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2
Atomic Structure
Atom
John Dalton proposed (in 1808) that atom is the smallest indivisible
particle of matter. Atomic radii are of the order of 10−8 cm. It contains
three subatomic particles namely electrons, protons and neutrons.

Electron
Electron was discovered as a result of study of cathode rays by
JJ Thomson. It was named by Stony.
It carries a unit negative charge ( −1.6 × 10−19 C).
Mass of electron is 9.11 × 10−31 kg and mass of one mole of electron is
0.55 mg. Some of the characteristics of cathode rays are:
(i) These travel in straight line away from cathode and produce
fluorescence when strike the glass wall of discharge tube.
(ii) These cause mechanical motion in a small pin wheel placed in
their path.
(iii) These produce X-rays when strike with metal and are deflected
by electric and magnetic field.

Charge to Mass Ratio of Electron

In 1897, British physicist JJ Thomson measured the ratio of electrical
charge (e) to the mass of electron ( me ) by using cathode ray tube and
applying electrical and magnetic field perpendicular to each other as
well as to the path of electrons. Thomson argued that the amount of
deviation of the particles from their path in the presence of electrical or
magnetic field may vary as follows:
(i) If greater the magnitude of the charge on the particles, greater
is the deflection.
(ii) The mass of the particle, lighter the particle, greater the
deflection.
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16 Handbook of Chemistry

(iii) The deflection of electrons from its original path increase with
the increase in the voltage. By this Thomson determined the
value e/ me as 1.758820 × 1011 C kg −1.

Proton
Rutherford discovered proton on the basis of anode ray experiment.
It carries a unit positive charge (+1.6 × 10−19 C).
The mass of proton is 1.007276 u.
e e
The ratio of proton is 9.58 × 10−4 C /g. ( ratio is maximum for
m m
hydrogen gas.)
Some of the characteristics of anode rays are:
(i) These travel in straight line and possess mass many times
heavier than the mass of an electron.
(ii) These are not originated from anode but are produced in the
space between the anode and the cathode.
(iii) These also cause mechanical motion and are deflected by electric
and magnetic field.
 e
(iv) Specific charge   for these rays depends upon the nature of
 m
the gas taken and is maximum for H 2.

Neutron
Neutrons are neutral particles. It was discovered by Chadwick (1932).
The mass of neutron is 1.675 × 10−24 g or 1.008665 amu or u.
9
4 Be + 42He → 12
6C + 1
0n
(α ′ − particles) ( Neutron)

Some Other Subatomic Particles

(a) Positron Positive electron ( +10 e), discovered by Dirac (1930)
and Anderson (1932).
(b) Neutrino and antineutrino Particles of small mass and no
charge as stated by Fermi (1934).
(c) Meson Discovered by Yukawa (1935) and Kemmer. They are
unstable particles and include pi ions [π + , π − or π 0].
(d) Anti-proton It is negative proton produced by Segre and
Weigland (1955).
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Atomic Structure 17
Thomson’s Atomic Model
Atom is a positive sphere with a number of electrons distributed within
the sphere. It is also known as plum pudding model. It explains the
neutrality of an atom. This model could not explain the results of
Rutherford scattering experiment.

Rutherford’s Nuclear Model of Atom

It is based upon α-particle scattering experiment. Rutherford
presented that
(i) most part of the atom is empty.
(ii) atom possesses a highly dense, positively charged centre, called
nucleus of the order 10−13 cm.
(iii) entire mass of the atom is concentrated inside the nucleus.
(iv) electrons revolve around the nucleus in circular orbits.
(v) electrons and the nucleus are held together by electrostatic
forces of attraction.

Drawbacks of Rutherford’s Model

(i) According to electromagnetic theory, when charged particles are
accelerated, they emit electromagnetic radiations, which comes
by electronic motion and thus orbit continue to shrink, so atom is
unstable. It doesn’t explain the stability of atom.
(ii) It doesn’t say anything about the electronic distribution around
nucleus.

Atomic Number (Z)

Atomic number of an element corresponds to the total number of
protons present in the nucleus or total number of electrons present in
the neutral atom.

