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CHEMISTRY I CHAPTER 3

ATOMIC STRUCTURE
DALTONS ATOMIC THEORY:
Matter consists of small, indivisible, indestructible particles called atoms.

MODERN THEORY:
Atoms are complex organizations of matter and energy. Many particles have been discovered within the atom.
These subatomic particles include : i) electron ii) proton iii) neutron iv) positron v) neutrino vi) mesons vii)
hyprons.

EXPERIMENTS WHICH LEAD TO THE INDICATION OF EXISTANCE OF

FUNDAMENTAL SUBATOMIC PARTICLES ARE AS BELOW:
1.
2.
3.
4.
5.

Faradays experiment indicates the existence of electrons.

Crookes tube experiments show the presence of electrons and protons.
Radioactivity further confirms the presence of electrons and protons.
Chadwicks experiment shows the presence of neutrons.
Spectroscopic experiments reveal the electronic structure of atoms.

FARADYS EXPERIMENT:
(Passage of electricity through solutions)
Faraday observed that when two metal plates called electrodes are placed in an electrolytic solution and electric
current is passed, the solution breaks up into charged particles called ions.
These are positive and negative ions depending upon the type of charge they carry. These ions travel towards the
oppositely charged electrodes where they give up their charge and are liberated as neutral particles.

RESULT:
This experiment shows that there is some elementary unit of electric charge associated with these ions. The ions
were observed to carry some integral multiple of this charge. The basic unit of electric charge was later names by
Stoney as ELECTRON.

CROOKES TUBE EXPERIMENT OR DISCHARGE TUBE EXPERIMENT:

(Passage of electricity through gases at low pressure)
INTRODUCTION:
We know that air or gases normally do not conduct electricity, unless a very high voltage is applied. The work on
the passage of electricity through gases was initiated by a German instrument maker. This work was later
extended by W.Crookes.

CONSTRUCTION OF THE TUBE:

Discharge tube consists of:
i.
ii.
iii.
iv.

A glass tube filled with a gas.

Two sealed metallic electrodes are connected on both ends.
A high voltage battery is connected to two electrodes.
A vacuum pump is also connected to reduce pressure.

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WORKING:
At ordinary pressure, no discharge occurs, unless a very high voltage is applied. If the gas present inside is
evacuated, the number of moles of gas present inside is reduced and fewer molecules inside make it convenient
for the spark to pass.

OBSERVATIONS:
When a potential difference of a few thousand volts is applied, then following observations are obtained:

At 1 cm of Hg, spark passes like a flash of lightening.

At few mm of Hg, both electrodes glow while rest of the space remains dark.
At 1 mm of Hg, the tube is filled with a glow extending from positive electrode and is called positive column.
The colour of this glow depends upon the gas filled in the tube.
At 0.001 mm of Hg, the glow disappears and the walls of the glass tube begin to glow with a brilliant green
light.

RESULT:
It is obvious that some sort of radiation is passing between the two electrodes. This radiation consisted of the
vast swarm of particles emitted by the cathode and were called cathode rays.

PROPERTIES OF CATHODE RAYS:

1. These rays travel in straight lines as they produce sharp shadows of the objects placed in their path.
2. These rays emerge from the cathode and can be focused by using a concave cathode.
3. These rays penetrate small thicknesses of matter, like aluminium or gold foil without producing any
perforations in the foils.
4. These rays can easily be deflected by a magnetic field or an electric field.
5. They carry a negative charge.
6. These rays consist of particles now called electrons, carrying a fixed unit charge and a fixed mass.
7. These rays were seen neither to depend upon the material of electrode nor upon the gas inside the tube.
8. These rays can exert mechanical pressure showing they possess kinetic energy.
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9. Since their charge to mass (e/m) ratio is constant, hence electrons could be produced from any type of matter
and hence these were found to be constituent of all matter.

POSITIVE RAYS
(PROTONS):

During the study of passage of

electricity through gases at low
pressure, it was observed by Goldstein
that if thin holes are made in the
cathode, then radiations also appear
behind the cathode. These rays were
found to be positively charged and
hence are called positive rays.

CHARACTERISTICS OF
POSITIVE RAYS:

1. They consist of atoms and ions of

the gases present inside the tube.
2. They carry positive charges which
are either equal to or some integral multiple of the electronic charge e.
3. The value of their e/m depends upon the gas present in the Crookes tube.
4. They travel in the direction opposite to that of cathode rays.
5. They does not emerge from anode but arise due to the ionization of air.
6. The lightest positive particle was obtained from hydrogen which was 1836 times heavier than electron, and
was named as PROTON.

RADIOACTIVITY:

The phenomenon in which certain elements emit invisible radiation is called radioactivity and the elements which
give out these radiations are called radioactive elements.
Most of the elements after lead (Pb, Z=82) in the periodic table are naturally occurring radioactive substances.

EXPLANATION:

Pitchblende was found to produce a clear image of itself even when the photographic plate was wrapped in a
black paper and there was no light.
Henry Becqueral examined it under different conditions. Pitchblende could be heated or cooled or it might be
compressed or drawn into thin sheets. But all these changes could not affect the rate of emission of radiation. It
was also found that these radiations could only be stopped when the mineral Pitchblende was wrapped in lead
sheet.
Similarly, Pierrie Curie and Marie Curie isolated a new element Radium from a mineral which was also found to
be very radioactive.
An element after giving out radiations breaks down to a more stable element.

