxides or superoxides, i.e. M2O2 and MO2.
v. Lithium halides, being covalent in nature, are soluble in organic solvents while other alkali
metal halides are not.
vi. Li2O is much less basic (almost amphoteric) in nature while monoxides, M2O, of other alkali
metals are highly basic. Therefore, LiOH is a weak base, MOH of other alkali metals are
strong bases.
vii. Most of the lithium salts are only sparingly soluble in water while the corresponding salts of
other alkali metals are freely soluble. This is either because of high lattice energy or covalent
nature of Li-salts.
viii. The carbonate and hydroxide of lithium are thermally less stable and decompose to
give Li2O:
Li2CO3 ∆ Li2O + CO2↑
∆
2LiOH Li2O + H2O
The same salts of other alkali metals are stable to heat and do not decompose.
ix. Li- nitrate on heating decomposes easily to evolve NO2 and O2 but other metal nitrates are
converted to nitrites and O2:
4 Li NO3 ∆ 2 Li2O + 4NO2↑ + O2↑
2NaNO3 ∆ 2NaNO2 + O2 ↑
Diagonal relationship of Li with Mg
Though lithium, the first element of alkali metal series and the member of Group 1 and
period 2, shows a number of dissimilarities from other alkali metals yet it exhibits close

resemblance with Mg, the element of the next higher group (Group 2) and the next higher
period (Period 3) located diagonally opposite to it in the periodic table, in many respects.
This sort of relationship between the two elements in the periodic table is called diagonal
relationship:
Group 1 Group 2
Period 2 Li Be
Period 3 Na Mg
The resemblance between these diagonal neighbours is because of:
(i). Close similarity in atomic and ionic sizes, i.e.

r (Li) = 1.34Å, r (Mg) = 1.36Å
+
r (Li ) = 0.60Å, r (Mg2+) = 0.65Å
(ii).On moving down the group, the periodic properties, viz. ioniziation energy and
electronegativity decease and electropositive character increases from Li to Na But the same
properties have the reverse trend on moving across the period from Na to Mg, i.e. the first
two properties increase and the last one decreases. The net effect is that both Li and Mg have
almost the same values of these parameters.
Some points of similarity between Li and Mg are as follows:
a. Both the elements have almost similar polarizing power due to small size and high charge
density of the ions.
b. Both Li and Mg decompose water only slowly liberating H2.
c. Both the elements combine with nitrogen to give nitrides:
6Li + N2 2 Li3N
3Mg + N2 Mg3N2
d. The chlorides of both these elements are deliquescent and are separated from aqueous
solutions as hydrated crystals, i.e. LiCl. 2H2O and MgCl2 6H2O
These chlorides are also hydrolyzed in the similar way in water unlike those of other alkali
metals.
e. The nitrates, carbonates and hydroxides of both Li and Mg decompose on heating to evolve
O2 & NO2 (nitrates), CO2 (carbonates) and H2O vapours (hydroxides):

∆
4Li NO3 2 Li2O +4NO2↑ + O2↑
∆
2Mg (NO3)2 2MgO+ 4NO2 + O2↑
∆
Li2CO3 Li2O + CO2↑
∆
MgCO3 MgO + CO2↑
∆
2LiOH Li2O + H2O
∆
Mg(OH)2 MgO + H2O
7.8. SUMMARY
The course material of this unit deals with the general characteristics of the alkali metals such
as their electronic configuration, physical state, density, hardness, atomic and ionic radii
along with their atomic volume, their melting and boiling points as well as heats of
atomization, ionization energies, electron affinities and electronegativity, their electropositive
or metallic character and reducing properties, the photo electric effect and flame colouration
along with its use in qualitative and qualitative analysis. A brief account of their polarizing
power and the uses of alkali metals and their compounds have also been taken care of. The
general discussion of oxides and hydroxides of alkali metals with their preparation and
properties has been given in short. An account of the cause of solubility of alkali metal
compounds and its connection with hydration has also been given. The complexation of alkali
metal cations, anomalous behaviour of lithium and its diagonal relationship with magnesium
have been discussed with appropriate reasoning.
7.9. Terminal questions.
i. The element used in photoelectric cells is ?
(a) Li (b) Na (c) Mg (d) Cs

ii. Which one of the following has maximum reducing power in aqueous solution ?
(a) Li (b) Na (c) K (d) Cr
iii. The element imparting crimson red to Bunsen flame is ?
(a) Li (b) Na (c) K (d) Rb
iv. The least stable among the following is ?
(a) RbNO3 (b) KNO3 c) NaNo3 (d) LiNO3
v. Write a note on reducing property of alkali metals ?
vi. What is photo electric effect ?
vi. How does the electropositive character of the alkali metals vary in the group and why ?
viii. Li gives only monoxide but not higher oxides Explain?
ix. What happens when alkali metal nitrates are heated?
x. Differentiate between lattice energy and hydration energy?
xi. How does Li2CO3 differ from K2CO3?
xii. Salts of lithium, in general, are covalent while those of other alkali metals are ionic.
Explain.
7.10. Answers.
i. (d)
ii. (a)
iii. (a)
iv. (d)
v. Please refer to reducing properties.
vi. Kindly see the photoelectric effect.
vii. Please see the electropositive character.
viii. Please refer to oxides.

ix. Kindly refer to the anomalous behaviour of lithium.

x. Kindly refer to solubility and hydration of alkali inetal compounds.
xi. Please see the anomalous behaviour of Li
xii. Please refer to the polarizing power of alkali metal ions.

UNIT 8: THE ALKALINE EARTH METALS

8.1 Objectives
8.2 Introduction
8.3 General characteristics and uses
8.4 Halides and hydrides of beryllium
8.4.1 Preparation and properties of Be-halides
8.4.2 Preparation and properties of BeO hidrides
8.5 Complexation behavior of alkaline earth metals
8.6 Anomalous Behavior of Beryllium
8.7 Summary
8.9 Answers
8.1. OBJECTIVES
The course material of this unit, i.e. on the alkaline earth metals, has been written to give a
summarized view of the general characteristics and their gradation in the group and to
acquaint the readers about the properties as well as the uses of these metals and their salts in
the light of the said properties, the preparation and properties of the halides and hydrides of
beryllium, the complexation behaviour of alkaline earth metal ions along with the anomalous
behaviour of beryllium in contrast to other group members.
8.2. INTRODUCTION
The alkaline earth metals, the members of Group 2 (or IIA) of the modern periodic table,
consist of the six elements, viz. beryllium (Be4), magnesium (Mg12), calcium (Ca20),
strontium (Sr38), barium (Ba56) and radium (Ra88). The name alkaline earth metals was taken
from the fact that in old days the word ‘earth’ was applied for the metallic oxides and the
oxides of three of these metals, viz. calcium, strontium and barium were known much earlier
than the metals themselves and occurred in nature as lime (CaO), strontia (SrO) and baryta
(BaO). These oxides were called alkaline earths since they were alkaline in nature and
produced alkaline solution in water as well as they existed in nature as the earths (oxides).
Later when these elements were discovered, they were named as alkaline earth metals. After

the discovery of other members of this group, viz. Be, Mg and Ra, this term was used to
include all the elements of the group (Group 2).
However, because radium corresponds to the alkaline earth metals in its chemical properties
but it is a radioactive element, therefore, it is studied separately along with other radioactive
elements.
These elements are also said to belong to s-block of the elements because in the atoms of
these elements too, like group IA elements (or alkali metals), the differentiating or last
electron enters the s-subshell of the ultimate shell. These elements are also placed at the
extreme left portion of the periodic table after the alkali metals.
These metals are never found free (in metallic form) in nature because of their active
reducing behaviour like alkali metals and react readily with a variety of non-metals.
Magnesium is the second most abundant metallic element in the sea water and also occurs in
a variety of silicate minerals. Beryllium occurs as beryl minerals. Calcium is found
abundantly as carbonate in marble, lime stone and chalk. Strontium and barium are found
most frequently as the sulphates. Radium is a member of decay chain of U238. All these
metals can be prepared by the electrolysis of their halides or by the reduction of their oxides
with the available strong reducing agents.
8.3. GENERAL CHARACTERISTICS OF ALKALINE EARTH

METALS AND THEIR USES
The general characteristics of alkaline earth metals can be summarized as follows:
(i) Electronic configuration:
The valence (or ultimate) shell electronic configuration of the metals of the group IIA is
invariably ns2 where n is the principal quantum number or the shell number of the ultimate
shell and s denotes the subshell which receives the last electron. The penultimate shell, like
alkali metals, except Be has eight, i.e. (n-1)s2p6, electrons in these elements. Be has two
electrons i.e. (n-1)s2 in the penultimate shell. If the valence electrons are ejected from the
metal atoms of these elements, they are converted to M2+ ions having the inert gas
configuration in the outer shell. These ions are colourless and diamagnetic in nature, i.e. the
elements form colourless ionic salts and are bivalent. Due to their alike electronic structure,
these elements resemble closely in their physical and particularly in chemical properties.

(ii) Physical state, hardness and density:
All these metals are silvery white solids exhibiting grayish white metallic lustre when freshly
cut but tarnish soon after their exposure to air. They are also malleable and ductile but less
than alkali metals and are harder than alkali metals. This is because of stronger metallic
bonding in the crystal lattice. The hardness of these metals increases with increasing atomic
number. They have high electrical as well as thermal conductivity because the two valence
electrons can move easily through the crystal lattice.
These metals have higher density than alkali metals because they can be packed more tightly
due to greater charge and smaller radius. The density first decreases up to calcium and then
increases, i.e. there is irregular trend due to different crystal structures of the metals.
(iii) Atomic and ionic radii and atomic volume:
The atomic radii of these elements, though large enough, are smaller than those of the
neighbouring alkali metals in the same period due to higher nuclear charge of the atoms
which tends to draw the valence electrons inwards. The atomic radii increase down the group
from Be to Ra due to the inclusion of an extra shell of electrons at each step.
The ionic radii of M2+ ions of these elements are smaller than those of the alkali metal ions
and larger than those of other elements of the respective periods (with the same charge).
These radii also have the increasing trend as that of atomic radii down the group. This is clear
from both atomic and ionic for these elements as given below:
Elements Be Mg Ca Sr Ba Ra
Atomic radii (Å) 1.12 1.60 1.97 2.15 2.22 ----
Ionic radii (Å) 0.31 0.65 0.99 1.13 1.35 1.40
(of M2+ type ions)
The atomic volume of these elements has been found to increase on moving down the group
from Be to Ra as happens in the case of atomic radii.
(iv) Melting and boiling points and heat of atomization:

Both the melting and boiling points do not show regular trend. These are, however, higher
than those of the neighbouring alkali metals due to smaller size as compared to those
elements and much stronger bonds in solid state due to the presence of two electrons in the
valence shell.
Heat of atomization decreases from Be to Ra. Though it falls considerably from Be to Mg but
the difference is small in the subsequent elements. This reveals that the metallic bond
strength is maximum in the case of beryllium among all the alkaline earth metals.
(v) Ionization energies and oxidation states:
These elements have higher ionization energy values (1st ionization potential) than those of
the neighbouring alkali metals. This is due to the smaller size and greater nuclear charge of
the atoms of these elements as compared to alkali metals which exert stronger pull on outer
electrons. The outer ns2 electrons of these elements are removed from their atoms one by one
in steps on supplying energy and thus two ionization energy values are observed for each
element. The first as well as the second ionization energy values of these elements decrease
on going down the group from Be to Ba as expected because of increasing atomic size in the
group. However, The ionization energies of Ra are slightly higher than those of Ba but no
satisfactory explanation is available for this anomaly. Thus beryllium has the highest values
and barium has the lowest values of ionization energies among these elements. It has been
noticed that the second ionization energy is approximately double to the first ionization
energy for each element as is evident from the following table:
Table 8.1 First and Second Ionization Energies of Alkaline Earth Metals
Ionization IE(1) 899.5 738 590 549.5 503 509.5

Energies IE(2)
(kJmol-1) 1757 1451 1145.5 1064 965 979
It is interesting to note that in view of the much higher second ionization energy values of
these elements than the first ionization energy values, it appears that these metals would
prefer to form M+ ions rather than M2+ ions. However, in actual practice, these metals form
only M2+ ions, viz, Be2+, Mg2+ etc. If ionization energy were the only factor involved, they

would have formed only M+ ions rather than M2+ ions but actually they only form M2+ ions.
This anomaly has been explained by the fact that the M2+ ions are excessively hydrated and a
large amount of energy known as energy or enthalpy of hydration is released in the process
which more than counterbalances the higher value of the second ionization energy in each
case. The hydration energy values have been given below and could be compared with IInd
I.E. values of the elements:
Enthalpy of
-2455 -1900 -1565 -1415 -1275 -
hydration
(kJ mol-1)
(vi) Electropositive character and reducing property:
Because of their large size and having comparatively low ionization energies, the alkaline
earth metals are strongly electropositive elements as the change M M2+ + 2e- can be
brought about fairly readily. However, these are less electropositive than group IA elements
of their respective periods. That is why these metals do not show photoelectric effect on
exposure to light.
Among these elements beryllium has the least electropositive character and hence also has
least tendency to form Be2+ ions. That is why its compounds with nitrogen, oxygen, sulphur
and halogens are covalent whereas the corresponding compounds of other members of this
group are ionic. Also the hydroxides of these elements become more and more basic as we
move from Be to Ba.
The reducing properties (based on values of standard electrode potential) are also high for
these elements which increase down the group from Be to Ba though this property is lower
than that exhibited by alkali metals. This infers that these metals are less electropositive and
weaker reducing agents than the alkali metals of the corresponding periods inspite of high
enthalpy of hydration because of their higher sublimation and ionization energies.
(vii) Flame colouration:
The alkaline earth metals and their salts impart characteristic colours to the Bunsen flame,
viz. calcium-brick red, strontium-crimson red, barium-apple green and radium-crimson red.

The reason for this is that when energy is supplied to these elements or their compounds by
putting them in the flame, their outer electrons are excited to higher energy levels by
absorbing energy. On returning back to the ground or original level, the electrons emit or
release the absorbed energy in the form of visible light of a particular wavelength which
appears in the form of characteristic colours as given above.
In the atoms of Be and Mg elements and their salts because of their smaller size and stronger
force of attraction between the outer electrons and the nuclear charge, these electrons are not
excited to the higher levels by the energy of the flame which is unable to overcome the
attractive force. Therefore, they do not give any colour to the Bunsen flame.
(viii) Polarizing power of alkaline earth metal ions:
The polarizing power of bivalent cations of the group IIA metals for a given anion goes on
decreasing from Be2+ to Ra2+ due to increasing ionic size. This results in the formation of
covalent compounds by smaller cations, as expected, with an anion. This is the reason why
most of the Be-compounds are covalent in nature.
(ix) Hydration of alkaline earth metal ions:
The M2+ ions of alkaline earth metals are extensively hydrated to form the hydrated cation,
[M(H2O)x]2+ and in this process a large amount of energy called energy or enthalpy of
hydration is released as has already been discussed (see subsection v). The hydration energy
values and extent of hydration of the cations decrease with increasing ionic radii of
2+ 2+ 2+
anhydrous M ions, i.e. Be to Ba ion.
The hydration energy values for alkaline earth metals are higher than those of the alkali
metals in the respective periods and hence the alkaline earth metal compounds are hydrated to
the larger extent. For example, magnesium and calcum chlorides exist as MgCl2.6H2O and
CaCl2.6H2O, respectively while NaCl and KCl do not form hydrates.
(x) Solubility in liquid ammonia:
Like alkali metals, alkaline earth metals also dissolve in liquid ammonia yielding coloured
solutions. On evaporation, the metal-ammonia solutions give hexa-ammoniates, [M(NH3)6].
These ammoniates are good conductors of electricity and decompose at high temperature.

The tendency of ammoniate formation is decreased with increasing size of metal atom, i.e.
down the group.
Uses of alkaline earth metals:
(a) Beryllium (pure) is used in the nuclear reactors as the source of neutrons.
(b) Due to high permeability to X-rays, Be-sheets are used for windows of X-ray tubes. It is also
used for imparting hardness to alloys, e.g. Cu-Be alloy.
(c) Mg is used as a structural metal because of its lightness and alloying property with other
metals.
(d) Being a powerful reducing agent, Ca is used in the extraction of Be, Cr and Th metals from
their oxides which are otherwise difficult to be reduced by carbon.
(e) When alloyed with lead, Ca is used as cable covering.
(f) Since, Ca and Ba have great affinity for oxygen and nitrogen, these are used for removing air
from vacuum tubes and as deoxidizer in the manufacture of steel.
(g) Sr and Ba are also used as scavengers for removing last traces of air in steel production and
from vacuum tubes.
(h) Various Ca-salts are used industrially as follows:
(i) CaO: manufacture of bleaching powder, calcium carbide and as basic lining in furnaces.
(ii) Ca (OH)2: preparation of sodalime [Ca(OH)2 + NaOH] which is a good adsorbent for a
number of gases and as a decarboxylating agent in organic chemistry.
(iii) Gypsum : manufacture of plaster of paris.
(iv) CaCO3 : manufacture of cement.
(i) Ba salt, BaSO4 is used to prepare white pigment-lithopone (BaSO4 + ZnS)
(j) Ra-salts are used in radiotherapy for the treatment of cancer and in luminous paints.
8.4. HALIDES AND HYDRIDE OF BERYLLIUM
8.4.1 Preparation and properties of Be-halides:
Beryllium reacts directly with halogens at appropriate elevated temperatures to form halides,
Be X2:
∆
Be + X2 Be X2

BeF2, though covalent, yet is more soluble in water than other alkaline earth fluorides.
Anhydrous BeCl2 is made by the action of carbon tetra chloride on BeO at high temperature
of about 8000C (This is a standard method for preparing metal chlorides).
BeCl2 has lower melting and boiling points as well as much lower electrical conductivity in
the fused state than other alkaline earth metal chlorides because of its covalent nature (due to
high polarization power of Be2+ ions). This is hygroscopic and fumes in air, is soluble in
some organic solvents. BeCl2 is hydrolysed in aqueous solution and makes it an acidic
solution.
BeCl2 + 2H2O Be (OH)2 + 2HCl
In the gas phase, BeCl2 is a linear symmetric molecule which is consistent with a description
of the bonding in terms of sp-hyprid orbitals around the Be-atom. In the solid state, beryllium
chloride displays the Be-Cl-Be bridged structure in which each Be atom is tetrahedrally
surrounded by four Cl-atoms through covalent bonds as shown below:
Cl Cl Cl Be-Cl-Be
Be Be Be Be or
Cl Cl Cl Cl-Be-Cl
Structure of polymeric beryllium chloride
The two Be-Cl covalent bonds in the polymeric solid BeCl2 are normal covalent bond and
rest two bonds are coordinate covalent bonds with each chlorine donating a lone pair of
electrons to the Be-atom (2c-2e bonds). This compound sometimes taken as a polymer
involving a three centre-two electron (3c-2e) or multicentre bonds formed by the overlapping
of an unpaired sp-hybrid orbital of one Be, unpaired atomic orbital of Cl-atom and an empty
atomic orbital of another Be-atom.
BeCl2 is sometimes used as a Friedel –Crafts catalyst.
8.4.2 Preparation and properties of Be-hydride (BeH2):
Beryllium shows only a slight tendeny to react with hydrogen, hence BeH2 cannot be
prepared by direct combination of Be and H2. Therefore, this is prepared by reducing BeCl2
with LiH or LiAlH4 in ethereal medium.
Ether
BeCl2 + 2 LiH BeH2 + 2 LiCl
Ether

2 BeCl2 + LiAlH4 2 BeH2 + LiCl + AlCl3
Beryllium hydride is a covalent compound and reacts very slowly with water liberating
hydrogen, hence used as reducing agent.
BeH2 + 2H2 O Be(OH)2 + 2H2↑
It is a polymeric hydride (BeH2)n and exists as a solid. It contains hydrogen bridges between
Be-atoms forming three centre-two electron (3c-2e) bonds in which a banana shaped
molecular orbital covers three atoms i.e., Be-----H----Be and contains two electrons.
H H H
Be Be Be Be
H H H
Structure of polymeric beryllium hydride
The formation of three centre two electron or multicentre bonds in this polymeric hydride can
be explained in the similar way as has been done for the polymeric BeCl2. The only
difference being H atom in place of Cl- atom (see above). There is no possibility of the
existence of a coordinate bond as in case of BeCl2.
8.5. COMPLEXATION BEHAVIOUR OF ALKALINE EARTH

METALS
The complex formation by a metal is favoured mainly by the small size, highly
charged ion and availability of suitable empty orbitals. The cations of group IIA elements do
not possess these characteristics, hence are not having a significant tendency to form
complexes, however the tendency is more than those of alkali metals by virtue of their higher
charge density.
However, Be forms a number of complexes with many oxygen and nitrogen containing
organic compounds. It also gives stable complexes with F- ion due to its small size, e.g.
[BeF3]-, [BeF4]2- etc. in which Be F2 accepts electron pairs from F- ions:
BeF2 + F- [BeF3]-
(Be is sp2 hybridised and contains two normal covalent bonds and one coordinate bond.)
BeF2 + 2F- [BeF4]2-

(Be is sp3 hybridised and contains two normal and two coordinate bonds: F- BeF2)
Be2+ ion also gives [Be(H2O)4]2+ complex with four coordinate bonds of H2O Be type
2-
and [Be(oxalate)2] type complex with oxalic acid.
It gives MI2[BeCl4] with alkali metal chlorides which are decomposed by water. In aqueous
medium, Be forms stronger complex with fluoride than chloride ions. The fluoride, aquo and
oxalate complexes may be shown as:
F - F 2- H2 O 2+
Be Be Be2+
F F F F F H2 O H2 O H2 O
trigonal tetrahedral tetrahedral
2-
O = C O O C =O
Be2+
O = C O O C =O
Tetrahedral
In [Be(H2O)4]2+ complex, Be2+ ion withdraws electronic charge from oxygen atoms of water
towards itself and facilitates the removal of protons forming [Be(OH)4]2- complex ion.
(H2O)3 Be2+ ←O−H→(H2O)3 Be2+ - OH- + H+ and so on (4steps)
Thus [Be (H2O)4]2+ is an acid and [Be(OH)4]2- is a base.
Be has been found to have a unique property of forming a series of stable and volatile
molecular oxide-carboxylate complexes of general formula [OBe4(RCOO)6] where R = H,

Me, Et, Pr, Ph etc. These are white crystalline compounds readily soluble in organic solvents
but are insoluble in water or lower alcohols.
Basic beryllium acetate, R = CH3, is a common and typical example. They are best prepared
by refluxing the oxide or hydroxide with the carboxylic acid. Mixed oxide carboxylates can
be prepared by reacting a given compound with another organic acid or acid chloride. The
structure of the acetate complex (Fig. 8.1) features a central oxygen atom surrounded
tetrahedrally by four Be-atoms. The six edges of the tetrahedron so formed are bridged by the
six acetate groups in such a way that each Be atom at the corner of tetrahedron is also
coordinated tetrahedrally by four oxygen atoms.
Fig. 8.1 Structure of basic beryllium acetate
Be also forms numerous chelating and bridge complxes with ligands such as the oxalate ion
given earlier, alkoxides, β-diketonates and 1,3- diketonates.
The tendency to form complexes goes on decreasing when we move down the group which is
attributed to increasing size of the metal ions. However, Mg2+ and Ca2+ form complexes with
multidentate, ethylene diammine tetra acetate ion and Mg2+ alone with 8-hydroxy guinoline
(oxine) etc. This property is used in quantitative analysis for the estimation of these metal
ions.
8.7 Anomalous behaviour of beryllium
Beryllium, the first element of the alkaline earth metals, though shows various chemical
similarities with other group members, yet also differs from them in many respects. This
anomaly has been attributed to its small size, high charge density (charge/size) and high
electronegativity as compared to other members of the group. The main points of difference
are as follows:

(i) Beryllium is the hardest metal of all the elements of the group with the highest melting and
boiling points.
(ii) It has the tendency to form covalent compounds with anions due to its high polarizing power
and high electronegativity. At the same time its highest ionization energy among the group
IIA elements does not allow it to form Be2+ ions easily to give the ionic compounds.
(iii)It does not react with water even at high temperatures. Other alkaline earth metals decompose
water to liberate H2 as given below:
M + H2 O MO + H2 (M = alkaline earth metals except Be)
(iv) Beryllium has the lowest standard oxidation potential among all the group members and
hence has the least electropositive character. This is evident from the nature of its oxide and
hydroxide which are amphoteric, i.e. they dissolve both in acids and alkalies to form salts and
beryllates respectively:
BeO + 2HCl BeCl2 + H2O
BeO + 2NaOH Na2BeO2 + H2O
The corresponding compounds of other alkali earth metals are basic in nature, the basicity
increasing down the group.
(v) BeO is covalent and has 4:4 types ZnS (wurtzite) structure but other elements give (MO type)
oxides with 6:6 type NaCl structure and are ionic.
(vi) Beryllium does not react directly with hydrogen while other elements of the group IIA do so
easily. Further, BeH2 and MgH2 are covalent but other elements give MH2 compounds which
are electrovalent.
(vii) Beryllium on heating with carbon forms Be2C type carbide which when treated with
water evolves methane. The other members of the family form ionic carbides of the type MC2
if the metals or their oxides are heated with carbon. These ionic carbides when treated with
water evolve acetylene.
Be2C + 2H2O 2BeO + CH4 ↑
CaC2 + H2O CaO + C2H2 ↑
8.6. ANOMALOUS BEHAVIOR OF BERYLLIUM

(SIMILARITIES BETWEEN Be AND Al)
Be shows similarities in some of its properties with aluminum, the element of Group 13 (or
IIIA) and period 3 situated diagonally opposite to it. This is called diagonal relationship.

Group 2 (or IIA) Group 13(or IIIA)

Period 2 Be B
Period 3 Mg Al
The main points of similarities are given as follows:
(i) Both the elements (Be and Al) have strong tendency to form covalent compounds due to high
polarizing power which is based on the small size and high charge density of the metal ions
(charge/radius ratio: Be2+ = 6.45 and Al3+ = 6.0).
(ii) Both of them have the same value of electronegativity (1.5).
(iii)Both have almost similar values of standard oxidation potential:
Be = + 1.70 V, Al = + 1.67V
(iv) The oxides of both the elements are amphoteric in nature, i.e. dissolve in acids as well as
alkalies.
BeO + 2HCl BeCl2 + H2O
BeO + 2Na OH Na2BeO2 + H2O
Al2O3 + 6HCl 2AlCl3 + 3H2O
Al2O3 + 2NaOH 2NaAlO2+ H2O
(v) The Carbides of both Be and Al evolve methane (CH4) on treatment with water.
Be2C + 2H2O 2BeO + CH4 ↑
Al4C3 + 6H2O 2Al2O3 + 3CH4 ↑
(vi) Both the metals on reacting with dilute mineral acids or caustic alkalies liberate hydrogen
gas.
Be + 2HCl BeCl2 + H2↑
Be + 2NaOH Na2BeO2 + H2 ↑
2Al + 6HCl 2AlCl3 + 3H2↑
2Al + 2NaOH + 2H2 2NaAlO2 + 3H2↑
(vii) Both Be and Al are rendered passive on treating with conc. HNO3 due to the
formation of protective oxide coating on the metal surface.
8.7. SUMMARY
In the text of this unit, a detailed description of the general characteristics such as their
electronic configuration, hardness, density, atomic and ionic radii, ionization energies,

reducing property and electropositive character, melting and boiling points, flame
colouration, polarizing power, hydration property and solubility in ammonia along with the
uses of alkaline earth metals and their salts has been given. A detailed account of the halides
and hydride of beryllium has also been given in the light of their preparation, properties and
structural details. The complexation behaviour of the alkaline earth metals in general and that
of beryllium in particular has been discussed with example. The anomalous behaviour of
beryllium and its diagonal relationship with aluminum, the element of the next higher group
and period has also been taken care of.
8.8. Terminal questions.
i. Which one of the following is more basic ?
(a) Be(OH)2
(b) Mg(OH)2
(c) Ba(OH)2
(d) Ca(OH)2
ii. Which oxide of the following is amphoteric ?
(a) BaO
(b) SrO
(c) CaO
(d) BeO
iii. The metal used in nuclear reactors is
(a) Be
(b) Ca
(c) Ba
(d) Ra

iv. The alkaline earth metal having the lowest ionization energy value is
(a) Be
(b) Ca
(c) Ba
(d) Ra
v. The two alkaline earth metals imparting crimson red flame colouration are
(a) Be and Mg
(b) Mg and Ca
(c) Ca and Sr
(d) Sr and Ra
vi. Though the alkaline earth metals have two ionization energy values, yet in aqueous
solution they exhibit only + 2 Oxidation state. Explain.
vii. why do Be and Mg not give any colour in the Bunsen flame?
viii. Why are these metals used as deoxidizers?
ix. Discuss briefly the bonding in BeH2.
x. Discuss the structural aspects of basic beryllium acetate.
xi. How do Be and Al react with acids and alkalis?
xii. What factors are responsible for anomalous behaviour of Be in contrast other group
members?
8.9 ANSWERS
i. (c)
ii. (d)

iii. (a)
iv. (c)
v. (d)
vi. Please see ionization energies and oxidation state.
vii. Please refer to flame colouration.
viii. Due to their high affinity for oxygen and air.
ix. Please refer to hydrides of Be.
x. Please see the complexation behavior of group IIA elements.
xi. Please see the diagonal relationship.
xii. Please refer to anomalous behaviour of Be.

UNIT 9: ELEMENTS OF GROUP -13
CONTENTS:
9.1 Objective
9.2 Introduction
9.4 Hydrides of boron diborane and borazine
9.4.1 Diborane
9.4.2 Borazine
9.5 Halides of boron and aluminium
9.5.1 Boron trihalides
9.5.2 Aluminium halides
9.6 Oxides of boron and borates
9.6.1 Oxides of boron
9.6.2 Borates
9.7 Anomalous behaviour of boron
9.8 Summary
9.10 Answers
9.1 OBJECTIVES
The text of the study material of this unit, i.e. on the elements of Group 13 or group IIIA, has
been prepared to throw light on the general characteristics and uses of the elements of boron
family, to make the readers understand the interesting and important aspects of hydrides of
boron particularly diborane and borazine in terms of their preparation and properties as well
as their structure, the halides of boron and aluminium and oxides of boron and borates. The
readers have to be well acquainted with anomalous behaviour of boron in contrast to other
family members of this group.
9.2 INTRODUCTION

Group 13 (or group IIIA) of the long form of periodic table contains five elements, namely
boron (B5), aluminium (Al13), gallium (Ga31), indium (In49) and thallium (Tl81). This group is
also known as boron group. All these elements are said to belong to the p-block of elements
as the differentiating electron in the atoms of these elements enters the p-subshell of the
outermost or the valence shell. The first element boron is semimetal while other members of
this group are metals as is indicated by their properties, i.e. boron is closer to non-metals is its
properties but the rest of the members show metallic properties.
Boron occurs rather sparsely, aluminium is the third most abundant element found in earth’s
crust, i.e. it is the most abundant element of these all, gallium, indium and thallium are not
found in concentrated deposits and do not find much of commercial applications.
9.3 GENERAL CHARACTERISTICS
The inclusion of these elements in the same group of the periodic table is justified by the
following general characteristics of these elements but these have been found to show a wider
range of variations and also notable contrast in their properties.
These elements are characterized by three electrons in the valence shell, two of which are s-
electrons and one a p-electron, i.e. the valence shell configuration of the atoms of these
elements is ns2np1, n being the principal quantum number, the ultimate shell which varies
from 2 for boron to 6 for thallium. Unlike the s-block elements, the electronic configuration
of the penultimate shell of the atoms of these elements varies from inert gas to pseudo inert
gas type. Boron has helium configuration (i.e.1s2), aluminium has octet (2s2p6) and rest of the
elements have (n-1)s2p6d10 type configuration (i.e. n-1 = 3 for Ga, 4 for In and 5 for Tl) in the
penultimate shell. This difference in the electronic configuration in the penultimate shell,
though the valence shell has the same configuration, is responsible for the abrupt variation in
the properties of these elements.
(ii) Density, melting and boiling points and heat of sublimation:
The density, in general, increases on moving down the group, however, Al has exceptionally
low density. Melting point decreases considerably from B to Ga and then increases up to Tl
but boiling point shows a regular decreasing trend down the group. Similar trend is observed

in heats of sublimation also indicating that the atoms of the elements are held less and less
closely as we move down the group. Very low melting point of Ga (300C) which is about ten
times less than that of Tl and about seventy times less than that of B is explained on the basis
that its structure contains Ga2 molecules.
(iii) Ionization energy:
The first ionization energy of these elements corresponds to the removal of np1 electron
which is invariably held with nucleus less tightly and has low value. Its value decreases, as
expected from B to Al because Al has larger size but then increases slightly in Ga. This is
because from Al to Ga though atomic size increases but d-electron in the penultimate shell
(with s2p6d10 configuration) in Ga not able to shield the nuclear charge effectively and the
valence electrons in this element are more firmly held to the nucleus thereby having slightly
higher ionisation energy value. Thallium has unexpectedly higher ionisaton energy due to the
inclusion of f-electrons as well as d-electrons in the inner shells and their low shielding
effect.
These elements have been assigned three successive ionization energies (i.e. I1, I2 and I3), the
first belonging to the removal of p-electron and last two to the ejection of s-electrons one by
one for each elements I3> I2 >I1. Boron has the highest values of all the three ionisation
energies among these elements. Though the nuclear charge of these elements is larger and
their size is smaller than those of Group 2 elements, yet their first ionisation energies are
unexpectedly lower than those of the alkaline earth elements in the respective periods. This is
due to the fact that the p-electrons are less penetrating and lie at larger distance from the
nucleus than the s-electrons and hence can be removed more easily.
(iv) Oxidation state:
Boron gives mainly covalent compounds and has least tendency to from B3+ ion which is
unstable because of very small size and very high ionization energy of its atoms but it may be
arbitrarily assigned +3 oxidation state in its compounds with more electronegative elements.
Aluminium has high charge density due to small size and high charge of Al3+ ion, hence its
compounds, in general, are ionic in solution (having high hydration energy) and are covalent
in gaseous phase. In solid state, its compounds have high lattice energy. In general sense it
can be assigned + 3 oxidation state.

