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Class- XI Chemistry
Chapter -2 : STRUCTURE OF ATOM
Fundamental particles of an atom
Name Symbol Absolute Relative Mass Mass/u Approx. Discovered by
charge (C) charge (Kg) mass / u
Electron e -1.6 X 10-19 -1 9.1 X 10-31 0.00054 0 J J Thomson
Proton p +1.6 X 10-19 +1 1.67 X 10-27 1.00727 1 Goldstein
Neutron n 0 0 1.67 X 10-27 1.00867 1 James Chadwick

Charge on electron was determined by R A Millikan by “Oil drop experiment”

Terms to specify an atom

 Atomic number (Z)= number of protons in the nucleus = number electrons in
a neutral atom
 Mass number (A) = number of protons(Z) + number of neutrons(n)
 Protons and neutrons are collectively termed as Nucleons.

Representation of an atom-
Eg: ,

Isotopes- atoms with identical atomic number but different atomic mass number
are known as Isotopes. Eg: [ , , ],[ , ]. All the isotopes of a given
element show same chemical behavior due the presence of same number of
electron and protons.

Isoelectronic species: These are those species which have the same number of
electrons. Ne , Na+ , Mg2+
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Isobars- Isobars are the atoms with same mass number but different atomic
number. Eg: ,

Atomic models
Thomson model of atom (Plum pudding model)

 J. J. Thomson, in 1898, proposed that an atom possesses a spherical shape

(radius approximately 10-10 m) in which the positive charge is uniformly
distributed and the electrons are embedded into it in such a manner as to
give the most stable electrostatic arrangement.
 This model can be visualised as a pudding or watermelon of positive charge
with plums or seeds (electrons) embedded into it.

 An important feature of this model is that the mass of the atom is assumed to
be uniformly distributed over the atom.

 It explained the overall neutrality of the atom.

 Contradiction arised when Rutherford showed that “mass of an atom is
concentrated at the center.”
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Rutherford’s Nuclear Model of Atom

Rutherford and his students bombarded very thin
gold
foil (thickness 100 nm) with high energy –
particles. The thin gold foil had a circular fluorescent
zinc sulphide screen around it. Whenever –
particles struck the screen, a tiny flash of light was
produced at that point.

The observations and conclusions of –

particles scattering experiments are following :

(i) most of the – particles passed through the

gold foil undeflected showing a lot of empty space
in atom.

(ii) a small fraction of the –particles was deflected by small angles indicating
that positive charge must be concentrated in a very small volume

(iii) a very few – particles ( 1 in 20,000) bounced back, that is, were deflected
by nearly 180 .Rutherford showed by calculations that volume occupied by the
nucleus is very small
as compared to the size of whole atom.

On the basis of above observations and conclusions,

Rutherford proposed the nuclear model of atom
(after the discovery of
protons). According to this model :
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(i) The positive charge and most of the mass of the atom was densely
concentrated in extremely small region. This very small portion of the atom was
called nucleus by Rutherford.

(ii) The nucleus is surrounded by electrons that move around the nucleus with a
very high speed in circular paths called orbits. Thus, Rutherford’s model of atom
resembles the solar system.

(iii) Electrons and the nucleus are held together by electrostatic forces of attraction.

Drawbacks of Rutherford model:

1. It does not account for the stability of atom. According to Maxwell a charged
particle moving in circular path is accelerated
continuously and emits electromagnetic radiations, thus
energy is lost and the radius of the orbit will shrink and
finally the electron will fall in the nucleus.

2.It says nothing about the electronic configuration.

DEVELOPMENTS LEADING TO THE BOHR’S MODEL OF ATOM

Two developments played a major role in the formulation of Bohr’s model of
atom. These were:
(i) Dual character of the electromagnetic radiation (wave as well as particle
nature).
(ii) Experimental results regarding atomic spectra which can be explained only by
assuming quantized electronic energy levels in atoms.
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Characteristics of wave:
Wavelength (λ)-distance between two
successive crest or trough. Units- m, cm
Frequency (ʋ) – The number of waves that
pass through a given point per second. Units-
sec-1 or Hz
Wavenumber (ῡ = 1/ λ )- number of
wavelengths per unit length. Units- m-1
Velocity (c) of wave,
c= ʋX ʋc / 

Dual nature of electromagnetic radiations

Radiations possess both wave like nature (explained by Maxwell) as well as

particle nature (explained by Planck).