FOR EXAMPLE:
92U238 on
92U238

emission of -particles would be converted to 90Th234.

========>
90Th234 +
2He4
-particles
The emission of radiation would continue until the formation of lead as stable end product.

SEPARATION OF , AND RAYS:

Soon after the discovery of Radium, it was suspected that the rays given out by Radium and other radioactive
substances are not of the same kind.
In 1902, Rutherford performed an experiment to separate different kinds from each other.

METHOD:
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The radiation emitted by radium was subjected to a magnetic field perpendicular to the direction of emission.

OBSERVATIONS:

The radiations emitted were found to split up into three different streams of rays, which were labelled as , and
rays.
The rays which bent towards negative plate were said to carry positive charge and were named as -rays.
The rays which bent towards positive plate were said to carry negative charge and were named as -rays.
The rays which passed the field without suffering any deflection were said to carry no charge and were
as rays.

PROPERTIES OF -RAYS:

1. -rays are fast moving helium nuclei.

2. They ionize air i.e. they knock out electrons from other atoms.
3. They produce bright flashes on fluorescent screen.
4. They have a very small range (1 - 2 cm ) in air before they are completely stopped.
5. They carry positive charge.
6. Their penetrating power is very low.
7. Their velocity is about 1/10th the velocity of light.
A
X
--------------> Z-2YA-4 +
Z
2He4

PROPERTIES OF -RAYS:
1.
2.
3.
4.

These are fast moving electrons.

They carry negative charge.
They have a range of 1-2 m in air.
They can pass through small thickness of matter and their penetrating power is greater than that of rays.
5. These can ionize gases to a lesser extent.
6. Their velocity is almost equal to that of light.

PROPERTIES OF RAYS:
1.
2.
3.
4.
5.
6.
7.

These are short wave electromagnetic radiations like X-rays.

These are extremely penetrating rays.
These can pass through 15 20 cm of lead.
On passing through matter, these rays eject high speed electrons from the matter.
They are very weak ionizer of gases.
They travel with a velocity equal to that of light.
They carry no charge or mass.

CHADWICKS EXPERIMENT- Discovery of Neutron:

(Artificial Radioactivity)

Chadwick investigated the effect of radiation on other elements both in the solid and in the gaseous state.

EXPERIMENT:

During his studies with beryllium, Chadwick found that very penetrating radiations were given out when
beryllium was bombarded with -particles.

SUGGESTION:

Chadwick put forward the suggestion that these penetrating radiations were due to the material particles with
mass comparable with that of an atom of hydrogen but carrying no charge. These particles were called neutrons.
It is indicated by the equation:
======>
4Be9 +
2He4
6C12
0n1
Neutron is a neutral particle having a mass of 1.009 a.m.u which is almost equal to that of Hydrogen atom.

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SUMMARY OF SUBATOMIC PARTICLES:

ELECTRONS:
1.
2.
3.
4.

They carry a negative charge of 4.803 x 10-10 esu (1.602 x 10-19 Coulomb).
Mass of an electron Me is 9.115 x 10-31 KG (0.00055 a.m.u).
Their e/m ratio is 1.758 x 108.
They are denoted by e.

PROTONS:

1. They carry a positive charge of 4.803 x 10-10 esu (1.602 x 10-19 Coulomb).
2. Mass of a proton Mp is 1.67 x 10-27 KG (1.008 a.m.u).
3. They are denoted by P or H+.

NEUTRONS:

1. They carry no charge.

2. Mass of a proton Mn is 1.675 x 10-27 KG (1.009 a.m.u).
3. They are denoted by 0n1.

RUTHERFORDS ATOMIC MODEL:

(Evidence for nucleus and arrangement of particles)
INTRODUCTION:

Though the nature of proton was well-established by 1900, the role of this positive particle in the structure of
atom was uncertain. A clue to the arrangement of positive and negative particles within the atoms was finally
provided by the experiments of Rutherford.

RUTHERFORDS EXPERIMENT:

Rutherford took a thin gold foil and bombarded it with -particles obtained from radioactive polonium. These
particles are examined on ZnS screen after bombardment.

OBSERVATIONS:

Most of the -particles penetrated the foil and emerged undeflected on the other side.
A number of particles suffered deflections of varying degrees.
One out of 8000 particles suffered a deflection equal to or greater than 90.

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ASSUMPTIONS (CONCLUSION):

To explain the scattering of particles, Rutherford made some basic assumptions:

1. The greater part of atomic volume comprises of empty space, as most of the -particles passed through
the foil without any deflection.
2. The mass of the atom is concentrated in its nucleus.
3. The deflection of very small number of -particles shows that the dimensions of nucleus are negligible in
comparison with the radius of atom.
4. The nucleus carries a positive charge, +Ze.
5. There must be Z number of negatively charged electrons outside the nucleus and at fairly large distance,
arranged in some manner.
6. Electrons are moving around the nucleus continuously loosing energy.