The higher elements exhibit both +1 and +3 oxidation states, +1 state becoming more and
more stable down the group from Ga to Tl. Thus in Ga, +3 state has been found more stable
than +1 state but in Tl, +1 state is more stable. This peculiar property of these elements is due
to the inert pair effect which increases from Ga to Tl down the group. In the compounds of
Ga, In and Tl with +1 oxidation state, the np1 electron only takes part in combination and ns2
electron pair remains inert due to its penetration in the inner shell and strong attractive force
operating between nucleus and ns2 electrons.
The relative stability of +1 and +3 oxidation states in the last three elements can be shown as
follows:
Ga3+ > In3+ > Tl3+ and Ga+ < In+ < Tl+
(v) Electropositive character:
The electropositive or metallic character of these elements increases form B to Tl down the
group. Boron is a semi-metal and all the other elements are distinctly metallic and good
conductors of electricity having almost equal electropositive character as well as close
ionisation energy values.
(vi) Tendency to form ionic or covalent compounds:
From the electronic configuration of these elements, all of them would be expected to form
M3+ type ions and the compounds would be ionic. However, the second and third ionisation
energies of boron are so high that it has little tendency to form B3+ ion and other elements
have higher tendency to form such ions under suitable conditions due to lower ionisation
energies. Thus these elements form ionic compounds.
Further if trivalent ions are formed, the smaller ions will have more polarising power and will
tend to give covalent compounds. This tendency goes on decreasing down the group. That is
why B gives covalent compounds, Al forms both covalent and ionic compounds and the
higher members result mainly in ionic compound formation.
(vii) Oxidation potential:
With the exception of B, the standard oxidation potential values for the elements
corresponding to the conversion; M [M (aq)]3+ + 3e-, are quite high because of large

quantity of hydration energy associated with the [Maq]3+ ions in solution inspite of their large
values of ionization energies. These high potential values for these elements may be
attributed to the high charge and small radii of M3+ ions (i.e. high charge density).
(viii) Gradation in chemical properties:
Some chemical properties of these elements along with their gradation in the group are
discussed below:
(a) Action of air and water:

Boron is almost unreactive at ordinary temperature but when heated it reacts with air (O2). It
does not react with water but is attacked by hot conc. acids, e.g. H2SO4.
Aluminium readily reacts with air even at ordinary temperature to form a protective layer of
the oxide which protects it from further action of air. It decomposes cold water.
Galium and Indium do not react with water in absence of O2. Thallium forms an oxide
coating on the surface when treated with air.
(b) Nature of oxides and hydroxides:
All the elements form oxides and hydroxides. B2O3 and B(OH)3 both are acidic. This is
because hypothetical B3+ ion, being very small, has very high positive charge density. Hence
when placed in water, it tends to pull off electrons from water molecule towards itself
sufficiently strongly by rupturing the O-H bond in water molecule. This results in the rapid
hydrolysis of hypothetical B3+ ion by H2O releasing H+ ions. B(OH)3 dissolves in strong
alkalies to form metaborates, e.g.
B(OH)3 + NaOH NaBO2 + 2H2O
3+ 3+
The Trivalent Al and Ga ions, being relatively larger have smaller capacity to rupture the
O-H bond in H2O molecule by pulling off electrons. Consequently they are hydrolysed to a
smaller extent than the hypothetical B3+ ion. Hence the oxides and hydroxides of Al and Ga
are amphoteric. The In3+ and Tl3+ ions are very large and their interaction with water is very
slow. The O-H bond in water is hardly affected by these ions. This makes the oxides and
hydroxides of In and Tl distinctly basic. It can be concluded from above that on moving
down the group of these elements, the oxides and hydroxides change from acidic through
amphoteric to basic in character.
(c) Halides:
All the elements of this group react with halogens to form the trihalides. B-halides are
covalent due to its small size and high charge density.

The fluorides of other elements of the group are ionic and have high melting points while the
other halides are covalent when anhydrous. For example, anhydrous AlCl3 is covalent but in
water it is hydrolyzed to give Al3+(aq) ions. This is due to the high hydration energy of Al3+
ions.
The normal trihalides are planar triangular in shape (sp2 hybridization). One vacant
unhybridised p-orbital is present in the central atom of these halides which can accommodate
one electron pair from the donor molecules or ligands, thus acting as Lewis acids. Boron
trihalides have strong tendency to form complexes of BX3L type where L is a neutral
molecule or anionic donor (i.e. ligand). These complexes are tetrahedral with three normal
and one coordinate bonds.
Boron trihalides exist as discrete molecules while trihalides of other elements exist as dimers
both in vapour state and in non-polar solvents making use of vacant p-orbital.
(d) Hydrides:
These elements do not react directly with hydrogen to form hydrides. Howener, hydrides of
all these elements have been prepared by indirect methods. Boron forms a large number of
covalent polymeric hydrides called boranes. Aluminium forms only one high molecular
weight polymeric hydride, (AlH3)n containing Al-atoms octahedrally surrounded by six H-
atoms. Gallium gives only one volatile and unstable liquid hydride-gallane (Ga2H6). Indium
forms polymerized solid hydride, (InH3)n but Tl hydrides are unstable. These elements also
form the complex anionic hydrides with alkali metal hydrides like Li+[BH4]-, Li+[AlH4]- etc.
where H- ion acts as electron pair donor. These complex hydrides are used as reducing
agents.
Uses of Group 13 elements:
Boron and aluminium are more commonly used elements.
(i) Boron is used as deoxidiser, in the casting of copper, for making boron steels which being
very hard are employed as control rods in atomic reactors, in the manufacture of thermo
regulators etc.
(ii) Its hydrides are used as fuels for rockets, borides and boron carbide are used as abrasives.
(iii)Boric acid is used in antiseptics and eye lotions etc.
(iv) Aluminium-alloys find extensive use in industry, Al itself for making utensils, frames, coils
for motors and cable wire for electrical transmission, in the extraction of chromium and
manganese.

(v) Aluminium-powder is used in making silvery white paints, in fireworks, flash light powders
and thermite welding.
(vi) Ga, In and Tl elements do not find important applications but their salts are sometimes used
for various purposes.
9.4 HYDRIDES OF BORON: DIBORANE AND BORAZINE
Boron forms a large number of polymeric hydrides called boranes, e.g. B2H6, B4H10, B5H9,
B5H11 etc. Diborane (B2H6) is an import member of this series.
9.4.1 Preparation of diborane (B2H6):
Diborane can be prepared by the following methods:
(i) By the action of ionic hydrides like NaH or CaH2 on BCl3
6NaH + 3BCl3 B2H6 + 6NaCl
3CaH2 + 2BCl3 B2H6 + 3CaCl2
(ii) By the reduction of BF3 with Li H, Li (BH4) or Na (BH4)
8BF3 + 6LiH B2H6 + 6LiBF4
BF3 + 3Na(BH4) 2B2H6 + 3Na F
(iii) By the reduction of BCl3 with Li [AlH4]
4BCl3 + 3Li(AlH4) 2B2H6 + 3LiCl + 3AlCl3
(iv) By the reduction BCl3 vapours with molecular hydroge.

2BCl3 (vapours) + 6H2 B2H6 + 6HCl
Properties:
It is an inflammable colourless gas, extremely toxic and reactive and stable only at low
temperatures in absence of moisture.
(A) Decomposition:
(i) By heat:

When heated between 1000C and 2500C, it changes into a number of boranes:
1000C
2B2H6 B4H10 + H2
0
100 C
5B2H6 B10H14 + 8H2
1050C
5B2H6 2B5H11 + 4H2
2500C
5B2H6 B5H9 + B5H11 + 5H2

120mm
(ii) By water:
B2H6 is readily decomposed (hydrolysed) by water into boric acid and H2.
B2H6 + 6H2O 2H3BO3 + 6H2O
(iii) By aquous alkalies:

On passing B2H6 into an aq. solution of alkalies, e.g. KOH, at 00C, potassium hypoborate, K2
[B2H6O2], is obtained solution.
0 0C
B2 H6 + 2KOH K2[B2 H6O2] (pot. hypoborate)
On diluting this solution, potassium metaborate is formed.

K2[B2H6O2] + 2H2O 2KBO2 + 5H2
Evolution of H2 in alkaline medium makes it a useful reducing agent.
(B) Combustion:
B2H6 is an extremely reactive gas hence under controlled conditions, if reacted with O2, gives
large amount of energy at room temperature.
250C
B2H6 + 3O2 B2O3 + 3H2O + Energy (Rocket fuel)
(C) Action of halogens and halogen acids:

Under different conditions it reacts with halogens (except iodine) and halogen acids.
250C
B2H6 + 6Cl2 2BCl3 + 6HCl (vigorous reaction)

1000C

B2H6 + Br2 B2H5Br + HBr (slow reaction)

temp.
B2 H6 + HX B2H5 X (X = Cl, Br, I) + H2.

catalyst
(D) Reaction with alkali metal hydrides:
Alkali hydrides suspended in ether react with diborane and give alkali metal borohydrides
which are used as reducing agents.
B2H6 + 2LiH 2Li[BH4]

B2H6 + 2NaH 2Na[BH4]
(E) Reaction with ammonia:

Under different experimental conditions, diborane reacts with ammonia giving various
products:
(i) At low temperature of about 1200C, excess of ammonia gives an addition compound,
diammoniate of diborane.
low tem.
B2 + H6 + 2NH3 B2H6.2NH3 (white non-volatile solid)
(ii) At high temperature, it reacts with excess of ammonia forming boron ritride.
high temp.
nB2H6 + 2nNH3 2(BN)n + 6nH2
(iii) At high temperature, B2H6 and NH3 in 1:2 ratio, react together to form borazine (or
borazole), B3N3H6.
high temp.
3B2H6 + 6NH3 2B3N3H6 + 12H2

Structure of diborane:
The electron diffraction and infra-red spectroscopic studies of B2H6 molecule have shown
that this molecule has hydrogen bridge structure (Fig. 9.1a) in which two irregular BH4
tetrahedra have one edge in common and thus two B atoms (B1 and B2) and four terminal H-
atoms (Ht) are coplanar (lie in the same plane) while remaining two bridging H-atoms (Hb)
are located at the centre above and below the plane, the two planes are perpendicular to each
other.

Fig 9.1a Bridged structure of diborane
From the figure it is clear that the B2H6 molecule possesses four B-Ht bonds, two bonds
attached with each B atom with the bond distance = 1.19Å (2c-2e bonds), two bridging B1-
Hb-B2 bonds with bond length of B1 - Hb= 1.37Å. The B1-B2 distance is 1.77Å. The bond
angles between Ht atoms and each B atom = 1220 and that between Hb atoms and each B
atom = 970, Both the B-Hb-B bonds are bridging bonds (3c-2e type).
The formation of the bridging (3c-2e) B1-Hb-B and terminal (2c-2e) B-Ht bonds in this
molecule may also be explained on the basis of hydrisation. According to this concept each B
atom is sp3 hybridization thereby giving four hybrid orbitals one of which is vacant and the
other three are singly filled (B has ns2p1 ns1px1Py1Pz0 configuration in the ground and
excited states).
The formation of four terminal normal (2c-2e) covalent bonds, two each by both B atoms,
occurs by the overlapping of two singly-filled sp3 hybrid orbitals on each B atom with half-
filled orbitals of four Ht atoms (two each with each B atom). Thus these are sp3-s type bonds.
Each B atom is now left with one singly-filled and one vacant sp3 hybrid orbitals which
participate in the formation of the bridging bonds. One half-filled sp3 hybrid orbital on B1
atom and one vacant sp3 hybrid orbital on B2 atom then overlap jointly with half-filled 1s-
orbital on one Hb atom to form a B1-Hb-B2 bridging bond. Another such bond is formed by
overlapping of vacant sp3 orbital on B1atom, half-filled sp3 hybrid orbital on B2 atom and
half-filled 1s-robital on another Hb atom. These two bonds are called 3 centre-2electon (3c-
2e) bonds because 2 electrons hold 3 centres together (Fig. 9.1b)

Fig. 9.1b Formation of 3c -2e bonds
9.4.2 Borazine or borazole (B3N3H6):

This compound is also sometimes known as inorganic benzene and is isoelectronic with
benzene.
Preparation:
(i) Heating a mixture of B2H6 and NH3:
As has been given earlier in the properties of diborane, this compound is formed when
diborane and ammonia are reacted at high temperature in 1:2 molar ratio.
high temp.
3B2H6 + 6NH3 2B3N3H6 + 12H2

Diammoriate of diborane formed at low temperature by mixing B2H6 and NH3 may also be
converted to borazine by heating at high temperature.
low temp.
B2H6 + 2NH3 B2H6.2NH3

high temp.
3(B2 H6.2NH3 2B3N3H6 + 12H2

(ii) Reaction of Li [BH4] on NH4Cl:
This reaction is carried at high temperature.
3NH4Cl + 3Li[BH4] B3N3H6 + 3LiCl + 9H2

(iii) Heating BCl3 with NH4Cl:

When BCl3 is heated with NH4Cl in chlorobenzene (C6H5Cl) in presence of a catalyst (e.g.
Fe, Ni, Co etc) at 1330C, trichloroborazine is obtained which on being reduced by Li[BH4] in
polyether gives borazine (yield by this method is about 50-60%).
∆, C6H5Cl
3BCl3 + 3NH4Cl Cl3B3N3H3+ 9HCl

(Fe cata.)
Redu.
2Cl3B3N3H3 + 6Li[BH4] 2B3N3H6 + 6LiCl + 3B2H6

Properties:
Borazine is a colourless and volatile liquid. Its important chemical properties are;
A. Hydrolysis:
(i) It is slowly hydrolysed by water to produce boric acid, H3BO3, ammonia and H2 which is
favoured by increasing temperature.
B3N3H6 + 9H2O 3B(OH)3 + 3NH3 + 3H2
(ii) It has also been reported that under certain conditions, borazine reacts with three molecules
of water to produce tri-hydroxylbora-zine, (OH)3B3N3H3, in which OH groups are attached
with B-atoms.
B3N3H6 + 3H2O B3N3H3(OH)3 + 3H2
B. Addition reactions:
(i) It has been found that one molecule of borazine adds three molecules of H2O, CH3OH, CH3I,
HCl or HBr in the cold without a catalyst. Since B-atom is less electronegative than nitrogen
atom in B-N bond, more negative groups or atoms of these molecules are generally attached
with boron. HCl derivative of this compound when heated at 50-1000C, loses H2 molecules
to gives B-trichloro borazine (Cl-atoms attached to B-atoms).
∆
B3N3H6 + 3HCl B3N3H9Cl3 B3N3H3Cl3

-3H2
(ii) One molecule of borazine also adds three molecules of Br2 at 00C giving B-tribromo-N-
tribromoborazine which on heating at 600C, loses three molecules of HBr to form B-
tribrimoborazine.
+3Br2 600C
B3N3H6 B3N3H6Br6 B3N3H3Br3 + 3HBr

00C
C. Hydrogenation:
Borazine can be converted to cyclotriborazine, B3N3H12 as shown below:

+3HCl +3NaBH4
B3N3H6 B3N3H9Cl3 B3N3H12 + 3/2B2H6 + 3NaCl

Cyclotriborazine
Structure:
Electron diffraction studies and various chemical reactions of this compound have shown that
this is isoelectronic with benzene and its structure is similar to that of benzene. It has a planar
hexagonal structure containing six-membered ring with alternate B and N atoms, i.e.-BH-and
-NH groups.
H H
N N
HB BH HB BH
HN NH HN NH
B B
H H
Each of B-N bond distances is 1.44Å which is approximate average of single B-N (1.54Å)
and double B-N (1.36Å) bond distances. All the angles are equal to 1200. Like benzene, this
compound is also said to have aromatic π electron cloud which is delocalized over the atoms
of the ring. The B-N bonds are polar with π-cloud localized more on N- atoms. This weakens
the π-bonding in the ring and hence polar species like HCl can attack this double bond
between B and N and the molecule can undergo addition reactions readily.
All the B and N atoms in the ring presumably use sp2 hybrid orbitals to form three B-N σ
bonds and B-N π- bonds arise from the sideways overlapping of the unhybridised p-orbitals
of B and N atoms which are at right angles to the plane of the ring and π-electrons are not
derived from all the six atoms of the ring but from the three N-atoms only.

9.5 HALIDES OF BORON AND ALUMINIUM

9.5.1 Boron trihalides, BX3 (X = F, Cl, Br, I)
Boron reacts with halogens and forms all the trihalides, BX3 where X = F, Cl, Br, I.
Preparation of BX3 (halides):
All the trihalides of boron, with the exception of trifluoride, can be prepared by the treatment
of a mixture of B2O3 and carbon with the appropriate halogen at higher temperatures.
B2O2 + 3C + 3X2 2BX3 + 3CO (X = Cl, Br, I)
The trifluoride has been prepared by the treatment of H2SO4 on the mixture of calcium
fluoride and boron oxide.
3CaF2 + B2O3 + 3H2SO4 3CaSO4 + 3H2O + 2BF3
Or by the action of HF on B2O3.
B2O3 + 6HF 2BF3 + 3H2O
Properties:
BF3 and BCl3 are gases, BBr3 is a liquid and BI3 is a solid at room temperature.
(i) Covalent character:

All the boron trihalides are covalent in character due to the small size and high charge density
of B3+ ion. As liquids they do not conduct electricity. i.e. are non-electrolytes. They exist as
discrete molecular species and have very low boiling points.
(ii) Geometry and formation of complex halides:
They all have planar triangular geometry resulting from sp2 hybridisation of B-atoms. One p-
orbital in B-atom remains unhybridised which can accept a lone pair of electrons. Hence the
trifluorides are strong electron acceptors or Lewis acids and are capable of complex ion
formation, e.g. [BF4]- with coordination number 4 but not beyond 4 due to non-availability of
d-orbitals in its valence shell. BF3 + F- [F3B ← F-]
(iii) Addition compounds-electron-acceptor property:
Due to the availability of vacant p-orbital on B-atoms, all the trihalides act as electron-
acceptors because they are electron-deficient (two electrons short of an octet). They can
accept an electron pair from the donor atoms of the molecules having lone pair (s) of

electrons like N in NH3, O in H2O, P in PH3 etc. to form adducts or addition compounds in
the way as they form complex halides (given above)
BF3 + :NH3 BF3.NH3 = [F3B←NH3]
BF3 + :OH2 BF3.OH2 = [F3B←OH2]
This property of BF3 makes it an extremely useful catalyst in organic chemistry.
Though BX3 molecules have plane triangular geometry, the addition compounds attain
tetrahedral shape, the central atom using all its orbitals in the valence shell, three half-filled
and one vacant and undergoing sp3 hybridisation.
The order of electron-acceptor ability of boron trihalides is BF3 < BCl3 < BBr3 < BI3 due to
pπ-pπ back bonding in the molecules which decreases in the order: BF3 > BCl3 > BBr3 > BI3
with increasing atomic size of halogen atoms.
(iv) Hydrolysis:
B-trihalides are easily hydrolysed to form boric acid.
BX3 + 3H2O H3BO3 + 3HX (X = Cl, Br, I)
BF3, however, gives fluoroboric acid which is resulted by the combination of H+ion and BF4 -
ions.
BF3 + 3H2O H3BO3 + 3HF
[HF H+ + F-] x 3
[BF3 + F- BF4-] x 3
___________________________
4BF3 + 3H2O H3BO3 + 3H+ + 3BF4-
Or 4BF3 + 3H2O H3BO3 + 3HBF4
BCl3, BBr3 and BI3 are more readily hydrolysed by H2O than BF3 showing that they are
stronger Lewis acids than BF3 itself.
9.5.2 Aluminium halides:

Aluminium forms all the halides. AlF3 is ionic while other halides are covalent when
anhydrous. AlCl3 is the most important of all the halides which will be discussed here.
Preparation of AlCl3:

(i) When aluminum metal or its hydroxide is treated with HCl, solution of hydrated aluminum
chloride is obtained.
2Al + 6HCl 2AlCl3+ 3H2↑
Al(OH)3 + 3HCl AlCl3+3H2O
On evaporating the solution, crystals of AlCl3.6H2O are obtained.
(ii) Anhydrous AlCl3 is prepared as follows:
(a) By passing dry chlorine or HCl gas over heated Al-powder.
AlCl3 vapours are condensed to get AlCl3.
∆
2Al + 3Cl2 2AlCl3
∆
2Al + 6HCl 2AlCl3+ 3H2↑
(b) By heating a mixture of alumina and coke in a current of chlorine.

∆
Al2O3 + 3C + 3Cl2 2AlCl3 + 3CO↑
(c) By heating alumina in a current of S2Cl2 vapour and Cl2.

This method is used for its commercial preparation
∆
4Al2O3 + 3S2Cl2 + 9Cl2 8AlCl3 + 6SO2
(d) AlCl3 can also be obtained by heating alumina in a current of carbonyl chloride (COCl2)
Al2O3 + 3COCl2 2AlCl3 + 3CO2↑
Propertius of Aluminium chloride:
Anhydrous salt is a white crystalline solid, is hygroscopic and fumes in moist air, it sublimes
at ~ 1800C below its melting point (1930C at 2atm. pressure). It is a typical covalent
compound soluble in organic solvents like C6H6, CS2 etc. and shows poor conductivity in the
fused state.
(i) Hydrolysis:
It undergoes hydrolysis in water to give an acidic solution due to the liberation of HCl.
AlCl3 + 3H2O Al (OH)3 + 3HCl
Similar reaction occurs in moist air to give fumes of HCl.
(iii) Its solution gives white precipitate of Al (OH)3 with NH4 OH.
AlCl3 + 3NH4 OH Al (OH)3↓ + 3NH4Cl
ppt
(iii) With excess of NaOH, the salt solution gives soluble meta aluminate, NaAlO2.
AlCl3 + 3NaOH Al(OH)3↓ + 3NaCl
ppt
Al(OH)3 + NaOH NaAlO2 + 2H2O

(iv) It forms adducts or addition compounds with a number of donor molecules like NH3, PH3,
COCl2 etc.
AlCl3 + 6NH3 AlCl3.6NH3 (hexa ammoniate of Al Cl3)
Uses:
It is used in organic chemistry as a catalyst in friedel-Crafts reaction and manufacture of

dyes, drugs and perfumes.
Structure
In solution and at very high temperature of 750 – 8000C, it has mono meric formula, AlCl3
but at 350 - 4000C, its vapour density corresponds to the dimeric formula, Al2Cl6. In the
dimer, the halogen atoms are tetrahedrally arranged around the Al-atoms.
The dimeric formula is retained when it is dissolved in non-polar solvents like benzene.
Cl Cl Cl
Al Al
Cl Cl Cl
Dimeric AlCl3
9.6 OXIDE OF BORON AND BORATES

9.6.1 Oxide of boron (B2 O3):
Preparation:

When boron is heated in presence of oxygen, B2O3 is formed

7000C
4B + 3O2 2B2 O3
Properties of B2O3:
B2O3 is a solid of high melting point.
(i) Acidic character:
Its acidic character is revealed by the fact that it reacts with strong alkalies or fused metal
oxides to give metaborates.
B2O3 + 2NaOH 2NaBO2 + H2O
B2O3 + MO M(BO2)2 (MO = metal oxide)
(ii) Feeble basic character:
It is also very weakly basic in nature since it also reacts with HF. This method is sometimes
used to prepare BF3.
B2O3 + 6HF 2BF3 + 3H2O
It also reacts with HCl forming BCl3.
B2O3 + 6HCl 2BCl3 + 3H2O
(iii) Hydrolysis:
When treated with water, it undergoes hydrolysis to produce boric acid.
B2O3 + 3H2O 2H3BO3
(iv) Reduction:
It is reduced by Mg or alkali metals to the free state.
B2O3 + 3Mg 3MgO + 2B
B2O3 + 6K 2B + 3K2O
(v) Formation of carbide:
On heating with carbon in an electric furnace, it gives boron carbide.
∆
2B2O3 + 7C B4C + 6CO

(vi) Reaction with Cl2:
When B2O3 is heated with carbon in a current of dry Cl2, BCl3 is formed.
B2O3 + 3C + 3Cl2 2BCl3 + 3CO
9.6.2 Borates:

Borates are the salts of weak boric acids, viz. orthoboric acid (H3BO3), metaboric acid
(HBO2), pyroboric acid (H6B4O9) and tetraboric acid (H2B4O7) and are named on the basis of
the name of the acid, e.g. orthoborates, metaborates, tetraborates etc.
The most important borate, known as sodium tetraborate or Borax, is being discussed here.
Borax or sodium tetraborate (Na2B4O7):
This compound is the sodium salt of tetraboric acid.
Preparation:
It occurs naturally as well as can be prepared artificially.
It can be prepared by the action of sodium carbonate or alkalies on boric acid.
4H3BO3 + Na2CO3 Na2B4O7 + 6H2O + CO2
4H3BO3 + 2NaOH Na2B4O7 + 7H2O
Properties:
Borax exists in three forms: (a) ordinary or prismatic borax which is decahydrate, Na2B4O7.
10H2O. It is obtained when a solution of the salt is crystallized at room temperature,. (b)
Octahedral or Jeweller’s borax which is pentahydrate, Na2B4O7.5H2O and is obtained when
the solution is crystallized above 600C. (c) Borax glass is the anhydrous from Na2B4O7 and is
obtained by heating the ordinary borax above its melting point until all of lattice water is
given off.
(i) Basic nature:
Though this compound is sparingly soluble in cold water, yet is fairly soluble in hot water
and the solution is alkaline because borax is hydrolyzed to give NaOH and H3BO3.
Na2B4O7 + 7H2O 4H3BO3 + 2NaOH
(ii) Action of heat:
On heating above its melting point, it loses its lattice water and swells up to a white porous
mass. On further heating, it melts to a liquid which then solidifies to a transparent glassy
mass consisting of NaBO2 and B2O3.
∆ ∆
Na2B4O7.10H2O Na2B4O7 2NaBO2 + B2O3

-10H2O
(iii) Action of Acids:

Being basic in nature it reacts with conc. acids to form boric acid.
Na2B4O7 + 2HCl + 5H2O 4H3BO3+ 2NaCl
(iv) Action of NH4Cl:
When heated with NH4Cl, it forms boron nitride.

Na2B4O7 + 2NH4Cl 2BN +2NaCl + B2O3+ 4H2O

Uses:
Borax is used
(i) In borax bead test for the detection of basic radicals.
(ii) In the manufacture of enamels and glazes for pottery.
(iii) In making borosilicate glassware.
(iv) As a preservative for food.
9.7 ANOMALOUS BEHAVIOUR OF BORON

Boron, the first element of Group 13 (or IIIA), though shows similarity in some of its
properties with other members of the group, yet there are dissimilarities also among them.
These dissimilarities in the properties of boron from other member of its group are attributed
to (i) its small size, (ii) high charge density, (iii) high electronegativity and (iv) non-
availability of the d-orbitals in the ultimate shell of boron. The main points of difference
among these elements are:
(i) All the compounds of boron are covalent while other elements give covalent as well as
electrovalent compounds.
(ii) Maximum covalency of boron is 4 while other elements may have covalency higher than this.
i.e. 6 or more due to the availability of vacant d-orbitals in their ultimate shell.
(iii)Electron accepting power, i.e. Lewis acid character of boron compounds is higher than those
of other elements.
(iv) It does not exhibit inert pair effect at all while the elements beyond Ga show this property.
Both boron and aluninium are closer in some of their properties but the higher members have
distinctly different behaviour.
Diagonal Relationship between B and Si
Boron resembles silicon, the element of higher group and higher period in many of its
properties to which it is diagonally related. These are:
(i) Both the elements can be prepared by reducing their oxides with Mg metal.
B2O3 + 3Mg 2B + 3MgO
SiO2 + 2Mg Si + 2MgO
(ii) Both the elements are not attacked by water but dissolve in alkalies (in fused state) forming
metaborate and metasilicate liberating H2.
2B + 2NaOH + 2H2O 2NaBO2 + 3H2↑
Si + 2NaOH + H2O Na2SiO3 + 2H2↑

(iii)Both the elements do not occur in free state, are typical non-metals hence bad conductors of
heat and electricity and exist in two allotropic forms, viz. amorphous and crystalline.
(iv) Both of them have almost the same density, ionization potential electronegativity and boiling
point but differ in their melting points.
(v) Both the elements are inert at ordinary temperature but reactivity increases with rise in
temperature and both form mainly covalent compounds like hydrides, halides, oxides etc. The
oxides have macromolecular structure.
(vi) Both the metals combine with metals like Mg forming borides and silicides respectively
2B + 3Mg Mg3B2 (boride)
Si + 2Mg Mg2Si (Silicide)
These products when treated with HCl give hydrides.
Mg3B2 + 6HCl 3MgCl2 + B2H6 + higher boranes
Mg2 Si + 4HCl 2MgCl2 + SiH4 + higher silanes
9.8 . SUMMARY
The text of this unit comprises of the general characteristics of the elements of Group 13 (or
IIIA). i.e. boron group and their gradation such as their electronic configuration, ionisation
energy, oxidation state, electropositive character, oxidation potential and action of various
reagents and nature of compounds. Hydrides of boron specifically diborane and borazine
have been discussed in detail in terms of their preparation, properties and structure. The
halides of boron and aluminium, the oxides of boron, borates and anomalous behaviour of B
in the group and its diagonal relationship with silicon, the element of next higher period and
higher group have been taken in detail.
9.9 . TERMINAL QUESTIONS

i. Which element has the highest ionisation energy?
(a) Boron
(b) Aluminium
(c) Galium
(d) Thaleum
ii. In Tl, the last element, + 1 oxidation state is
(a) Less stable than + 3 state
(b) More stable than + 3 state
(c) Equally stable to + 3 state

(d) None of the above.

iii. The electron-acceptor capacity of boron trihalides is
(a) BF3< BCl3< BBr3< BI3
(b) BF3< BCl3> BBr3< BI3
(c) BF3> BCl3>BBr3 > BI3
(d) BF3> BCl3> BBr3< BI3
iv. Boron shows diagonal relationship with
(a) Aluminium
(b) Beryllium
(c) Silicon
(d) Lithium
v. Discuss the structure of boron trihalides
vi. What happens when boron is heated?
9.10 . ANSWERS
i. (a)
ii. (b)
iii. (a)
iv. (c)
v. & vi. For their answers please refer to the text.