Wave nature of electromagnetic radiations

 James Maxwell (1870) suggested that when electrically charged particle

moves under acceleration, alternating electrical and magnetic fields are
produced and transmitted. These fields are transmitted in the form of waves
called electromagnetic waves or radiations. Both the fields are mutually
perpendicular to each other as well as perpendicular to the direction of
propagation.
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 Maxwell was the first to suggest that light is also a form of electromagnetic
radiation.
 Electromagnetic radiations do not require any medium for propagation.
 The phenomenon of diffraction and interference have been explained by
considering the wave nature of light.
 The increasing order of the wavelength and decreasing order of these
radiations is as follow

Particle nature of electromagnetic radiations

 Wave nature of electromagnetic radiations could not explain the black

body radiation, photoelectric effect, line spectra of atoms specially
hydrogen.
 Max Planck (1900) first explained the phenomenon of black body
radiation by suggesting the particle nature of electromagnetic radiations
known as “Planck’s Quantum Theory”
 According to Planck’s Quantum Theory- atoms or molecules emit (or
absorb) energy in the form of small discrete packets of energy, known as
quantum. In case of light it is called photon.
 The energy of the quantum (E) is directly proportional to its frequency
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E=h
h is Planck’s constant, 6.626 X 10-34J sec
 Photoelectric effect- the phenomenon of emission of electrons from the
surface of metals (like K, Rb, Cs) when electromagnetic radiations like
light strikes on it is called photoelectric effect.
The emitted electrons are called photoelectrons.
Photoelectric effect was first observed by Hertz.
His observations on photoelectric effects are
following:

I. Electrons are ejected as soon as light strikes on the surface.

II. Number of electrons ejected is directly proportional to the intensity
of light.
III. Each metal has a characteristic minimum frequency, below
which photoelectric effect is not observed. This minimum
frequency is called threshold frequency. Kinetic energy of the
ejected electrons increases with the frequency of light.

 Einstein explained photoelectric effect using Planck’s Quantum

Theory
I. When a photon of sufficient energy strikes an electron in the metal,
it transfers its energy instantaneously to the electron during
collision and that comes out without any time lag.
II. Greater the energy possessed by the the photon, greater will be the
KE of electron.
III. The minimum amount of energy required to eject the electron is
called work function and the extra energy is used as kinetic energy
of electron.
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If his the energy of photon, here 

Work function W0= h

Kinetic energy of the electron => me v2 = h h

total energy of the photonhh me v2

me is the mass of electron and v is its velocity

On the basis of Maxwell’s theory and Planck’s Quantum Theory, the dual nature
of electromagnetic radiation was accepted by the scientists. It was concluded that
light behaves like wave during propagation and shows particle nature when
interacted with matter.

Atomic spectra: evidence for quantized energy level

The splitting of white light into a series of colour bands is called dispersion and the
series of colour bands is known as spectrum. The spectrum of white light is called
continuous spectrum as violet is merged to indigo, indigo to blue, blue to green and
so on.

Atomic spectra is the spectrum of electromagnetic radiation formed when

electromagnetic radiation interacts with matter. The study of atomic spectra is
called spectroscopy.

Atomic spectra can be classified as (i) Emission spectra and (ii) Absorption spectra

 Emission spectra- the spectrum of radiation emitted by a substance in

excited state or that has absorbed energy. When energy is absorbed by
electrons of atoms, electrons move to higher energy levels, it is said to be
in excited state. The excited state is very unstable. In order to attain
stability, excited electrons have to release energy to return to their ground
state. The frequency of radiations emitted in such cases form the
emission spectrum. Emission spectrum consists of coloured lines in
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between dark bands, that’s why called line spectrum. Line spectrum is a
characteristic feature of an element.
 Absorption spectra- the spectrum of light absorbed by the atom in
ground state is called absorption spectrum. Absorption spectrum consists
of dark lines in-between the coloured bands. The dark lines corresponds
to the frequency of light absorbed.
 Absorption spectra is just like a negative plate of an emission spectra.

 Elements like Rb, Cs, Tl, In , Ga, Sc were discovered when their minerals
were analysed by spectroscopic studies. Helium was discovered in sun by
spectroscopic method.

Line spectrum of hydrogen

All the series of lines in the hydrogen spectrum can be described by Johannes
Rydberg’s expression
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The value 109677 cm-1 is called Rydberg constant.