WEAKNESSES OF RUTHERFORDS ATOMIC MODEL:

The weaknesses of Rutherfords atomic model are as follows:

1. According to classical theory, any charged particle must emit energy if accelerated around an oppositely
charged particle. If the revolving electron emits energy, its energy contents would decrease and the radius
of the orbit would become smaller. This would go on till the electron falls into the nucleus, charting a
spiral path. Practically it does not occur.
2. An electron moving through orbitals of ever decreasing radii would give rise to radiations of all possible
frequencies. In other words, it would give rise to a continuous spectrum. But practically atom gives
discontinuous spectrum. Thus a/c to classical principles of physics, the Rutherford model of the atom
could not exist.

PLANCKS QUANTUM THEORY:

(Quantization of energy)
This theory was proposed in 1900 by the German physicist Max Planck to account for the observed radiations
from heated bodies.

THEORY:

A/c to this theory:

1. Energy is emitted from a body due to the vibration of atoms or subatomic particles of an atom.
2. Energy could not be emitted or absorbed by the atoms in an arbitrary quantity, but only in specified
amounts called quanta. In other words, an atom can not change its energy continuously but only by a
series of steps.
3. The amount of energy depends upon the frequency () of radiation absorbed or emitted.
4. It is given by:
E=h
5. Where h is the Plancks constant and its value is given as:
h=6.625 x 10-34 J.s
=6.625 x 10-27 erg.sec
6. The amount of energy gained or lost is quantized i.e energy change occurs in small packets or multiples
of these packets, h, 2 h, 3 h & so on.
7. Quanta or Photon are the packets of energy which are defined as the smallest unit of radiation which can
exist independently.

SPECTRA:

A spectrum is an array of waves or particles spread out a/c to the increasing or decreasing of the same property.

e.g:

EMISSION SPECTRUM:

When an element absorbs sufficient energy, for example, from a flame, it emits radiant energy. When this
radiation is passed through a prism in a spectroscope, it is separated into component wavelengths to form an
image called an EMISSION SPECTRUM.

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Emission spectra are of two type.

1. Continuous spectrum
2. Line spectrum

CONTINUOUS
SPECTRUM:

When white light from

sun
or
any
incandescent lamp is
allowed
to
pass
through a prism, the
light breaks up into its
constituent colours.
This phenomenon is
known as dispersion.
The band of colours
into which the incident light breaks up is called spectrum. The colours of the spectrum are so mixed up that there
is no line of demarcation b/w different colours. Such a spectrum is called continuous spectrum.

LINE SPECTRUM:

When light from an excited gaseous source is passed through a prism, some discrete sharp lines on a completely
dark background are obtained. Such spectrum is known as line spectrum or discontinuous spectrum. Each line in
a line spectrum corresponds to a definite wavelength.
Each element produces a characteristic set of lines so the line spectra serves as the finger prints for the
identification of elements.

X-RAYS:

When fast moving electrons from the cathode of the Crookes tube experiment strikes the anode, extremely
penetrating rays are emerged from it. These were labelled as X-rays as these were previously unknown. These
are also called Roentgen rays (after the discoverer).
These rays had the ability to penetrate paper, rubber, glass, metal and human flesh. These were soon identified
as short wave, high energy electromagnetic radiation.

X-RAYS AND ATOMIC NUMBER:

Henry Moseley studied different wavelengths of X-rays

produced from anodes of different metals. He noticed
that the wavelengths of X-rays emitted decreased
regularly with increasing atomic mass. He also found that
the no. of positive charges on the nucleus increases from
atom to atom by single electronic unit. He called the no.
of positive charges the atomic no. Thus atomic no. of an
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element is the number of protons present in its nucleus, and is denoted by Z ". It was also found that it is the
atomic no. not the atomic mass which distinguishes one element from other.

Explanation of Sub-atomic Structure by X-rays:

The X-rays explain the subatomic structure as follows:

a) The atom consists of a small, dense, positively charged nucleus, containing protons.
b) The nucleus is surrounded by a number of electrons equal to that of protons in the nucleus.
c) The atomic no. Z of an atom is equal to the number of protons in the nucleus & therefore, also equal to the
number of electrons surrounding the nucleus.
d) The masses of fundamental particles on C12 scale are as below:
Mass of proton =1.008 a.m.u
Mass of neutron=1.009 a.m.u
Mass of electron=0.00055 a.m.u

BOHR'S THEORY:

To explain the line spectra of elements a Danish physicist Neil Bohr proposed a theory for the structure of an
atom in 1913.
1. There exists certain orbits in which electron may not give out radiation. Such orbits were called stationary
states.
2. Electrons revolving in stationary states would be completely stable.
3. Stationary states were considered to be circular orbits around the nucleus.
4. An electron revolving in a certain stationary state has a certain energy and it neither absorbs nor radiates
energy as far as it keeps revolving in that orbit.
5. If an electron absorbs energy equal to the energy difference between the two orbits, it gets excited and
jumps to higher energy state.
6. If it radiates energy equal to the energy difference between two orbits, it fails back to lower energy orbit.
7. All the transitions that electron make between the two orbits yield a single unique spectral line.
8. Stationary states were only those orbits in which product of momentum (mv) and circumference (2r)
was equal to Planck's constant "h" or some integral multiple of it.
i.e for nth orbit
mv x 2r=nh
Where n=1, for 1st orbit
n=2 , for 2nd orbit and so on
It can also be written as:
mvr=nh/2
Here mvr becomes angular momentum. Thus, above statement can also be written as:
"Only those orbits were possible in which the angular momentum of the electrons would be an integral multiple
of h/2."
These stationary states correspond to energy levels in the atom.