CONTENTS:
10.1 Objective
10.2 Introduction
10.3 General characteristics
10.4 Oxides of carbon and silicon
10.4.1 Oxides of carbon
10.4.2 Silicon oxide
10.5 Halides of carbon
10.6 Organosilicon compounds: silicones
10.7 Anamolous behaviour of carbon
10.8 Summary
10.10 Answers
10.1. OBJECTIVE
The objective of writing the course material of this unit, i.e. on the elements of Group 14 or
group IVA of the periodic table, is to make the readers to understand their various aspects
such as their general characteristics and uses, the oxides of carbon and silicon, halides of
carbon, organo-silicon compounds-an important class of useful compounds and anomalous
behaviour of carbon in contrast to that of other members of carbon family.
10.2. INTRODUCTION
Group 14 (or Group IVA) of the long form of periodic table containe five elements, viz.
carbon (C6), silicon (Si14), germanium (Ge32), tin (Sn50) and lead (Pb32). This group is also
known as carbon group. All these elements belong to p-block of elements as the last electron
in the atoms of these elements enters the p-subshell of the valence or ultimate shell. The first
element carbon is distinctly non-metal, Si is non-metal with the characteristics of a semi-
metal, Ge is a semimetal. The last two elements, Sn and Pb, are distinctly metals. Carbon
occurs upto 0.1% in the earth’s crust. However, combined with oxygen and hydrogen it
occurs in all living tissues of plant or animal kingdom and also in petroleum and coal

deposits. Silicon is the most abundant element, next to oxygen, in earth’s crust (~28%)
present as silica and silicates.
10.3. GENERAL CHARACTERISTICS
These elements have been included in the same group of the periodic table and this is
justified by the following general characteristics of these elements. There occurs an
appreciable extent of variation also in their properties.
The atoms of these elements have four electrons in their valence or ultimate shell, two of
which are in s-orbital while the remaining two are in p-orbitals with ns2np2 type
configuration, n being the principal quantum number (the valence shell). Like the elements of
Group 13, atoms of these elements also have different arrangements of electrons in the
penultimate shells, i.e. varying from inert gas to pseudo-inert gas configuration. Thus carbon
has helium configuration (i.e. 1s2), silicon has an octet (i.e. 2s2p6) and rest of the elements
from Ge to Pb have (n-1) s2p6d10 type arrangement of electrons in their respective penultimate
shells. This difference in the configuration in the last but one shell, though the valence shells
have the same configuration, is responsible for the variation in the properties of these
elements. Thus carbon differs from Si and these two (i.e. C & Si) from other members of the
group.
(ii) Occurrence:
Only Carbon occurs in the free state as diamond, graphite and coal. In the combined state it
occurs as hydrocarbons, carbohydrates and carbon dioxide (in the atmosphere). Silicon is a
major constituent of rocks. Germanium is a rare element. Tin is found as tin stone, SnO2
while lead is present in nature as galena (PbS).
(iii) Density, atomic and ionic radii, atomic volume:
The density, atomic radii and atomic volumes of these elements show a regular increasing
trend as usual. The ionic radii (of the ions with similar charge) also show the same trend as
other physical properties given above.
(iv) Melting and boiling points

These properties generally decrease down the group though the trend is not regular. These
values for C and Si are high because of their tendencies to form giant molecules.
(v) Metallic and non-matallic character:
The best illustration of the change from non-metallic to metallic character with increasing
atomic number is provided by this group. The first two elements are non-metals, though Si
shows some properties of metalloids, Ge is a semi-metal and the last two elements are metals.
(vi) Ionisation energy and electronegativity:

As expected, the ionisation energy values decrease down the group from C to Pb, though in
an irregular manner. This is due to the presence of d-orbitals in case of Ge and Sn and f-
orbitals in Pb in the penultimate shell which are not able to screen the valence electrons
effectively in these elements.
The electronegativity also shows the same trend but the change is abrupt in the first two
elements and then only a slight change is observed among other elements.
(vii) Valency and oxidation state:

All the elements show a covalency of 4 and are tetra covalent involving sp3 hybridisation.
Due to high ionisation energy values, the existence of simple M4+ ions is unlikely. Their low
electronegatity also makes them unavailable for the formation of M4- ions. The elements, C
and Si, being non-metals do not have the tendency to form electrovalent compounds but Ge,
Sn and Pb, the higher congeners of these elements, exhibit tetra and bi-electrovalency
forming both M2+ and M4+ ions. Thus the oxidation state of +2 and + 4 is shown by them in
their compounds. The stability of tetravalent ions (+4 oxidation state) goes on decreasing
from Ge to Pb. i.e. Ge4+ > Sn4+ > Pb4+ and that of +2 oxidation state (bivalent ions) increases
down the group, i.e. Ge2+ < Sn2+ < Pb2+. This behaviour of the ions of Ge, Sn and Pb is
attributed to the inert pair effect which is more prevalent in the heavier p-block elements, i.e.
maximum for Pb in this group. That is why Sn (II) salts are used as reducing agents while Pb
(IV) salts are strong oxidising agents, i.e. Sn2+ < Sn4+and Pb2+ > Pb4+.
The nature of the compounds of M2+ and M4+ cations can be predicted by Fajan’s rules,
according to which the smaller cations cause more polarization of anions and make the
compounds more covalent in nature. For example, Sn4+ ion is smaller than Sn2+ ion, hence Sn
(IV) compounds are covalent while Sn (II) compounds are ionic in nature, similarly Pb (IV)
compounds are covalent and those of Pb (II) are ionic.

(viii) Catenation or Self-linkage:
This depends on the tendency of the elements to form homo-chains. The atoms of all the
elements of this group have this tendency of linking with themselves to form long chains
called homo-chains. This property of the elements is known as catenation or self-linkage
which decreases down the group from C to Pb. Thus carbon has maximum property of
catenation while tin and lead hardly show this tendency, i.e. C > Si > Ge > Sn > Pb. This is
because of decreasing M-M bond energy values for these elements (C= 348 kJmol-1, Pb =
155 kJmol-1). The result is that it is easy to prepare compounds centaining C-C chains up to
twenty or even more carbon atoms while for Si and Ge, it is not possible to extend Si-Si or
Ge-Ge chains beyond six units. For Sn and Pb, the Sn-Sn or Pb-Pb chain can not be extended
beyond two units.
(ix) Allotropy:
All the elements, except Pb, of this group show allotropy, i.e. exist in different forms, e.g.
carbon exists in the two forms: crystalline-diamond and graphite, and amorphous- coal, coke,
charcoal etc. Silicon and Ge also exist in two forms: crystalline and amorphous. Tin has three
allotropic forms: white tin, grey tin and rhombic tin.
(x) Formation of oxides:
These elements form three types of oxides, viz. mon-oxides (MO type), dioxides (MO2 type)
and other oxides such as C3O2, Pb3O4, Pb2O3 etc.
(xi) Formation of hydrides:
All the dements of this group form hydrides which are covalent in nature though the number
of stable hydrides and the ease with which these are formed decreases as we move from C to
Pb. The MH4 type hydrides (monomers) are in the gaseous state. The thermal stability of
these hydrides decreases steadily from CH4 to PbH4, as is evident from their decomposition
temperature: CH4 = 8000C, SiH4 = 4500C, GeH4 = 2850C, SnH4 = 1500C and PbH4 = 00C and
decreasing M-H bond energy. This infers that the hydrides of higher elements are thermally
unstable.
(xii) Formation of halides and halo complexes:

All the members of this group form halides either of simple type, MX4 (e.g. CCl4, SiCl4 etc.)
or MX2 (e.g. SiCl2, SiI2 etc.) or those in which H-atoms are also present, MH3X (e.g. CH3Cl),
MHX3 (e.g. CHCl3, SiHF3 etc.) or catenated type halides (e.g. Si10Cl22).
The tetra halides of these elements can be prepared by a common method which employs the
heating of element with appropriate halogen. These trahalides are having decreasing thermal
stability down the group, i.e. CX4 is most stable and PbX4 is least stable. The tetra halides,
MX4 of Si, Ge, Sn and Pb when reacted with X- ions, form the hexahalo complex ions, e.g.
SiF4 + 2F- [Si F6]2-
Other examples are: [GeX6]2-, X = F, Cl; [Sn X6]2-, X = F, Cl, Br, I and [Pb Cl6]2-
(xiii) Acid formation:
All the elements give acids of H2MO3 type whose sodium salts are stable. The elements,
Carbon and Silicon also form acids of (MOH)2 type, e.g. (COOH)2 : oxalic acid, (SiOOH)2 :
silico oxalic acid.
Uses of group 14 elements:
(a) Carbon is an essential element of the plant and animal kingdom. All fuels also contain
carbon. SiC is an important compound of C used as an abrasive and B4C is the hardest
artificially made abrasive used for cutting diamonds.
(b) Si and Ge containing an impurity of Group 13 or Group 15 elements are used as the semi
conductors. Silica (SiO2) is an assential material for glass industry. Silicones are important
polymers.
(c) Sn is used in the preparation of a number of useful alloys, in tin plating of iron sheets and tin
amalgam for making mirrors.
(d) Pb is used for making cable covering, protective sheets for roofs and drains, water pipes and
lining of the chambers in sulphuric acid manufacture and many important compounds, alloys
etc.
10.4 OXIDES OF CARBON AND SILICON
10.4.1 Oxides of carbon:

Three oxides of carbon are known, e.g. carbon monoxides (CO), carbon dioxide (CO2) and
carbon suboxide (C3O2).
(a) Carbon Suboxide (C3O2):
This oxide of carbon is formed by heating malonic acid with phosphorous pentoxide.
COOH ∆
CH2 C3O2 + 2H2O

COOH P2O5
Thus, this oxide is the anhydride of malonic acid and exists as a gas. It is stable at room
temperature and polymerises on warming. It explodes when sparked with oxygen.
This oxides has linear structure, i.e. O = C = C = C = O with each carbon atom undergoing sp
hybridesation and each C = O and C = C double bond involving one σ and one π bond due to
axial and lateral overlapping of orbitals of carbon and oxygen atoms.
(b) Carbon monoxide (CO):
Preparation:
(i) This oxide is obtained when formic acid or oxalic acid is dehydrated using H2SO4.
H2SO4
HCOOH CO + H2O
H2SO4
(COOH)2 CO + CO2 + H2O

(CO2 is removed by NaOH or KOH solution)
(iii) Reduction of carbon dioxide or heavy metal oxides with carbon, gives CO.
∆
CO2 + C 2CO (impurity of CO2 is removed by caustic soda solution)

∆
ZnO + C Zn + CO
∆
Fe2O3 + 3C 2Fe + 3CO

(iv) The action of steam on red hot coke also gives CO.
C (hot) + H2O (vapours) CO + H2 (water gas)
CO is separated by liquefaction. The mixture is used as water gas. This method is used for
large scale production of CO and H2.
Properties:
It is only slightly soluble in water. It is highly poisonous, to such an extent that one part of
the gas in 500 parts of air produces unconsciousness in about an hour and one part in
100parts causes death in a few minutes. It liquefies at (-)191.50C and solidifies at (-)2000C.
(i) It is an unsaturated compound and hence forms addition products with H2, O2, Cl2, S etc. to
give various useful products under specific conditions.
ZnO-Cr2O3
CO + 2H2 CH3 OH (methanol)

2CO + O2 2CO2
1:1 volume
CO + Cl2 COCl2 (phosgene)

∆
CO + S (vap) COS (carbonyl sulphide)
(ii) CO is absorbed in NaOH solution under pressure to give sodium formate.

CO + Na OH HCOONa (sod. formate)
(iii) It combines with many metals such as Fe, Co, Ni, Cr etc. to form carbonyls, e.g.
500C
Ni + 4 CO Ni (CO)4
(iv) It is a good reducing agent and is used in metallurgical processes to reduce metal oxides to
free metals.
Fe2O3 + 3CO 2Fe + 3CO2

ZnO + CO Zn + CO2
Uses:
(a) It is used as an essential constituent of fuel gases like water gas, producer gas etc. because on
burning in air it forms CO2 and evolves a large amount of heat.
(b) It is used in the manufacture of methanol by its reaction with hydrogen at3000C and 300 atm.
pressure in presence of a catalyst (ZnO + Cr2O3).
3000C
CO + H2 CH3 OH

300 atm.
(c) It is used in the reduction of metallic oxides in metallurgy.

(d) It is used in Mond’s process for the refining of nickel.
Structure:
The carbon atom involves sp hybridization, one hybrid orbital containing a single electron
which forms σ bond with O-atom and another hybrid orbital having an electron pair remains
unbonded. There is one normal π-bond formed between C and O-atoms. The empty orbital of
C-atom overlaps with a paired orbital O-atom forming a dative type π bond (O→C). Thus a
triple bond exists in the molecule. The structure is : C ≡ O:
(c) Carbon dioxide (CO2):
It occurs free in atmosphere up to 0.03 – 0.05 % and in minerals as carbonates like dolomite,
limestone, etc.
Preparation:
Carbon dioxide may be prepared by the complete combustion of coke or by the action of heat
or dilute acids on carbonates and bicarbonates.
C + O2 CO2
∆
CaCO3 CaO + CO2

Na2CO3 + 2HCl 2NaCl + CO2 + H2O
NaHCO3 + HCl NaCl + CO2 + H2O
Laboratory preparation:
In the laboratory, CO2 gas is prepared by the action of cold and dilute HCl on marble
(CaCO3).
Ca CO3 + 2HCl CaCl2 + CO2 + H2O
Manufacture of CO2:
(i) From combustion gases:

Large amount of it is produced during the combustion of coal or coke along with N2, CO, O2,
other gases and vapours. This mixture on passing through a tower (packed with coke)

upwards which is being sprayed with a solution of potassium carbonate downwards, CO2 gets
absorbed in solution.
K2CO3 + CO2 + H2O 2KHCO3
The solution is boiled when CO2 is liberated
∆
2KH CO3 K2CO3 + H2O + CO2

The solution containing K2CO3 can be used again for absorbing more CO2.
(iii) From Lime-Kilns:

CO2 is also obtained as a by-product in the calcination of lime stone in the manufacture of
lime (CaO).
Ca CO3 CaO + CO2
The gas can be purified by absorbing in a solution of potassium carbonate as above.
(iv) From fermentation industries:
Large amount of this gas is also obtained as a by-product during the fermentation of starch or
sugar in the manufacture of alcohol.
Properties:
This gas is only slightly soluble in water under ordinary pressure but at high pressure the
solubility increases appreciably. It can be liquefied by cooling at 200C and 56 atmospheric
pressure.
(i) Acidic Character:

CO2whendissolves in water gives carbonic acid which forms salts with alkalies.
CO2 + H2O H2 CO3
H2CO3 + 2NaOH Na2CO3 + H2O
With excess of CO2, the carbonate is converted to bicarbonate.
Na2CO3 + H2O + CO2 2NaHCO3
(ii) Action on lime water:
It gives a white precipitate of insoluble CaCO3 hence turns lime water milky. On passing
more quantity of the gas, the white ppt. dissolves.
Ca (OH)2 + CO2 CaCO3 + H2O
Ca CO3 + H2O + CO2 Ca (HCO3)2 (soluble)
Cal. bicarbonate

(iii) Decomposition:
CO2 is neither combustible nor a supporter of combustion and thus a burning splinter gets
extinguished when introduced into the gas. But burning Mg, Na or K continues to burn in the
gas decomposing the gas into carbon.
CO2 + 2Mg 2MgO + C
CO2 + 4Na 2Na2O + C
Na2O + CO2 Na2CO3
(iv) Reduction:
When heated with red hot charcoal, it is reduced to CO.
CO2 + C 2CO
(v) Photosynthesis:
CO2 is converted into starch and other carbohydrates by plants in presence of chlorophyll and
sunlight liberating oxygen.
Chlorophyll
6nCO2 + 5nH2O (C6H10O5)n + 6nO2

Sunlight starch
Uses:
(a) CO2 is used as fire extinguisher.

(b) It is used in aerated water due to its increased solubility under pressure.
(c) Solid carbon dioxide (dry ice) is used in freezing mixture to produce low temperature.
(d) It is used as a germicide and for artificial respiration.
Structure:
CO2 has linear structure with C-O double bonds. C-atom in excited state has four unpaired
electrons and undergoes sp hybridization forming two σ bonds with two O-atoms by axial
overlapping. Two π bonds are formed between C and O atoms by lateral overlapping. Its
structure can be shown as π π
O =C= O
σ σ
Solid carbon dioxide: Dry Ice:
Dry ice is the solid carbon dioxide. It changes directly into the gaseous state at atmospheric
pressure. It can be obtained by cooling the gaseous CO2 at ordinary pressures. If the gas is

compressed to a pressure of ~70 atmospheres, it condenses to the liquid state. This liquid is
released through a jet into an evaporator at ~35 atms. and remains in liquid state. This liquid
is introduced through a jet into press chamber kept at 5.2 atm. pressure. Here the liquid
solidifies giving dry ice. Any gaseous CO2 left in the evaporator or press chamber is drawn
back and passed through the compressor at ~70 atms. to change it into the liquid state. The
process is repeated to get more and more dry ice which is collected as the block and then cut
into small cubes and transferred to a cold storage.
It is used as a refrigerant, as a substitute of ice in cold drinks and in the preparation of ice-
cream. Mixed with ether or acetone, it provides freezing mixture of very low temperature. It
is extensively used in the transport of parishable food-stuffs as it kills undesirable bacteria.
10.4.2 Silicon Oxide (SiO2):

Silicon forms two oxides, SiO (monoxide) and SiO2 (dioxide) SiO2 is more important and is
known as silica. Quartz is the most common naturally occurring form of silica.
Preparation:
Pure silica, in the amorphous form, can be prepared as a white powder by the action of water
on SiCl4 or Si F4.
-4HCl ∆
SiCl4 + 4H2O Si(OH)4 SiO2 + 2H2O
Properties:
Silica is an inert substance and gives only a few reactions.
(i) Silica is insoluble in water and in all acids except hydrofluoric acid with which it forms
tetrafluoride.
SiO2 + 4HF SiF4 + 2H2O
(iii) It dissolves in hot conc. alkalies forming sodium silicate.
SiO2 + 2NaOH Na2SiO3 + H2O
On adding HCl to this mixture, hydrated gelatinous silica is reprecipitated which is separated
from NaCl by washing with water.
Na2SiO3 + 2HCl 2NaCl + H2O + SiO2
(iv) It is non-volatile substance hence on heating with acid salts it displaces volatile acids from
them.
Na2SO4 + SiO2 Na2SiO3 + SO3
Ca3(PO4)2 + 3SiO2 3CaSiO3 + P2O5

(v) At very high temp; it reacts with coke to give SiC, a refractory material.
SiO2 + 3C SiC + 2CO
Uses:
(a) Transparent quartz is used in making optical instruments and lenses.

(b) The coloured varieties of quartz are used as gems.
(c) The opaque quartz is used in making acid and alkali resistant vessels and apparatus which are
used in place of glass.
(d) Silica is used in making refractory bricks for furnace linings.
(e) Sand is used in the manufacture of glass, mortar and porcelain and is also an important
construction material when mixed with lime or cement.
Structure:
It does not exist as discrete molecules like CO2, rather it forms giant molecules by linking
together a number of tetrahedra in which each Si atom is bonded to four oxygen atoms as is
revealed by X-ray study of its crystal structure.
This is due to the fact that carbon has the properly of multiple bond formation but Si does
not. It forms four single bonds with four o-atoms arranged tetrahedrally around it and various
tetrahedra so formed are linked together by sharing of the O-atoms between two adjacent
tetrahedra thereby forming a giant molecule with a three dimensional structure (Fig 10.1).
This structure of silica is highly stable and explains its hardness and high melting point.
−O−Si−O−Si−O−
O O
O−Si−O− Si−O−
O O
(Fig. 10.1 Structure of silica)
10.5. HALIDES OF CARBON

Carbon forms a number of halides with various halogens but mostly these are the derivatives
or substitution products of hydrocarbons. The tetra halides of carbon may be prepared either

by heating the element with the appropriate halogen or by passing dry halogen over a heated
mixture of the dioxide and carbon.
∆
C + 2X2 CX4
CO2 + 2C + 2X2 CX4 + 2CO
These tetrahalides are thermally stable and thermal stability and volatility of various
tetrahalides decrease from F- to I-, Thus:
CF4 > CCl4 > CBr4 > CI4 Thermal stability decreasing.
The fluorides are, therefore, most stable and inert. The tetrahalides of carbon are not
hydrolysed. This is because C, being a member of second period of the periodic table, does
not have d-orbitals in the valence shell and is unable to accommodate the lone pair of
electrons donated by the O-atom of water molecule to form the unstable intermediate
compound as is done by higher members of this family. Thus there is no action of water
molecules on these halides.
However, if sufficient energy is provided for the reaction to occur, CCl4 undergoes hydrolysis
when treated with superheated steam.
∆
CCl4 + H2O (steam) COCl2 + 2HCl
The reactions and properties of carbon halides are studied in organic chemistry hence can be
discarded.
Fluorocarbons:
These are the derivatives of the hydrocarbons obtained as a result of substitution of H-atoms
by F-atoms, i.e. fluorination. Fluorine reacts explosively with hydrocarbons and gives rise the
complex mixture of fluorinated hydrocarbons called fluorocarbons, e.g. CH3F, CH2F2, CHF3,
CF4, C2F6 etc. Therefore, the formation of fluorocarbons is carried out by using fluorine
diluted with nitrogen. Under controlled conditions these can be synthesised by:
(i) The replacement of halogen (other than F) in alkyl halides by F atom using a metal fluoride.
This can be shown as:
RCl + AgF AgCl + RF
(iii) The stepwise replacement of halogen atom by F-atom in anhydrous HF.
+HF +HF +HF
CCl4 + HF CCl3F CCl2F2 CClF3 CF4 (Mixture of freons)

Cl -HCl
CHCl3 + 2HF CHClF2 + 2HCl
The Chlorofluorocarbons obtained from CCl4 are called freons. The above reactions can be
activated by using SbCl5 as catalyst at high pressure and high temperature.
(iv) Electrolytic fluorination of organic compounds.
Organic compounds in liquid HF, if electrolysed in steel cells using Ni-anode and steel
cathode, fluorination takes place at anode. This method has been used in laboratory and also
as an industrial method.
(C2H5)2O (C2F5)2O
H2O
CH3COOH CF3COOF CF3COOH
(v) Direct replacement of H2 by F2.

The mixture of reacting compound and F2 is subjected to electrolysis in nitrogen atmosphere.
Cu-gauze or CsF or CoF3 is used as catalyst.
Cu-gauze
C6H6 + 9F2 C6F12 + 6HF

temp.
Properties and uses:

(a) The freons are used as non-toxic and non-corrosive inert refrigerants, aerosol bomb
propellants and heat transfer and fire extinguishing agents. Freons are chemically inert. This
property makes them useful solvents, lubricants and insulators.
Being non-toxic, Freon-12 (dichlorodifluoromethane, CCl2F2) is used in refrigeration and air
conditioning. It is also used as a solvent for D.D.T. and other insecticides.
(b) Like ethylene, tetrafluoroethylene, C2F4, can be polymerized to form poly
tetrafluoroethylene, (C2F4)n. This polymer is called Teflon and is a plastic like inert material,
insoluble in any solvent and unaffected by strong acids, alkalies and oxidising agents. Hence,
it is used in the construction of chemical plants and as an insulating material in cables.

10.6. ORGANOSILICON COMPOUNDS: SILICONES

An important and useful class of organosilicon compounds is the organosilicon polymers
known as silicones. These are synthetic polymeric materials containing-Si-O-Si-O-Si---
linkages along with C-C linkages present as the side chains.
When SiCl4 is subjected to the Grignard reaction under suitable conditions, Cl-atoms in SiCl4
are substituted by alkyl or aryl groups (R) and give mono-(RSiCl3), di (R2SiCl2) or tri
substituted (R3SiCl) chlorosilanes.
Ether
SiCl4 + 3RMgX R3SiCl + 3 MgClX (X is mainly Cl or Br and

R = alkyl or aryl)
Ether
SiCl4 + 2RMg X R2SiCl2 + 2 MgClX
Ether
SiCl4 + RMgX RSiCl3 + MgClX
These mono, di or tri, alkyl or aryl substituted chlorosilanes when subjected to hydrolysis
followed by condensation, result in the formation of either long-chain (linear) or cyclic or
cross linked three dimensional polymeric materials called silicones. The nature of silicone
depends on the type of substituted chlorosilane. Accordingly, the silicones are of the
following type:
(a) Long chain (linear) silicones
(b) Cyclic silicones
(c) Three dimensional (cross-linked) silicones.
(a) Linear (long chain) silicones:
These silicones are obtained as a result of hydrolysis and subsequent condensation of dialkyl
or diaryldichlorosilane, R2SiCl2. This occurs in the following steps:
Hydrolysis
R2SiCl2 + 2H2O R2Si(OH)2 + 2HCl (R= alkyl or aryl group)
Condensation
R2Si(OH)2 + R2Si(OH)2 + R2Si(OH)2 + ---- linear long chain polymer

Thus the length of the chain can be increased to any extent.
(b) Cyclic silicones:

These silicones are also obtained from di-substituted chlorosilanes, first hydrdysing and then
condensing them.
Hydrolysis
R2 SiCl2 + 2H2O R2Si(OH)2
The silicol molecules on condensation give cyclic polymers.
(c) Cross-linked silicones:

The hydrolysis of mono alkyl or aryl trichlorosilane, RSiCl3 and subsequent condensation of
silicol molecules gives a complex three dimensional, cross linked polymer involving the
following steps.
Hydrolysis
RSiCl3 + 3H2O RSi(OH)3 + 3HCl

Condensation
RSi(OH)3 + RSi(OH)3 + RSi(OH)3 + ----- complex three dimensional cross linked

polymer. Evidently the structure can be extended in two dimension to any length and in any
manner.

However it is to be noted that tri substituted chlorosilane. R3SiCl, on hydrolysis and

condensation produces only dimer.
Hydrolysis
R3SiCl + H2O R3SiOH + HCl
R3SiOH + HOSiR3 R3Si-O-SiR3 + H2O
Properties:
The peculiar property of silicon to hold three hydroxyl groups in the compound RSi(OH)3 or
two hydroxyl groups in R2Si(OH)2 in contrary to carbon atom which cannot hold more than
one OH group, makes the formation of organosilicon polymers possible. Depending on the
length of the chain and the nature of groups attached to the silicon atom, they can be obtained
in the form of oils, viscous fluids, resins or even rubber like solids.
Thus the lower silicones are only liquids but the higher members containing long chains or
ring (cross linking) structures are waxy and rubbery solids. These are thermally stable,
chemically inert, non-toxic and not wetted by water. Silicone oils remain unaffected at high
and low temperatures, i.e. their viscosity does not change on increasing or lowering the
temperature.
Uses:
(a) Being non-volatile and highly stable at high temperature, silicone oils are used for high
temperature oil baths, high vacuum pumps etc.
(b) There is no effect of cooling on the oils, hence they are used for low temperature lubrication.
(c) They are also used in making vaseline like greases which are used as lubricants in aeroplanes.
(d) Being water-repellents, they are used in making water proof cloth and paper by exposing the
object to silicone vapours.
(e) They are also used as insulating materials for electric motors and other electrical appliances.

(f) They are mixed in paints and enamels to make them resistant to the effects of high
temperatures, heat, sunlight and chemicals and damp.
10.7. ANOMALOUS BEHAVIOUR OF CARBON

Carbon, the first element of the group 14 (or IVA), shows some properties which are close to
those of silicon but most of its properties differ from the rest of the members of its family.
This is attributed, as usual, to its small size, high electronegativity, non-availability of d-
orbitals in the valence shell etc. Some of its properties in contrast to other members of this
group are summarised here:
(a) Though all the elements have four electrons (ns2p2) in the valence or ultimate shell, only
carbon has helium configuration in its penultimate shell. Si has 8 and others have 18 electrons
in their penultimate shells.
(b) Only carbon is distinctly non-metal, Si, though non-metal, has electrical conductivity like
semi-metals (Ge). Other elements are distinctly metals.
(c) Carbon, like silicon, shows tetracovalency but does not form M4+ ions. Other elements
(except Si) form M2+ and M4+ type ions.
(d) Carbon has a great tendency of catenation (self-linkage). Si shows catenation property to
some extent but other elements do not have this property.
(e) Dioxides of carbon and silicon are acidic but those of other elements are amphoteric.
(f) Carbon forms a large number of hydrides, Si forms less number of hydrides while other
elements give only a few hydrides.
(g) The tetrahalides of carbon are not hydrolysed by water but those of higher members get
readily hydrolyse due to the availability of vacant d-orbitals in their valence shells and ability
to form unstable intermediate compound with water which then eliminates HX molecules and
forms hydroxide.
CX4 + 4H2O no action.
MX4 + 4H2O. MX4 4H2O M (OH)4 + 4HX
(h) Carbon is not attacked by caustic alkalies while all others are attacked and evolve hydrogen
gas.
Si + 2NaOH + H2O Na2SiO3 + 2H2↑
Pb + 2NaOH Na2PbO2 + H2↑
10.8. SUMMARY

The course material on the elements of Group 14 contains the introduction, the general
characteristics of the elements like electronic configuration, occurrence, atomic and ionic
radii, melting and boiling points, metallic and non-metallic character, ionisation energy and
electronegativity, valency and oxidation state, catenation, allotropy, formation of oxides,
halides, hydrides, acids and halo complexes etc. Also the oxides of carbon and silicon,
halides of carbon and organosilicon compounds have been discussed in detail. At the end,
the anomalous behaviour of carbon in contrast to other members of this family has been taken
into account.
i. Graphite is a form of
(a) Carbon
(b) Silicon
(c) Tin
(d) Lead
ii. The metallic character of the elements of Group 14
(a) Increases down the group
(b) Decreases down the group
(c) Remain the same in the group
(d) First decreases and the increases
iii. The stability of M2+ ions decreases in the order
(a) Pb2+ > Sn2+< Ge2+
(b) Pb2+ < Sn2+< Ge2+
(c) Pb2+ > Sn2+> Ge2+
(d) Pb2+ < Sn2+> Ge2+
iv. The gas used as fire extinguisher is
(a) N2 + Co mixture
(b) CO

(c) CO + CO2 mixture
(d) CO2
v. How are crosslimked three dimensional silicon polymers prepared?
vi. White a note on use of CO2 in photosynthesis
vii. SiO2 exists as a giant molecule, explain.
viii. Give the uses of Freon-12.
10.10. ANSWERS
i. (a)
ii. (a)
iii. (c)
iv. (d)
v. to viii. Please refer to the text of the unit.


CONTENTS:
11.1 Objective
11.2 Introductions
11.3 General characteristics
11.3.1 Electronic configuration
11.3.2 Occurrence
11.3.3 Physsical state and elemental structure
11.3.4 Metallic and nonmetallic character
11.3.5 Density, hardness,atomic radii and atomic volume
11.3.6 Ionization energy, electronegativity and heat of atomization
11.3.7 Melting and boiling points
11.3.8 Oxidation staes
11.3.9 Electron donor-acceptor properties
11.3.10 Allotropy
11.3.11 Catenation
11.3.12 Electrical and thermal conductivity
11.3.13 Combination with active metals
11.3.14 Chemical reactivity
11.4 Hydrides of elements
11.4.1 Preparation
11.4.2 Properties
11.5 Halides of elements
11.5.1 Preparation
11.5.2 Properties
11.5.3 Structure
11.6 Oxides and oxo acids of elements
11.6.1 Properties and structures of oxides
11.6.2 Oxyacids
11.7 Anomalous behavior of Nitrogen
11.8 Summary
11.10 Answers

11.1. OBJECTIVES
The objective of the preparation of the study material of this unit, i.e. on the elements of
Group 15 (group VA) of the periodic table, is to provide the reader, the subject matter which
they can easily understand and become acquainted with the various aspects of their general
characteristics and uses, the study of their hydrides, halides, properties and structure of oxides
and oxoacids and also the anomalous behavior of nitrogen in contrast to that of other
members of nitrogen family.
11.2. INTRODUCTION
The group 15 (group VA) of the extended or long form of periodic table contains five
elements, namely nitrogen (N7), phosphorous (P15), arsenic (As33), antimony(Sb51) and
bismuth (Bi83). This group is also known as nitrogen group. All the elements of this group
belong to p- block due to the filling of p- orbital (or subshell) of the valance shell by the last
electron of the atoms of these elements.
The first two elements (N and P) are distinctly non metals.
The next two elements (As and Sb) are semimetals and the last element Bi, is metallic in
nature.
These elements, except phosphorous, do not occur very abundantly in nature. Nitrogen
constitutes only about 0.0045%, phosphorous 0.116%, As, Sb and Bi nearly 10-4 % of the
rocks of earth. The phosphorous ranks tenth in abundance among all the elements known,
nitrogen constitutes nearly 78 percent by volume of the atmosphere.
11.3. GENERAL CHARACTERISTICS
The inclusion of nitrogen group elements in the same group of modern periodic table is
justified by the following general characterstics of these elements. These elements furnish
another example in which there is a systematic gradation of properties and there is a change
of character from a true non metal like nitrogen to a nearly true metal, e.g. bismuth.