Of all the elements hydrogen atom has the simplest line spectrum. The Balmer
series of lines are the only lines in the hydrogen spectrum which appear in visible

region.

From the line spectrum of different elements, it can be concluded that:

I. Line spectrum of an element is unique.

II. There is regularity in the line spectrum of each element

Bohr’s model for hydrogen

Neil Bohr (1913) proposed a new model of atom based on Planck’s quantum
theory.

Bohr’s postulates of atomic model for hydrogen:

1) The electron in the hydrogen atom can move around the nucleus in a circular
path of fixed radius and fixed energy. These paths are called orbits,
stationary states, shell or allowed energy states. These orbits are arranged
concentrically around the nucleus.
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2) The energy of an electron in the orbit is fixed. However, electron can move
from one energy level to another either by absorbing/emitting energy.
3) The frequency of radiation absorbed/emitted is given by Bohr’s frequency
rule:

are the energy of lower and higher allowed energy states.

4) The angular momentum of an electron in given energy state is quantized.

The angular momentum must be an integral multiple of .

(n=1, 2,3…)

Bohr’s theory for hydrogen atom:

1. The stationary states for electron are numbered n=1,2,3…. These integral
numbers are known as Principal quantum numbers.
2. The radii of stationary orbit is given by,
Here , . The radii increases with the value of n.

3. Energy of the stationary state or orbit is given by, ( )

n=1,2,3… and is Rydberg constant and its value is 2.18 X 10-18 J.

The energy assigned to a free electron is 0, when it comes under the
influence of nucleus energy is emitted (that’s why energy is negative).
4. For hydrogen like ions i.e one electron system (He+, Li2+, Be3+ ) the energy
and radii of the stationary orbit are given by
( )
( ) and

Where is the atomic number. As Z is increased energy becomes more

negative and radii smaller means electron is tightly bounded to nucleus.
5. It is also possible to calculate the velocities of electrons moving in these
orbits. Although precise equation is not given here, qualitatively the
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magnitude of velocity of electron increases with positive charge of nucleus

and decreases with increase in principal quantum number.

Explanation of line spectrum of hydrogen

The energy absorbed or emitted during the transition of electrons is given by

( ) ( )

Frequency associated with absorption and emission is given by

( )

ni and nf are initial and final orbit.

For absorption spectrum ni < nf , is positive, showing energy is absorbed.

For emission spectrum ni > nf , is negative, showing energy is released.

Limitations of Bohr’s model

1. It fails to explain the doublet observed in the spectrum of hydrogen.

2. It didn’t explained the spectrum of atoms other than hydrogen.
3. It was unable to explain the splitting of spectral line in the presence of
magnetic field (Zeeman effect) or an electric field (Stark effect).
4. It does not account for the ability of atoms to form molecules by chemical
bonds.

Towards quantum mechanical model of the atom

Quantum mechanics is a theoretical science that deals with the study of the
motions of the microscopic objects that have both observable wave like and
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particle like properties. Two important developments that lead to the formation of
quantum mechanical model were:

 Dual behaviour of matter (by de Broglie in 1924)- just like radiations

matter also exhibit particle as well as wave nature. The wavelength
associated with a particle of mass (m), moving with velocity (v) and
momentum( p) is given by

 Heisenberg’s Uncertainty Principle (by Heisenberg in 1927)- It is

impossible to determine simultaneously, the exact position and exact
momentum (or velocity) of an electron. Mathematically, it can be given as

( )

Where =uncertainty in position, =uncertainty in momentum,

=uncertainty in velocity of the particle.
If position of the electron is known with high accuracy i.e is very small
then velocity will be uncertain ( is large) and vice versa.
Heisenberg’s Uncertainty Principle rules out the existence of fixed path of
electrons and other similar particles. Heisenberg’s Uncertainty Principle is
significant only for microscopic objects.

Now some more points of failure of Bohr’s model arised:

a. It ignores the dual behavior of matter.
b. It contradicts Heisenberg’s uncertainty principle.
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It, therefore, means that the precise statements of the position and momentum of
electrons have to be replaced by the statements of probability, that the electron has
at a given position and momentum. This is what happens in the quantum
mechanical model of atom.

Quantum Mechanical Model of Atom

Quantum mechanics was developed independently by Heisenberg and Schrödinger

in 1926.