BOHR'S THEORY ANDMYDROGEN ATOM

The truth of the basic assumptions of Bohr was established when applied to hydrogen atom.

Radius of Hydrogen Atom:

The hydrogen atom consists of a single electron revolving around a single

positively charged nucleus. Let 'e' be the charge on an electron and 'm' be the
mass of electron, 'Ze' be the positive charge on the nucleus (Z=atomic number),
'r' be the radius of the orbit in which electron is moving with a velocity 'v'.
If we equate centrifugal force (mv2/r) to the centripetal force which is due to
the attraction between the electrons and the nucleus i.e. Coulombs electrostatic
force which is given by:
F=K q1 q2/r2 = KZe2/r2
with k=1 if charge is taken in esu (electrostatic
unit). Thus,

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(1)

According to Bohrs theory, only those stationary orbits are possible in which the product of momentum of
electron and circumference of orbit is equal to an integral multiple of Plancks constant (h).
i.e. mv x 2r = nh
or

Substituting eq (2) in eq(1)

(2)

(3)

This equation gives the radii of all the possible stationary states. All the quantities on the right hand side of the
equation are known and if we substitute Z=1 for hydrogen atom. n=1 for the first orbit.
We can replace the constants h, , m, Z and e by a single constant known as Bohrs radius (a) which is equal to
the radius of first orbit of hydrogen.
Value of these constants are given below:
h = 6.625 x 1027 erg sec. (or 6.625 x 1034J.S. which is the S.I. Unit).
m = 9.11 x 1028g(or 9.11 X 1031Kg which is the S.I. unit)
e = 4.802 x 1010 esu (or. 1.602 X 1019C which is the S.l. unit)

Hence equation (3) becomes:

r = n2a
for first orbit n=1
r1= (1)2 0.529x108 cm (108 cm = 1 )
r1 = 0.529
r1 = 0.529 is the radius of the first stationary state for the hydrogen atom.
Similarly, for second orbit, put n=2
r2 = (2)2 x 0.529

Conclusion:

Thus, it is clear that the radius is directly proportional to the square of n.

DETERMINATION OF ENERGY:

For any orbit, the total energy is given by the sum of potential energy and kinetic energy.
E=P.E + K.E
(4)
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Potential Energy:

The potential energy is due to the position of isolated electron from the nucleus. If r be the distance between the
electron and nucleus, the potential energy is given by:
P.E = negative work done = F.d
P.E = Ze2/r2
x
r
P.E=Ze2/r
(5)

Kinetic Energy:

The kinetic energy of electron of mass m moving with a velocity v is given by:
K.E = mv2
If we equate centripetal and centrifugal forces acting on an electron, we get:

Dividing both sides by 2

(6)
Now putting equation (5) and (6) in (4)

Putting value of r from equation (3)

We get,

This is the expression of energy of an electron in any orbit.

Expression for frequency and wave number:

Energy of an electron in a lower orbit (n1) and higher orbit (n2) can be expressed as follows:

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When an atom or gas is electrically heated, its electrons jump to higher orbit. In this state, it is said be excited.
The excited state is unstable. Electron has to come back to Original ground level by radiating energy equal to the
difference of energies of the excited and ground State. Then,
Energy emitted = E = E2 E1 = hu

The above expression gives frequency of the electron.

since c = u or u = c/

Z=1 for Hydrogen

Above expression gives wave number.

The Hydrogen Atom Spectrum:

It is well known that when a gas is heated in a discharge tube at low pressure, it emits radiation. This radiation
forms emission spectrum.

Lyman Series:

Lyman discovered a series of lines in ultraviolet region which is obtained when electron jumps from any higher
orbit to 1st orbit. Wave number of each line can be found by the following formula:

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Balmer Series:

Balmer in 1885, studied spectrum of hydrogen gas. He found

a series of lines in visible region (i.e. having between 4000
to 8000 A). It is obtained when electron jumps from any
higher orbit to 2nd orbit. They were called Balmer series. He
proposed an empirical formula to find wave number of each
line.

Paschen Series:
Paschen discovered a series of lines in infrared region which
is obtained when electron jumps from any higher orbit to
3rd orbit. Wave number of each line can be found by the
following formula:

Brackett Series:
Brackett discovered a series of lines in far infrared region which is obtained when electron jumps from any higher
orbit to 4th orbit. Wave number of each line can be found by the following formula:

Pfund Series:

Pfund discovered a series of lines in far infrared region which is obtained when electron jumps from any higher
orbit to 5th orbit. Wave number of each line can be found by the following formula:

General Expression:
General expression can give wave number of each line of each series. It is:

BOHR'S THEORY AND HYDROGEN SPECTRUM:

Bohr's theory success lies in the fact that it provided logical proof and reason for the formation of hydrogen
spectrum.
According to Bohr's theory,

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At ordinary temperature, the electron in hydrogen atom resides in lowest energy level i.e. first orbit or ground
state. When electrically it is heated at low pressure in a discharge tube, the electrons of different hydrogen atoms
absorb different amount of energy and jump to an appropriate high energy level. They are now said to be in
excited state.
All the atoms in excited state, due to their high energy, are unstable. So now the electrons jump back to the original
first orbit directly or to some other level of lower energy. In doing so they emit energy equal to the difference of
two level. These energetic waves are separated by a prism according to their wavelength and thus hydrogen
spectrum is obtained.