11.3.1 . Electronic configuration.
There are five electrons in the valance or ultimate shell of the atoms of these elements, i.e.
ns2p3 where n is the principal quantum number of the valance shell. Two of these electrons
are in the s- subshell and the rest three are occupying the p- subshell according to the Hund’s
rule among the three p- orbitals. Because of exactly half- filled orbitals, the elements are
fairly stable and not so reactive. The penultimate shells have variation in the number of
electrons. The first element, N, has helium configuration s2, P has inert gas octet s2p6 and
other elements have pseudo inert gas, s2p6d10, configurations, respectively in the penultimate
shells of their atoms. This variation in the configuration is responsible for gradation of
properties in the group.
11.3.2 Occurrence:
Nitrogen occurs in the free State as the diatomic gas in nature while all the remaining
elements occur in the combined state. In the combined state it occurs mainly as nitrates.
Being very reactive, phosphorous does not occur in the native state, rather it occurs as
phosphates in its ores. As, Sb and Bi are less abundant and occur chiefly as sulphide ores.
11.3.3 Physical state and elemental structure:
Nitrogen is a gas, phosphorous is a soft, lustreless solid, others are hard solids, Sb and Bi
having characteristic metallic lustre. Nitrogen gas exists as a diatomic molecule, N2 while P,
As and Sb exist as tetratomic molecules, P4, As4 and Sb4. These are not capable of forming
diatomic molecules like N2 because they do not form pπ - pπ bonds as their larger atoms
cannot come closer to each other to form such bonds as well as due to the increased
repulsions from the non bonding electrons of penultimate shell. The repulsion from the
electrons of penultimate shell, 1s2, in nitrogen atoms is not appreciable. Further, formation of
π bonds in the N2 molecule satisfies the valency requirements of N- atoms while non
formation of such bonds in other elements compels them to join with more atoms hence M4
molecules are formed. These elements thus form giant lattices in which the bonding changes
from covalent to metallic from P to Bi.
11.3.4 Metallic and non-metallic character:
The change from non- metallic to metallic character with increasing atomic number in the
same group, exhibited by group 14, is observed equally well in this group also, the only
metallic element being Bi, the last element of the family which has the lowest value of
ionization energy. This is revealed by the variation in the properties both physical and
chemical.
11.3.5 Density, hardness, atomic radius, and atomic volume:
On going from P to Bi (N- being a gas excluded) these properties increase regularly and
markedly. The atomic radius and atomic volume also increase down the group with the
exception of atomic volume of As which has low value.
11.3.6 Ionization energy, electro negativity and heat of atomization:
With increasing size from N to Bi, the values of first ionization energies decrease on
descending the group. Similar is the trend in the electro negativity and heat of atomization.
This gradation confirms the gradual increasing metallic character of the elements.
11.3.7 Melting and boiling points:
The melting points (expect for Sb and Bi ) and the boiling points both increase with
increasing atomic number. The melting point of Bi is unusually low perhaps because of non-
availability of ns2 electron pair for bonding in the metallic crystal. The elements of this group
are more volatile than their immediate neighbours of group14.
11.3.8 Oxidation states:
(i) Formation of M5+ and M3+ cations
M5+ cations are formed when all the valance electrons, ns2p3, are used by the elements for
bonding. N and P cannot lose all the five valance electrons due to prohibited energy
considerations, i.e. because they have high ionization energies and electronegativities and
hence do not form M5+ ions. These elements also do not form M3+ ions as such but these
oxidation states, i.e.+3 and +5 can be assigned to them arbitrarily in their compounds with
more electronegative elements, viz. O and F if formed. M3+ cations are formed by the
elements if they lose only p- electrons from ns2p3 configuration of the valence shell and ns2
electron pair remains inert (inert pair effect). Since this effect increases down the group, the
heavier elements, viz. Sb and Bi are expected to form M3+ ions by losing three p- electrons
only and retaining the ns2 electron pair, though they can form M5+ ions as well. Thus only As
and Sb will give salt with +5 and +3 oxidation states and Bi gives only Bi3+ ions.
(ii) Formation of M3- anions
In order to achieve noble gas configuration, these elements accept three electrons from
electropositive elements and form M3- ions, e.g. N in NH3 has -3 oxidation state. As the size
of the atoms increases on moving down the group, the ionization energy and electronegativity
values decrease and hence the attraction of the nucleus for the newly added electrons
decreases. Thus the tendency of the elements to give M3- ions also decreases. In fact, N-atom,
being smallest in size, has strongest tendency to form N3- ion, P forms P3- ions less readily
and Bi, the last member of the group, hardly exhibits negative oxidation state.
(iii) Covalency of 3 and 5
Each of these elements has two paired s- electrons and three unpaired p- electrons in the
valence shell. If these elements form three covalent bonds using only the p- electrons, they
attain the noble gas configuration (ns2p6). This gives the covalency of 3 to these elements.
Except nitrogen, these elements also have vacant d- orbitals in the valence shell. Under
suitable conditions of energy, one of the electrons of s level may be promoted to the vacant
d–orbital, thus possessing five unpaired electrons. These five unpaired electrons may be used
to form five covalent bonds, thereby giving the covalency of 5 to these elements. This
covalency is common among P, As and Sb. That is why N forms only trihalide and other
elements form tri as well as pentahalides.
11.3.9 Electron donor – acceptor properties:
All the elements in the trivalent state have a tendency to act as electron pair donors. Nitrogen
having this tendency to the maximum extent. For example NH3 and PH3 molecules act as
Lewis bases towards H+ to form NH4+, PH4+ etc. due to presence of lone pair of electrons on
N and P- atoms, thereby N showing a maximum covalency of 4, P, As and Sb show a
covalency of 6 in [ PCl6]-, [ AsF6]- and [SbF6]- complex ions in which their salts act as
electron pair acceptors.
PCl5 + Cl- [PCl6]-
11.3.10 Allotropy:
All the elements, except Bi, show allotropy. Nitrogen in solid state exists in two allotropic
forms viz. α-nitrogen and β – nitrogen. Phosphorous exists in various forms such as white,

red, scarlet, α–black, β–black and violet. Arsenic exists in grey, yellow and black allotropic
forms while antimony in the forms as yellow, black, β- and explosive.
11.3.11 Catenation (Self linkage):
Although the catenation is considered to be a property peculiar to carbon, yet it is shown to

some extent, by the elements lying close to carbon in the periodic table. The elements of this
group have been found to show this property but to a much smaller extent than carbon. Thus,
unstable compounds containing chains of upto eight N- atoms have been prepared but stable
azide ion has a chain of three N- atoms, i.e. (N-N-N)- skeleton and H2N–NH2 has two N-
atoms. In case of phosphorous, P-P links are limited to two atoms (e.g.P2H4 ). Other elements
of the group have no tendency of self linkage. Thus tendency for catenation decreases on
moving down the group because of gradual decrease in bond energies of M-M bonds.
11.3.12 Electrical and thermal conductivity:
Both these properties increase as we move down the group because of increased
delocalization of electron from nitrogen to bismuth (with a metallic crystal lattice). Thus N
and P are non conductors, As is a poor conductor, Sb is a good conductor and Bi is an
excellent conductor.
11.3.13 Combination with active metals:
All these elements form compounds with metals, e.g. N forms nitrides: LiN, Mg3N2 etc;
phosphorous forms phosphide Ca3P2 etc., Arsenic gives arsenides Na3As etc. , Sb gives
antimonides Mg3Sb2 and Bi forms bismuthides Mg3Bi2 etc. The nitrides among these
compounds are most stable. The last two types of compounds are rare and Sb and Bi, infact,
form alloys on combining with metals.
11.3.14 Chemical reactivity:
These elements differ from one another appreciably in their chemical reactivity. Nitrogen is
chemically non–reactive. It does not combine under ordinary conditions. It combines with
elements such as Li, Al, Ca, Mg etc to form nitrides at high temperature only and combines
with oxygen only when heated in an electric arc to a temperature of the order of 25000C and
above forming nitric oxide. On the other hand white phosphorous, an allotropic form of P, is
extremely reactive. It burns readily in oxygen forming oxides of phosphorous. The heavier

elements, viz. As, Sb, Bi burn only when heated in air or oxygen, to form oxides. This can be
attributed largely to difference in the electro negativities of the five elements.
Uses:
(i) Nitrogen is an essential element for the growth of plants. It is generally added to the soil in
the form of the fertilizers (compounds of Nitrogen) or atmospheric nitrogen is fixed by nature
and this is absorbed by soil. From the soil it goes to the plants and then to the animals.
(ii) Red variety of P being non-poisonous is mostly used in match industry.
(iii)Phosphorous is also used as rat poison and in the manufacture of tracer bullets as well as in
producing smoke screens.
(iv) As-Pb alloy is used in making lead shots.
(v) Antimony is mainly used in the manufacture of lead storage batteries as it is harder and acid
resistant.
(vi) Bi-alloys have low melting points and are called fusible alloys. These are used in making
automatic electrical fuses, fire alarms, sprinklers, safety plugs on boilers etc.
11.4 HYDRIDES OF ELEMENTS
All the elements of this group form hydrides of the type MH3 : ammonia (NH3), phosphine
(PH3), arsine (AsH3), stibine (SbH3) and bismuthine (BiH3). N and P also form dihydrides of
the type M2H4 : hydrazine (N2H4) and phosphorous dihydride (P2H4). In addition to these, N
also forms a third hydride of M3H type : hydrazoic acid, N3H.
11.4.1 Preparation:
The MH3 type hydrides of these elements are prepared by the action of water or dilute acid
on the binary metallic compounds such as Mg3N2, Ca3P2 , Zn3As2, Mg3Bi2 etc.
Mg3N2 + 6H2O 3Mg(OH)2 + 2NH3↑
Ca3P2 + 6H2O 3Ca(OH)2 + 2PH3↑
Zn3As2 + 6HCl 3ZnCl2 + 2AsH3↑
Mg3Bi2 + 6HCl 3MgCl2 + 2BiH3↑
Hydrazine, N2H4 , is prepared by the oxidation of excess ammonia in NaOH solution by

sodium hypochlorite at 80 -900C. The reaction take place in two stages.

NH3 + OCl- NH2Cl + OH-
NH4Cl + NH3 + OH- H2N – NH2 + Cl- + H2O
The reaction is catalysed and side reaction between NH4Cl and N2H4 formed is inhibited by
adding glue or gelatin.
P2H4 is formed together with phosphine in the hydrolysis of impure calcium phosphide which
contains Ca2P2
Ca2P2 + H2O 2Ca(OH)2 + P2H4
Hydrazoic acid, N3H, is obtained by the distillation of an acidified solution of sodium azide
which is formed during the oxidation of molten sodamide with powdered sodium nitrate at
1750C.
3NaN2 + NaNO3 NaN3 + 3NaOH + NH3
2NaN3 + H2SO4 2N3H + Na2SO4
11.4.2 Properties:
All the trihydrides of these elements are colourless gases with specific odour. Ammonia has
characterstic odour, phosphine has rotting fish odour and arsine and stibine both have garlic-
like odours. The gradation in the electrochemical character of these elements is evidenced by
the properties of their gaseous hydrides.
(i) Basic character:
The basic character, i.e. the ability to act as electron pair donor, decreases from NH3 to BiH3.
Ammonia (NH3) is distinctly a base and readily coordinates with H+ ions to give a stable
cation, NH4+. It also readily forms salts with acids both weak and strong, viz. (NH4)2CO3,
NH4Cl etc. PH3 is also a base but much weaker than ammonia and forms less stable PH4+
ions. Still it is strong enough to form halides called phosphonium halides, PH4X which are
readily decomposed by water. The MH4+ ions for As, Sb and Bi elements do not exist
meaning thereby that these have no basic character, rather the last hydride, BiH3, has feebly
acidic character and dissolves in strong alkalies. It has been noticed that the electron donor
ability of the hydrides is increased by the replacement of H–atoms by alkyl groups. Thus
P(CH3)3 shows stronger basic character, than PH3.

NH3 is the strongest electron pair donor because N – atom has the smallest size and the
electron density of the lone pair of electrons present in one of the four sp3 hybrid orbitals of
this atom is concentrated over a small region. As we move down the group, the increasing
atomic size of the central atom causes the electron density of the lone pair to diffuse over the
large region and thus the ability to donate the electron pair and hence the basic character
decreases.
N2H4 is a colourless liquid, less volatile than phosphine due to H – bonding. It is a weak base
and gives weakly alkaline solution with water.
N2H4 + H2O N2H5+ + OH-
Perhaps the hydrogen bonding between the N2H5+ + OH- ions decreases the alkalinity of the
aqueous solution. P2H4 does not show basic properties. N3H is a colourless liquid having
melting point of 236K. It is freely soluble in water forming an acidic solution.
N3 H + H2 O H3O+ + N3-
(ii) Thermal Stability:
The thermal stability of the MH3 hydrides decreases gradually from NH3 to BiH3 with
increasing size of the central atom. This is evident from the decreasing temperature of their
decomposition into their elements, i.e. NH3 (5000C) ˃ PH3 (4400C) ˃ AsH3 (2800C) ˃ SbH3
(2700C) ˃ BiH3 (very unstable). The least stable nature of BiH3 (half life period = 20
minutes under normal conditions) confirms the fact that only trace quantities of this hydride
have been prepared and identified. Thus we infer that the strength of M-H bond goes on
decreasing as the thermal stability decreases from NH3 to BiH3. N2H4 and N3H both are fairly
stable towards mild heating but P2H4 is highly unstable and is spontaneously inflammable.
(iii) Reducing properties:
All the MH3 type hydrides are reducing agents and with the progressive fall in stability, the
reducing character of these hydrides goes on increasing due to the weakening of M–H
bonds and increasing ease of their decomposition. Thus NH3 is a mild reducing agent and is
not oxidized readily, if oxidized, the product is usually nitrogen, e.g. when NH3 burns in
oxygen, it gives N2 and water but if heated with oxygen in the presence of a Pt – catalyst, NO
is formed.

4NH3 + 3O2 2N2 + 6H2O
Pt
4NH3 + 5O2 , 4NO + 6H2O
Phosphine, PH3, is stronger reducing agent than NH3 and is much more easily oxidized, i.e.
when ignited in air, it gives phosphorous pentoxide.
4PH3 + 8O2 P4O10 (or 2P2O5) + 6H2O
SbH3 and BiH3 are powerful reducing agents and are oxidized very easily.
Anhydrous N2H4 burns readily in oxygen or air forming N2.
N2H4 + O2 N2 + 2H2O
Aqueous hydrazine can act both as reducing and oxidizing agent.
As reducing agent: Alkaline solution: N2H4 + 4OH- N2 + 4H2O + 4e-
Acidic solution: N2H5+ N2 + 5H+ + 4e-
As oxidising agent: Alkaline solution: N2H4 + 2H2O + 2e- 2NH3 + 2OH-
Acidic solution: N2H5+ + 3H+ + 2e- 2NH4+
P2H4 is a powerful reducing agent and is instantaneously oxidised in air or O2:
P2H4 + 7O2 P4O10 + 4H2O
Aqueous hydrazoic acid can act either as a reducing agent or as an oxidizing agent.
As a reducing agent: Alkaline solution: 2N3- 3N2 + 2e-
Acidic solution: 2HN3 3N2 + 2H+ +2e-
As oxidizing agent: Alkaline solution: N3- + 7H2O + 6e- N2H4 + NH3+ 7OH-
Acidic solution: HN3 + 3H+ + 2e- NH4+ +N2
(iv) Covalent character:
The NH3 molecule has more ionic character than PH3 (NH3 ˃ PH3) due to more
electronegativity difference between N and H than between P and H. Similarly, it can be

shown that the ionic character of MH3 molecules decreases and covalent character increases
down the group from NH3 to BiH3.
(v) Shape of hydride molecules and H-M-H bond angles:
The shape of MH3 type of hydrides is trigonal pyramidal. This shape may be regarded as
tetrahedral shape having one lone pair of electrons occupying one of the four tetrahedral
positions (involving sp3 hybridisation of the central atom). The HMH bond angle in all the
four MH3 hydrides (M = N, P, As, Sb) is never equal to ideal tetrahedral angle of 109.50 but
less than this value due to low electronegativities of the central atoms. N3H is the linear
molecule:
H–N N≡N. Actually it is a resonance hybrid or two canonical forms.
(vi) Hydrogen bonding:
Ammonia is least volatile among the MH3 hydrides because in ammonia, intermolecular
hydrogen bonding occurs resulting in the formation of cluster of molecules. This happens due
to the development of strong polarity in the bonds of the NH3 molecules and association of
molecules (dipole – dipole type interaction).
11.5 HALIDES OF NITROGEN GROUP ELEMENTS

The elements of nitrogen group form two types of halides namely trihalides, MX3 and
pentahalides, MX5 . All these halides have been given in table 11.1.
11.5.1 Preparation:
The trihalides are formed by all the elements and prepared by the two methods:
(a) By the reaction of excess element with halogen (except nitrogen)
2M + 3X2 2MX3 (M = As, Sb, Bi and X = Cl, Br, I)
(b) By the reaction of hydrogen halide with the trioxide of the element.

M2O3 + 6HX 3H2O + 2MX3
The pentahalides of nitrogen are not known due to the non availability of d- orbitals in its
atom but all other elements, except Bi, form pentahalides which are prepared as follows:
(a) By the reaction of excess halogen with the element.
2M + 5X2 2MX5
(b) By the reaction of halogen on the trihalide.
MX3 + X2 MX5
In Bi, the ns2 electron pair is inert (inert pair effect) and does not participate in bond
formation, Therefore, BiX5 compounds if formed, immediately converted to BiX3 by
decomposition and these are said to be non- existent.
11.5.2 Properties:
The trihalides of nitrogen are least stable except NF3 which has strong N – F bond due to the
small size of both N and F atoms. With the exception of BiF3, all other trihalides have
covalent character which decreases as we descend the group. Except NF3 and BiF3, all other
trihalides are readily hydrolysed by water.
NCl3 is an explosive compound and NBr3 as well as NI3 exist only as ammoniates. The
explosive nature of these compounds is due to much lower stability or bond energy of N - Cl,
N - Br, and N – I bonds.
(i) NX3 (X= Ci, Br, I ) trihalides are completely hydrolysed by water giving NH3 and HOX
(hypohalous acid)
NCl3 + 3H2O NH3 + 3HOCl
For PX3, AsX3 and SbX3, the ease and extent of hydrolysis generally increase with decreasing
eletronegativity of halogen atom (I to F) and decrease with increasing metallic character of
the central atom ( P to Bi). Different chlorides on hydrolysis give different products.
PCl3 + 3H2O H3PO3 + 3HCl
2AsCl3 + 3H2O As2O3 + 6HCl

Sb and Bi trichlorides are only partly and reversibly hydrolysed.
SbCl3 + H2O SbOCl + 2HCl
BiCl3 + H2O BiOCl + 2HCl
(ii)All trihalides except NX3 and PF3, can act as Lewis acid.
SbF3 + F- SbF4- SbF4- ≡ [SbF3←F]-
But PF3 acts as Lewis base, e.g.
Ni(CO)4 + PF3 (CO)4Ni←PF3
NX3, except NF3 molecules are strong Lewis bases.
(iii) N– trihalides are not oxidized at all but the trihalides of other elements are oxidized and
the ease of oxidation decreases down the group, i.e. P ˃ As ˃ Sb ˃ Bi.
Properties of pentahalides:
(a) Pentahalides dissociate into MX3 and X2, the tendency of dissociation decreases in the
order of M and X: P ˃ Sb ˃ As ˃ Bi and F ˃ Cl ˃ Br
(b) These halides are hydrolised to give the acid of the M element or hydrated oxides along
with HX mineral acid.
PX5 + H2O POX3 + 2HX
POX3 + 3H2O H3PO4 + 3HX
PX5 + 4H2O H3PO4 + 5HX
2SbX5 + 7H2O Sb2O5.2H2O + 10 HX
Except BiF5 all are Lewis acids.
PF5 + F- PF6- ≡ [PF5←F]-
11.5.3 Structure:
The structure of MX3 trihalides is similar to that of NH3 in gas phase, i.e. central atom is sp3
hybridised, one of the sp3 hybrid orbitals contains a lone pair of electrons (bonded pairs=

3, lone pair = 1) and molecules attain a trigonal pyramidal shape, i.e. distorted form of
tetrahedral geometry.
X–Ray studies of MX5 halides in the liquid and gaseous phases have revealed that these
molecules possess trigonal bipyramidal shape (resulting from sp3d hybridization of the
central M-atoms (postulated by VBT). In solid state these are ionic and exist as [PCl4]+
[PCl6]-, [PBr4]+ Br- etc. The shape of [PX4]- ion is tetrahedral and that of [PX6]- ion is
octahedral. But different solid pentahalides have different structures. PI5 does not exist due
to large size of iodine atom.
11.6 OXIDES AND OXO ACIDS OF ELEMENTS
Almost all the elements of this group form oxides and oxo (oxygen containing) acids. More
important oxides are trioxides (M2O3), tetraoxides (MO2 or M2O4) and pentoxides (M2O5). In
addition to these, nitrogen also gives nitrous oxide (N2O) and nitric oxide (NO). Bismuth also
forms bismuth monoxide (BiO). All these oxides are shown in Table 11.2
11.6.1 Properties and structures of oxides:
All the oxides of nitrogen are thermodynamically unstable because compounds containing
single N–O bonds tend to be dissociated because of low N–O bond enthalpy. Thermal
stability and acidic character of M2O3 type oxides (trioxides) decreases from N2O3 to Bi2O3.
Thus N2O3 and P2O3 are completely acidic and give nitrous and Phosphorous or phosphoric
acids with water.
N2O3 + H2O 2HNO2
P2O3 + 3H2O (cold) 2H3PO3
2P2O3 + 6 H2O (hot) 3H3PO4 + PH3

As2O3 and Sb2O3 are amphoteric and form salts with acids as well as alkalies.
As2O3 + 6HCl 2AsCl3 + 3H2O
As2O3 + 6NaOH 2Na3AsO3 + 3H2O

Sod.arsenite
(Similar reactions are given by Sb2O3 also.)
Bi2O3 is predominantly basic and forms salts with acids. It also shows feebly acidic character
since it dissolves in conc. alkalies due to the formation of bismuthites.
Bi2O3 + 6HCl 2BiCl3 + 3H2O
Bi2O3 + 2NaOH 2NaBiO2 + H2O
sod. bismuthite
The decreasing acidic character from N2O3 to Bi2O3 is due to larger extent of interaction
between smaller N3+ ion and H2O thereby giving acidic N2O3 as compared to that between
larger Bi3+ ion and water giving basic Bi2O3.
The reason of an oxide in lower oxidation state being less acidic than that in higher oxidation
state can also be explained on the same ground that smaller ion with higher oxidation state
interacts more strongly with water to give stronger acid. For example, N2O (oxidation state of
N= +1) is neutral while N2O4 (oxidation State of N= +4) is acidic. The decreasing acidic
character from N2O3 to Bi2O3 is also consistent with the increasing metallic character of the
elements on passing from nitrogen to bismuth.
P2O3 is readily oxidised to P2O5 (P2O3 +O2 P2O5) while the trioxides of other
elements are rather stable towards oxidation to pentoxides. Bi2O3 shows maximum stability
towards oxidation.
All the Pentoxides (M2O5) are acidic but the acidic character decreases from N2O5 to Bi2O5
with increasing atomic mass of the element M. Thus N2O5 is the strongest acidic oxide and
Bi2O5 is the weakest. N2O5, P2O5 and As2O5 are exclusively acidic and react with water or
alkalies to form oxo acids or their salts.
N2O5 + H2O 2HNO3
P2O5 + H2O(cold) 2HPO3
P2O5 + 3H2O (hot) 2H3PO4
Sb2O5 is less acidic but forms salts called antimonates. Bi2O5 is only feebly acidic and forms
salts when fused with alkalies called bismuthates.
Bi2O5 + 6NaOH 2Na3BiO4 + 3H2O

Sod. bisluthate
The decreasing acidic character from N2O5 to Bi2O5 is due to increasing size of M5+ ion from
N5+ to Bi5+ and also due to increasing metallic character of the elements from N to Bi. The
first three pentoxides, viz. N2O5, P2O5 and As2O5 are readily soluble in water and form acids
while Sb2O5 and Bi2O5 are relatively insoluble. Thus the solubility of these oxides decreases
from N2O5 to Bi2O5.
N2O5 is thermally least stable and gets dissociated into nitrogen dioxide (NO2) and O2 even at
room temperature. P2O5 is stable but sublimes on heating. As2O5 decomposes into trioxide
(As2O3) and O2 at red heat.
Sb2O5 is less stable and decomposes into Sb2O3 and O2 above 4500C.
N2O5 is the strongest oxidising agent among the pentoxides which, except P2O5, show
oxidising property.
The properties of some other oxides of nitrogen have been given below along with P4O8
(=2P2O4).
(i) Nitrous oxide9N2O):
(a) It is slightly soluble in water, has faint sweet smell and is inert at 250c but
decomposes at higher temperature to N2 and O2. Therefore, it is better oxidising agent than
oxygen itself.
2N2O 2N2 + O2
(b) It does not react with water, acids and alkalies.
(ii) Nitric oxide(NO):

(a) It is sparingly soluble in water. It quickly reacts with oxygen to form the brown
coloured gas NO2
2NO + O2 2NO2
(b) It reacts vigorously with burning phosphorous and boiling sulphur.
S + 2NO SO2 + N2
(c) On heating nitric oxide decomposes to N2 and O2
2NO N2 + O2
(d) Reducing Nature:
It reduces O2, Cl2 and acidified potassium permanganate as follows:
2NO + O2 2NO2
2NO + Cl2 2NOCl2
- +
2MnO4 + 4H + 5NO 3Mn2+ + 5NO3- + 2H2O

(e) Oxidising nature:

It acts as oxidising agent and is reduced to nitrogen and ammonia.
2NO + 2H2 sparking N2 +2H2O
2NO + 5H2 Pt –black 2NH3 + 2H2O
(f) It forms dark brown nitrosyl complex with FeSO4 solution, [Fe(NO)(H2O)5]2+.
(iii) Nitrogen dioxide (N2O4⇌2NO2 ):
(a) It is soluble in water, highly poisonous, has pungent smell and corrodes the skin.
(b) It changes its colour and physical state with temperature.
1400C 260C -570C

2NO2 ⇌ 2NO2 ⇌ N2O4 ⇌ N2O4
reddish pale coloured yellow colourless
brown gas gas liquid solid
(c) Acidic nature:
NO2 is acidic towards litmus and neutralises alkalies to form nitrates and nitrites.
2NO2 + H2O HNO2 + HNO3
2OH- + 2NO2 NO-2 + NO-3 + H2O
(d) Oxidising nature

Some oxidising reactions of NO2 are as follows:
2FeSO4 + H2SO4 + NO2 Fe2(SO4)3 + NO + H2O
2I- + H2O + NO2 I2 + 2OH- + NO
2MnO4- + 2H2O + 10NO2 2Mn2+ + 4H+ + 10NO-3
(iv) P4O8 ⇌ 2P2O4
It reacts with water to produce H3PO4 and H3PO3
P2O4 + 3H2O H3PO4 + H3PO3
(ic) (ous)
Structure of oxides:
N2 O
It is isoelectronic with CO2 and is almost linear. Fig 11.1 (a)
NO

INORGANIC CHEMISTRY
CHEMISTRY-I BSCCH
BSCCH-101
It is an odd electron molecule with a total of 11 electrons. The unpaired electron is

delocalised (paramagnetic). Has linear structure. Fig 11.1 (b)
NO2
It has two normal bonds (1 σ and 1 π ) and one coordinate bond and also an unpaired electron
(paramagnetic). Has bent structure. The diner has planar structure. Fig 11.1 (c)
N2O5. In vapour phase it has a symmetrical structure. Fig 11.1 (d)
P4O6 ⇌ 2P2O3
It has a tetrahedral structure with four P
P-atoms
atoms lying at the corners of a tetrahedron and six O-
O
atoms along the edges, P-O
O bond length being between a single and a double bond due to
considerable double bond character formed as O →P: pπ-dπ dative bond. Fig
ig 11.2 (a)
P4O8 ⇌2P2O4
It has two additional oxygen atoms as compared to P4O6 which are attached to two P-
P
atoms. Structure is similar to that of P4O6. Fig 11.2 (b).
P4O10 ⇌2P2O5. Each P atom of this molecule forms a double bond with terminal O-atom
O
(pπ-dπ) and three single bonds with three bridged O
O-atoms.
atoms. The structure is similar to those of
P4O6 and P4O8. Fig 11.2 (c)
The structure of As2O5, Sb2O5 and Bi2O5 are not known.

11.6.2 Oxoacids:
Nitrogen forms four oxo acids, viz. Hyponitrous acid (H2N2O2), nitrous acid (HNO2), nitric
acid (HNO3) and pernitric acid (HNO4). Phosphorous forms a number of oxo acids which can
be classified according to formal charge of the phosphorous atom. The oxo acids of other
elements (H3AsO3& H3AsO4, H2SbO3 (unstable), HBiO3 etc.) are, perhaps, not so important
and their details do not appear in the literature.
Properties:
(i) H2N2O2
(a) On exposing to air, the acid decomposes slowly giving HNO2 and HNO3 but aqueous
solution of the acid decomposes on heating to give N2O.
2H2N2O2 + 3O2 2HNO2 + 2HNO3
H2N2O2(aq.) N2 O + H2 O
(b) It is a weak dibasic acid, soluble in water and organic solvents. It acts as a reducing agent and
is oxidised by acidified KMnO4 to nitrate.
5H2N2O2 + 8KMnO4 +12H2SO4 8MnSO4 + 10HNO3 + 4K2SO4 + 12H2O
(ii) HNO2 (the readers have studied this acid in detail earlier, hence only a short account is being
given here)
(a) It is also a weak acid, unstable and even in cold undergoes auto decomposition. At higher
temperature, it decomposes into NO and NO2.
3HNO2 HNO3 + 2NO + H2O
2HNO2 H2O + N2O3 NO + NO2
(b) It is a good oxidising agent due to liberation of O-atom.
2 HNO2 2NO + H2O + O
It oxidises H2S S, KI I2, SnCl2 SnCl4, SO2 H2SO4,
FeSO4 Fe2(SO4)3, AsO33- -
AsO4 etc.
(c) It also acts as a reducing agent due to its easy oxidation to HNO3
HNO2 + O HNO3
It reduces X2 X- (X=Br, I), H2O2 H2O, MnO4- Mn2+ (acid),
Cr2O72- Cr3+ (acid) etc.
(iii) HNO3 (The details of this acid have been studied by the readers in previous classes, hence
only a short description will be given here.)
(a) Nitric acid is a strong oxidising agent because of its easy decomposition to give nascent
oxygen.

2HNO3 2NO2 + H2O + O

Thus non-metals, e.g. S, I2, C, P etc, metalloid (As etc.) are converted to acids, most of the
metals except Au, Pt etc, are attacked by HNO3. Some of them like Sn and Sb give oxides
and others form nitrates. During the reaction, depending on the concentration of the acid,
temperature and nature of the metal, various by-products such as NO, NO2, N2O, NH2OH or
even NH3 are obtained.
(b) Mg and Mn are the only metals which liberate H2 from dilute HNO3.
Mg + 2HNO3 (dilute) Mg (NO3)2 + H2↑
(c) 1 part of conc. HNO3 and 3 part of conc. HCl is known as aqua regia dissolves even the
noble metals, viz. Au, Pt etc due to the action of nascent chlorine on the metals.
HNO3 + 3HCl NOCl + 2H2O + 2Cl (nascent chlorine)
+
(d) It produces NO2 ions (nitronium) in presence of conc. H2SO4 which cause nitration of
organic compounds by replacing hydrogen.
HNO3 + 2H2SO4 NO2+ + 2HSO4- + H3O+
C6H6 +NO2+ + HSO4- C6H5NO2 + H2SO4
HSO4- + H3O+ H2SO4 + H2O
C6H6 + HNO3 C6H5NO2 + H2O

(e) HNO3 shows strong acidic property: HNO3⇌ NO3- + H+.
Thus it reacts with metal salts forming metal nitrates.
(iv) Hypophosphorous acid (H3PO2), a mono basic acid (H3PO2⇌ H+ + H2PO2-) and ortho
phosphorous acid (H3PO3), a dibasic acid (H3PO3⇌ 2H+ + HPO32-) show similar properties,
i.e. on heating give PH3 and are reducing agents:
2H3PO2 PH3 + H3PO4
0
4H3PO3 200 C 2H3PO4 + PH3
H3PO2 + 2H2O H3PO4 + 4H
H3PO3 + H2O H3PO4 + 2H
(liberation of H makes them strong reducing agents).
(v) Hypophosphoric acid (H4P2O6) is a tetra basic acid (H4P2O6⇌ 4H+ + P2O64-)
and decomposes to H3PO3 and HPO3 on heating above its melting point.
H4P2O6 H3PO3 + HPO3
But when heated at 1800C gives PH3 along with acids.
4H4P2O6 2H3PO4 + 4HPO3 + PH3

On hydrolysing it gives H3PO4 and H3PO3.