Mass Number (A)

The mass of the nucleus is due to protons and neutrons, thus they are
collectively called nucleons. The total number of nucleons is termed
as mass number of the atom.
Mass number of an element = number of protons + number of neutrons

Representation of an Atom
Mass number A
Symbol of the element
Atomic number Z
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18 Handbook of Chemistry

Different Types of Atomic Species

(a) Isotopes Species with same atomic number but different mass
number are called isotopes, e.g. 1H1 , 1H 2.
(b) Isobars Species with same mass number but different atomic
number are called isobars, e.g. 18 Ar40 , 19K 40.
(c) Isotones Species having same number of neutrons are called
isotones, e.g. 1H3 and 2He4 are isotones.
(d) Isodiaphers Species with same isotopic number are called
isodiaphers, e.g. 19K39 , 9F19.
Isotopic number = mass number − [2 × atomic number]
(e) Isoelectronic Species with same number of electrons are
called isoelectronic speices, e.g. Na + , Mg2+ .
(f) Isosters Species having same number of atoms and same
number of electrons, are called isosters, e.g. N 2 and CO.

Developments Leading to the Bohr’s Model of Atom

Two developments played a major role in the formulation of Bohr’s model:
(i) Dual character of the electromagnetic radiation which means
that radiation possess wave like and particle like properties.
(ii) Atomic spectra explained by electronic energy level in atoms.

Electromagnetic Wave Theory (Maxwell)

The energy is emitted from source continuously in the form of
radiations and magnetic fields. All electromagnetic waves travel with
the velocity of light (3 × 108 m/ s) and do not require any medium for
their propagation.
An electromagnetic wave has the following characteristics:
(i) Wavelength It is the distance between two successive crests
or troughs of a wave. It is denoted by the Greek letter λ (lambda).
(ii) Frequency It represents the number of waves which pass
through a given point in one second. It is denoted by ν (nu).
(iii) Velocity (v) It is defined as the distance covered in one second
by the waves. Velocity of light is 3 × 1010 cms− 1.
(iv) Wave number It is the reciprocal of wavelength and has units
cm − 1. It is denoted by ν (nu bar).
(v) Amplitude (a) It is the height of the crest or depth of the
trough of a wave.
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Atomic Structure 19
Wavelength ( λ ), frequency ( ν ) and velocity ( v ) of any electromagnetic
radiations are related to each other as v = νλ.
Electromagnetic wave theory was successful in explaining the
properties of light such as interference, diffraction etc., but it could not
explain the
1. Black body radiation
2. Photoelectric effect
These phenomena could be explained only if electromagnetic waves are
supposed to have particle nature. Max Planck provided an explanation
for the behaviour of black body and photoelectric effect.

Particle Nature of Electromagnetic Radiation :

Planck’s Quantum Theory
Planck explain the distribution of intensity of the radiation from black
body as a function of frequency or wavelength at different
temperatures.
hc
E = hν = (Q c = νλ )
λ
where, h = Planck’s constant = 6.63 × 10−34 J-s
E = energy of photon or quantum
ν = frequency of emitted radiation
If n is the number of quanta of a particular frequency and ET be total
energy then
ET = nhν

Black Body Radiation

If the substance being heated is a black body, the radiation emitted is
called black body radiation.

Photoelectric Effect
It is the phenomenon in which beam of light of certain frequency falls
on the surface of metal and electrons are ejected from it.
This phenomenon is known as photoelectric effect. It was first observed
by Hertz.
W 0 = hν 0 hν
1 mv 2
hc
W0 = 2
λ max Metal hν0 [work function]
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20 Handbook of Chemistry

Threshold frequency ( ν 0 ) = minimum frequency of the radiation

Work function (W 0 ) = required minimum energy of the radiation
E = KE + W 0
1
∴ mv 2 = h( ν − ν 0 ) [Kinetic energy of ejected electron = h( ν − ν 0 )]
2
where, ν = frequency of incident radiation
ν 0 = threshold frequency

Electromagnetic Spectrum
The different types of electromagnetic radiations differ only in their
wavelengths and hence, frequencies. When these electromagnetic
radiations are arranged in order of their increasing wavelengths or
decreasing frequencies, the complete spectrum obtained is called
electromagnetic spectrum.