HEISENBERG'S UNCERTAINTY PRINCIPLE:

An electron in Behr's theory was considered to be a particle whose momentum and the path along which it moved
was known precisely. Electron also behaves as a wave, according to de Broglie concept. Thus dual nature of an
electron makes the concept of the circular orbits unclear and meaningless.
Heisenberg in 1925 enunciated a principle known after him and called Heisenberg's Uncertainty principle.

According to this principle:

It is not possible to determine simultaneously the position and momentum of a moving particle.
If one is known exactly, it would be impossible to know the other exactly. It would therefore be impossible to
chase an electron around its path or to locate it.

Mathematically:

If Px is the uncertainty in the determination of the momentum of a particle and x be the uncertainty in the
simultaneous determination of its position, then the product of these two uncertainties is of the order of h, the
Planck's constant.

Thus if one of the two i.e. p, or x was known exactly, then the uncertainty in its determination could be zero and
that of the other would become infinite. As a matter of fact, it is applicable to a very small particle when the
ordinary laws of mechanics are not obeyed.

Conclusion:
1.
2.
3.
4.

It is impossible to think of an electron to be at rest.

Energy of an electron cannot be zero.
Location of an electron cannot be determined.
The Bohr's orbits thus lose meaning as a circular path. The Heisenberg's principle, therefore explains the
basic incompleteness of the Bohr's model of atom.

Defects of Bohrs Atomic Model:

Bohrs model of atom explains satisfactorily the stability of atom and the spectra of hydrogen like atoms or ions
e.g Li+, yet it fails to account for the following:
1. It cannot explain the spectral series of larger atoms.
2. It cannot account for the fine structures in the line spectrum of hydrogen atom, according to which a single
line is actually a collection of several lines.
3. When spectrum of hydrogen atom is placed in a magnetic field, some new lines are created. This
phenomenon is known as Zeeman effect. Bohr has no explanation for this effect.
4. Bohr assumed that an electron in an atom is located at a definite distance from the nucleus, and it is
revolving around it with definite velocity. This is against the Heisenbergs uncertainty principle.

ENERGY LEVELS:

All the possible paths on which electron revolve around the nucleus are called orbits, shells or energy levels.
Bohr suggested the existence of certain circular orbits at definite distance from the nucleus. These orbits are with
definite energy of the electron increasing outwards from the nucleus. The difference of energies between the
shells goes on decreasing as they become away from the nucleus.
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The Bohr's circular orbits are usually referred to as "Energy levels" or "Shells".
These are designated as K, L, M, N etc with their principle quantum numbers (n) = 1, 2, 3, 4 respectively. The
maximum possible number of electrons a shell 'n' can accommodate is given by 2n2 i.e. 2, 8, 18, and 32 respectively
in the first, second, third and fourth energy level.
In the outermost shell of any atom, the maximum number of electrons is 8 except hydrogen and helium whose
outermost shell is filled by 2 electrons.

SUB ENERGY LEVELS:

Electrons in a certain energy level can have slightly different energies due to different angular momentum. These
regions within a shell having different angular momentums are called sub energy levels or energy sublevels.
The spectral lines, which correspond to the transition of an electron from one energy level to another, have for
the most part, a fine Structure, i.e. each line actually consists of several separate, close lying lines as doublets,
triplets and so on indicating that some of the electrons of the given energy level have different energies. That is
to say, that the electrons belonging to same energy level may differ in their energy. The energy levels are
accordingly divided into sub energy levels denoted by the letters s, p, d, f, for the first four series of lines in the
spectra of the alkali metals, based on the terms Sharp, Principal, Diffuse and Fundamental. The number of sub
level in a given energy level or shell is equal to its value of 'n.
For example, for 1st shell (n=1), the no. of sublevels=1 i.e. s sublevel.
for 2nd shell (n=2), the no. of sublevels=2 i.e. s and p sublevels.
for 3rd shell (n=3), the no. of sublevels=3 i.e. s, p and d sublevels.
for 4th shell (n=4), the no. of sublevels=4 i.e. s, p, d and f sublevels.
The maximum no. of electrons in these sub-shells are 2,6,10,14 respectively.

ORBITAL:

It is the region of three dimensional space around the nucleus in an orbit, where the probability of finding an
electron is maximum.

ORBIT

ORBITAL

It is well-defined circular path followed by

electron around nucleus.
It represents two dimensional motion of
electron around nucleus.
The maximum no. of electrons in an orbit is 2n2.
Orbit is circular in shape.

It is a region of space around the nucleus where

the probability of finding an electron is maximum.
It represents three dimensional motion of
electron around nucleus.
The maximum no. of electrons in an orbital is 2.
Orbitals have different shapes.

SHAPES OF ORBITALS:
S ORBITALS:

All 's' orbitals are spherical in shape with the nucleus at the centre. Therefore in an 's' orbital, the probability of
finding the electron is uniformly distributed around the nucleus. It has only one possible orientation in space in
the magnetic field because it spreads over all the three axes uniformly. It has no nodal plane.