(vi) Ortho phosphoric acid (H3PO4) is a tri basic acid (H3PO4⇌ 3H+ + PO43-) and is an
important member of acid series of P.
(a) Action of heat. When heated strongly it gives a series of products as given below:
2H3PO4 2500C H4P2O7 3200C 2HPO3 600-7000C P2O5
-H2O -H2O red heat, -H2O
(b) Reaction with alkalies. It forms three series of salts with alkalies.
H3PO4 +NaOH NaH2PO4 +NaOH Na2HPO4 +NaOH Na3PO4

-H2O primary -H2O secondary -H2O tertiary sod.
phosphate
(b) Reaction with magnesia mixture. It reacts with magnesia mixture (MgCl2 + NH4OH) to
produce a white ppt. of NH4MgPO4 (ammonium magnesium phosphate).
H3PO4 + MgCl2 + NH4OH NH4Mg PO4 + 2HCl + H2O.
(c) Reaction with ammonium molybdate. When phosphoric acid and phosphates are treated
with conc. HNO3 and ammonium molybdate, a canary yellow ppt. of ammonium
phosphomolybdate is obtained on warning to about 570C.
H3PO4 + 12(NH4)2MoO4 + 21HNO3 (NH4)3PO4.12MoO3 + 21NH4NO3 +
12H2O yellow ppt.
(vii) Pyrophosphoric acid (H4P2O7) is a tetra basic acid (H4P2O7 ⇌ 4H+ +P2O74)
but forms only two types of salts, i.e. M4P2O7 and M2P2O7 type. On heating it gives
metaphosphoric acid (HPO3).
H4P2O7 2170C 2HPO3 + H2O
(viii) Meta phosphoric acid (HPO3) is also known as glacial phosphoric acid. Its aqueous solution
is gradually converted into H3PO4 on standing.
H3PO4 + H2O H3PO4 (ortho acid)
(ix) Peroxy phosphoric acids are the derivatives of H2O2, i.e. H3PO5 and H4P2O8.
Structures of oxo acids:
H2N2O3. This acid is said to contain an azo group, -N=N- and assigned the structure, HO –
N=N-OH. Because of the double bond, cis-trans isomerism may be there. But experimental
evidences support the trans-structure of the acid. Fig 11.3 (a)
HNO2. The infrared study of the acid vapour has proposed the trans structure for the acid.
Raman and X-ray study of crystalline salts of the acid have shown that NO-2 ion has an
angular structure as shown below: Fig 11.3 (b)
INORGANIC CHEMISTRY
CHEMISTRY-I BSCCH
BSCCH-101
HNO3. It is a mono basic acid, i.e. has replaceable hydrogen attached to N-

N-atom through
oxygen. The electron diffraction studies have indicated a planner structure to the acid in
vapour state as shown here. NO3- ion has trigonal planner geometry (sp2 hybridisation)
hybridisat
postulated by VBT. Fig 11.3 (c)
Oxo acids of phosphorous :

The structure of various oxo acids of phosphorous have been shown in Fig. 11.4. In general
various atoms or groups are arranged tetrahedrally around P atom (s) of the acids, i.e. there is
no direct link between adjacent P
P-atoms.
11.7 ANOMALOUS BEHAVIOU

BEHAVIOUR OF NITROGEN
Nitrogen, the
he first element of the group VA, differs considerably, like other first elements of
the respective earlier groups, from other elements of its group. This is, as stated earlier also,

because of the inherent properties of nitrogen, i.e. its small size, high electro-negativity and
non-availability of d-orbitals in the valence shell.
The main points of difference are:
(i) Nitrogen is a gas while other dements are solids.
(ii) Nitrogen molecule is diatomic (N2) while other molecules are to tetra-atomic (P4, As4, Sb4
etc). This is due to the formation of pπ-pπ bond in nitrogen.
(iii) All the elements except N and Bi show allotropy.
(iv) Nitrogen occurs in free state in nature but other elements occur as ores.
(v) Nitrogen behaves as an inert (non-reactive) element but other elements are fairly reactive.
This is because N≡N bond is present in N2 and other elements have low M-M bond energy.
(vi) Nitrogen shows a large number of oxidation states, e.g. -3(NH3), -2(N2H4), -
1(NH2OH), +1(N2O), +2(NO), +3(N2O3), +4(NO2) and +5(N2O5). Other elements do not
show such a variety of oxidation states.
(vii) Its trihydride, NH3, is highly stable and non-poisonous while the trihydrides of the other
elements are progressively less stable and poisonous. Also, hydrogen bonding occurs only in
NH3 and not in other MH3 compounds.
(viii) NCl3 is explosive, highly reactive and unstable while the trichlorides of the remaining
elements are more stable and less reactive. N does not form pentahalides but other elements
except Bi form such halides because N cannot expand its octet due to the non-availability of
d-orbitals in the valence shell.
(ix) Maximum coordination number of nitrogen is 4 and that for other elements is 6, e.g. [M F6]-
11.8. SUMMARY
The text of the study material of this unit contains the introductory part along with a detailed
account of the general characteristics of the nitrogen group elements such as their electronic
configuration, occurrence, physical state, elemental structure, metallic and non-metallic
character, hardness, atomic radius and atomic volume, ionisation energy, electronegativity,
heat of atomisation, melting and boiling points, oxidation states, electron donor- acceptor
properties, allotropy, catenation, electrical and thermal conductivity, chemical reactivity etc.
The preparation and properties of hydrides and halides of these elements have been given in
detail along with their structural aspects. The properties and structure of oxides and oxo acids
have been discussed elaborately with examples. At the end, the points of anomalous
behaviour of nitrogen in contrast to other elements of its family have been mentioned.


i. The penultimate shell of phosphorous has
(a) 1s2 configuration
(b) 2s2p6 configuration
(c) 3s2p6d10 configuration
(d) 2s2p6d10 configuration
ii. The elements that do not form pentahalides are:
(a) N and P
(b) N and As
(c) P and As
(d) N and Bi
iii. Hydrazoic acid is a hydride of
(a) N
(b) P
(c) As
(d) Sb
iv. Among the pentoxides, the strongest oxidising agent is
(a) N2O5
(b) P2O5
(c) As2O5
(d) Sb2O5
v. The only metals which liberate H2 on reacting with dilute HNO3 are
(a) Zn and Sn
(b) Mn and Sn
(c) Cu and Zn
(d) Mg and Mn
11.10 ANSWERS
i. (b)
ii. (d)
iii. (a)
iv. (a)
v. (d)

Literature Consulted (List of Books)

1. Principles of Inorganic Chemistry : B.R. Puri, L.R. Sharma and K.C. Kalia, Milestone
publishers and Distributers, Meerut (2013)
2. Advanced Inorganic Chemistry : Satya Prakash, G.D. Tuli, S.K. Basu and R.D. Madan, Vol
I, 17Ath Edn., S. Chand & Co. Ltd., New Delhi (1998)
3. Comprehensive Inorganic Chemistry : Sulekh Chandra, NewAge International (P) Ltd.,
Publishers, New Delhi (2004)
4. Satya Prakash’s Modern : R.D. Madan, S. Chand & Inorganic Chemistry Company Ltd.,
New Delhi (1997)

UNIT 12: ELEMENTS OF GROUP - 16
CONTENTS:
12.1 Objectives
12.2 Introduction
12.4 Oxides of sulphur
12.4.1 Sulphur dioxide
12.4.1.1 Preparation
12.4.1.2 Properties
12.4.1.3 Uses
12.4.1.4 Structure
12.4.2 Sulphur trioxide
12.4.2.2 Properties
12.4.2.3 Uses
12.4.2.4 Structure
12.5 Oxoacids of sulphur
12.5.1 Sulphurous acid series
12.5.1.1 Sulphurous acid
12.5.1.2 Thiosulphurous acid
12.5.1.3 Hyposulphurous acid
12.5.1.4 Pyrosulphurous acid
12.5.2 Sulphuric acid series
12.5.2.1 Sulphuric acid
12.5.2.2 Thiosulphuric acid
12.5.2.3 Pyrosulphuric acid
12.5.3 Peroxysulphuric acid series
12.5.3.1 Peroxymonosulphhuric acid
12.5.3.2 Peroxydisulphuric acid
12.5.4 Thionic acid series
12.5.4.1 Dithionic acid
12.5.4.2 Polythionic acid

12.6 Halides of sulphur and their properties

12.6.1 Preparation, properties and structure of sulphur halides
12.6.1.1 Dihalides
12.6.1.2 Tetrahalides
12.6.1.3 Dimeric monohalides
12.6.1.4 Hexahalides
12.6.1.5 Dimeric pentafluoride
12.6.2 Preparation, properties and structure of sulphur halides
12.7 Anomalous behaviour of oxygen
12.8 Summary
12.10 Answers
12.1 OBJECTIVES
This unit will help readers to answer the following questions:
(a) What are Chalcogens?
(b) How elements of 16-group are useful?
(c) What is dπ-pπ bonding?
(d) What are the structures of oxides and oxoacides of 16-group elements?
(e) How oxygen is different from other elements in the group?
12.2 INTRODUCTION
In continuation of group-15 elements, within this unit you will learn about general properties,
structure and uses of 16-group elements. There are five elements in this group, of which the
first four are non-metals. All the elements of this group are solid except oxygen. Oxygen,
sulphur and selenium are non-metals, tellurium metalloid while polonium is metallic in
nature. These are also called as chalcogens. Chalcogens means ore-forming elements, as a
large number of metal ores are oxides or sulphides.
Several reagents of this group element are commercially important. Sulphuric acid (H2SO4),
sodium sulphite (Na2SO3) and hydrogen peroxide (H2O2) are some of them. The elements can

be divided into metal (polonium, Po) and non-metals (oxygen, sulphur, selenium and
tellurium; O, S, Se and Te).
Oxygen shows different properties from the other members of this family because oxygen has
strong tendency to form π bond while sulfur has greater tendency to form chains and rings.
Selenium, tellurium and polonium form toxic compounds which should be handled with great
care.
12.3 GENERAL CHARACTERISTICS AND USES
Atomic radius, density and metallic character increase from oxygen to polonium while
ionization potential decreases from oxygen to polonium. Oxygen is a diatomic gas while
sulphur, selenium and tellurium are octa-atomic S8, Se8 and Te8. Electronic configurations of
each element of this group are given below. All elements except oxygen exhibit –2, +2, +4
and +6 oxidation states. All the elements of 16th group exhibits allotropy. Se, S, Te, Po and
oxygen have 6, 4, 2, 2 and 2 allotropes, respectively. Out of 6 allotropes of Se, three are red
non metallic, one amorphous red and two grey metallic forms. Allotropes of sulphur are α–
(rhombic or octahedral sulphur), β-(monoclinic or prismatic sulphur), γ-(monoclinic sulphur)
and λ– (plastic) sulphur. Te has one metallic and one non-metallic allotrope while Po has 2
allotropes; one α–cubic and the other β–rhombohedral. The two allotropes of oxygen are O2
(oxygen) and O3 (ozone). Elements of group 16 form a number of binary and ternary
compounds. Among binary compounds; hydrides, halides and oxides are the main
compounds.
Sixteenth group elements (VIA group) form H2M type hydrides. All hydrides are covalent in
nature.. All hydrides are poisonous gases with unpleasant and foul smell. Group 16 elements
form monohalides (M2X2 type), dihalides (MX2 type), tetrahalides (MX4 type) and
hexahalides (MX6 type) where M is an element of 16th group and X may be F, Cl, Br or I.
The oxides formed by group 16 elements are dioxides (MO2 type) and trioxides (MO3 type).
Other important ternary complexes formed by elements of 16th group are oxoacids (-ous and -
ic acids) such as sulphurous (H2SO3) and sulphuric (H2SO4) acids, sodium thiosulphate
(Na2S2O3, 5H2O) etc.
Electronic configuration of 16 group elements
Oxygen (O) – 1s2 2s2 2p4

Sulphur (S) - 1s2 2s2 2p6 3s2 3p4
Selenium (Se) - 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p4
Tellurium (Te) - 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 4d10 5s2 5p4
Polonium (Po) - 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 4d10 4f14 5s2 5p6 5d10 6s2 6p4
We know that dioxygen (O2) is used in respiration by both plants and animals.
Besides this, it is also used in steel plants. Along with air, dioxygen is used in blast furnaces
for the reduction of iron-oxides to impure pig iron by coke. Dioxygen is also used in oxy-
acetylene welding, metal cutting, manufacture of HNO3 from NH3 and ethylene oxide from
ethane. Titanium dioxide is used as a white pigment in paint and paper and as filler in
plastics. Dioxygen is also used as oxidant in rockets. Sulphur is the minor constituent of
certain amino acids such as cystine, cysteine and methionine. Sulphuric acid (H2SO4) is used
for making fertilizers while sulphite (SO32–), hydrogen sulphites (HSO3–) and sulphur dioxide
(SO2) are used in bleaching. Sulphur is also used in the manufacture of carbon disulphide
(CS2), rubber, fungicides, insecticides and an explosive–gunpowder. Both sulphur and
selenium dehydrogenate saturated hydrocarbons. Selenium metal (Se) is used to decolorize
glass. Photoreceptors of photocopiers are made up of selenium. Selenium is an essential trace
element and a component of many enzymes such as glutathione and peroxidase. When taken
in larger quantity, it becomes toxic to the human beings. Tellurium (Te) is used in the
manufacture of steel and non-ferrous alloys. Selenium and tellurium when absorbed in human
body, excreted as foul smelling organic compounds along with breath and sweat. Polonium
(Po) is a radioactive element.
12.4 OXIDES OF SULPHUR
Sulphur mainly forms dioxides (SO2), trioxide (SO3) and sesquioxide (S2O3).
12.4.1 Sulphur dioxide (SO2).
12.4.1.1 Preparation:
Sulphur dioxide can be prepared by
(i) Burning sulphur (S) or sulphide ores in excess of air. This is the commercial process of SO2
production.

S + O2 → SO2
2ZnS + 3O2 → 2ZnO + 2SO2
(iii) Reaction of concentrated H2SO4 with Cu turnings, S, charcoal, Ag and Hg (Laboratory
method)
Cu + 2H2SO4 → CuSO4 + SO2 2H2O
(iii) Large amount of SO2 is produced as a waste product during coal and/or other fossil fuel
burning. This SO2 is harmful for environment.
12.4.1.2 Properties:
Physical properties
Sulphur dioxide is a colourless gas with suffocating smell. It solidified at –76ºC and liquefied
to a colorless liquid at –10ºC.
Chemical properties
The different chemical properties of SO2 are given below:
(i) At 1200ºC, it decomposes into SO3 and S.
3S + O2 → 2SO3 + S (at 12000C)
(ii) SO2 is an acidic oxide. In aqueous solution, it shows acidic properties.
SO2 + H2O H2SO3 (Sulphurous acid)
Due to its acidic nature, it also reacts with basic oxides to form sulphides.
SO2 + 2NaOH Na2SO3 + H2O

SO2 + CaO CaSO3
(iii) Formation of addition compounds
As maximum covalency of sulphur atom is six, SO2 (with four covalency), can form
addition compound with O2, Cl2, PbO2 and BaO2 to attain maximum covalency of six.

Pt or V2O5
SO2 + O2 2SO3
Sunlight
SO2 + Cl2 SO2Cl2
or camphor
SO2 + PbO2 PbSO4
(iv) Oxidizing properties
SO2 (S = +4) acts as a good oxidizing agent with strong reducing agents and reduces
itself to S (S = 0).
SO2 + 2H2S 2H2O + 3S
SO2 + 2CO 2CO + S
SO2 + 4HCl + 2SnCl2 2SnCl4 + 2H2O + S
(v) Reducing properties
In presence of moisture, SO2 can act as reducing agent as it liberates nascent

hydrogen on reaction with moisture (The nascent hydrogen acts as a reducing agent).
SO2 + H2O SO3 + 2H

(moisture)
During reduction process, SO2 get oxidized to SO3 or H2SO4.
5SO2 + 2KMnO4 + 2H2O → K2SO4 + 2MnSO4 + 2H2SO4
3SO2 + K2CrO7 + H2SO4 → K2SO4 + Cr2(SO4)3 + H2O

SO2 + 2H2O + Fe2(SO4)3 → 2FeSO4 2H2SO4
12.4.1.3 Uses:
(i) SO2 is used for the production of other chemicals such as NaHSO3, Na2CO3 and Na2S2O3
(ii) SO2 is also used as a non-aqueous solvent. Liquid SO2 is a useful solvent as a number of
inorganic and organic compounds are soluble in this solvent.
12.4.1.4 Structure:
In the first excited state, sulphur attains 3s23p33d1 valence shell configuration. Then it
undergoes sp2 hybridization. Sulphur forms two bonds two σ bonds (p –p ,p –d ) with
oxygen atoms. The bond angle is 119º30’. Due to the presence of one lone pair of electyrons
on S atom, its geometry became V-shaped.
12.4.2 Sulphur trioxide (SO3):
Sulphur trioxide can be prepared by the following methods:
(i) Oxidation of SO2
Pt
2SO2 + O2 2SO3
400º-450º

SO2 + H2O2 SO3 + H2O
(ii) By the reaction of HNO3 with SO2
SO2 + 2HNO3 2NO2 + SO3 + H2O
(iii) By the reaction of NO2 with SO2
SO2 + NO2 SO3 + NO
(iv) By heating pyrosulphuric acid
H2S2O7 + H2O H2SO4 + SO3
12.4.2.2 Properties
(i) Physical properties
SO3 exists in three following allotropic forms:
(a) α-form : chemically active form, ice-like transparent crystals with m.p. 17ºC
(b) β-form: Needle-like white crystals, above 50ºC. This form changes to α-form. The m. p. is
32.5ºC.
(c) γ–form: like β-form and obtained by complete drying of β-form. Its m.p. is 62.2ºC at 2 atm.
pressure.
(ii) Acidic nature
In aqueous solution, it shows acidic properties, hence, acidic in nature.
SO3 + H2O H2SO4
SO3 also reacts with basic oxides to form corresponding sulphates
(iii) Dissociation
SO3 dissociates into SO2 and O2 at 1000ºC.

2SO3 2SO2 + O2
(iv) Reaction with H2SO4
With conc. H2SO4, SO3 forms pyrosulphuric acid (fuming sulphuric acid / oleum)
SO3 + conc. H2SO4 H2S2O7

Pyrosulphuric acid
(v) Oxidizing property
Sulphur trioxide is a good oxidizing agent. During oxidation, SO3 reduces to SO2.
5SO3 + 2P 5SO2 + P2O5

SO3 + 2HBr SO2 + Br2 + H2
SO3 + PCl3 SO2 + Cl2 + POCl3
(vi) Reaction with H2O2
SO3 reacts with H2O2 to form per-oxy monosulphuric acid (H2SO5)
SO3 + H2O2 (anhydreres) H2SO5

Peroxy monosulphuric acid
12.4.2.3 Uses:
SO3 is used in manufacture of H2SO4 and H2S2O7 and also as drying agent of gases.
12.4.2.4 Structure of SO3.
SO3 molecule in gaseous state exists as monomer with trigonal planar geometry. In solid
state, α-form exists as a trimer (SO3)3 having ring structure; β and γ-forms are dimeric,
(SO3)2 with linear layer structure. In SO3 molecule, sulphur is sp2 hybridized.
S (2pπ – dπ bond)
(1pπ – pπ bond)
O O
Hybridization on sulphur is sp2

Trigonal planar geometry of gaseous SO3 molecule
O O O
S O S O S O
O O O
Hybridization on sulphur is sp2
Structure of β & γ-forms of SO3 (Linear layer structure)
The other oxides formed by sulphur are S2O, S2O3, S6O to S10O. The oxides from S6O to
S10O can be prepared by dissolving the cyclo forms of S6, S7, S8, S9 and S10 in CS2 or CH2Cl2
and oxidizing with trifluoroperoxoacetic acid (CF3COOOH) at –10ºC to –30ºC.
These compounds are orange-yellow in colour and have original rings of S-atoms. One
oxygen atom attached via a double bond to one of the ring S-atom.
12.5 OXOACIDS OF SULPHUR.
Sulphur forms a number of oxoacids. The acids exist either in free State or in the form of
their solutions or salts. Sulphur forms mainly four series of oxoacids as shown in the
following flow chart (Flow chart 12.1)

Flow chart 12.1 Classification of oxoacids of sulphur

Polythionic acids include H2S3O6 (trithionic acid), H2S4O6 (Tetrathionic acid), H2S5O6
(Pentathionic acid) and H2S6O6 (hexathionic acid).
12.5.1 Sulphurous acid series:
This series includes sulphurous acid (H2SO3), thiosulphurous acid (H2S2O2), pyrosulphurous
acid or disulphurous acid (H2S2O5) and hyposulphuric acid (H2S2O4).
12.5.1.1 Sulphurous acid (H2SO3)
This acid is unstable and is known only in solution.
(a) Preparation:
(i) SO2 on dissolution in water, forms sulphurous acid.
SO2 + H2O H2SO3
(ii) Reaction of thionyl chloride (SOCl2) with water generates H2SO3.
SOCl2 + 2H2O H2SO3 + 2 HCl
(b) Properties:
(i) Acidic nature:
H2SO3 is dibasic in nature. It ionizes in two stages :-
H2SO3– H+ + HSO3 (Bisulphite ion)
HSO3– H+ + HSO32– (Sulphite ion)
Thus, sulphurous acid forms two types of salts, namely bisulphites and sulphites.
(ii) Decomposition:
The solution of H2SO3 decomposes at 150ºC to form H2SO4.
3H2SO3 2H2SO4 + H2O + S
(iii) Oxidising properties:
During oxidation of other substances, it reduces itself into sulphur.

H2SO3 + 2H2S 3S + 3H 2O
H2SO3 + 2SnCl2 + 4HCl S + 3H2O+ 2SnCl4
H2SO3 + 2Hg2Cl2 + 4HCl S + 3H2O + 4HgCl2
H2SO3 + 2CO S + H2O + CO2
H2SO3 + 3Mg 2MgO+ MgS + H2O
H2SO3 + 3Fe 2FeO + FeS + H2O
H2SO3 + 4HI S + 3H2O + 2I2
(iv) Reducing properties:
H2SO3 also acts as reducing agent and during reduction of certain substances, it is oxidized to
H2SO4.
H2SO3 + H2O H2SO4 + 2H
H2SO3 + H2O + X2 H2SO4 + 2HX
5H2SO3 + 2KMnO4 K2SO4 + 2MnSO4 + 2H2SO4 + 3H2O
3H2SO3 + K2Cr2O7 +H2SO4 K2SO4 + 2Cr (SO4)3 + 4H2O
H2SO3 + H2O + Fe2 (SO4)3 2H2SO4 + 2FeSO4
5H2SO3 + 2KIO3 4H2SO4 + K2SO4 + H2O + I2
(v) Bleaching properties:
Nascent hydrogen liberated during oxidation of certain substances by H2SO3, changes

coloured matter to colourless matter. Hence, H2SO3 can acts as a bleaching agent.
H2SO3 + H2O H2SO4 + 2H
Coloured matter + H Colourless matter

The bleaching action of H2SO3 is temporary, as colourless matter can again regains its colour
when exposed to air.
Colourless matter + O Coloured matter

(air)
(c) Uses:
H2SO3 is used as an oxidizing agent and reducing agent in many reduction and oxidation
reaction.
(d) Structure of H2SO3:
Two structures have been proposed for sulphurous acid.
Support for structure I
(i) H2SO3 is prepared by the hydrolysis of SOCl2 which is symmetrical.
(ii) H2SO3 is a dibasic acid and this indicates symmetrical structure for H2SO3.
Support for structure II
Reaction of NaHSO3 with KOH forms NaKSO3 while of KHSO3, with NaOH form KNaSO3.
Both NaKSO3 and KNaSO3 have different structures. If H2SO3 has symmetrical structure,
NaKSO3 and KNaSO3 should have the same structures. Thus H2SO3 is unsymmetrical in
shape.

You can see that the above reactions support both symmetrical and asymmetrical structures.
Hence, the actual structure of H2SO3 is the tautomeric mixture of these two structures.
Trigonal pyramidal Tetrahedral
12.5.1.2 Thiosulphurous acid (H2S2O2):
When one oxygen is replaced by sulphur in H2SO3, it is known as thiosulphuric acid. It is a

dibasic acid
H2S2O2 is trigonal pyramidal in shape and hybridization on sulphur is sp3.
12.5.1.3 Hyposulphurous acid (H2S2O4):
It is also called as dithionous acid.
(a) Preparation:
Zinc hyposulphite on reaction with Ca(OH)2 and oxalic acid (H2C2O4) forms hyposulphurous
acid.
ZnS2O4 (aq) + Ca (OH)2 CaS2O4 (solution) + Zn(OH)2 ppt

CaS2O4 + H2C2O4 CaC2O4 + H2S2O4 (Hyposulphurous acid)

(b) Properties:
(i) Acidic nature:
It is a dibasic acid and gives only one type of salts with S2O42– ions.
(ii) Decomposition:
Hyposulphurous acid decomposes on heating to sulphurous acid.
2H2S2O4 2H2S2O3
H2S2O3 H2SO3 + S
(iii) Reducing properties:
This acid is strong reducing agent. During reduction of the other substances, they themselves
oxidize to sulphite or bisulphite.
H2S2O4 + 2H2 O 2H2SO3 + 2H
H2S2O4 + 2H2 O 2HSO3– + 2H+ +2e–
(iv) Oxidation:
H2S2O4 solution easily oxidized in presence of air to H2S2O5.
2H2S2O4 + O2 2H2S2O5
(c) Uses: The acid is used as reducing agent.
(d) Structure of H2S2O4:
Each sulphur atom in hyposulphurous acid is sp3 hybridised.

12.5.1.4 Pyrosulphurous acid (H2S2O5):
This acid is also called as disulphrous acid. It is also a dibasic acid. Each sulphur atom is sp3
hybridised and consists of two SO3 molecules joined together through oxygen atom (Flow
chart 12.2).
Flow chart 12.2 Flow chart to learn sulphurous acid series
12.5.2 Sulphuric acid series:
12.5.2.1 Sulphuric acid
It is also known as oil of vitriol and formula is H2SO4.
(a) Preparation:
(i) Lead chamber process:
Mixture of SO2, air and NO is treated with steam to form H2SO4. Nitric oxide (NO) acts as a
catalyst in this process.
2SO2 + O2 + 2H2O + [NO] 2H2SO4 + [NO]
(ii) Contact process:

This is a four step process. In the first step, SO2 is prepared, in the second step, SO3 is
formed, in third step, H2S2O7 and in the last step, H2SO4 is formed.
S + O2 SO2 .......... Step 1
V2O5
SO2 + O2 2SO3 ......... Step 2
SO3 + H2SO4 H2S2O7 ....... Step 3

Oleum/Fuming
Sulphuric acid
H2 S 2 O 7 + H 2 O 2H2SO4
Sulphuric
acid
(b) Properties:
(i) Pure H2SO4 is a colourless liquid and forms a constant boiling mixture with water. Its
boiling point is very high (340ºC) and this is due to the hydrogen bond between its molecules.
(ii) H2SO4 is soluble in water and this is an exothermic reaction. Heat is produced during
dilution and may be due to the formation of hydrates like H2SO4, H2O, H2SO4. 2H2O.
2H2SO4 + Ca3(PO4)2 + 5H2O [Ca (H2PO4). H2O+ 2 (Ca SO4.2H2O)]
Superphosphate of lime

(c) Uses
H2SO4 is used in manufacturing of fertilizer, explosives, many chemicals like Na2CO3, alums,
metal sulphates etc., in storage batteries, as laboratory regent and an oxidizing and
dehydrating agents.
(d) Structure of H2SO4:
Actual structure of H2SO4 is the resonance hybrid of the following two structures:
In these structures, S is sp3 hybridized and the geometry is tetrahedral.
12.5.2.2 Thiosulphuric acid (H2S2O3):
(a) Preparation:
Thiosulphuric acid is stable at –78ºC but unstable at ordinary temperature. It is prepared by

the reaction of SO3 with H2S.
SO3 + H2S H2S2O3
(b) Properties:
The acid is unstable, hence, decomposes easily to give SO2 and sulphur.
H2S2O3 S + SO2 + H2O

or
S + H2SO3
(iii) Acidic nature:
It is a dibasic acid and forms bisulphate ion (HSO4–) and sulphate ion (SO42–) when dissolved
in water. It reacts with alkali to form salt and water.
(ii) Oxidising properties:
Hot concentrated sulphuric acid is a powerful oxidizing agent and reduces itself to SO2 when
reacts with reducing agents.

2H2SO4 + C 2H2O+ 2SO2 + CO2

5H2SO4 + 2P 2H3PO4 + 5SO2
2H2SO4 + Cu CuSO4 + SO2 + 2H2O
2H2SO4 + Zn ZnSO4 + SO2 + 2H2O
H2SO4 + 2HBr SO2 + 2H2O+ Br2
H2SO4 + H2 2H2O+ SO2
5H2SO4 + 8KI H2S + 4K2SO4 + 4H2O+ 4I2
Besides these properties, H2SO4 can react with Ba (+2) and Pb (+2) salts to form insoluble
sulphates, with SO2 to form oleum and also used in the manufacturing different types of
fertilizers like superphosphate of lime and ammoniated phosphate sulphate.
H2SO4 + 3NH3 + H3PO4 (NH4)(H2PO4).

(NH4)2SO4
Ammonated phosphate sulphate
(d) Structure of H2S2O3:
It is a dibasic acid and the actual structure is resonance hybrid of the following two
structures.
O O
HO S SH HO S OH
O S
In both the structures, central sulphur atom is sp3 hybridized and hence, the geometry is
tetrahedral.
H2SO4 –O H2 S2 O3
+S
Sulphuric acid Thiosulphuric acid
(Oxidation state of (oxidation state of
S is +6) S is +2)
H2SO4 –H2O
H2S2O7
Pyrosulphuric acid
(oxidation state of
S is +6)
Flow chart 12.3 Flow chart to learn sulphuric acid series
12.5.2.3 Pyrosulphuric acid, H2S2O7:

It is also known as disulphuric acid or oleum.
(a) Preparation:
(i) It can be prepared by the reaction of SO3 with conc. H2SO4.
SO3 + Conc. H2SO4 H2S2O7
(b) Properties:
(i) Oleum is a brown oily liquid.
(ii) It is called as fuming sulphuric acid because it gives fumes in air.
(iii) It is dibasic and on warming, changes into H2SO4.
H2S2O7 Warm H2SO4 + SO3
(iv) Pyrosulphuric acid solidifies on cooling below 0ºC. It is used in the preparation of dyes
and explosives.
(c) Uses:
Oleum is used in the manufacture of explosives, drugs and dyes.
(d) Structure:
The acid is dibasic and each sulphur atom is sp3 hybridised.
O O
HO S O S OH
O O
Structure of oleum
12.5.3 Peroxysulphuric acid series:
12.5.3.1 Peroxymonosulphuric acid ) H2SO5):
This acid is also called as Caro’s acid.
(a) Preparation:

(i) By Caro’s method (Reaction of potassium peroxydisulphate; K2S2O8 with conc. H2 SO4)
K2S2O8 + H 2O Conc. H2SO4 K2SO4 + H2SO5
(ii) Ahrle’s method (Reaction of SO3 or Conc. H2SO4 on very concentrated H2O2).
SO3 + H2O2 H2SO5

Conc. H2SO4 + H2O2 H2SO5 + H2O
(iii) d’Ans and Friedrich method (Reaction of anhydrous H2O2 with chlorosulphuric acid,
SO2 (OH) Cl.
–HCl
(OH)SO2 Cl + H2O2 H2SO5 + HCl
(b) Properties:
(i) It is a white crystalline hydroscopic solid and its melting point is 45ºC.
(ii) It reacts with H2O2 and release O2.
H2SO5 + H2O2 H2SO4 + H2O + O2
(iii) With dil. H2SO4, H2O2 is obtained.
dil H2SO4
H2SO5 + H2O H2SO4 + H2O2
(iv) Oxidizing properties
During oxidation of other substances, it reduces to sulphate. Nascent oxygen is responsible

for its oxidizing action.
H2SO5 + 2FeSO4 Fe2(SO4)3 + H2O

H2SO5 + KX K2SO4 + H2O + X2
H2SO5 + Zn ZnSO4 + H2O
(c) Uses:
Caro’s acid is used for preparation of dyes, oxidation of olefins to glycols, oxidation of
ketones to lactones or esters and in bleaching compositions.
(d) Structure:

H2SO5 is a mono basic acid. Sulphur atom is sp3 hybridised. The two π–bonds (S = O) are pπ
– dπ bonds.
OH
O S O O H
Structure of H2SO5
12.5.3.2 Peroxydisulphuric acid (H2S2O8):
It is also called as Marshall’s acid.
(a) Preparation
(i) Berthelot’s method:
Reaction of SO2, O2, and H2SO4 give peroxydisulphuric acid.
SO2 + O2 + H2SO4 H2S2O8
(ii) Electrolysis of (NH4)2SO4 aqueous solution containing H2SO4.
Aqueous solution of (NH4)2SO4 in presence of H2SO4 forms peroxydisulphuric acid. Platinun

is used as anode and graphite as cathode.
(NH 4)2SO4 + H 2SO 4 2NH4 HSO 4
NH 4HSO4 H+ + [(NH4 ) SO4]–
2 [(NH4) SO4]– (NH4)2 S2O8 + 2e– (anode)
2 H+ 2e– H2(g) (cathode)
(NH4)2 S2O8 quickly distilled with H2SO4 to obtain H2S2O8.
(NH 4)2 S2O8 + H2 SO4 (NH4 )2 SO4 + H2 S2O 8
(iii) Eletrolysis of H2SO4 solution

Electrolysis of 50-60 % H2SO4 solution forms H2S2O8 at anode. The anode is made up of
platinum wire while cathode of copper wire.
H2SO4 2H+ + 2HSO4–
2HSO4– H2S2O8 + 2e– (anode)
2H+ + 2e– H2(g) (cathode)
(iv) d’Ans and Friedrich method
Pure H2S2O8 is formed by the reaction of H2O2 with chlorosulphuric acid.
–2HCl
2(OH)SO2Cl + H2O2 (HO) SO2 – O – O – SO2 (OH)
Chlorosulphuric Peroxydisulphuric
acid acid
(b) Properties:
(i) Peroxydisulphuric acid is a colourless, crystalline solid with melting point = 65ºC.
(ii) On heating, it releases O2 and SO3.
2H2S2O8 2H2SO4 + 2SO3 + O2
(iii) It is used to prepare 30% H2O2. When H2S2O8 is distilled with dil H2SO4, H2O2 yielded.
dil H2SO4
H2S2O8 + H2O 2H2SO4 + H2O2
(iv)On standing the aqueous solution of H2S2O8 for some time, it gets hydrolysed into H2SO4
and H2SO5.
On standing
H2S2O8 + H2O H2SO4 + H2SO5
Peroxy monosulphuric
acid
(v) Oxidizing properties
During oxidation of certain species, perdisulphuric acid reduces itself to SO42–/HSO4–.