Different Types of Radiations and Their Sources

Type of radiation Wavelength (in Å) Generation source

Gamma rays 0.01 to 0.1 Radioactive disintegration

X-rays 0.1 to 150 From metal when an electron strikes on it

UV-rays 150 to 3800 Sun rays

Visible rays 3800 to 7600 Stars, arc lamps

Infrared rays 7600 to 6 × 10 6

Incandescent objects

Micro waves 6 × 106 to 3 × 109 Klystron tube

Radio waves 3 × 1014 From an alternating current of high

frequency

Electromagnetic spectra may be emission or absorption spectrum on

the basis of energy absorbed or emitted. An emission spectrum is
obtained when a substance emits radiation after absorbing energy. An
absorption spectra is obtained when a substance absorbs certain
wavelengths and leave dark spaces in bright continuous spectrum.
A spectrum can be further classified into two categories such as
(i) Continuous or band spectrum A spectrum in which there is
no sharp boundary between two different radiations.
(ii) Discontinuous or line spectrum A spectrum in which
radiations of a particular wavelength are separated from each
other through sharp boundaries.
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Atomic Structure 21
Bohr’s Model
Neils Bohr proposed his model in 1931. Bohr’s model is applicable only
for one electron system like H, He+ , Li2+ etc.
Assumptions of Bohr’s model are
1. Electrons keep revolving around the nucleus in certain fixed
permissible orbits where it doesn’t gain or lose energy. These
orbits are known as stationary orbits.
circumference of orbit
Number of waves in an orbit =
wavelength
2. The electrons can move only in those orbits for which the angular
h
momentum is an integral multiple of , i.e.
2π
nh
mvr = ( n = 1, 2, 3..... )
2π
where, m = mass of electron; v = velocity of electron;
r = radius of orbit
n = number of orbit in which electrons are present
3. Energy is emitted or absorbed only when an electron jumps from
higher energy level to lower energy level and vice-versa.
hc
∆E = E2 − E1 = hν =
λ
4. The most stable state of an atom is its ground state or normal
state.
From Bohr’s model, energy, velocity and radius of an electron in
nth Bohr orbit are
(i) Velocity of an electron in nth Bohr orbit
Z
( vn ) = 2.165 × 106 m/s
n
(ii) Radius of nth Bohr orbit
n2 n2
(rn ) = 0.53 × 10−10 m = 0.53 Å
Z Z
Z2
(iii) En = − 2.178 × 10−18 2 J/atom
n
Z2
= − 1312 2 kJ/ mol
n
Z2
= − 13.6 2 eV/atom
n
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22 Handbook of Chemistry

 1 1
∆E = − 2.178 × 10−18  2 − 2  Z 2 J/atom
 n1 n 2 
where, n = number of shell; Z = atomic number
As we go away from the nucleus, the energy levels come closer,
i.e. with the increase in the value of n, the difference of energy
between successive orbits decreases.
Thus, E2 − E1 > E3 − E2 > E4 − E3 > E5 − E4, etc.

Emission Spectrum of Hydrogen

According to Bohr’s theory, when an electron jumps from ground state to
excited state, it emits a radiation of definite frequency (or wavelength).
Corresponding to the wavelength of each photon of light emitted, a
bright line appears in the spectrum.
The number of spectral lines in the spectrum when the electron comes
n( n − 1)
from nth level to the ground level =
2
Hydrogen spectrum consist of line spectrum.

Series Region n1 n2

(i) Lyman UV 1 2, 3, 4, …

(ii) Balmer Visible 2 3, 4, 5, …

(iii) Paschen IR 3 4, 5, 6, …

(iv) Brackett IR 4 5, 6, 7, …

(v) Pfund far IR 5 6, 7, …

(vi) Humphery far IR 6 7, 8, 9, …

Wave number ( ν ) is defined as reciprocal of the wavelength.

1  1 1
ν= ⇒ ν = RZ 2  2 − 2 
λ  n1 n 2 
where, n1 = 1, 2 ......
n 2 = n1 + 1, n1 + 2 ......
Here, λ = wavelength
R = Rydberg constant = 109677.8 cm –1
First line of a series is called line of longest wavelength (shortest
energy) and last line of a series is the line of shortest wavelength
(highest energy, n 2 = ∞).
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Atomic Structure 23
Sommerfeld Extension to Bohr’s Model
According to this theory, the angular momentum of revolving electron
h
in an elliptical orbit is an integral multiple of , i.e.
2π
kh
mvr =
2π
nh
From Bohr model, mvr =
2π
For K shell, n = 1, k = 1 Circular shape
L shell, n = 2, k = 1, 2 Circular
M shell, n = 3, k = 1, 2, 3 Elliptical
N shell, n = 4, k = 1, 2, 3, 4 Elliptical

Limitations of Bohr’s Theory

(i) It is unable to explain the spectrum of atom other than hydrogen
like doublets or multielectron atoms.
(ii) It could not explain the ability of atom to form molecules by
chemical bonds. Hence, it could not predict the shape of
molecules.
(iii) It is not in accordance with the Heisenberg uncertainty principle
and could not explain the concept of dual character of matter.
(iv) It is unable to explain the splitting of spectral lines in the
presence of magnetic field (Zeeman effect) and electric field
(Stark effect).