Erwin Schrödinger, in 1926, proposed an equation called Schrödinger equation to

describe the electron distributions in space and the allowed energy levels in atoms.
Schrödinger equation for a system (such as atom or molecule whose energy does
not change with time) is written as

Where is a mathematical operator called Hamiltonian, is the total energy of the

system and is the wave function.

Important features of the Quantum Mechanical Model of Atom:

1. The energy of electrons in atoms is quantized (i.e., can only have certain
specific values).

2. The existence of quantized electronic energy levels is a direct result of the

wave like properties of electrons and are allowed solutions of Schrödinger
wave equation.
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3. Both the exact position and exact velocity of an electron in an atom cannot
be determined simultaneously (Heisenberg uncertainty principle). Therefore,
only probability of finding an electron at different points is required.

4. An atomic orbital is the wave function for an electron in an atom.

Whenever an electron is described by a wave function, we say that the
electron occupies that orbital. In each orbital, the electron has a definite
energy. An orbital cannot contain more than two electrons. In a multi-
electron atom, the electrons are filled in various orbitals in the order of
increasing energy.

5. The probability of finding an electron at a point within an atom is

proportional to the square of the orbital wave function i.e.∣ψ∣2 at that point.
∣ψ∣2 is known as probability density and is always positive. From the value
of .∣ψ∣2 at different points within an atom, it is possible to predict the
region around the nucleus where electron will most probably be found.

Orbitals and Quantum numbers

Orbital: The region of space around the nucleus where the probability of finding an
electron is maximum is called an orbital.
Quantum numbers: There are a set of four quantum numbers which specify the
energy, size, shape and orientation of an orbital. To specify an orbital only three
quantum numbers are required while to specify an electron all four quantum
numbers are required.

I. Principal quantum number (n)- this quantum number describes the size and
energy of the orbital means the energy level. The value of principal quantum
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number is a positive integer i.e n=1,2,3… . The principal quantum number is also
identifies the shell, represented by
n = 1 2 3 4 …
shell = K L M N …

All the orbital of a given value of n constitute a shell. The maximum

number of orbitals in a shell is n2 , maximum number of electrons in given
shell is 2n2.

II . Azimuthal quantum number or subsidiary quantum number or orbital

angular momentum ( l )- it defines the three-dimensional shape of the orbital. Its
value varies from 0 to (n-1) i.e l = 0, 1, 2,…,(n-1). Each shell consist of one or
more different sub-shell. The sub-shell corresponding to different values of l are

Value of l 0 1 2 3 4 5 …
Notation for s p d f g h …
sub-shell
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III. Magnetic orbital quantum number (ml)- It designates the orientation of the
orbital within a sub-shell. It gives the total number of orbitals in given sub-shell.
For given l, the possible values of ml are:
ml = - l , - (l-1) , -(l-2) , … , 0 , … , (l-2) , (l-1) , l
there are total (2l + 1) values of ml for given l.
Value of l 0 1 2 3
Sub-shell s p d f
No. of orbitals 1 3 5 7
Possible value of 0 -1, 0, +1 -2, -1, 0,+1, -3, -2, -1, 0, +1, +2, +3
ml +2

IV.Electron spin quantum number (ms)- It describes the spin of the electron in
its orbital. Electron spin around its own axis while moving in orbital and the spin

may be clockwise or anti-clockwise. The possible value of ms is or .

Shapes of atomic orbitals

The shapes of atomic orbitals may be represented by boundary surface

diagrams. The probability of finding electron is not uniform within the orbital,
the probability density function varies according to the shape of the orbital.

There are some points and places within the boundary surface diagram of
orbital where there is no probability of finding electron, these points and places
are called nodes. So, nodes are the region with zero probability density
function.

There are two types of nodes:

i. Radial nodes – The spherical region

around the nucleus where probability of
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finding electron is zero. The number of radial nodes is (n-l-1).

ii. Angular nodes- The plane passing through the
nucleus where probability of finding electron is
zero. The direction of the plane is specified by an
angle. The number of angular nodes is l. Total
number of nodes = n-1

Shapes of p and d orbitals

Energies of the orbital

The energy of an electron in a hydrogen atom is determined solely by the principal
quantum number. Thus the energy of the orbitals increases as follows :
1s < 2s = 2p < 3s = 3p = 3d <4s = 4p = 4d = 4f <
The orbitals having the same energy are called degenerate orbitals eg: the three
orbitals in p-subshell, 2s and 2p orbitals.