H2S2O8 + FeSO4 Fe2(SO4)3 + H2SO4
H2S2O8 + Mn(OH)2 MnO2 + 2H2SO4
Salt of perdisulphuric acid (K2S2O8) oxidizes AgNO3 to AgO, Cr to CrO42–, I2 to IO3– and KI
to I2.
K2 S2 O8 + AgNO3 2AgO+ 2KHSO4 + 2HNO3 + + 2H2O
2K2S2O8 + Cr + 4H2O H2CrO4 + 3K2SO4

+ 3H2SO4
5K2S2O8 + I2 + +6H2O 2HIO3 + 5K2SO4 + 5H2 SO4
K2S2O8 + 2KI 2K2SO4 + I2
(c) Uses:
Peroxydisulphuric acid is used as oxidizing and bleaching agent as it oxidizes aniline to

aniline black and bleaches in indigo. It is also used in the preparation of H2O2 and
photography.
(d) Structure:
Peroxydisulphuric acid is dibasic in nature and the two sulphur atoms are SP3 hybridized. All
the (S – O) π bonds are pπ – dπ bonds. The structure is
OH OH
O S O O S O
O O
12.5.4 Thionic acid series:
12.5.4.1. Dithionic acid
This acid is present in solution. Its formula is H2S2O6.
(a) Preparation:

Reaction of barium dithionate with weighed amount of H2SO4 produce dithionic acid.
BaS2O6 (aq) + H2SO4 (aq) H2S2O6(aq) + BaSO4

Bariumdithionate Dithionic acid
(b) Properties:
The acid is stable only in solution and when we concentrate the solution; it decomposes to
SO2 and H2SO4.
H2S2O6 SO2 + H2SO4
On hydrolysis, the acid gives H2SO4 and H2SO3.
H2S2O6 + H2O H2SO4 + H2SO3
(c) Uses:
Dithionates are good reducing agents
(d) Structure:
Dithionic acid is a dibasic acid. The two sulphur atoms are sp3 hybridised and each of the π–
bonds (S = O) is pπ – dπ bond. The two SO3 units are joined via S – S bond to give H2S2O6.
O O
HO S S OH
O O
12.5.4.2 Polythionic acids (H2SnO6; n = 3 to 6):
(a) Preparation:
(i) Direct hydrolysis of sulphur monochloride (S2Cl2): By this method, small quantities of
H2S3O6, H2S4O6 and H2S5O6 are obtained.
S2Cl2 + 3H2O → H2SO3 + H2S + 2HCl
Sulphur monochloride
6H2SO3 + 2H2S → H2S3O6 + H2S5O6 + 6H2O

3H2 SO3 + H2 S → H2S4O6 + 3H2O
(ii) Electrolytic oxidation of thiosulphate by H2O2, SO2, I2, FeCl3 or electricity yields
individual polythionates.
Na2S2O3 + 3SO2→ 2Na3 S2O6 + S
NaOH
2Na2S2O3 + 4H2O2 Na2S3O6 + 4H2O+ Na2 SO4
Cold solution)
2Na2S2O3 + I2→ Na2S4O6 + 2NaI
2Na2S2O3 + 2FeCl3→ Na2S4O6 + 2FeCl2 + 2NaCl
2– Electrolytic 2–
2S2O3 S4O6 + 2e–
oxidation
(b) Properties:
(i) Solutions of different polythionates get decomposed on heating to SO2 and S.
2– 2–
S3O6 SO4 + SO2 + S
S4O62– 2–
SO4 + SO2 + 2S
2– 2–
S5O6 SO4 + SO2 + 3S
(ii) With sodium amalgam, S3O62– form S2O32– and SO32–; S4O62– yields only S2O32– while
with potassium amalgam, S5O62– gives S2O32– and S2–.
Na/Hg 2–
S3O6 2–+ 2Na S2O3 + 2Na+ + SO3 2–
Na/Hg 2–
S4O6 2–+ 2Na S2O3 + 2Na+
S5O62– + 4K → 2S2O32– + S2– + 4K+
(iii) On reaction with S2– (sulphide), S3O62– gives only S2O62– while S4O62–, S5O62– and S6O62–
give a mixture of S2O32– and sulphur.

S3O62– + S2–→2S2O32–
S4O62– + S2–→ 2S2O32- + S
S5O62– + S2–→2S2O32- + 2S
S6O62– + S2–→ 2S2O32- + 3S
(iv) On reaction with SO32– (sulphite), S3O62– gives no reaction while S4O62–, S5O62 and S6O62
give S2O32– and lower polythionates
2–
S3O62– SO3 No reaction
S4O62– + SO32– S2O32– + S3O62–
S5O62– + SO32– S2O32– + S4O62–
S6O62– + SO32– S2O32– + S5O62–
(v) Reducing properties
S3O62– and S4O62– get easily oxidized to SO42– and H2SO4 in the presence of an oxidizing
agent.
4O + 2H2O + S3O62–→ SO42– + 2H2SO4
S4O62– + 3H2O + 7O → SO42– + H2SO4
Trithionic acid (H3S3O6)
(a) Preparation:
(i) Trithionic acid is prepared by the action of sulphur monochloride with water.
S2Cl2 + 3H2O → H2SO3 + H2S + 2HCl
6H2SO3 + 2H2S → H2S3O6 + H2S5O6 + 6H2O
(ii) Reaction of potassium trithionate (K2S3O6) with hydrofluosilic acid acid, H2SiF6.
K2S3O6 + H2SiF6→ H2S3O6 + K2SiF6

(b) Properties:
(i) Trithionic acid decomposes on standing.
H2S3O6→ S + SO2 + H2SO4
(ii) Trithionic acid does not react with BaCl2 solution.
(iii) H2S3O6 on reaction with AgNO3 forms yellow precipitate of Ag2S3O6
H2S3O6 + 2AgNO3→ Ag2S3O6 + 2HNO3
(c) Structure:
In trithionic acid two sulphonic acid group (HSO3) joined together via –S– link. The each
sulphur atom of sulphonic acid is sp3 hybridised and it is a dibasic acid. All the double bonds
are pπ – dπ type.
O O
HO S S S OH
O O
Structure of trithionic acid
Tetrathionic acid (H2S4O6)
(a) Preparation:
(i) Tetrathionic acid is also prepared by hydrolysis of S2Cl2.
S2Cl2 + 3H2O → H2SO3 + H2S + 2HCl
(ii) Tetrathionic acid is also prepared by the reaction of barium or lead tetrathinonate with
measured quantity of dil H2SO4.
MS4O6 + H2SO4 (dil) → H2S4O6 + MSO4↓ where M = Ba or Pb
(c) Structure:
Tetrathionic acid is also a dibasic acid and here the two sulphonic acid units (HSO3) are
joined via – S – S – bond. The two sulphur atoms of sulphonic acid are sp3 hybridised and all
the π bonds are pπ – dπ bonds.

O O
HO S S S S OH
O O
Properties:
H2S4O6 solution (aqueous solution) is stable, but it decomposes on heating.
H2S4O6→ H2SO4 + SO2 + 2S
Pentathionic acid (H2S5O6)
(a) Preparation:
Pentathionic acid is prepared by the reaction of H2S with H2SO3 in solution.
5H2S + 10H2SO3→ 3H2S5O6 + 12H2O
(b) Properties:
Pentathionic acid is stable in solution but decomposes on heating.
H2S5O6→ H2SO4 + SO2 + 3S
(c) Structure:
Pentathionic acid is a dibasic acid. Two sulphonic acid (HSO3) units are joined via –S–S–S–
linkage. Each sulphur atom in sulphonic acid unit is sp3 hybridised and all double bonds are
pπ – dπ bonds.
O O
HO S S S S S OH
O O
Hexathionic acid (H2S6O6)
This acid is also stable in solution. Its salt potassium haxathionate (K2S6O6) is an important
salt which is stable in the solid state.
Structure:

Hexathionic acid is a dibasic acid and two sulphonic acid units (HSO3) are joined together by
–S–S–S–S– unit to form hexathionic acid. The two sulphur atoms of sulphonic acid are units
are sp3 hybridized and all the π–bonds are pπ – dπ types.
O O
HO S S S S S S OH
O O
Structure of hexathionic acid
12.6 HALIDES OF SULPHUR
Halides of Sulphur
Sulphur forms the following type of halides with different molecular formula.
MX6 MX4 MX2 M2 X 2 (MX5)2
S SF6 SF4 SF2 S2F2 (SF5)2
S2Cl2
SCl4 SCl2 S2Br2
12.6.1 Preparation, Properties and structure of sulphur halides:
12.6.1.1 Dibalide (MX2)
Sulphur form dihalides like SCl2 and SF2.
(a) Preparation:
Dihalides of sulphur can be prepared from sulphur monochloride
S2Cl2 + Cl2→ 2SCl2
(b) Properties:
(i) Hydrolysis

SCl2 is readily hydrolysed by H2O.
2SCl2 + 2H2O → S + SO2 + 4HCl
Or
2SCl2 + 3H2O → S + H2SO3 + 4HCl
(ii) Action of NaF
SF4 is obtained when SCl2 is treated with NaF.
3SCl2 + 4 NaF 75ºC SF4 + Na Cl + S2 Cl2
(c) Stability
It is very unstable and decomposes easily.
(d) Structure
SCl2 has angular structure (V–shaped) like H2O with two lone pairs of electrons where the
central atom, S is having sp3 hybridization.
12.6.1.2 Tetrahalide (MX4):
Sulphur forms tetrahalides like SF4, SCl4 but does not form SBr4, SI4.
(a) Preparation:
S + 2Cl2→ SCl4
S2Cl2 + Cl2→ 2SCl4
(b) Properties:

SF4 is gaseous in nature. SF4 is used as fluorinating agent.
SCl4 forms addition compounds with metal chlorides e.g. SCl4, AlCl3, SCl4.
(c) Structure:
All the tetrahadides (MX4) possess see saw geometry.The central atom S, undergoes sp3d
hybridization.
12.6.1.3 M2X2 Dimeric monohalide:
Sulphur can form M2X2 type halides e.g. S2F2, S2Cl2, S2Br2.
(a) Preparation:
2AgF + 3S (Molten) → Ag2S + S2F2
2S (fused) + Cl2→ S2Cl2
3S + 2SOCl2→ 2S2Cl2 + SO2
2S + SO2Cl2→ S2Cl2 + SO2
CS2 + 3Cl2→ CCl4 + S2Cl2 (Liquid mixture)
2S + Br2→ S2Br2
(b) Properties:

S2F2 is a gas while all other monahalides are liquids. On hydrolysis, S2X2 reduced to sulphur.
2S2X2 + 3H2O → 3S + H2SO3 + 4HX
2S2X2 + 2H2O → 3S + SO2 + 4HX
With chlorine, S2Cl2 forms SCl2.
20ºC
S2Cl2 + Cl2 2SCl2
(e) Structure:
These halides are like H2O2 in geometry having non-linear and non-planner structure.
12.6.1.4 Hexahalide (MF6):
Sulphur also forms SF6.
(a) Preparation:
Sulphur hexafluoride can be prepared by the following reaction:
S + 3F2→ SF6
(b) Properties:
SF6 is extremely stable and chemically inert.
Covalent character
These fluorides have low boiling points and high volatility which indicates that these are
highly covalent compounds.
Action of boiling sodium
SF6 gets decomposed, when it is passed through boiling sodium.

SF6 + 8Na → Na2S + 6NaF
(c) Structure:
SF6 has regular octahedron geometry
12.6.1.5 Dimeric sulphur pentafluoride (SF5)2 on S2F10
Only sulphur petafluroride is known and it is dimeric S2F10.
(a) Preparation:
It is obtained in traces along with SF6 when sulphur is directly fluorinated.
(b) Properties:
It is dimeric liquid and is stable compound.
(c) Structure:

Structure of halides of sulphur at a glance
Type of Name Shape Hybridization

(Formula)
M 2X 2 Dimeric monohalide Non-planner sp3
MX2 Dihalide V-Shaped sp3
MX4 Tetrahalide See-Saw sp3d
MX6 Hexahalide Octahedral sp3d2
(MX5)2 or Dimeric sulphur Dimer sp3d2

M2X10 petafluoride
12.7 ANOMALOUS BEHAVIOUR OF OXYGEN
Oxygen shows anomalous behaviour means, it is different from its other family members
such as S, Te, Se and Po due to its small size, high electronegativity and ionization potential
and absence of d-subshell in its valence shell. Generally all the first members of the p-block
elements show anomalous behaviour due to the same reasons.
It is different from other family members in the following ways:
(a) Physical state-Oxygen is a diatomic gas while its other group members are polyatomic
solids at room temperature.
(b) Oxidation state-The most stable oxidation state is -2, sometimes +2 (F2O) and -1 (H2O2
or other peroxides) but not more than 2. The other family member elements show oxidation
state beyond 2 (+4 or +6) due to the presence of vacant d-orbitals.
(c) Maximum covalency-Maximum covalency of oxygen is 2 while other elements have 6

covalency due to the presence of vacant d-orbitals.
(d) Magnetic behavior-Except oxygen, all the other member of this family are diamagnetic
in nature. Oxygen is paramagnetic due to the presence of unpaired electrons in its
antibonding molecular orbitals.

(e) Nature of compounds formed-Oxygen forms more ionic and polar covalent compounds
as compared to the other members due to its high electronegativity. R–O–H, R–COOH,
RCOR are polar in nature.
(f) Hydrogen bonding-Due to high electronegativity, it can form hydrogen bonds while the
other elements cannot form hydrogen bond due to their large size. Hence, compounds of
oxygen like H2O, R-OH etc. have hydrogen bonding while compounds like H2S and H2Se are
liquid and solid, respectively due to absence of hydrogen bond.
(g) Nature of bond-Oxygen has a tendency to form pπ–pπ multiple bonding while other
members have tendency to form pπ–dπ bond.
12.8 SUMMARY
Sixteenth group has five elements naming, oxygen (O), sulphur (O), selenium (Se), tellurium
(Te) and polonium (Po). These are p-block elements. These are also called as chalcogens
(ore-forming). The periodic properties such as atomic radius, density and metallic character
increases as we go from oxygen to polonium while the reverse was true for ionization
potential. Sulphur, selenium and tellurium are octa-atomic (S8, Se8 and Te8) while oxygen is a
diatomic gas (O2). Except oxygen, all the elements exhibit –2, +2, +4 and +6 oxidation states.
All the elements of 16th group show allotropy. The 16th group elements form hydrides (H2M),
halides (M2X2, MX2, MX4 and MX6). They have a tendency to form oxides of MO2 and MO3
type. These are the binary compounds formed by 16th group elements. The ternary
compounds such as H2SO3, H2SO4 and Na2S2O3, 5H2O are also formed by these elements.
The 16th group elements are very useful to various biological systems as;
i. O2 is used in respiration by both plants and animals.
ii. Commercially, it is also used in steel plants, blast furnaces, welding, metal cutting,
manufacture of HNO3 and ethylene oxide, as oxidant in rockets.
iii. Sulphur is a minor constituent of certain amino acids such as cystine, cysteine and
methionine. It is also used in manufacturing carbon disulphide, rubber, fungicides,
insecticides and explosives.
iv. Selenium is also an essential trace element but becomes toxic to the human beings when
taken in large quantities. It is an active part of many enzymes such as glutathione and
peroxidase.

v. Selenium is useful for making red and pink coloured glass and photoreceptors for
photocopiers.
vi. Tellurium is useful in the manufacturing of steel and non-ferrous alloys.
vii. Polonium is a radioactive in nature.
12.9 TERMINAL QUESTIONS.
A) State True (T) or False (F)
i. Chalcogens means ore-forming elements.

ii. Oxygen has strong tendency to form π bond while sulfur has greater tendency to form
chains and rings.
iii. Oxygen is an octa-atomic gas.
iv. The two allotropes of oxygen are O2 (oxygen) and O3 (ozone).
v. Electronic configuration of tellurium (Te) is 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 4d10 5s2
5p4.
vi. Oxygen is the minor constituent of certain amino acids such as cystine, cysteine and
methionine.
vii. Sulphur is a radioactive element.
viii. Sulphur has a tendency to form addition compounds.
ix. During oxidation process, SO2 reduces itself into sulphur.
x. SO2 is trigonal planar in shape as sulphur atom is sp2 hybridized.
xi. SO3 is prepared by thermolysis of pyrosulphuric acid.
xii. SO3 is used as drying agent of gases.
xiii. SO3α-form exists as linear layer structure.
xiv. Polythionic acids include H2S3O6 (trithionic acid), H2S4O6 (Tetrathionic acid), H2S5O6
(Pentathionic acid) and H2S6O6 (hexathionic acid).
xv. Sulphuric and sulphurous acids are dibasic acids.
xvi. H2SO3 oxidizes to H2SO4 during reduction of other substances.
xvii. H2SO3 has a strong bleaching action.
xviii. Thiosulphuric acid is trigonal pyramidal in shape and hybridization on sulphur is sp3.
xix. Hyposulphurous acid is H2S2O4.
xx. Oleum is fuming sulphuric acid.

xxi. Marshall’s acid is also called as peroxydisulphuric acid.

xxii. Oxidation state of sulphur in peroxysulphuric acid is 6.
xxiii. Trithionic acid is H3S3O7.
xxiv. Sulphur pentafluoride is trimeric in nature.
B) Fill in the blanks
i. Allotropes of sulphur are ………………………………………………..

ii. ……………….. is also used in oxy-acetylene welding, metal cutting manufacture of HNO3
from NH3 and ethylene oxide from ethane.
iii. ……………… is used in the manufacture of steel and non-ferrous alloys.
iv. SO3 reacts with H2O2 to form per-oxy ……………………………
3H2SO3 + K2Cr2O7 +H2SO4 K2SO4 + 2Cr (SO4)3 + 4H2O
v. reaction shows
…………………. property of sulphurous acid.
vi. ……………………… is also called as dithionous acid.
vii. Very high boiling point (340ºC) of sulphuric acid is due to the …………………………
between its molecules.
viii. …………………. acid is also called as Caro’s acid.
ix. Salt of perdisulphuric acid (K2S2O8) oxidizes AgNO3 to ………, Cr to ………, I2 to

…………. and KI to ………….
x. Dihalides of sulphur can be prepared from ………………………….

xi. Sulphur tetrafluoride possess ………………… geometry.
xii. Oxygen shows anomalous behaviour is due to its…………….., high ……………….. ,
…………….. and absence of ………………. in its valence shell.
C) Long answer questions
i. Write a note on general characteristics and uses of 16th group elements.

ii. How sulphur dioxide prepared? Give reactions.
iii. Describe in detail the structure of sulphur trioxide.
iv. Discuss oxoacids of sulphur in detail.
v. What are thionic acids. Write down it detail.
vi. Classify halides of 16th group elements with examples.
vii. Give in detail, preparation, properties and structure of sulphur halides.
viii. Oxygen is different from other members of the group. Explain.

12.10 ANSWERS
A) State True or False
i. T
ii. T
iii. F
iv. T
v. T
vi. F
vii. F
viii. T
ix. T
x. F
xi. T
xii. T
xiii. F
xiv. T
xv. T
xvi. T
xvii. T
xviii. F
xix. T
xx. T
xxi. T
xxii. T
xxiii. T
xxiv. F
B) Fill in the blanks
i. α–(rhombic or octahedral sulphur), β-(monoclinic or prismatic sulphur), γ-(monoclinic
sulphur) and λ– (plastic) sulphur
ii. Dioxygen
iii. Tellurium (Te)
iv. monosulphuric acid (H2SO5)

v. reducing
vi. Hyposulphurous acid/ H2S2O4
vii. hydrogen bond
viii. Peroxymonosulphuric
ix. AgO, CrO42–, IO3– and I2
x. sulphur monochloride
xi. see saw
xii. small size, electronegativity, ionization potential and d-sub shell
Bibliography
a) Br. R. Puri, L. R. Sharma and K. C Kalia. Principles of Inorganic Chemistry, Milestone

Publishers & Distributors, Meerut, 2013.
b) G. S. Sodhi, Textbook of Inorganic Chemistry, Viva Books Private Limited, New Delhi,
2013.
c) M. S. Yadav. Quick Review in Inorganic Chemistry, Anmol Publications Pvt. Ltd., New
Delhi, 2004.
d) P. Mishra, Advanced Inorganic Chemistry, Jagdamba Publishing Compan, New Delhi, 2011.
e) R. L. Madan, Chemistry for degree students, B.Sc. I year, S. Chand & Company Ltd., New
Delhi, 2011.
f) S. Prakash, G. D. Tuli, S. K. Basu, and R. D. Madan. Advanced Inorganic Chemistry, Vol. I,
S. Chand & Company Ltd., New Delhi, 2007.
g) W. U. Malik, G. D. Tuli, and R. D. Madan. Selected Topics in Inorganic Chemistry, S. Chand
Publication, Delhi, 2013.

UNIT 13: ELEMENTS OF GROUP- 17
CONTENTS:
13.1 Objectives
13.2 Introduction
13.3.1 Physical properties of halogens
13.3.1.1 Physical state
13.3.1.2 Melting and boiling point
13.3.1.3 Ionization potential
13.3.1.4 Electronegativity
13.3.1.5 Electron affinity
13.3.1.6 Odour
13.3.1.7 Non metallic character
13.3.1.8 Bond energy and reactivity
13.3.1.9 Oxidation state
13.3.1.10 Stability of halogens
13.3.2 Chemical properties
13.4 Halides and halogen oxides
13.4.1 Characteristics of hydrogen halides
13.4.2 Oxides of halogens
13.5 Oxoacids of halogens
13.5.1 Oxoacids of chlorine
13.5.2 Oxoacids of bromine
13.5.3 Oxoacids of iodine
13.6 Interhalogen compounds
13.7 Polyhalides
13.8 Basic properties of halogen

13.9 Anomalous behavior of fluorine
13.10 Summary
13.12 Answers

13.1 OBJECTIVES
You will be able to answer the following questions after reading this unit.
(a) What are halogens?
(b) What are the characteristics and uses of halogens?
(c) Acidic behaviour of oxides and oxoacids.
(d) How fluorine is different from other halogens?
(e) What are the basic properties of halogens?
13.2 INTRODUCTION
Halogens belong to VIIA/17th group of the periodic table. It consists of five elements viz.
flourine (F), Chlorine (Cl), bromine (Br), iodine (I) and astatine (At). These are non metallic
elements and also called halogens. The term halogen is derived from the Greek halo (=salt)
and gens (=born) meaning salt producers because most of the elements exist in sea water,
such as chlorides. Halogens contain 7 (seven) electrons in their valence shell. Astatine is
radioactive. Flourine is the most electronegative, highly reactive and is called as super
halogen. Halogens are not found in free state because they are highly reactive. They are
found in sea water in the form of halides.
Astatine is a radioactive element and formed artificially. General electronic configuration of

VIIth group elements is ns2 np5. They are very reactive and found in diatomic form like F2,
Cl2, Br2, I2 (Table 13.1).
Table 13.1 Electronic configuration of halogen family
Elements Atomic Electronic Configuration Noble gas with

no. configuration
2 2 5
Fluorine (F) 9 1s 2s 2p (He) 2s2 2p5
Chlorine 17 1s2 2s2 2p8 3s3 3p5 (Ne) 3s2 3p5
(Cl)
Bromine 35 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p5 (Ar) 3d10 4s2 4p5
(Br)

Iodine (I) 53 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 4d10 (Kr) 4d10 5s2 5p5
5s2 5p5
Astatine (At) 85 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 4d10 (Xe) 4f14 5d10 6s2
5s2 5p6 6s2 6p5 6p5
13.3.1 Physical properties of halogens (Table 13.2 and Table 13.3)
Table 13.2 Atomic halogens
Properties F Cl Br I At
Atomic number 9 17 35 53 85
Atomic mass 19 35.45 79.90 126.90 210
Covalent radii (Å) 0.64 0.99 1.14 1.33 –
Ionic radii (Å) 1.33 1.84 1.96 2.20 –
-1
Ionic enthalpy (KJmole ) 1680 1256 1142 1008 –
Electronegativity 4 3.2 3 2.7 2.2
-1
Electron affinity (KJmole ) –333 –349 –325 –296 –270
Table 13.3 Molecular halogens
Properties F2 gas Cl2 gas Br2 liquid I2 solid

Colour Yellow Green Yellow Red Brown Deep Violet
Density g/cm3 (Liquid form) 1.51 1.66 3.19 4.94
Melting point (0C) -219 -101 –7 114
Boiling Point (0C) -188 -35 60 185
Bond length(Å) 1.43 1.99 2.28 2.66
Bond Dissociation Enthalpy 158.5 242.6 192.8 151.1
(KJmole-1)
13.3.1.1 Physical state:

All halogen are non polar solvent and diatomic molecules and their physical state are
F2 Cl2 Br2 I2
Gas Gas Liquid Solid

Difference in the physical state depends upon their van der Waals force which further
depends on their atomic size and molecular weight. Size and atomic weight of chlorine and
fluorine are less and thus, the van der Waals forces are weak. Hence, Cl2 and F2 are in gases
phase. Size of Br2 is more than Cl2 and F2 which is liquid and I2 is much higher in size and it
forms in solid phase.
13.3.1.2 Melting and boiling points:
As size of the elements in group increases, van der Waals force also increases and thus, m.p.
and b.p. of molecules also increases. The order of m.p. and b.p. of the halogens follow the
order:
F2< Cl2< Br2< I2
13.3.1.3 Ionization enthalpy or ionization potential:
Due to the small atomic size, halogens have higher ionization energy and less power to
remove electron to form X+ ion. Ionization enthalpy increases down words in a group
because their size increase.
F > Cl > Br > I (I.P.)
13.3.1.4 Electronegativity:
Group 16 elements have higher electronegativity because of small size of the atoms and
fluorine is most electronegative element in the periodic table.
F > Cl > Br > I (see table 13.2)
13.3.1.5 Electron affinity:

Electron affinity of halogens upto chlorine increases and after chlorine decreases. Flourine
has lower electron affinity because of the small size of fluorine. The outer most shell has
higher electron density and due to electron-electron repulsion, it cannot gain electron easily.
13.3.1.6 Odour:
All the halogens have very pungent odours. If inhaled, even in very small quantities, they
cause inflammation of the mucous membrane of the throat and nose. Thus, responsible for
irritation of respiratory duct. Large quantities may have fatal effect.
13.3.1.7 Non metallic character:

All halogens are non metallic. Downward in a group, their non metallic character decreases
and metallic character increases and iodine shows some metallic properties such as:
(i) Iodine is solid (ii) Iodine has metallic luster (iii) Iodine can form cation.
13.3.1.8 Bond energy and reactivity:

Halogens are diatomic molecules and iodine has the least bond energy because as the size
increases, nucleus will be far apart from outermost shell. Thus, the subshell has weaker over
lapping tendency. Bond energy of fluorine is less than chlorine and bromine due to the size of
fluorine and non bonding electron-electron repulsion in fluorine molecule.
Cl2 > Br2 > F2 > I2 (Order of bond energy)
13.3.1.9 Oxidation state:

Electronic configuration of halogen family is ns2np5. It can gain 1e– to attain noble gas
configuration. Except fluorine, other elements of the group have d orbitals. Hence, fluorine
shows (–1) oxidation state only. Other elements show –1, +1, +3, +5, +7 oxidation states.
13.3.1.10 Solubility of halogens:

Halogens are nonpolar in nature, hence, are slightly soluble in water. Their solubility
decreases from Cl to I. Flourine is not soluble as it decomposes with water librating O2 and
O 3.
2F2 + 2H2O → 4HF + O2
3F2 + 3H2O → 6HF + O3
The halogens are more soluble in organic solvents like CCl4, CHCl3, CS2 and hydrocarbons.
In organic solvents like CHCl3 and CCl4, Cl2 gives yellow, Br2 gives brown colour and I2
gives violet colour. In the presence of sun light, they are decomposed. Cl2 is more reactive
than Br2.
Sun light
Cl2 + H2O → HCl + HClO

Br2 + H2O → HBr + HBrO
13.3.2 Chemical properties of halogens:

Halogens are chemically more reactive due to high electronegativity, high electron affinity
and low dissociation energy. Among halogens, F is the most reactive element and reactivity
decreases as : F > Cl > Br > I.
13.4 HALIDES AND HALOGEN OXIDES
13.4.1. Characteristics of hydrogen halides:

Halides are mainly of three types: (i) Ionic halides like LiF, CaF2, SrF2, BaF2 (ii) Molecular
or covalent halides (OsCl4, OsBr4, BCl3, PCl3, PCl5, CCl4 etc.) and (iii) Bridging halides
(AlCl3, BeF2, BeCl2, HbF5, TaF5 etc).
Hydrogen halides have general formula HX, where X is halogen (Cl, Br, I, F). Their aqueous
solutions are called as hydrohalic acids or halogen acids. All the halogens react with
hydrogen to form hydrides (HX). Reactivity of halogens toward hydrogen decreases down a
group. Fluorine violently reacts with hydrogen. Hydrogen reacts with chlorine very slowly in
the dark, faster in day light and explosively in sunlight. Reaction of hydrogen with iodine is
very slow at room temperature.
The other characteristics of hydrogen halides are discussed in following section.
(a) Physical state: Except HF which is liquid at room temperature, other halogen halides
are found in gas state. In liquid state of HF, due to the intermolecular hydrogen bonding, the
HF molecules associate with each other to form liquid. The other halogens do not form
hydrogen bond and hence, they are gases at room temperature.
Hydrogen bonding in HF molecule
(b) Thermal stability: Stability of halides decrease from HF to HI. HF is highly stable
and HI is the least. From HF to HI, thermal stability decreases.
HF > HCl > HBr > HI
This trend is observed due to the hydrogen bonding in HF.
(c) Acidic behaviour: Downwards in the group, the acidic nature increases because size
increases and release of hydrogen become more easy.
HF < HCl < HBr < HI

(d) Reducing properties: Downwards in a group, reducing properties increase because

bond energy decreases.
HF < HCl < H Br < HI

Order of reducing property
13.4.2 Oxides of halogens:
The electronegativity difference between the halogens and oxygen is very small; hence, the
bonds in halogen oxides are covalent. Most of the oxides of halogens are unstable and
explosive in nature (when exposed to light or shock). The oxides of iodine are the more stable
then the chlorine oxides. While the oxides of bromine are very unstable as they decompose
below room temperature. Oxides with higher oxidation states are more stable as compared to
lower states.
The different oxides formed by halogens are OF2, O2F2, F2O4, Cl2O, ClO2, Cl2O7, Cl2O6,
ClO3, Br2O, BrO2, I2O5, I4O9 and I2O4. Among these, ClO2, Cl2O, I2O5 and OF2 are the most
useful. ClO2 is used in paper industry, bleaching clothes and purification of water. OF2 and
Cl2O7are strong oxidizing agents. In this section, you will read detailed chemistry of some
halogen oxides.
Oxygen difluoride (OF2)
It is a pale yellow gas used as an oxidizing agent and rocket fuel. It vigorously reacts with
metals, S, P and halogens to give fluorides and oxides. It has V-shaped geometry as in case of
H2O molecule.
Dioxygen difluoride (O2F2)
It is an unstable orange yellow solid with oxidizing and fluorinating properties. Structurally,
it is similar to H2O2.
Dichlorine monoxide (Cl2O)
It is a yellow brown gas used in the preparation of hypochlorites such as NaOCl, Ca(OCl)2,
chlorinated solvents and as bleaching agent. It is also V-shaped but the bond angles of the
three oxides (F2O, Cl2O, Br2O) increases in following order:
F2O < Cl2O < Br2O
The different bond angles are due to the steric crowding of the larger halogen atoms.

Chlorine dioxide (ClO2)
It is a yellow gas and used for bleaching purpose, purifying drinking water and
manufacturing NaClO2. It is paramagnetic due to the presence of an odd electron. It does not
dimerize because, the odd electron is delocalized.
Dichlorine hexaoxide (Cl2O6)
It is a dark red liquid and solidifies at –180ºC. It is a strong oxidizing agent and explodes
when comes in contact with grease. The probable structure of Cl2O6 is–
O
O O
O O
Cl Cl
O Cl Cl O
O
O O
O O
Dichlorine heptoxide (Cl2O7)
It is a colourless liquid and shock sensitive and less reactive than lower oxides.
Oxides of bromine are less important as those of chlorine. Br2O is a dark brown liquid while
BrO2 is a pale yellow solid.
Oxides of iodine are more stable as compared the other halogen oxides. Iodine pentaoxide
(I2O5) is useful in analyzing gases. I2O5 is having a three dimensional network.
O O
I O I
O O
The other iodine oxides are moderately or less stable.
13.5 OXOACIDS OF HALOGENS

The oxoacids formed by halogens are discussed in this section.
Halogen Hypohalous acid Halous acid Halic Acid Perhalic acid

Oxidation No. +1 Oxidation No.+3 Oxidation No. +5 Oxidation No.+7
Chlorine (Cl) HClO HClO2 HClO3 HClO4
Bromine (Br) HBrO – H BrO3 HBrO4
Iodine (I) HIO – HIO3 HIO4

The above table shows that the oxidation number of the central atom is 1, 3, 5, 7 respectively.
F is more electronegative than O atom and does not have orbital to receive the electron pair
by back donation and it does not give any oxoacids.
13.5.1 Oxyacids of chlorine:
Hypochlorons acid (HClO)
The acid is known only in solution. HClO is prepared by
(i) Passing Cl2 through H2O or in to a suspension of CaCO3
Cl2 + H2O → HCl + HClO
CaCO3 + H2O + 2Cl2→ CaCl2 + CO2 + 2HClO
(iii) The action of CO2 with NaOCl
NaOCl + CO2 + H2O → NaHCO3 + HOCl
Properties:
(i) The concentrated solution of HClO is yellow, while the dilute solution is colourless. It is a
weak acid.
(ii) Disproportion of the acid- the dilute solution of the acid is fairly stable in the dark but when
concentrated solution exposed to light, it become unstable and disproportionate into Cl2 and
HClO3.
5HClO → 2Cl2 + HClO3 + 2H2O
When aqueous solution of HClO is heated it undergoes disproportionation in to HCl and

HClO3.
(iii) On distillation HClO decomposes into H2O and Cl2O.
2HClO → Cl2O + H2O
(iv) Action on metals - it dissolves in Mg to give H2
Mg + 2HClO → Mg (OCl)2 + H2↑
(v) Oxidizing and bleaching properties

The aqueous solution of HClO gives nascent oxygen [O] which shows oxidizing and
bleaching properties.
(vi) Acidic nature

HClO is a monobasic in nature.
HClO (aq) → H(aq)+ + ClO(aq)-
NaOH + HClO → NaOCl + H2O

(vii) Action of AgNO3
HClO reacts with AgNO3 to give AgOCl which is unstable and give AgCl and AgClO3.
HOCl + AgNO3 → AgOCl + HNO3
3AgOCl → AgCl + AgClO3
Structure of HOCl:
It is V-shaped and oxygen is sp3 hybridized.
Chlorous acid (HClO2)
This acid is obtained in the aqueous solution by treating a suspension of barium chlorite with
dilute H2SO4.
Ba(ClO2)2 + H2SO4→ 2HClO2 + BaSO4↓
HClO2 can also be obtained when ClO2 reacts with H2O
2ClO2 + H2O → 2HClO2 + O2
Properties:
(i) The freshly prepared solution of the acid is colourless but it soon decomposes into ClO2.
(ii) It gives a violet colour with FeSO4.
(iii) HClO2 undergoes disproportionation on heating in an alkaline solution.