Towards Quantum Mechanical Model of the Atom

Two important developments which contributed significantly in the
formulation of such a model were given below

1. de-Broglie Principle (Dual Nature)

de-Broglie explains the dual nature of electron, i.e. both particle as well
as wave nature.
h h
λ= or =λ [ p = mv (momentum)]
mv p
where, λ = wavelength; v = velocity of particle; m = mass of particle
h
λ=
2m × K E
where, KE = kinetic energy.
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24 Handbook of Chemistry

2. Heisenberg’s Uncertainty Principle

According to this principle, ‘‘it is impossible to specify at any given
instant both the momentum and the position of subatomic particles
simultaneously like electron.’’
h
∆x ⋅ ∆p ≥
4π
where, ∆x = uncertainty in position; ∆p = uncertainty in momentum

Quantum Mechanical Model of Atom

It is the branch of chemistry which deals with dual behaviour of
matter. It is given by Werner Heisenberg and Erwin Schrodinger.
Schrodinger wave equation is
∂ 2ψ ∂ 2ψ ∂ 2ψ 8π 2m
+ + + (E − U ) ψ = 0
∂x 2 ∂y 2 ∂z 2 h2
where, x , y , z = cartesian coordinates
m = mass of electron, E = total energy of electron
U = potential energy of electron, h = Planck’s constant
ψ (Psi) = wave function which gives the amplitude of wave
ψ 2 = probability function
For H-atom, the equation is solved as
H$ ψ = Eψ
where, H$ is the total energy operator, called Hamiltonian. If the sum
of kinetic energy operator (T ) and potential energy operator (U ) is the
total energy, E of the system,
H = T +U
(T + U )ψ = Eψ

The atomic orbitals can be represented by the product of two wave

functions (i) radial wave function (ii) angular wave function.
The orbital wave function, ψ has no significance, but ψ 2 has
significance, it measures the electron probability density at a point in
an atom. ψ can be positive or negative but ψ 2 is always positive.
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Atomic Structure 25
Difference between Orbit and Orbital
Orbit Orbital
1. An orbit is a well defined circular path An orbital is the three dimensional space
around the nucleus in which the around the nucleus within which the
electron revolves. probability of finding an electron is maximum.
2. The maximum number of electrons in The maximum number of electrons present
any orbit is given by 2 n2 where n is the in any orbital is two.
number of the orbit.

Shapes of Atomic Orbitals

The shapes of the orbitals are
s-spherical, p-dumb bell, d-double-dumb-bell, f-Diffused
These orbitals combine to form subshell.
(i) s-subshell will have only one spherical orbital.
Y
Z

(ii) p-subshell has three orbitals ( px , py , pz ).

px py pz
z z z

x x x

y y y

(iii) d-subshell has five orbitals ( dxy , d yz , dzx , dx 2 − y 2 and dz 2 ).

dxy dxz
z z

x
x
y y
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26 Handbook of Chemistry

dyz dx2_ y2
z z

y
x x
y
dz2
z

Wave function distribution

The orbital wave function ( ψ ) for an electron in an atom has no
physical meaning. It is a mathematical function of the coordinates of
the electron.

ψ ψ
(r ) 1s (r ) 2s
+ +
Node
r – r

Probability Diagrams
The graph plotted between ψ 2 and distance from nucleus is called
probability diagram.

ψ2 ψ2 2s
(r) 1s (r)

r (nm) Node r (nm)

Variation of ψ 2 with distance from
the nucleus for 1s and 2s orbitals.
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Atomic Structure 27
Node
A region or space, where probability of finding an electron is
maximum, is called a peak, while zero probability space is called node.
Nodes are of two types :
(a) Radial nodes (b) Angular nodes
(i) ( n − l − 1) = radial node
(ii) ( l ) = angular node
(iii) ( n − 1) = total nodes

Number of Peaks and Nodes for Various Orbitals

S. No. Type of orbital Number of peaks Number of nodes

1. s n n −1
2. p n −1 n−2
3. d n−2 n− 3
4. f n− 3 n− 4

Quantum Numbers
Each electron in an atom is identified in terms of four quantum numbers.
Principal Quantum Number (Neils Bohr)
It is denoted by n. It tells us about the main shell in which electron
resides. It also gives an idea about the energy of shell and average
distance of the electron from the nucleus. Value of n = any integer.
Azimuthal Quantum Number (Sommerfeld)
It is denoted by l. It tells about the number of subshells ( s, p, d , f ) in
any main shell. It also represents the angular momentum of an
electron and shapes of subshells. The orbital angular momentum of an
h
electron = l( l + 1)
2π
Value of l = 0 to n − 1.
l = 0 for s, l = 2 for d
l = 1 for p, l = 3 for f
Number of subshells in main energy level = n.
Magnetic Quantum Number (Lande)
It is denoted by m. It tells about the number of orbitals and orientation
of each subshell. Value of m = − l to +l including zero.
Number of orbitals in each subshell = ( 2l + 1)
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28 Handbook of Chemistry

S. No. Subshell Orbital

1. s 1
2. p 3
3. d 5
4. f 7

Number of orbitals in main energy level = n . 2

Maximum number of electrons in nth shell = 2n 2

Spin Quantum Number (Ublenbeck and Goldsmith)

It is denoted by ms or s. It indicates the direction of spinning of
electron, i.e. clockwise or anti-clockwise.
Maximum number of electrons in main energy level = 2n 2

Electronic Configuration
Arrangement of electrons in various shells, subshells and orbitals in an
atom is known as electronic configuration.

Filling of Orbitals in Atom

Aufbau Principle
According to this principle, in the ground state of an atom, the
electrons occupy the lowest energy orbitals available to them, i.e. the
orbitals are filled in order of increasing value of n + l. For the orbitals
having the same value of n + l, the orbtial having lower value of n is
filled up first.
The general order of increasing energies of the orbital is
1s < 2s < 2 p < 3s < 3 p < 4s < 3d < 4 p < 5s < 4d < 5 p < 6s < 4 f < 5d
< 6 p < 7s < 5 f < 6d < 7 p
Thus, the filling of electrons in various subshells within the atom can
be summerised through following figure.
1s
2s 2p
3s 3p
4s 3d 4p
5s 4d 5p
6s 4f 5d 6p
5f 6d
7s 7p

The energy of atomic orbitals for H-atom varies as

1s < 2s = 2 p < 3s = 3 p = 3d < 4s = 4 p = 4d = 4 f
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Atomic Structure 29
Pauli Exclusion Principle
It states, no two electrons in an atom can have identical set of four
quantum numbers.
The maximum number of electrons in s subshell is 2, p subshell is 6,
d subshell is 10 and f subshell is 14.
Hund’s Rule of Maximum Multiplicity
It states,
(i) In an atom no electron pairing takes place in the p, d or f-orbitals
until each orbital of the given subshell contains one electron.
(ii) The unpaired electrons present in the various orbitals of the
same subshell should have parallel spins.

Methods of Writing Electronic Configuration

(i) Orbital method In this, the electrons present in respective
orbitals are denoted. e.g. Cl(17) = 1s2 , 2s2 , 2 p6 , 3s2 , 3 p5 .
(ii) Shell method In this, the number of electrons in each shell is
continuously written. e.g. Cl (17) = 1s2 , 2s2 , 2 p6 , 3s2 , 3 p5

K L M
2, 8, 7
(iii) Box method In this method, each orbital is denoted by a box
and electrons are represented by half-headed ( ) or full-headed
( ↑ ) arrows. An orbital can occupy a maximum of two electrons.
e.g.
Cl(17) =
1s2 2s2 2p6 3s2 3p5

Half-filled and completely filled electronic configurations are

more stable. Hence, outer configuration of Cr is 3d5 4s1 and Cu is
3d10 4s1.
Electronic Configuration of Ions
To write the electronic configuration of ions, first write the electronic
configuration of neutral atom and then add (for negative charge) or
remove (for positive charge) electrons in outer shell according to the
nature and magnitude of charge present on the ion. e.g.
O( 8) = 1s2 , 2s2 2 p4, O2− (10) = 1s2 , 2s2 2 p6