(n+l) rule- The lower the value of (n+l) for an orbital, the lower is its energy. If
two orbitals have the same value of (n + l), the orbital with lower value of n will
have the lower energy.
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Energies of the orbitals in the same subshell decrease with increase in the atomic
number (Zeff e). For example, energy of 2s orbital of hydrogen atom is greater than
that of 2s orbital of lithium and that of lithium is greater than that of sodium and so
on, that is,
E2s(H) > E2s(Li) > E2s(Na) > E2s(K).

Shielding effect or screening effect: Due to the presence of electrons in the inner
shells, the electron in the outer shell will not experience the full positive charge on
the nucleus. So, due to the screening effect, the net positive charge experienced by
the electron from the nucleus is lowered and is known as effective nuclear charge
(Zeff e). Effective nuclear charge experienced by the orbital decreases with increase
of azimuthal quantum number (l).

Filling of Orbitals in Atom

The filling of electrons into the orbitals of different atoms takes place according to:
aufbau principle which is based on the Pauli’s exclusion principle, the Hund’s rule
of maximum multiplicity and the relative energies of the orbitals.

 Aufbau Principle
In the ground state of the atoms, the orbitals are
filled in order of their increasing energies.

The order in which the energies of the

orbitals increase and hence the order in which the
orbitals are filled is as follows
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1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 4f,
5d, 6p, 7s...
The order may be remembered by using the method given in above figure .

 Pauli Exclusion Principle

Given by the Austrian scientist Wolfgang Pauli (1926). According to this principle
No two electrons in an atom can have the same set of four quantum numbers.
Pauli exclusion principle can also be stated as :
“Only two electrons may exist in the same orbital and these electrons must
have opposite spin.”

 Hund’s Rule of Maximum Multiplicity

It states : pairing of electrons in the orbitals belonging to the same subshell (p,
d or f) does not take place until each orbital belonging to that subshell has got
one electron each i.e., it is singly occupied.
Since there are three p, five d and seven f orbitals, therefore, the pairing of
electrons will start in the p, d and f orbitals with the entry of 4th, 6th and 8th
electron, respectively.

 Electronic Configuration of Atoms

The distribution of electrons into orbitals of an atom is called its electronic

configuration. The electronic configuration of different atoms can be represented
in two ways:
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Electronic configurations of some of the elements is given below:

In the box electron is represented by arrow ( ) a positive spin or an arrow ( ) a
negative spin. (sometimes half-headed arrow is also used:

The electrons in the completely filled shells are known as core electrons (electronic
configuration of noble gas of previous period) and the electrons that are added to
the electronic shell with the highest principal quantum number are called valence
electrons
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.eg: Na- 1s22s22p63s1 here 1s22s22p6 is electronic configuration of Ne.

This gives a new idea of writing electronic configuration: in place of core electrons
we can write noble gas followed by valence electrons. Eg

Na- [Ne] 3s1

Fe-1s22s22p63s23p64s23d6 = [Ar] 4s23d6

Extra stability of halfp-filled and completely filled orbitals

In certain elements such as Cu, or Cr, where the two subshells (4s and 3d) differ
slightly in their energies, an electron shifts from a subshell of lower energy (4s) to
a subshell of higher energy (3d), provided such a shift results in all orbitals of the
subshell of higher energy getting either completely filled or half filled.

Therefore, the valence electronic configurations of Cr and Cu, therefore, are 3d5
4s1 and 3d10 4s1 respectively and not 3d4 4s2 and 3d9 4s2. It has been found that
there is extra stability associated with these electronic configurations.

So, chromium and copper has only one electron in 4s orbital, because exactly half
filled and completely filled d-orbitals attain extra stability due to:

i. Symmetrical distribution of electrons- symmetry leads to stability

ii. Exchange energy is released due to exchange of position of electrons
in degenerate orbitals.
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What is the utility of knowing the electron configuration?

The modern approach to the chemistry, in fact, depends almost entirely on

electronic distribution to understand and explain chemical behaviour.

For example, questions like

why two or more atoms combine to form molecules?
why some elements are metals while others are nonmetals?
why elements like helium and argon are not reactive but elements like the halogens
are reactive?....

find simple explanation from the electronic configuration. A detailed

understanding of the electronic structure of atom is, therefore, very essential for
getting an insight into the various aspects of modern chemical knowledge.

Prepared by :

Dolly Singh
PGT(Chemistry)
K V CRPF Mokamaghat