5HClO2→ 4ClO2 + NaCl
(iv) HClO2 shows oxidizing properties due to nascent oxygen.

HClO2→ HCl + 2[O]
HClO2 liberates I2 from KI solution.
HClO2 + 2H2O + 4KI → 4KOH + HCl + I2
(v) In acid solution, HClO2 rapidly decomposes as follows:
4HClO2→ 2ClO2 + HClO3 + HCl + H2O
Structure:
13.5.1.3 Chloric acid (HClO3):

This acid is the only oxoacid exists in solution. It can be prepared
(i) By the action of dil. H2SO4 on Ba(ClO3)2
Ba (ClO3)2 + H2SO4→ BaSO4↓ + 2HClO3.
(ii) By the action of hydrofluosilicic acid (H2SiF6) on KClO3
2KClO3 + H2SiF6→ K2SiF6 + 2HClO3.
Properties:
(i) Concentrated solution of the acid is colourless and pungent smelling liquid.
(ii) It is stable in dark and in light, it decomposes and become yellow.
(iii) When organic substances like cotton, wool paper etc come in contact with the acid, they
catch fire.
(iv) The acid is very powerful oxidizing and bleaching agent.
(v) When iodine is evaporated with HClO3, iodic acid (HIO3) is obtained.
2HClO3 + I2→ 2HIO3 + Cl2

This reaction is used for the preparation of HIO3.
(vi) HClO3 is a monobasic acid
Structure of HClO3:
..
Cl
OH
O O
Hybridization on chlorine is sp3, with one lone pair of electron
13.5.1.4. Perchloric acid (HClO4):
(i) It is prepared by heating HClO3
(ii) Anhydrous acid is obtained by distilling a mixture of potassium per chlorate (KClO4) with
conc. H2SO4.
Ba (ClO4)2 + H2SO4→ 2HClO4 + BaSO4↓
Properties:
(i) Anhydrous HClO4 is a colourless, mobile, hygroscopic and oily liquid. It fumes
strongly in moist air and dissolves in water with a hissing sound due to the liberation
of heat.
(ii) It forms hydrates with 1, 2, 2.5, 3 and 3.5 molecules of water as water of
crystallization.
(iii) It is highly dangerous acid and produces wounds on the skin.
(iv) On dehydration with P2O5 at –10ºC, it gives Cl2O7.
(v) HClO4 is the strongest acid among all the acids.
(vi) The metals like Zn, Fe etc dissolve in the aqueous HClO4 solution and form the soluble
per chlorates.
Zn + 2HClO4→ Zn (ClO4)2 + H2↓
(vii) The acid is not reduced by nascent hydrogen but get reduced to chlorine by the strong
reducing agent like SnCl2, CrCl2 etc.

Uses:
The aqueous solution of the acid is used for the estimation of potassium grammatically.
Structure of HClO4
13.5.2 Oxoacids of bromine:
13.5.2.1. Hypobromous acid (HBrO):
Like HClO, HBrO is also known only in solution.
Preparation:
(i)It is prepared by shaking Br2 water with freshly precipitated HgO or Ag2O
2Br2 + 2HgO + H2O → HgBr2. HgO + 2HBrO

2Br2 + Ag2O + H2O → 2AgBr + 2HBrO
(ii)It is also obtained by distilling a mixture of Br2 and concentrated AgNO3 solution.
Br2 + AgNO3 + H2O → HBrO + HNO3 + AgBr
Properties:
(i) The aqueous solution of the acid is starve-yellow in colour and is always contaminated
with the products which are obtained due to the decomposition.
(ii) HBrO is a strong oxidizing and bleaching agent. HBrO oxidizes H2O2 to O2.
HOBr + H2O2→ H2O + O2 + HBr
13.5.2.2. Bromic acid (HBrO3):
Like HClO3, HBrO3 is also known in solution.

Preparation:
(i)By passing Cl2 in bromine water.
Br2 + 5Cl2 + 6H2O → 2HBrO3 + 10HCl
(ii)By shaking AgBrO3 with bromine water

5AgBrO3 + 3Br2 + 3H2O → 5AgBr + 6HBrO3
Properties:
(i) On evaporating the aqueous solution of the acid, it decomposes as follows :

4HBrO3→ 3Br2 + 5O2 + 2H2O
(ii) The aqueous solution of HBrO3 decomposes on heating and gives Br2 and nascent
oxygen (O) that acts as a good oxidizing agent.
Also reduces H2S to sulphur.

2HBrO3 + 5H2S → Br2 + 6H2O + 5(S)
Reduces SO2 to H2SO4
2HBrO3 + 5SO2 + 4H2O → Br2 + 5H2SO4
13.5.3 Oxoacids of iodine:
13.5.3.1 Hypoiodous acid (HIO):
It is also known only in solution like as HClO and HBrO.
Preparation:
It is prepared by shaking a solution of finally powdered iodine with freshly precipitated HgO
2I2 + 2HgO + H2O → HgI2.HgO + 2HIO
Properties:
It is the weakest acid of all the hypohalous acid. The acid acts as a very weak base, since it
also gives OH– ions

Like HOCl and HOBr, HOI also undergo disproportionation forming I2 and HIO3.
5HIO → 2I2 + HIO3 + 2H2O
13.5.3.2 Iodic acid (HIO3):
It is the most stable oxoacid of iodine.
Preparation:
(i) By oxidation of iodine with boiling conc. HNO3.

I2 + 10HNO3→ 3HIO3 + 10NO2 + 4H2O
(ii) By passing Cl2 into suspension of iodine in water.
I2 + 5Cl2 + 6H2O → 2HIO3 + 10HCl.
(iii) By dissolving I2O4 in hot water.
5I2O4 + 4H2O → 8HIO3 + I2
Properties:
(i) It is colourless crystalline solid, very soluble in water but in soluble in alcohol.
(ii) Action of heat:
When heated at 240ºC, it decomposes to give I2O5.
(iii)Action of metals:
When reacts with Sn, Au, Pb or Zn, it evolves H2 gas.
Zn + 2HIO3 → Zn(IO3)2 + H2
(iv) Oxidizing properties:
Like HBrO3, it also acts as a good oxidizing agent. During oxidation of other species, it itself
reduced to I2.
5H2S + 2HIO3 → I2 + 6H2O + 5S
2HIO3 + 5SO2 + 4H2O → I2 + 5H2SO4
HIO3 + 5HI → 3I2 + 3H2O

(v) Formation of salt:
HIO3 is a monobasic acid and it gives normal salt (e.g. KIO3). On action of conc. H2SO4, I2O4
is obtained.
4HIO3 + 2H2SO4 → 2I2O4 + 2(H2O)+ HSO4- + O2
13.5.3.3. Meta periodic acid (HIO4):
Preparation:
It is obtained by heating para periodic acid (H5IO6).
Properties:
i. It is a weak acid and dissociates as –
ii. When dissolved in water, it changes back to H5IO6.
HIO4 + 2H2O → H5IO6
iii. HIO4 is a strong oxidizing agent in acidic medium and reduces itself to I2.
13.5.3.4. Paraperiodic acid (HIO4.2H2O or H5IO6):
(i) It is obtained by decomposing silver mesoperiodate Ag3IO5 with Cl2.
4Ag3IO5 + 6Cl2 + 10H2O → 4H5IO6 + 12Ag Cl + 3O2
(ii)By heating a suspension of I2 in HClO4.
2HClO4 + I2 → 2H5IO6 + Cl2
Properties:
i. It is a colourless crystalline solid and deliquescent in nature. It is soluble in water but slightly
soluble in alcohol and ether.
ii. It is strong monobasic while weak dibasic acid in nature.

iii. When heated at 138ºC, it decomposes in to I2O5, H2O and O2.
When heated in vacuum at 80ºC, H4I2O9 is obtained. On further heating at 100ºC, HIO4 is
obtained and on heating at 140ºC, it gives HIO3 and O2.
iv. The acid is a very good oxidizing agent and liberates I2 from KI in neutral and acidic
medium.
H5IO6 + 7KI + 7HCl → 4I2 + 7KCl + 6H2O
Structure of H5IO6
O
HO OH
I
HO OH
OH
Octahedral structure of H5IO6
H5IO6 has octahedral structure due to sp3d2 hybridization of I atom.
13.6 INTERHALOGEN COMPOUNDS
Interhalogen compounds are the compounds of more than one halogen. General formula is
ABn, where A and B are halogens, A is heavier than B (n = 1, 3, 5, 7). Most of the
interhalogen compounds are fluorides. They can be classified as:
i. Neutral – They are binary compounds such as BrF3 or IF7.

ii. Cations – They may be homonuclear I2+ or Cl3+ or heteronuclear I3Cl2+.
iii. Anions – Polyhalide anion such as I3– or IBrCl–.
iv. Covalent organic derivatives – ArAFn (Where Ar = arene; A = I or Br and n = 2 or 4).
13.6.1. General Properties:
(i) The interhalogen compounds are covalent diamagnetic molecules.

(ii) They are generally volatile solids or liquids except ClF which is a gas at 25ºC.

(iii) These are more reactive than parent halogens. All of them show halogenation reactions:
(BrF3, IF5, ICl are good halogenating agents)
(iv) Interhalogens can be hydrolysed by water or alkali to produce halide ion of the lighter
halogen.
AB + H2O → HB + HOA (AB type)
(v) Interhalogens can add to alkenes (addition reaction)

H2C = CH2 + ICl → ICH2 – CH2Cl
(vi) They are strong oxidants and can be used to halogenate metals and metal oxides.
(vii) They act as useful fluorinating agents. There reactivity order is as follows:
ClF3 > BrF > BrF5 > IF7 > ClF > IF5 > BrF
Thermal stability order of reactivity [(IF (1.5) > BrF (1.2) > ClF (1.0) > ICl (0.5) > IBr (0.3)
> BrCl (0.2)]
(viii) These are used as non aqueous solvents.
(ix) They are polar in nature.
(x) Reactions with non-metallic and metallic oxides: when react with oxide, form corresponding
fluorides
4BrF3 + 3SiO2→ 3SiF4 + 2Br2 + 3O2
(xi) Self ionization (halide ion transfer) – Show donor acceptor property (generally liquid
interhalogens have this quality).
ICl, IBr, BrF3, IF5
13.6.2 Preparation:
(A) (AB type interhalogen) – (ClF, BrF, BrCl, ICl, IBr)
(i) Direct reaction of halogens
(ii) By direct reaction of halogens with interhalogen compounds

13.6.3 Chemical Properties:
(A) AB type is terhalogen compounds
i. Halogenations reaction
ClF is a good fluorinating agent and reacts with many metals or nonmetals either at room
temperature or above and convert them to fluorides and liberate chlorine.
W + ClF → WF6 + 3Cl2
Se + 4ClF → SeF4 + 2Cl2
It can also act as a chlorofluorinating agent by addition across a multiple bond:
ii. Donor acceptor property

BrF3 + 2ClF → [Cl2F]+ [BrF4]–
iii. As solvent system
Both ICl and IBr partially dissociate into ions which gives rise to an electrical conductivity.
ICl + MCl → M+ [ICl2)–

2ICl + AlCl3 → [I2Cl]+ [AlCl4]–
PCl5 + ICl → [PCl4]+ [ICl2]–
SbCl5 + 2ICl → [I2Cl]+ [SbCl6]–
(B) AB3 type interhalogen compounds

Properties:
ClF3 and BrF3 are volatile liquid whereas IF3 and ICl3 are solids. ClF3 is the most reactive
chemical compound. It reacts explosively with water and with most organic substances. BrF3
is used for preparative work.
(i) Fluorinating agent

2AgCl + ClF3 → 2AgF + Cl2 + ClF
Co3O4 + 3ClF3 → 3CoF3 + 3/2Cl2 + 2O2
NH3 + 2ClF3 → 6HF + N2 + Cl2
2ClF3 → (ClF4)– [Cl2F]+

(ii) Donor acceptor property
MF5 + ClF3 → [ClF2]+ [MF6]– M = As, Sb or Pt
MF + ClF3 → [ClF4]– [M]+ M = K, Rb or Cs
BF3 + ClF3 → –
(BF4) [ClF2] +
(iii) Self ionization

(has high electrical conductivity)
BrF3 is decomposed bigorously by water. It is very reactive and displaces oxygen from
oxides such as B2O3, SiO2, As2O3, CuO etc.
4BrF3 + 3SiO2 → 3SiF4 + 2Br2 + 3O2
(C) AB5 and AB7 type interhalogen compounds (ClF5, BrF5, IF5 and IF7)
Properties
All are colourless volatile liquids or gases at room temperature.
(i) Fluorinating agent
IF7 is a stronger fluorinating agent than IF5.
IF7 + H2O → IOF5 + 2HF (Partial fluorination)

IF7 + 4H2O → HIO4 + 7HF
2IF7 + SiO2 → 2IOF5 + SiF4

(ii) Donor acceptor property
ClF5 + A5F5 → [ClF4]+ [AsF6]–
BrF5 + 2SbF5 → [BrF4]+ [Sb2F11]–
IF7 + A5F5 → (IF6)+ [A5F6]–
(iii) As solvent
KF + IF5 → KIF6
NOF + IF5 → [NO]+ [IF6]–
SbF5 + IF5 → [IF4]+ [SbF6]–
(iv) Reaction with water
Interhalogen compounds of this type react with water to from HF and corresponding halo
acids.
ClF5 + 2H2O → FClO2 + 4HF

BrF5 + 3H2O → HBrO3 + 5HF
IF5 + 3H2O → HIO3 + 5HF
IF7 + 4H2O → HIO4 + 7HF
13.6.4. Structure of interhalogen compounds:
i. AB type: Linear geometry due to the presence of three lone pair of electrons on central atom.
ii. AB3 type: ClF3 and BrF3 are T-shaped due to the presence of two lone pair of electrons and
the central atom is sp3d hybridized.
F
..
Cl F
..
F

Structure of ICl3 is entirely different, being comprised of planar I2Cl6 separated by normal
van der Waals distances between Cl atoms. The terminal ICl distances are similar to those in
ICl but bridging I-Cl distances are longer.
iii. AB5 type: Square pyramidal geometry due to the presence of one lone pair electron with
central atom. The central atom undergoes sp3d2 hybridization.
F .. F
Br
F F
F
iv. AB7 type: Example is IF7, where iodine undergoes sp3d3 hybridization. The geometry of the
molecule is pentagonal bipyramidal with bond angles 720 and 900.
13.6.5. Applications of interhalogen compounds:
i. ICl (Iodine monochloride) is used in the estimation of iodine number which is a measure of
the unsaturation in acids and fats.
ii. Liquid BrF3 and ClF3 are used as fluorinating agents.
iii. BrF5 is used as oxidizer for propellants.
13.7 POLYHALIDES

When halide ions associate with halogens or interhalogen, univalent ions are obtained and are
called as polyhalide ions and the compound of these are known as polyhalides.
Examples of polyhalides containing polyhalide anions, are K+[Cl3]–, NH4[I5]–, M+[Cl2]– (M+
= K+, Rb+, NH4+).
Examples of polyhalide cations are ICl2+, ClF2+, BrF4+, IF6+, BrF6+ etc.
Iodine has maximum tendency to form polyhalide ions. Cl, Br and I atoms can form triatomic
anions Cl3–, Br3– and I3–. Fluorine atom ion not able to form F3– ion as it does not contain d
orbitals in the valence shell.
13.7.1 Preparation:
General methods of preparation of polyhalides are:
(i) Polyhalides can be prepared by the action of halogen on metallic halides or another
polyhalides.
Cl2 + KCl → K[Cl3]

Cl2 + KI → K[ICl2]
I2 + KI → K[I3]
2I2 + NH4I → [NH4] I4
The value of n has been found to depend on the amount of I2 used in the reaction.
(ii) By the action of interhalogen on metals/metallic halides or other polyhaladies.

4BrF3 + 3K → 3K[BrF4]
16BrF3 + 6Nb → [6BrF3]+ [NbF6]– + 5Br2
2F2 + CsCl → Cs+[ClF4]–
ICl + KCl → K+[ICl2]–
ICl + KBr → K[ICBrCl]
(iii) Polyhalides can be converted in to the other type by the action of halogens or
interhalogen on them.
K[ICl2] + Cl2 → K[ICl4]
CsBr3 + I2 → Cs[IBr2] + IBr

13.7.2. General properties:

i. All the polyhalides are coloured compound. The intensity of the compound increase with
increased atomic number. Thus the bromo iodides are red while chloro iodides are yellow.
ii. Polyhalide compounds have low melting point.
iii. Polyhalides dissolved in liquid of high dielectric constant like water, acetone, alcohols etc.
13.7.3. Chemical properties:

i. These are ionic in nature. They tend to decompose on heating.
ii. The polyhalides having ICl4– anion dissociate in aqueous solution to metal chlorides and ICl3.
The latter than hydrolyze to iodine and IO3–
M+[ICl4]– → MCl + ICl3

5ICl3 + 9H2O → 3HIO3 + 15HCl + I2
+
M [ICl4] + 9H2O → 5MCl + 3HIO3 + 15HCl + I2
iii. Formation of complexes: Some of the polyhalides ions are able to form complexes with
organic donor molecules. Some examples of such complex are LiI3, 4C6H5CN, MI3.
3C6HSCN (M = Na and K)
iv. Replacement (substitution) properties: Halogen in the polyhalides may be replaced by a
more electronegative atom but the central metal is not replaceable. Chlorine cannot replace
central iodine atom in IBr2– but replace bromine in IBr2 to yield ICl2–
IBr2– + Cl2 → ICl2– + Br2

• Action of halogens: A halogen may be directly added to the polyhalides. This behaviour is
not exhibited by interhalogen compounds.
ICl2– + Cl2 → ICl4–
Structure and shapes of trihalide anions
Examples ICl2–, I3– IBr2–, IBF etc.
(i) Structure of ICl2–
This type of ion has symmetrical linear shape with sp3d hybridization on Iodine atoms. Iodine
atom can be considered as having eight electrons instead of seven electrons in the valence

shell. In ICl2–, I atom is surrounded by two σ bond pair (bp) of electrons and the rest six
electrons remain as three lone pair (lp) of electrons on Iodine atom 2bps + 3lps = 2 + 3 = 5
orbitals are sp3d hybridized in ICl2– as shown below.
Ground state in I atom

53
I = 5s2 5px2 5py2 5pz1, 5d0
Iodine atom gains 1e-
5s2 5px2 5py2 5pz1 5d1 (sp3d hybridization)
Liner shape of ICl2– ion with three blone pairs on a plane

(ii) Structure and shape of I3– ion is similar to that of ICl2– ion. I3– ion is also having liner shape
as shown below.
-
Cl
..
..
.. I
Cl
13.8 BASIC PROPERTIES OF HALOGENS
In the periodic table, metallic or basic properties of elements increase on descending in a

group and decrease in a period. In the group 4th, 5th, and 6thA, the first elements (C, N, O) are
non metals where as the heavier members (Pb, Bi and Po) are metals. Similarly, one can
expect the same trend for group 7thA. In 7thA group (that is 17th group);
i. Flourine is the most electronegative element of the periodic table and hence possessing no
basic or metallic properties.
ii. Chlorine shows a slight basic character.
iii. Bromine shows comparatively high basic properties in its complexes.
iv. Iodine shows the highest basic character i.e. the tendency of iodine atom to form cation is
easier.
v. Unfortunately, there is no evidence which may prove the basic character of astatine.
The basic character of I2 is well established and a large number of compounds contain basic
iodine.
13.8.1. Reasons for basic properties of iodine:

i. The electronegative character in halogens decreases from fluorine to iodine. Iodine is the
least electronegative and exhibits electropositive character.
F < Cl < Br < I (order of electropositive character)

ii. Low electronegativity
iii. Decrease in ionization potential. Iodine can remove electron easily to give positive iodine due
to its lowest ionization potential.
iv. Size of the atoms increase from fluorine to iodine. Iodine has biggest size amongst active
halogens.
F < Cl < Br < I order of size
v. Ionic radii values from fluorine to iodine also increase. Therefore, the electrons loose easily
to form unipositive I+ ion or tripositive I3+.
13.8.2. Evidence for I+:
i. When the compound like ICl, IBr, ICN, INO and I2SO4 in their molten state or as their
aqueous solutions are electrolyzed, iodine is liberated at cathode. The liberation of iodine at
cathode proves the existence of cationic iodine in these compounds.
ii. ICl acts as a strong electrophilic iodinating agent and converts salicylic acid into 3,5-di
iodosalicylic acid.
iii. When I2 dissolved in H2O, a variety of reactions take place.
I2 + 2H2O → [I(H2O)]+ + I–
[I (H2O)]+ + H2O → [I(OH)]0 + H3O+
13.8.3. Evidence for I3+:
i. Molten ICl3 conduct electricity, liberating iodine and chlorine at both the electrodes. Thus, its
ionization is probably as:
2ICl3→ ICl2+ + ICl4–

ii. If iodine is oxidized by fuming nitric acid in acetic anhydride, I(CH3COO)3 is obtained. It
this is electrolyzed using silver electrodes, one equivalent of AgI is liberated at the cathode
for the passage of 3 Faradays of electricity.
iii. When iodine is dissolved in olium, I3+ ion is formed. If the olium is concentrated, I– is
formed.
iv. Aubke (1995) spectroscopically confirmed the existences of I+3 ion by the reaction of iodine
with HSO3F.
13.9 ANOMALOUS NATURE OF FLUORINE
Fluorine shows different behaviour with other elements of the group due to the following
reasons.
(i) Small size

(ii) Lowest electronegativity
(iii) Low bond dissociation energy
(iv) Absence of d-orbitals in the valence shell
Low dissociation energy of fluorine is due to non-bonding electron repulsion and due to the
small size (causes high electronegativity), it forms ionic bond easily as compared to the other
elements. Consequently, ionic fluorides have larger negative free energies and enthalpies of
formation.
The main differences between fluorine and other members are:
i. Fluorine is the most reactive element among all the halogens because of lower bond
dissociation energy (F2 =158; Cl2 = 243; Br = 192 and I2 = 151 KJ mol–1)
ii. Fluorine shows only one oxidation state i.e. –1 due to the highest electronegativity and due to
the absence of d-orbitals in valence shell, does not show positive oxidation states. While, the
other halogens can show positive oxidation states (+1, +3, +5 and +7).
iii. Its hydride shows strong hydrogen bonding due to its smallest size and high electronegativity.
iv. Due to the highest strength of H–F bond, HF is the weakest acid among all the halogen acids.
v. HF is liquid while the other halogen acids are gases at room temperature.

vi. Fluorides have the maximum ionic character. Other halides are covalent in nature.
vii. HF forms acid salts of the type KHF2 due to the presence of H-bonding. On the other hand,
HCl, HBr and HI do not form such salts.
viii. Fluorine has the highest positive reduction electrode potential among halogens.
Hence, it is the strongest oxidizing agent.
ix. As HF reacts with silicates to form fluorosilicates, it cannot be stored in glass bottles.
Na2SiO3 + 6HF → Na2SiF6 + 3H2O
The other acids can be stored in glass bottles because they do not react with silicates.
i. Due to its ionic behaviour, AgF is soluble in water while AgCl, AgBr and AgI are insoluble
in water. In contrast, CaF2 is insoluble while CaCl2, CaBr2 and CaI2 are soluble in water.
ii. Fluorine cannot form polyhalide ions due to the absence of d-orbitals in their valence shell
while other halogens can form polyhalide ions.
3.10 SUMMARY
In 17th group of periodic table, five non-metallic elements known as halogens are present.
The term ‘halogen’ means ‘salt former’ and thus the compounds of halogens are called
‘salts’. The halogens are diatomic and exist in all three states of matter at room temperature:
Iodine, Astatine are solid; Bromine is liquid; Chlorine and fluorine are gases
There are 7 electrons in the valence shell of all halogens which are responsible for an
oxidation number of –1. Except for fluorine, all halogens also have +1, +3, +5 and +7
oxidation states. Due to the highest electronegativity of fluorine, extensive hydrogen bonding
in HF molecule occurs. Therefore, HF exists as liquid and has high melting point and boiling
point. You have also studied that all halogens are good oxidizing agents and among all
halogens, fluorine is the strongest oxidizing agent. All halogens can form hydrogen halides
(HX). Among halides, HI is the most acidic in nature. Halogens on reaction with other
halogens form interhalogen compounds which are non reactive than elemental halogen except
fluorine. Halogen also forms oxides with oxygen. Iodine forms the most stable oxides.
Halogens form oxoacids of type HOX, HOX2, HOX3 (where X is halogen). Fluorine forms
only oxoacid that is HOF.

Polyhalides is the other class of compound synthesized using halogens. Among all halogens,
iodine has maximum tendency to form poly halides. Among halogens, iodine shows the most
basic metallic character due to the lowest electronegative character.
13.11 TERMINAL QUESTION
13.11.1. State True (T) or False (F)
i. Halogens are present in VIIA / 17th group of the periodic table.

ii. Astatine is metallic in nature.
iii. Atomic number of iodine is 35.
iv. Cl2 and F2 are gases due to weak van der Waals forces.
v. The order of m.p. and b.p. of the halogens follow the order: F2 < Cl2 < Br2 < I2
vi. Among halogens, iodine shows some metallic character.
vii. Bond energy of fluorine is less than chlorine and bromine.
viii. Fluorine slowly reacts with hydrogen.
ix. Downwards in the group, the acidic nature of hydrogen halides increases.
x. OF2 is V-shaped.
xi. In HClO2, chlorine is sp3 hybridized with one lone pair of electron.
xii. HClO4 is the strongest acid among all oxoacids.
xiii. Chemical formula of para periodic acid is H5IO6.
xiv. Interhalogen compounds are chlorofluorinating agents.
xv. ClF3 and BrF3 are trigonal planar in shape due to the presence of two lone pair of electrons.
xvi. In ICl2-, iodine is sp3d hybridized.
xvii. Iodine is acidic in nature.
xviii. Fluorine is the strongest oxidizing agent.
xix. Fluorine forms polyhalide ions.
13.11.2. Fill in the blanks.
i. Halogen consists of five elements ………….., …………………, ……………….,

………….., ………………..
ii. Flourine is the most electronegative highly reactive and is called as……………….
iii. Astatine is a ……………… element and formed artificially.

iv. Electronic configuration of iodine is ……………………………………………….

v. Physical state of F2 and Cl2 is ………….., Br2 …………….. and I2 …………………….
vi. Melting point of halogens increases in order ……………………………………
vii. Halides are mainly of three types: a) …………………….., b) ………………………, c)
………………………….
viii. Stability of halides decrease from HF to …………...
ix. ClO2 is used in ………………………….., ……………………………. and
…………………...
x. …………………………… is a dark red liquid and solidifies at –180ºC.
xi. HClO disproportionate into ……………… and ……………….
xii. Anhydrous acid is obtained by distilling a mixture of ………………………………. with

……………………
xiii. The aqueous solution of …………….. decomposes on heating and gives Br2 and nascent (O)
that acts as a good oxidizing agent.
xiv. ………………. also undergo disproportionation forming I2 and HIO3.

xv. ……………….. is obtained by heating para periodic acid (H5IO6).
xvi. Paraperiodic acid is ………………..
xvii. Interhalogen compounds are the compounds of more than one …………….
xviii. Interhalogens can be hydrolysed by water or alkali to produce halide ion of the ……………
halogen.
xix. ClF3 and BrF3 are ………………….. whereas IF3 and ICl3 are ……………….
xx. AB3 type interhalogen compounds are ………….. shaped.
xxi. ………………. is used as oxidizer for propellants.
xxii. ……………………… has maximum tendency to form polyhalide ions.
13.11.3 Long questions
i. What are halogens? Discuss general characteristics and uses of halogens.

ii. Discuss characteristics of hydrogen halides.
iii. Give in detail preparation, properties, uses and structure of oxoacides of chlorine.
iv. Give in detail preparation, properties, uses and structure of oxoacides of bromine.
v. Give in detail preparation, properties, uses and structure of oxoacides of iodine.
vi. What are interhalogen compounds?
vii. Describe, in detail, the polyhalides.

viii. Iodine is basic in nature. Why?
ix. How fluorine is different from other elements of 17th group?
13.12. ANSWERS.
13.12.1. State True (T) or False (F)

i. True (T)
ii. False (F)
iii. False (F)
iv. True (T)
v. True (T)
vi. True (T)
vii. True (T)
viii. False (F)
ix. True (T)
x. True (T)
xi. False (F)
xii. True (T)
xiii. True (T)
xiv. True (T)
xv. False (F)
xvi. True (T)
xvii. False (F)
xviii. True (T)
xix. False (F)
13.12.2. Fill in the blanks:

i. Flourine (F), Chlorine (Cl), bromine (Br), iodine (I) and astatine (At)
ii. Super halogen
iii. Radioactive
iv. 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 4d10 5s2 5p5
v. Gas, liquid, solid

vi. F2 < Cl2 < Br2 < I2

vii. (a) Ionic halides (b) Molecular or covalent halides (c) Bridging halides
viii. HI
ix. Paper industry, bleaching clothes and purification of water
x. Dichorine hexaoxide (Cl2O6)
xi. Cl2, HClO3
xii. Potassium per chlorate (KClO4) with conc. H2SO4
xiii. HBrO3
xiv. HOI
xv. HIO4
xvi. H5IO6
xvii. Halogen
xviii. Lighter
xix. Volatile liquid, solids
xx. T
xxi. BrF5
xxii. Iodine

UNIT 14: CHEMISTRY OF NOBLE GASES
CONTENTS:
14.1 Objectives
14.2 Introduction
14.4 Compounds of Noble gases
14.4.1 Compounds formation under excited state conditions
14.4.2 Compounds formation through coordination
14.4.3 Compounds formation through dipole induced dipole interaction
14.4.4 Compounds formation through physical trapping.
14.5 Compounds of xenon
14.5.1 Structure and bonding in xenon compounds
14.5.2 Theories of bonding in xenon compounds
14.6 Summary
14.7.1 Fill in the blanks
14.7.2 State True (T) or False (F)
14.7.3 Answer the following questions.
14.8 Answer
14.1 OBJECTIVES
After carefully reading this unit, you will be able to answer the following questions:
What are noble gases?
What are inert gases?
What are the periodic properties of noble gases and how they vary in a periodic table?