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P ORBITALS:

The p orbitals are dumb-bell-shaped and they are oriented in space along the three mutually perpendicular axes
(x. y, z), and are called px, py and pz, orbitals.
All the three p orbitals are perpendicular to each other. These are
degenerate orbitals, which are of equal energy.
Each p orbital has two lobes. One of which is labelled (+) and the
other (-). Each lobe is like a pear. It is worthwhile to note that it
would be wrong to imagine an electron moving along from one lobe
to another. The point when the two lobes meet each other is usually
referred to as the nodal plane along which the probability of finding
the electron is zero.
Here we are not concerned with the shapes of d and f orbitals which
are rather more complicated.

DEGENERATE ORBITALS:

The orbitals which have same energies are called degenerate

orbitals e.g all three lobes of a p sub-shell (Px, Py, Pz) are degenerate orbitals. The orbitals given by a particular
value of if 'n' is same, have the same energy and such orbitals are called degenerate. Like l=1 gives three p orbitals
specified as px, py, pz and the p orbitals are said to be three fold degenerate. These orbitals are filled according
to Hund's Rule.

NODAL PLANE:

The point when the two lobes meet each other is usually referred to as the nodal plane along which the probability
of finding the electron is zero.
There are l nodal planes for a given atomic orbital.

QUANTUM NUMBER:

A total of four quantum numbers were developed to better understand the movement and pathway of electrons
in its designated orbital within an atom
1. Principle quantum number
2. Azimuthal quantum number
3. Magnetic quantum number
4. Spin quantum number

Principle Quantum Number:

It is denoted by the symbol 'n'

Significance:

1. The principal quantum number specifies the size of orbital. As the value of 'n' increases, the size and also
the energy of orbital increases.
2. This number gives the number of subshells in a given shell i.e. n=1 means shell has only one sub-shell, n=2
means two sub-shells and so on.
3. This is also used to determine the number of orbitals in a shell which is equal to n2 i.e. 1st shell (n=1) has
(1)2 = 1 orbital, 2nd (n=2) shell contains (2)2 = 4 orbitals, 3rd shell (n=3) contains (3)2 = 9 orbitals and
so on.
4. This number also represent the distance between the nucleus and electron. Larger vale of n means larger
distance and vise versa.
5. This number also helps in determining the maximum number of electrons in a shell which is given by 2n2.
For Example, for k shell (n=1), number of electrons = 2(1)2 = 2

for l shell (n=2), number of electrons = 2(2)2 = 8

AZIMUTHAL OR SUBSIDIARY QUANTUM NUMBER:

It is denoted by l.

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Significance:

1. It indicates the shape of the orbital in which the electron is present.

2. It also indicates the angular momentum of electron so it is also known as angular momentum quantum
number.
3. This can have values from l = 0 to l = n-1.
Thus, if n=1, l = 0
n=2, l = 1
n=3, l =2
n=4, l =3
4. When l =0, the orbital is s-orbital
l =1, the orbital is p-orbital
l =2, the orbital is d-orbital
l =3, the orbital is f-orbital
5. The number of orbitals in each sub-shell is determined by using l and is given by: 2 l +1
Thus, s, p, d, f orbitals have 1, 3, 5, 7 orbitals respectively.
6. The maximum number of electrons in a sub-shell is also determined by using this quantum number which
is given by 2(2 l +1). Thus, s, p, d, f sub-levels can accommodate 2, 6, 10 and 14 electrons respectively.

MAGNETIC QUANTUM NUMBER:

It is denoted by m.

Significance:

1. It gives different orientations of an orbital in space in applied magnetic field.

2. Its value depends upon the value of l and m= l to + l through zero.
For example, if l = 0, m = 0
If l = 1, m = -1,0,+1
If l = 2, m = -2,-1,0,+1,+2 and so on
3. The number of terms in the value of m is given by 2 l +1. Thus, if l = 0, m contains only one number
[2(0)+1], if l = 1, m contains 3 number [2(1)+1] and so on.

SPIN QUANTUM NUMBER:

It is denoted by S

Significance:

It specifies the spin of electron which may be either clockwise or anticlockwise. Thus, it can have only one of the
two possible values +1/2 or -1/2.

Conclusion:

Thus, these four quantum numbers give us position of any electron in energy level, sub-shell,in the orbital, and
also its direction of spin.

ELECTRONIC CONFIGURATION:

The distribution of electrons in the available orbitals is governed by certain rules or principles such as
(i) Pauli's exclusion principle
(ii) Aufbau principle
(iii) (n + l) Rule
(iv) Hund's Rule

PAULI'S EXCLUSION PRINCIPLE:

It was enunciated by Wolfgang Pauli in 1925 and states that:

"In an atom no two electrons can have the same set of all four quantum numbers."
In an atom, therefore, two electrons may have a maximum of three same quantum numbers of same values but
the fourth would different. Thus in any orbital, when the values of n, l and m are same, two electrons can occupy
the same orbital only if their spins are opposite. e.g if an electron occupies 1s orbital, n=1, l =0, m=0 and s may be

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+1/2 or -1/2. If it has +ve value i.e. then any other electron occupying the same 1s orbital would have ve value
i.e. s=-1/2

Conclusion:

1. Maximum number of electrons in an orbital was found to be 2.

2. The electrons which occupy the same orbitals must have opposite spin
The first energy level (K) contains only one orbital; therefore, it does not contain more than two electrons, it is
not strictly speaking divided into sub levels.
The second energy level (L) consists of four orbitals and maximum of eight electrons. One of the four orbitals is
an s orbital and the other three are p orbitals. Thus the second energy level consists of two sub levels, the 2s sub
level and 2p sub level, the 2 s sublevel consists of a single s orbital and the 2P sub level consists of three orbitals.
The third energy level (M), with a maximum of 18 electrons, contains three sub levels consisting of nine orbitals,
one s orbital, three p orbitals, five d orbitals.
The fourth energy level (N) consisting of four sub levels, contains 16 orbitals: one s, three p, five d and seven f
orbitals. The maximum number of electrons in the fourth level is 32.

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Aufbau Principle:

It states that:
For any given atom, the electrons are filled to the orbitals of lowest energy in
sequence, two electrons to each orbital.
In other words, the electrons are fed in order of increasing orbital energy
starting with the
1s orbital. Pauli called this principle the Aufbau principle( German Aufbau
means building up"). Hypothetically we can build up the electronic
configurations of the atoms by placing the electrons in the lowest available
orbitals until the number of electrons added is equal to the atomic number 'Z'.
The
sequence
of
increasing
orbital
energy
is:
1s,2s,2p,3s,3p,4s,3d,4p,5s,4d,5p,6s,4f,5d, . . .

(n+l) RULE:

"In building up the electronic configuration of the elements, the orbital with the
lowest value of (n + l) fillsfirst; when two orbitals have the same value of (n +
l) the orbital with the lower value of 'n' fills first".
Here 'n' and 'l' stand for the principal and azimuthal quantum numbers
respectively. This useful rule reminds us that the energy of an orbital of multielectron atom depends upon the value of both the quantum numbers, n and l, but mainly on the value of n. For
example, which fills first 3d or 4s Orbital? For the 3d Orbital (n = 3; l = 2); the value of (n + l) = 5; for the 4s orbital
(n =4; l = 0), the value of (n + l) = 4. Hence 4s which has the lower value of (n + l) and thus lower energy fills first.
Likewise. 4 p orbital fills before 5s although the (n +l) value for both is same, but 4porbital has the lower value of
the principal quantum number 'n

HUNDS RULE OF MAXIMUM MULTIPLICITY:

If the orbitals of equal energy are provided to the electrons, they will go to different orbitals while keeping their
spin parallel.
In other words, we can say that, the electrons are distributed among the orbitals of a sub-shell in such a way as
to give maximum number of unpaired electrons which have same direction of spin.

ATOMIC RADIUS:

The radius of an atom is taken as half the bond length between two homonuclear atoms in a diatomic molecule
like; HH; O=O; Cl Cl.
The values of the distances between the two nuclei arc determined from the spectroscopic data and X-ray
diffraction measurements. For example, the distance between two atoms of carbon in diamond is 1.54, giving
the radius of carbon atoms as 0.77 (1 = 10-8 cm). Similarly the internuclear distance between two sulphur

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atoms is 2.06, thereby giving the radius of sulphur atom as 1.03. Some atomic and ionic sizes are shown in the
table below.
It is difficult to determine the size of an atom because it is affected by a number of facts.
1. The electron could be anywhere around the nucleus and the electronic probability for an atom never
becomes exactly zero, even at greater distance from the nucleus. Thus an atom has no fixed boundary.
2. An atom may have different size in different combinations as the present of other atoms also affect the
outer charge distribution.
3. An atom cannot be isolated to measure its radius.
4. The exact position of outermost electron is uncertain (Heisenbergs uncertainty principle)
Thus, the atomic radius measured by electron diffraction method has only the probable value.

RADIUS
OF
MOLECULES:

HETERO-NUCLEAR

DIATOMIC

In case of hetero-nuclear diatomic molecules i.e. where two different kinds of atoms A, B are joined together, the
bond length is (rA + rB) and if any one of the radii is known the other can be found.

Application:

The knowledge of the atomic radii is useful in predicting chemical behaviour, e.g. phosphorus combines with
chlorine to give PCI5, but does not combine with iodine to give PI5. Tie reason is that the iodine atom is much
bigger than the Cl atom and 5 of the iodine atoms cannot be accommodated around a single phosphorus atom.

IONIC RADII:

Ions are formed by the gain or loss of electrons from outermost shell. Positive ions (formed by loss of electrons)
are called cations and negative ions (formed by gain of electrons) are called anions. Ionic radius is defined as:
The distance between the nucleus of an ion and the point upto which nucleus has influence over its electronic
cloud.
It is determined by X-ray analysis.
The magnitude of the charge on the ion depends upon the number of electrons removed or added to the neutral
atom.
e.g
M
M+
+
eM-

e-

M--

(i)IONIC RADII OF CATIONS:

When a neutral atom loses one or more electrons, positively charged ion is obtained which is called cation.

M+

M++

e-

Atom
cation
Metals tend to lose electrons to form cations.
Ionic radii show that the cations have smaller radii than neutral atoms. On removal of an electron the effective
charge on the nucleus increases and pulls the remaining electrons more firmly e.g.
Radius of Na atom = 1.57 A
Radius of Na+ ion = 0.95 A

(ii)IONIC RADII OF ANIONS:

When a neutral atom gains one or more electrons, negatively charged ion is obtained which is called anion.
M
+
e-
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Atom
anion
Non-metals tend to lose electrons to form anions.
Anions have a larger radii than the neutral atoms as an excess of negative charge results in greater electron
repulsion e.g.
Radius of Cl atom = 0.99 A
Radius of Cl- ion = 1.81 A
(iii)I S O - E L E C T R O N I C I O N S :
The ions which have the same electronic configuration are called isoelectronic.
In case of ions which have the same electronic configuration Iike Na+, Mg++, Al+++, (1s2, 2s2, 2p6) the radii
decrease with increasing nucleur charge.

IONIZATION POTENTIAL:

It is defined as:
The minimum amount of energy required to remove the least strongly bound electron from a neutral gaseous
atom, ion or molecule, is called Ionization potential or ionization Energy.
M+
M++
+
eIt is possible to remove more than one electron from an atom or ion, giving doubly or triply charged ions and the
energies needed are called:
M
M+
+
e- E = 1st Ionization potential
M+
M++
+
eE = 2ND Ionization potential
M++
M+++
+
eE = 3RD Ionization potential
The ionization potential is measured in Kilo-Joules per mole and is determined from spectroscopic methods or
by measurement of current passing through a discharge tube.

Factors on which Ionization Potential Dep ends:

1)Size of Atom/Distance between Electron and Nucleus:

The ionization potential depends upon the distance of the electron from the nucleus. Farther the electron is from
the nucleus more easily it is removed. If the size of atom is large the distance is also large and ionization potential
value is low and vise versa. Thus, if we move down in a group in periodic table, the ionization potential decreases.

2)Magnitude of Nuclear Charge:

If the nuclear charge is greater, the force of attraction on valence electron is also greater. Therefore, if we move
from left to right in a period of periodic table, the size of atom decreases and ionization potential increases.

3)Screening Effect:

The shells present between the nucleus and parent electrons decrease the effect of nucleus on valence electron.
This is called screening effect. It decreases the I.P values.
When one electron is removed, the positive charge on the nucleus becomes unbalanced and binds the remaining
electrons more firmly. It is therefore, becomes more and more difficult to remove the second and then the third
electron. Thus, the second I.P is greater than the first I.P and so on. Due to their larger distance, it is easier to
remove an electron from 'f' sub-shell than a 'd' sub-shell and removal from a 'd' sub-shell is easier than a 'p' shell.

ELECTRON AFFINITY:

The amount of energy liberated by an atom when an electron is inserted in it is called electron affinity.

Factors on which Electron Affinity depends:

1)Size of Atom:

If the size of atom is smaller, the force of attraction from the nucleus on the added electron will be higher and
hence the electron affinity will also be higher and vise versa.

2)Magnitude of Nuclear Charge:

Due to greater nuclear charge, the force of attraction on the added electron is greater, so the electron affinity of
the atom is also high.

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3)Electronic Configuration:

The atoms with the stable configuration has no tendency to gain an electron so the electron affinity of such
elements is zero or positive.
Following three types of configurations are stable:
1. Inert gas configuration or Fully filled orbitals
2. Half-filled orbitals
The electron affinities of group IA elements are somewhat negative, even though these elements have very little
attraction for the electron. The elements of group IIA, Be and Mg have positive electron affinities (change is
endothermic) because the electron is being added to higher energy p-level. In VA group elements such as
Nitrogen, the value is positive because the electron must enter the half-filled p-orbital and becomes paired, a
process which is not energetically favourable.
The addition of second electron to oxygen or sulphur must overcome the repulsion of the negative charge already
on O-1 and S-1. The process is, therefore, endothermic e.g. for O2- it is + 844 and for S2- it is + 532 KJ mole-1.

ELECTRONEGATIVITY:

In a molecule the tendency or power of an atom to attract a shared pair of electrons to itself is called the
electronegativity of that atom.
The polarity of covalent bond depends upon the electronegativities of held atoms.
The numerical values of the electronegativity of fluorine is fixed as 4 which is the highest value.1t is clear that the
E.N. values in general, increase as we go from left to right in any horizontal period, while they decrease as we go
down from top to bottom a group in the periodic table.

Predicting Nature of Bond Using Electronegativity:

On the basis of electronegativity values, it is predictable that what type of bond will be formed. If the difference
between E.N. values of any two bonded atoms is less than 1.7. The bond will be covalent. The polarity of covalent
bond also depends upon the E.N. values, that is, the covalent bond between two similar atoms (HH, OO, etc),
the E.N. are equal, the covalent bond is non-polar in character. The covalent bond between dissimilar atoms is
always polar in nature, the polarity increase with difference in their E.N. values. For example, bond between N
and H is more polar than bond between C and H, because E.N. difference in case of N and H is more than E.N.
difference between C and H.

Factors on which Electronegativity Depends:

1)Size of Atom/Distance between Electron and Nucleus:

If the size of atom is large the distance is also large and electronegativity value is low and vise versa. Thus, if we
move down in a group in periodic table, the electronegativity decreases.

2)Magnitude of Nuclear Charge:

If the nuclear charge is greater, the force of attraction on shared electron is also greater. Therefore, if we move
from left to right in a period of periodic table, the size of atom decreases and electronegativity increases.

3)Screening Effect:

The shells present between the nucleus and parent electrons decrease the effect of nucleus on valence electron.
This is called screening effect. It decreases the electronegativity values.

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