Why among noble gases, only xenon can form a number of compounds?
What are the uses of noble gase compounds?
What are the structures of different xenon compounds?
14.2 INTRODUCTION
Noble gases belong to the 18th group (VIIIA) in the periodic table. The noble gases are also
called as ‘inert gases’ or ‘rare gases’. Because, these gases are non reactive/unreactive, they
are also called as inert or noble gases. Their shells and subshells are completely filled and
thus, they have very stable configurations which can be related to their chemical inactivity.
The noble gases are also considered as rare gases because they represent not more than 1% of
air (<1%). Their electronic configurations are:
Element’s Atomic Name of element Electronic configuration

symbol Number
He 2 Helium IS2
Ne 10 Neon [He] 2s22p6
Ar 18 Argon [Ne] 3s23p6
Kr 36 Krypton [Ar] 3d104s24p6
Xe 54 Xenon [Kr]4d105s25p6
Rn 86 Radon [Xe] 4f145d106s26p6
Among these gases, except radon (Rn), all exists in the atmosphere. Rn is an element
generated through radioactive process and can be produced by the radioactive decay of
radium and thorium minerals.
226 222 4
Ra Rn + He
88 88 2

222
Rn is an α ray emitter.
88
Cavendish in 1784, for the first time separated a mixture of noble gases. Rayleigh in 1894
discovered argon and it was the first among the noble gases to be discovered. Neon, krypton
and xenon were discovered in 1898 by fractional evaporation of argon under varying reduced
pressure conditions. Radon was discovered by Dorn in 1902 as a radioactive disintegration
product of radium. The name of noble gases derived from Greek words and\their meaning is:
He: Helios; Neon: New; Argon: Lazy or inert; Krypton: Hidden and Xenon: Stranger
Helium is present in the atmosphere at a concentration of 5ppm, and can be obtained from
natural gas deposits. The most abundant noble gas is argon (Ar) (0.9% by volume in air).
Argon is produced by electron capture (β decay) of potassium.
140 0 140
K + e Ar
19 –1 18
Uses of noble gases/inert elements
As helium has the lowest boiling point (–269ºC) among noble gases, it is used as cooling gas
in nuclear reactor and also as a carrier gas in gas-liquid chromatography. It is also used in
cryoscopy. Helium is also preferable over hydrogen in airship due to inflammable nature of
hydrogen. Helium is also preferably used to dilute oxygen in gas cylinders in place of
nitrogen for divers. This is because helium is slightly soluble in blood while nitrogen gas is
more soluble in blood at high pressure and causes painful condition in patients (nitrogen
narcosis). Noble gases including neon are used in discharge tubes to give different colours
(Ne gives orange colour in discharge tubes). Argon (Ar) is used in welding stainless steel,
metallurgical processes of aluminum, magnesium and titanium. Argon is also used in electric
bulbs, fluorescent lamps etc. Radon is used in the cancer treatment due to its radioactive
nature.
At ordinary temperature and pressure, all noble gas elements are monoatomic gases except
Radon. They are chemically inert but under certain conditions, they can form complexes.
These gases are cololurless, odourless and tasteless. The other general properties are
explained below:

(a) Atomic Radü:
Their atomic radii are very large because the radii are van der Waal or non-bonded radii.
Atomic radii of elements increase from top to bottom in a group.
(b) Melting point (M.P.) and boiling point (B.P.):
Melting and boiling points of noble gases are very low because inter atomic forces are very
weak in these gases.
(c) Electron affinity:
Due to completely filled electronic configuration, the electron affinity of these gases is zero.
(d) Enthalpy of vaporization:
Enthalpy of vaporization is very low because the forces between the atoms are very weak
forces i.e. van der Waals forces.
(e) Ionisation energy:
Their ionisation energy is very high because they have very little tendency to accept or loose
electrons.
Physical Properties:
Adsorption:
All noble gases can be adsorbed on charcoal (wood) at low temperature and the order of their
adsorption is:
He < Ne < Ar < Kr < Xe
Diffusion:
All noble gases have a tendency to diffuse through glass, plastic and rubber materials.
Therefore, it became difficult to work with them in the laboratory. The order of diffusion
depends upon their size (gas with small size diffuse easily) which is as follows:
He > Ne > Ar > Kr > Xe
Electrical conductivity:

All noble gases have high electrical conductivity at low pressure and thus, can produce
characteristic coloured light during electric discharge at low pressure.
Liquification:
Due to the van der Waal forces (weak forces), they can be easily liquefied. The liquefaction
depends upon their atomic size (larger the size, more easily liquefiable gas). The order of
ease of liquefaction of noble gases is
Solubility behavior:
All noble gases are less or sparingly soluble in water. The solubility is due to dipole-induced
dipole interaction and increases from top to bottom with increase of the size of the atom.
Therefore, the increasing order of their solubility is:
Abnormal behaviour of helium:
Among noble gases, helium shows abnormal behaviour. It has some different properties from
other group members. Helium gas on cooling below (-)2690C changes to liquid (He-I). He-I
on further cooling at (-)2710C and at 1 atmospheric pressure changes to a liquid (He-II)
which has high thermal conductivity. Helium can be obtained in solid form under high
pressure (about 25 atmospheric). While all the other noble gases solidify on cooling. He-II
has a tendency to flow upwards. It acts as super-fluid.
Chemical properties:
The atoms of inert gases have completely filled shells and, therefore, they are chemically
inert. Under certain specified conditions, they combine and form some rare compounds.
14.4 COMPOUNDS OF NOBLE GASES
14.4.1 Compounds formation under excited state conditions (Helides)
These type of compounds are formed by helium. At low pressure, in the presence of
mercury, tungsten etc., helium forms HgHe2, HgHe10 and WHe2. One electron from1s orbital
of He excite and go to 2s orbital. This excitation costs about 460 kcal/mole energy.

1s1 2s1
460kcal/mole
He
1s2 excited He
He
These compounds are called helides which can survive only for a moment and can be
detected spectroscopically.
14.4.2 Compounds formation through coordination:
Noble gases have electron pairs in their valence orbitals. In the presence of strong
electron deficient groups, noble gas compounds can be prepared through coordination
(electron pairs of noble gases donated to empty orbitals of electron deficient groups). Among
noble gases, argon (Ar) forms a number of unstable compounds of the type Ar.xBF3 (X = 1,
2, 3, 4, 6, 8, 16), which can be easily dissociated at their M.P. (Figure 14.1).
Ar BF3
BF3 Ar BF3
BF3
BF3 Ar BF3
BF3
Figure 14.1. Different types of compounds formed through coordination
14.4.3 Compounds formation through dipole induced dipole interactions

(Formation of hydrates):
The inert gases such as Ar, Kr and Xe can form compounds with water through dipole
induced dipole interactions at low temperature and high pressure. These compounds are
known as hydrates.
Ar.6H2O.; Kr.6H2O; Xe.6H2O
14.4.4 Compounds formation through physical trapping (Clathrate

compound):

The inert gases such as Ar, Kr and Xe can form solid compounds with certain organic
molecules such as phenol and hydroquinone under a pressure of 10-40 atmosphere. In these
compounds, the noble gases (Ar/Kr/Xe) are trapped into the crystal lattices or cavities formed
by the organic molecules (Figure 14.2). The organic substances that form the cavities are
called the host while the atom of noble gases entrapped or enclosed in it, is called the guest.
Thus, it is also called as a guest host interaction.
H
H O
Ar O
H
O H
H
O
O
H
Figure 14.2. Clathrate compound of 1, 2 dihydroxy benzene and argon
In these compounds, the guest components are held together by van der Waals forces. Hence,
there is no chemical bonding (only weak interactions) involved in these compounds. This is a
kind of physical interaction. It is not necessary that all the cavities in the host lattice are
filled. Thus, the clathrates are also called as non-stoichiometric compounds. These weak
interactions can easily be broken and guest inert gas atom can escape from the host by simple
heating the crystal or by dissolving them in a suitable solvent such as alcohol.
For example, clathrates can be prepared by crystallization of an aqueous solution of quinol

(1,4-dihydroxybenzene) with Ar, Kr or Xe under a pressure of 10-40 atmosphere (quinol
forms cavities with a diameter of about 4Å in which the inert gas atoms trapped).
The smaller noble gases like He and Ne do not have tendency to form clathrate compounds
because they are too small to fit in the cavities and can easily escape from the cavities.
Synthetic zeolites can also form cavities in which heavier noble gas elements can fit easily.
Clathrates are very useful category of compounds because they can store radioactive Kr and
Xe produced in nuclear reactors.
14.5 COMPOUNDS OF XENON

(a) Preparation:
The first noble gas compound; Xe[PtF6] was prepared in 1962 by the reaction of PtF6 with Xe
in equal ratio at room temperature.
PtF6 + Xe Xe[PtF6]
(deep red)
Xe[PtF6] + PtF6 25ºC [XeF]+ [PtF6]–
60ºC
[[XeF]+ [PtF6]– + PtF6 [XeF]+ [Pt2F11]–
Xenon reacts directly only with F2 to form xenon complexes. However, oxygen compounds
can be prepared from the xenon fluorides. Xenon reacts directly with fluorine at 400ºC in a
sealed nickel vessel, and the final products depend on the Xe/F ratio.
(b) Properties:
The compounds XeF2, XeF4 and XeF6 are all white solids. They sublime at room
temperature, and can be stored in nickel containers for a long time. The higher fluorides can
be prepared from lower fluorides by heating with F2 under pressure.
(i) All the xenon fluorides are strong oxidizing agents. On reaction with hydrogen, they
reduce themselves to Xe.
XeF2 + H2 → 2HF + Xe
XeF4 + 2H2 → 4HF + Xe
XeF6 + 3H2 → 6HF + Xe
In similar manner, they oxidize I- to I2, Cl– to Cl2 and Ce3+ to Ce4+ and reduce themselves to
Xe.
XeF2 + 2HCl → 2HF + Xe + Cl2

XeF4 + 4 KI → 4KF + Xe + 2I2
SO42– + XeF2 + Ce2III (SO4)3 → 2CeIV (SO4)2 + Xe + F2
(ii) All the xenon fluorides are strong fluorinating agents. They fluorinate the other elements.
XeF4 + 2SF4→ Xe + 2SF6
XeF4 + Pt → Xe + PtF4
In the above reactions, XeF4 is fluorinating sulphur and platinum.
(iii) In organic synthesis
XeF2 is commercially used in synthetic organic chemistry. It does not react with alkyl or aryl
groups of organometallic compounds but attack / oxidize /fluorinate only the hetero atom in
the organometallic compound.
CH3I + XeF2 → CH3IF2 + Xe
C5H5I + XeF2 → C6H5IF2 + Xe
(C6H5)2S + XeF2 → (C6H5)2SF2 + Xe
In the presence of anhydrous HF, its reactivity increased and it may be due to the formation
of XeF+.
Pt + 3XeF2 HF
PtF6 + 3Xe
Mo (CO)6 + 3XeF2 HF MoF6 + 3Xe + 6CO
(iv) Reaction with water
All the fluorides have different reactivity with water. XeF2 reacts slowly with water and
reduce itself to Xe.
2XeF2 + 2H2O → 2Xe + 4HF + O2
While XeF4 violently reacts with water and form XeO3.
3XeF4 + 6H2O → 2Xe + 12HF + XeO3 + 3/2O2

XeF6 also reacts with water violently. On reaction with atmospheric moisture, XeF6 form
highly explosive solid XeO3.
XeF6 + 3H2O → XeO3 + 6HF
XeF6 on partial hydrolysis form colourless liquid XeOF4.
XeF6 + H2O → XeOF4 + 2HF
(v) Preparation of other Xenon compounds
Xenon trioxide (XeO3) is an explosive white hydroscopic solid soluble in water. It reacts with
XeF6 and XeOF4 to form XeOF4 and XeO2F2, respectively.
XeO3 + 2XeF6 → 3XeOF4
XeO3 + XeOF4 → 2XeO2F2
XeO3 forms xenate [HXeO4]- and perxenate ions [XeO6]4- in alkaline solution (pH > 10.5).
XeO3 + NaOH Na+ [HXeO4]–

Xenate ion
2 [HXeO4]– + 2OH– [XeO6]4– + Xe + O2 + 2H2O
Perxenate ion
Perxenate ions also act as strong oxidizing agents and oxidize HCl to Cl2, H2O to O2 and
Mn2+ to MnO4–. Perxenate ions; [XeO6]4– form volatile and explosive compound XeO4
(xenon telraoxide) on reaction with concentrated H2SO4.
[XeO6]4– + H2SO4 → XeO4
(vi) Complex formation
XeF2, XeF4 and XeF6 have tendency to form complexes with BF3, GeF4, SnF4, PF5, AsF5,
SbF5, NbF5, RuF5, OsF5, IrF5 and PtF5. In these complexes, fluorides act as fluoride donor.
The complexes of XeF2, XeF4 and XeF6 are as follows:
XeF2. MF5 → [XeF) +[MF6]-
XeF2. 2MF5 → [XeF]+ [M2F11]–

2XeF2. MF5 → [Xe2F3]+ [MF6]–
XeF4. PF5 → [XeF3] +[PF5]–
Similar complexes are formed with AsF5, SbF5, BF3 etc.
14.5 COMPOUNDS OF XENON
Xenon forms a large number of compounds as compared to the other noble gas elements
because ionization potential decreases from He to Rn, among these, He, Ne and Ar are inert
(due to high ionization potential) and Kr, Xe and Rn are noble. The structure and bonding in
different xenon compounds is discussed in this section.
15.5.1 Structure and bonding in Xenon Compounds.
(A) XeF2
XeF2 is linear in shape having three lone pairs of electrons. In the atom of xenon, one pair of
electrons of p orbital gets unpaired and one electron is promoted to d orbital. Then, central
xenon atom undergoes sp3d hybridization with trigonal bipyramidal orientation of five sp3d
hybrid orbitals. The hybrid orbitals with lone pair of electrons take equatorial position. The
remaining two orbitals with single electron in each take axial position and overlap with p
orbitals of fluorine atom. Due to the presence of lone pairs on a plane, its geometry appears
and is linear. (Figure 14.3).
Figure 14.3. Structure of XeF2
(B) XeF4

In XeF4, the central Xe atom is sp3d2 hybridized and the six sp3d2 orbitals should be present
on the 6 corners of octahedral geometry. But due to the presence of two lone pairs of
electrons at axial position, its actual geometry becomes square planar (Figure 14.4).
Figure 14.4. Geometry of XeF4
(C) XeF6
The central atom (Xe) in XeF6 is sp3d3 hybridized and the geometry should be pentagonal
bipyramidal. But due to the presence of one lone pair of electrons, its geometry become
distorted pentagonal bipyramidal in which the lone pair of electron pointing through one of
the faces of the octahedron (Figure 14.5).

Distorted pentagonal bipyramidal (Capped octahedron)
Figure 14.5. Geometry of XeF6
(D) XeO3
In XeO3, the central atom (Xe) is sp3 hybridized and due to the presence of one lone pair of
electrons, its geometry becomes pyramidal instead of tetrahedral. The thre unpaired electron
promoted to d orbitals, form three pπ–dπ bond with three oxygen atoms (Figure 14.6).
Figure 14.6. Geometry of XeO3
(E) XeO4
In XeO4, the Xe atom is sp3 hybridized and the geometry is regular tetrahedron. There are
only bonded pairs of electrons and no lone pair of electrons present in the structure. All the
Xe-O bonds are double bonds (pπ–dπ bonds) in XeO4 molecule (Figure 14.7).
Figure 14.7. Geometry of XeO4
(F) XeOF4
In XeOF4, Xe atom is sp3d2 hybridized and geometry of the molecule should be octahedral.
But due to the presence of one lone pair of electrons, its geometry becomes square pyramidal.
One Xe–O double bond is pπ–dπ type (Figure 14.8).

Figure 14.8. Geometry of XeOF4
(G) XeO2F2
In XeO2F2, the central atom Xe is sp3d hybridised and due to the presence of one lone pair of
electrons at equatorial position, its geometry became butterfly shaped. The two Xe–O double
bonds are pπ–dπ type (Figure 14.9).
Figure 14.9. Geometry of XeO2F2
(H) [XeO6]4– Perxenate ion
In perxenate ion, the central atom (Xe) is sp3d2 hybridized. Hence, the geometry is
octahedral. The two Xe–O double bonds are pπ–dπ type (Figure 14.10).

Figure 14.10. Geometry of [XeO6]4–
14.5.2 Theories of bonding in xenon compounds:
There are four theories for defining bonding in xenon compounds.
(i) Ionisation potential (IP) based theory (Ionic and covalent bond between Xe and F)
Element IP (eV)
F 17.4
Xe 12.1
Hence, due to lower ionisation potential of F, it can attract an electron of Xe toward itself and
form Xe+F–. Thus first bond is ionic in XeF2.
Now, it become very difficult to attract second electron of Xe+ because second IP of Xe is
very high. Hence, the second bond will be covalent bond.
Hence, XeF2 can show the two resonating structures.
F-Xe+-F– ↔ F–-Xe+-F
(ii) Valence Band Theory (VBT)
According to VBT theory, there are two covalent bonds in XeF2. The structures of oxygen
containing xenon compounds can be correctly defined by VBT.

(iii) Molecular Orbital Theory (MOT)
There are some limitations of VB structure for XeF2. These are:
a) Due to the large size of 5d orbitals, overlapping is very weak.
b) According to valence bond theory, atomic orbitals of same energy can overlap. While in case
of 5p and 5d orbitals of Xe, the energy difference is 960 KJ mol–1. Hence, overlapping cannot
occur easily.
However, MOT can easily explain polyatomic bonding in XeF2 molecule. Three atomic
orbitals (one of Xe and two of F (2p) orbitals) linearly combine to form three molecular
orbitals (MOs).
One Bonding MO; One Antibonding MO; One Nonbonding MO
Bonding involves the 2Pz orbital of two F atoms and the 5Pz orbitals of Xe atom because of
bonding to occur, only orbitals with the same symmetry must overlap.
Out of the four electrons, the two electrons occupy bonding molecular orbitals (BMOs), and
this pair of electrons is responsible for binding all the three atoms (Xe and 2F). The rest of
the two electrons occupy the non-bonding MO (Figure 14.11). Because the non-bonding
orbitals have more F character as compound to Xe character, these electrons are situated
mainly on the F atoms. This type of bonding is 3-centre, 4-electron σ bonding (3c-4e).
The following linear arrangement of the atoms gives the best agreement with its observed
structure.

Figure 14.11. Molecular Orbital Diagram of XeF4
The structure of XeF4 can be understood in similar way to that of XeF2. The 5px orbital of Xe
forms a three-centre MO with 2pz orbitals of two F atoms just as in XeF2. The 4py orbital of
Xe forms another three-centre MO involving the other F atoms. Thus, the two perpendicular
three-centre MOs are formed, which give rise to square planar geometry to XeF4
molecule.The MO theory cannot explain the structure of XeF6 because, three-centre MO
system that are perpendicular to each other would give a regular octahedral geometry. But,
the shape of XeF6 is capped octahedron.
14.6 SUMMARY
Now we can summarize that there are six noble gas elements found in group 18 of the
periodic table.
i. These include helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe) and radon (Rn)
in order of increasing atomic weight.
ii. These elements are also called as inert gases, as they have full filled electronic configuration.
iii. All the noble gas elements are found in minute quantities in the atmosphere except Rn which
is radioactive in nature, All the gases are monatomic. The boiling point of He is the lowest
4.2K (-2690C).
iv. The 1st ionization energy decreases on descending the group and the first ionization energy of
xenon is comparable with that of bromine. Hence, xenon can relatively easily forms
compounds with oxygen and fluorine. The different compounds formed are XeF2, XeF4,
XeF6, XeO3, XeOF2, XeOF4 etc. Xenon forms compounds with +2, +4, +6 and +8 oxidation
states.

v. The Noble Gases have important industrial functions. Helium is used cryoscopy, airship and
as carrier gas in Gas Chromatography. Helium-II has very high thermal conductivity
(approximately 800 times of copper).
vi. Argon and neon are used in discharge tubes. Argon is used in metallurgical processes as well
as welding of stainless steel. Radon is a radioactive element hence, is useful in the treatment
of cancer.
vii. The compounds of xenon are also very useful in different areas. Xenon trioxide is about 22
times more powerful explosive as compared to trinitrotoluene.
viii. Clathrates of argon, krypton and xenon are useful in transporting and handling noble
gases.
Compounds of Xenon at a glance
Compound Total electron Lone Hybridisation Geometry of

pairs pairs on xenon complexes
XeF2 5 3 sp3d Linear
Xenon difluoride
XeF4 6 2 sp3d2 Square planar
Xenon tetrafluoride
XeF6 7 1 sp3d3 Capped octahedron or

distorted pentagonal
Xenon hexafluoride
bipyramidal
XeO3 4 1 sp3 Pyramidal
Xenon trioxide
XeO4 4 NIL sp3 Tetrahedral
Xenon tetraoxide
XeOF4 6 1 sp3d2 Square pyramidal
Xenon

oxytetrafluoride
XeO2F2 5 1 sp3d Butterfly
Xenon
dioxydifluoride
[XeO6]4– 6 NIL sp3d2 Octahedral
Perxenate ion
14.7.1. Fill in the blanks:
i. Noble gases belongs to the …………..group in the periodic table.

ii. The noble gases are also called as ……………… or ……………….
iii. Their shells and subshells are ……………….. filled and thus, they have very …………….
configurations which can be related to their chemical inactivity.
iv. The electronic configuration of Xe is [Kr]………………….
v. The atomic number of Ar is ………
vi. The noble gas …………… is radioactive in nature.
vii. Rn is produced by radioactive decay of …………. and ……………. Minerals.
viii. ………………. in 1894 discovered argon.
ix. Radon was discovered by ………… in 1902 as a radioactive disintegration product of
radium.
x. Krypton was derived from Greek word …………….
xi. Argon is produced by electron capture ( decay) of ………………...
xii. ……………. is used as cooling gas in nuclear reactor and also as a carrier gas in gas-liquid
chromatography.
xiii. …………….. are used in discharge tubes to give different colours.
xiv. …………….. is used in welding stainless steel, metallurgical processes of aluminum,
magnesium and titanium.
xv. ……………. is used in the cancer treatment due to its radioactive nature.

xvi. Their atomic radii are very large because the radii are ……………. or ………….. radii.
xvii. Melting and boiling points of noble gases are very ……. because inter atomic forces are very
weak in these gases.
xviii. The electron affinity of inert gases is ………….
xix. Enthalpy of vaporization is very ………… because the forces between the atoms are very
weak forces.
xx. The ionization energy of inert gases is very ……….. because they have very little tendency to
accept or donate electrons.
xxi. The order of adsorption of noble gases in wood charcoal is
……………………………………….
xxii. All noble gases have ………….. electrical conductivity at low pressure.
xxiii. The order of ease of liquefaction of noble gases is ………………………………...
xxiv. The solubility of noble gases is due to ……………………………………………..
xxv. Compounds formation by noble gases under excited state conditions are called
…………………………
xxvi. Helides can be formed by ………….
xxvii. In the presence of strong electron deficient groups, noble gas compounds can be prepared
through ………………..
xxviii. The inert gases such as Ar, Kr and Xe can form compounds with water through dipole
induced dipole interactions at low temperature and high pressure. These compounds are
known as ……………..
xxix. Compounds formation by noble gases through physical trapping are called as
……………………………………
xxx. Interaction in clathrate compounds is also called as ……………………… interaction.
xxxi. The smaller noble gases like ……… and …………… do not have tendency to form clathrate
compounds because they are too small to fit in the cavities and can easily escape from the
cavities.
xxxii. Clathrates store radioactive …………. and ………….. produced in nuclear reactors.
xxxiii. The first noble gas compound; ……………….. was prepared in 1962 by the reaction of PtF6
with Xe in equal ratio at room temperature.
xxxiv. The compounds XeF2, XeF4 and XeF6 sublime at room temperature, and can be stored in
………… containers for a long time.
xxxv. SO42– + XeF2 + Ce2III (SO4)3→ ……………………… + Xe + F2

xxxvi. XeF6 + 3H2→ 6HF + …………….

xxxvii. XeF2 + 2HCl → 2HF + Xe + …………..
xxxviii. …………… + Pt → Xe + PtF4
xxxix. (C6H5)2S + XeF2→ ……………….. + Xe
xl. On reaction with atmospheric moisture, XeF6 form highly explosive solid
……………………….
xli. XeF6 on partial hydrolysis form colourless liquid ……………………..
xlii. XeO3 + XeOF4 → ………………………..
xliii. Perxenate ion is …………………….
xliv. Xenate ion is ………………..
xlv. Perxenate ions; [XeO6]4– form volatile and explosive compound ……………………………
on reaction with concentrated H2SO4.
xlvi. XeF2 is ……………. in shape having …………. lone pairs of electrons.
xlvii. In XeF4, the central Xe atom is ……………….. hybridized.
xlviii. The central atom (Xe) in XeF6 is ……………… hybridized and the geometry is
………………..
xlix. In XeO3, the central atom (Xe) is …………… hybridized and due to the presence of one lone
pair of e–, its geometry became ……………. There are ……………….. pπ–dπ bonds in
XeO3 molecule.
l. In XeO4, the Xe atom is ………. hybridized and the geometry is ………………………
li. In XeOF4, Xe atom is ……………. hybridized.
lii. In XeO2F2, the central atom Xe is …………….. hybridized and due to the presence of one
lone pair of e– at equatorial position, its geometry became …………………. shaped.
liii. In perxenate ion, the central atom (Xe) is ……………. hybridized. Hence, the geometry is
…………………..
14.7.2 State True (T) or False (F):
i. Noble gases belong to the group 18 (VIIIa) in the periodic table.

ii. The noble gases are reactive, hence, they are also called as inert or noble gases.
iii. The electronic configuration of Rn is [Kr] 4f145d106s26p6.
iv. Neon, krypton and xenon were discovered in 1898 by fractional evaporation of argon under
varying reduced pressure conditions.

v. Hydrogen is also preferable over helium in airship due to inflammable nature of helium.
vi. Xenon is used in the cancer treatment due to its radioactive nature.
vii. Atomic radii of noble gas elements increase from top to bottom in a group.
viii. Electron affinity of noble gases is one.
ix. Due to the van der Waal forces (weak forces), noble gases can be easily liquefiable.
x. The solubility of noble gases increases from top to bottom with increase of the size of the
atom.
xi. He-II acts as super-fluid.
xii. HgHe2, HgHe10 and WHe2 are helides.
xiii. In Ar → BF3, BF3 is an electron deficient compound.
xiv. Formation of Kr.6H2O compound takes place through dipole induced dipole interaction.
xv. 1,2 Dihydroxy benzene form complex with argon through coordination.
xvi. Synthetic zeolites can also form cavities in which heavier noble gas elements can fit easily.
xvii. XeF4 is prepared by reaction of two part of Xe and one part of F2.
xviii. Xenon fluorides act as fluorinating agents.
xix. XeF4 violently reacts with water to form XeO4.
xx. Formula of perxenate ion is [XeO6]4-.
xxi. XeF2. MF5 and [XeF) +[MF6]- are the same.
xxii. In XeF2. 2MF5, XeF2 acts as fluoride donor.
xxiii. Hybridization on Xe in XeF2 is sp type
xxiv. XeF4 is tetrahedral in shape.
xxv. The shape of XeO3 is trigonal planar.
xxvi. There are three pπ-dπ bonds in XeO2F2.
14.7.3 Answer the following questions:
i. Why the noble gases also called as inert and rare gases?
ii. Write down the electronic configuration of each noble gas.
iii. Show the reaction through which Rn prepared.
iv. In brief, note the uses of noble gases.
v. Write a note on the general characteristics of noble gases.
vi. How diffusion vary among noble gases?
vii. Define solubility behaviour of noble gases.
viii. How helium shows abnormal behaviour among noble gases?
ix. What are the different types of compounds prepared by noble gases?

x. Write short notes on

a. Host guest interactions
b. Structure of XeF2 on the basis of VBT
c. Preparation of XeO3
d. Reaction of xenon fluorides with hydrogen
e. Use of xenon compounds in organic synthesis
f. Structure of xenate ion
xi. Explain the structure of XeF4, XeO2F2 and XeOF4 on the basis of VBT.
xii. Describe ionization potential base theory for defining bonding in xenon compounds.
xiii. Use MOT to explain the structure of XeF2.
14.8 ANSWERS
14.8.1 Fill in the blanks:
i. Group 18 (VIIIA)
ii. inert or rare gases
iii. completely, stable
iv. 4d105s25p6
v. 18
vi. Rn
vii. Radium and thorium minerals
viii. Rayleigh
ix. Dorn
x. Hidden
140
K
xi. 19
xii. He
xiii. Ne
xiv. Ar
xv. Rn
xvi. van der Waal or non bonded radii.
xvii. low
xviii. zero
xix. low

xx. high
xxi. He < Ne < Ar < Kr < Xe
xxii. high
xxiii. He < Ne < Ar < Kr < Xe
xxiv. dipole induced dipole interaction
xxv. helides
xxvi. argon
xxvii. coordination
xxviii. hydrates
xxix. clathrates
xxx. guest host interaction.
xxxi. He and Ne
xxxii. Kr and Xe
xxxiii. Xe[PtF6]
xxxiv. nickel
xxxv. 2CeIV (SO4)2
xxxvi. Xe
xxxvii. Cl2
xxxviii. XeF4
xxxix. (C6H5)2SF2
xl. XeO3
xli. XeOF4
xlii. 2XeO2F2
xliii. [XeO6]4-
xliv. [HXeO4]-
xlv. XeO4.
xlvi. linear, three
xlvii. sp3d2
xlviii. sp3d3
xlix. sp3, pyramidal, 3
l. sp3, tetrahedral
li. sp3d2
lii. sp3d, butterfly
liii. sp3d2, octahedral

14.8.2 State True (T) or False (F):
i. T
ii. F
iii. F
iv. T
v. F
vi. F
vii. T
viii. F
ix. T
x. T
xi. T
xii. T
xiii. T
xiv. T
xv. F
xvi. T
xvii. F
xviii. T
xix. F
xx. T
xxi. T
xxii. T
xxiii. F
xxiv. F
xxv. F
xxvi. F
xxvii.
References:
a. Br. R. Puri, L. R. Sharma and K. C Kalia. Principles of Inorganic Chemistry, Milestone

Publishers & Distributors, Meerut, 2013.
b. G. S. Sodhi, Textbook of Inorganic Chemistry, Viva Books Private Limited, New Delhi,

2013.
c. M. S. Yadav. Quick Review in Inorganic Chemistry, Anmol Publications Pvt. Ltd., New
Delhi, 2004.
d. P. Mishra, Advanced Inorganic Chemistry, Jagdamba Publishing Compan, New Delhi,
2011.
e. R. L. Madan, Chemistry for degree students, B.Sc. I year, S. Chand & Company Ltd., New
Delhi, 2011.
f. S. Prakash, G. D. Tuli, S. K. Basu, and R. D. Madan. Advanced Inorganic Chemistry, Vol.
I, S. Chand & Company Ltd., New Delhi, 2007.
g. W. U. Malik, G. D. Tuli, and R. D. Madan. Selected Topics in Inorganic Chemistry, S.
Chand Publication, Delhi, 2013.

CONTENTS
BLOCK- 1 STRUCTURE OF ATOM AND PERIODIC PROPERTIES
Unit 1 Atomic Structures 1-33

Unit 2 The Periodic Table 34-49
Unit 3 Periodic Properties 50-77
BLOCK-2 CHEMICAL BONDING

Unit 4 Chemical bonding I 78-117
Unit 5 Chemical bonding II 118-147
BLOCK-3 s-BLOCK ELEMENTS
Unit 6 Hydrogen’s 148- 177

Unit 7 Alkali metals 178-194
Unit 8 Alkaline earth metals 195- 210
BLOCK- 4 p- BLOCK ELEMENTS
Unit 9 Elements of group-13 211- 232

Unit 14 Chemistry of noble gases elements 352- 377

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Unit Written By Unit No.

Title : Inorganic Chemistry I

Published by : Uttarakhand Open University, Haldwani, Nainital- 263139

UTTARAKHAND OPEN UNIVERSITY Page 2

de Broglie deduced a fundamental relation between the wave length of moving

E = mc2 (for a photon) ……….. (1.2)

or E = mv2 (for a particle where v ≠ c) ………...

UTTARAKHAND OPEN UNIVERSITY Page 3

(momentum p = mv, mass x velocity)

UTTARAKHAND OPEN UNIVERSITY Page 4

From equation 1.5, we have

Putting the value of ߣ in equation 1.7, we get

Fig. 1.1 a: in phase Fig. 1.1 b: out of phase

1.4. HEISENBERG’S UNCERTAINTY PRINCIPLE

According to classical mechanics, a moving electron behaves as a particle whose

UTTARAKHAND OPEN UNIVERSITY Page 5

1.5. CONCEPT OF PROBABILITY AND SCHRODINGER’S

UTTARAKHAND OPEN UNIVERSITY Page 6

δ2ψ + δ2ψ + δ2ψ + 4π2 ψ = o ……….(1.11)

This equation is known as Schrodinger’s wave equation.

UTTARAKHAND OPEN UNIVERSITY Page 7

UTTARAKHAND OPEN UNIVERSITY Page 8

UTTARAKHAND OPEN UNIVERSITY Page 9

1.6. SHAPES OF ATOMIC ORBITALS AND ANGULAR PROBABILITY

UTTARAKHAND OPEN UNIVERSITY Page 10

1s-orbital 2s-orbital 3s-orbital

UTTARAKHAND OPEN UNIVERSITY Page 11

Px orbital Py orbital pz orbital

Fig.1.4 The orientation of p- orbitals along x, y and z- axis.

UTTARAKHAND OPEN UNIVERSITY Page 12

dxy orbital dyz (or dxz) orbital dzxorbital

dx2-y2 orbital dz2 orbital

Fig. 1.5 Angular dependence and shapes of d-orbitals.

The characteristics of the d-orbitals may be summarised as follows:

1.7. QUANTUM NUMBERS

UTTARAKHAND OPEN UNIVERSITY Page 14

(i) Principal or Radial quantum number

UTTARAKHAND OPEN UNIVERSITY Page 15

Azimuthal quantum number (l) 0 1 2 3 4 ……

The subshells belonging to various shells are given below:

N L notation for the subshell

The main points to be noted for azimuthal quantum number are;

UTTARAKHAND OPEN UNIVERSITY Page 16

Subshell Value of l Values of m Total m values

UTTARAKHAND OPEN UNIVERSITY Page 17

(iv) Spin quantum number (s)

1.8. PAULI’S EXCLUSION PRINCIPLE

Values of quantum numbers

For any two electrons in an atom same same same different

UTTARAKHAND OPEN UNIVERSITY Page 18

For 1s2 electrons

UTTARAKHAND OPEN UNIVERSITY Page 19

1.9. HUND’S RULE OF MAXIMUM MULTIPLICITY

(a) (b) (c)

UTTARAKHAND OPEN UNIVERSITY Page 20

1.10. THE AUFBAU PRINCIPLE

Aufbau is a German word which means building up or construction. The building up

There are certain rules which constitute the Aufbau principle: