Atomic Structure

Rutherford's nuclear model

Rutherford carried out experiment on the bombardment of
thin (10–4 mm) Au foil with high speed positively charged  
particles.
He concluded that, an atom consists of
(i) Nucleus which is small in size but carries the entire mass
i.e. contains all the neutrons and protons.

Properties of the nucleus

(i) The small, heavy and positively charged portion of the
atom is known as nucleus. It is located at the centre of the
atom and discovered in 1911 by Ernest Rutherford.
(ii) Protons are positively charged particles.
(iii) Neutrons and protons are present in the nucleus hence
they are collectively known as nucleons.

Drawbacks of Rutherford's model

(i)According to it “An electron moving around the nucleus
continuously loses its energy and should set up spiral motion
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ultimately failing into the nucleus”’. Hence this model does
not able to explain how the moving electrons could remain
in its orbit.
(ii) It does not able to explain the discontinuous spectrum and
the line spectra of H  atom.
Planck's quantum theory
According to this theory, the energy of each quanta is directly
proportional to the frequency (  ) of the radiation, i.e.
Lets,
c hc
E   or E  hv; v  Thus, E 
 

Where, h is proportionality constant also known as Planck’s

constant.
h = 6.626 10 Joules sec. or 6.626×10–27 erg sec.
34

Photoelectric effect
Einstein’s photoelectric effect equation
According to Einstein,
Maximum kinetic energy of the ejected electron = absorbed
energy – threshold energy
1 1 1 
2
mv max  h   h  0  hc   
2    0 

Where,  and 0 0 are threshold frequency and threshold

wavelength.

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 Bohr’s atomic model
The Bohr postulates are,
(1) An atom consists of positively charged nucleus
(2) The electrons revolve around the nucleus in circular orbits
(3) The circular orbits are those for which the angular
momentum of an electron is an integral multiple of h / 2 where
h is the Planck’s constant.

L  mvr 
nh
2
; n  1 , 2, 3, …… 
Where L is the orbital angular momentum and n is the number
of orbit.
(4) When electrons move in permitted discrete orbits they do
not radiate or lose energy.

Advantages of Bohr’s theory

(i) Bohr’s theory satisfactorily explains the spectra of species
having one electron, viz. hydrogen atom, He , Li etc.
 2

(ii) Calculation of radius of Bohr’s orbit: According to Bohr,

radius of nth orbit in which electron moves is
 h2  n2
rn   2 2 .
 4 me k  Z

Where, n  Orbit number, m  Mass number 9.1  10 kg , e  Charge

31

on the electron 1.6  10  Z  Atomic number of element, k =

19

Coulombic constant 9  10 Nm c 
9 2 2

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After putting the values of m,e,k,h, we get.
n2
rn   0 . 529 Å
Z

(iii) Calculation of velocity of electron

1/2
2e 2 ZK  Ze 2  2 .188  10 8 Z
Vn 
nh
, Vn   
 mr 
;V n 
n
cm . sec 1

(iv) Calculation of energy of electron in Bohr’s orbit

Total energy of electron = K.E. + P.E. of electron
kZe 2 kZe 2 kZe 2
  
2r r 2r
 2 2 mZ 2 e 4 k 2
Substituting of r, gives us E
n 2h2
Where, n=1, 2,
3………. 
Putting the value of m, e, k, h,  we get
Z2
E  21 .8  10 12  erg per atom
n2
Z2 Z2
 21 .8  10 19  J per atom (1 J  10 7 erg) E  13 .6  eV per atom(1eV  1.6  10 -19 J )
n2 n2
Z2
 13 .6 
n2
k .cal / mole (1 cal = 4.18J)
1312
or n2
Z 2 k Jmol 1

When an electron jumps from an outer orbit (higher energy)

n to an inner orbit (lower energy) n , then the energy emitted in
2 1

form of radiation is given by

2 2 k 2 me 4 Z 2  1 1 
E  En2  En1  
h2  n2  n2 
 1 2 

 1 1 
 E  13 . 6 Z 2  2  2 eV / atom

 n1 n 2 

E
As we know that E  h  , c   and   1 
hc
,

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 2 2 k 2 me 4 Z 2  1 1 
  
ch 3  n2  n2 
 1 2 

 1 1 
This can be represented as 1

   RZ 2  2  2 
 1
n n 2 

2 2k 2me 4
Where, R
ch3
; R is known as Rydberg constant.

Spectral series

S.No. Spectral series Lies in the region Transition

n 2  n1

(1) Lymen series Ultraviolet region n1  1 ,

n 2  2,3, 4....

(2) Balmer series Visible region n1  2 ,

n 2  3, 4,5....

(3) Paschen series Infra red region n1 = 3,

n 2  4,5, 6....

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 (4) Brackett series Infra red region n1  4 ,

n 2  5, 6, 7....

(5) Pfund series Infra red region n1  5 ,

n 2  6, 7,8....

Dual nature of electron

According to the French physicist, Louis de Broglie, if light
has an electron then it behaves as both a material particle and
a wave.

The wavelength associated with a particle of mass m, moving

with velocity v is given by the relation
, where h = Planck’s constant.
h

mv

According to Planck’s equation, E  h 

h.c

 c
   
 

on the basis of Einstein’s mass energy relationship, E  mc 2

on equating both hc

 mc 2 or  
h
mc
which is same as de-Broglie
relation.  mc  p
Heisenberg’s uncertainty principle
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 This principle states “It is impossible to specify at any given
moment both the position and momentum (velocity) of an
electron”.
Mathematically it is represented as, x . p  4h
Where x  uncertainty is position of the particle, p 

uncertainty in the momentum of the particle

Now since p  m v
So equation becomes, x. m v  4h or x  v  4hm
In terms of uncertainty in energy, E and uncertainty in time t,

this principle is written as, E . t 

h
4

Schrödinger wave equation

(1) Schrodinger wave equation based on the dual nature of
electron, is given by Erwin Schrödinger in 1926.
(2) With the help of this wave equation, we can find the
probability of an electron at any point around the nucleus.
The probability of an electron at any point around the nucleus is-
2 2 2 8 2m
   (E  V )   0
x 2 y 2 z 2 h2

Here, x, y and z are the 3 space co-ordinates, m is the mass of

electron, h is Planck’s constant, E is Total energy, V is
potential energy of electron,  is amplitude of wave also
called as wave function and  is an infinitesimal change.
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Quantum numbers
Orbital in an atom is specified by a set of three quantum nu
mbers (n, l, m) and a set of four quantum numbers (n, l, m a
nd s) is specified for each electron.
(1) Principle quantum number (n)
The principal quantum number proposed by Bohr and denoted
by ‘n’. It describes the energy of an electron in an orbit and the
most probable distance between the electron and the nucleus. In
other words, it denotes the size of orbital.

(2) Azimuthal quantum number (l)

Azimuthal quantum number proposed by Sommerfield and
denoted by ‘l’. It is also known as angular
momentum quantum number or secondary quantum
number. It describes the shape and number of the orbital(sub
shells) to which the electron belongs. The value of l is always
equals to (n  1) . Where ‘n’ is the number of principle shell.
Thus, the lowest possible value of l is 0, and its highest possible
value, is n - 1. Following values of l are given below.

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 Value of l = 0 1 2 3…..(
n-1)
Name of = s p d f
subshell
Shape of = Sp Du Doub Com
subshell her mbb le plex
ical ell dumb
bell
It also represents the orbital angular momentum. That is equal
to 2h l(l  1)
(3) Magnetic quantum number (m)
Magnetic quantum number denoted by ‘m’. It
describes the number of permitted orientation of the
orbital(sub shell). The value of m varies from –l to +l
through zero. For a given value of ‘n’ the total value of
‘m = n ” , for a given value of ‘l’ the total value of ‘m =
2

2l  1" and the number of degenerate orbitals of s subshell =

0.
(4) Spin quantum numbers (s)
Spin quantum number denoted by ‘m’.It signifies the spin or
rotation or direction of electron on it’s axis during movement.

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The value of it is either 1/2 or-1/2
. If the spin of electron is
clockwise then value of S will be 1/2 and if its direction is
anticlockwise then value of S will be -1/2 .
It represents the value of spin angular momentum. That is
equal to 2h s(s  1).

Rules for filling of electrons in various orbitals

The atom is built up by filling electrons in various orbitals
according to the following rules,
(1) Aufbau’s principle
This principle states that the electrons are added one by one
to the various orbitals in order of their increasing energy
starting with the orbital of lowest energy. The increasing
order of energy of various orbitals is
1s  2 s  2 p  3 s  3 p  4 s  3d  4 p  5 s  4 d  5 p  6 s  4 f  5d  6 p  7 s  5 f  6d  7 p.........

(2) (n+l) Rule

In neutral isolated atom, the lower the value of (n + l) for an
orbital, lower is its energy. However, if the two different types
of orbitals have the same value of (n + l), the orbitals with
lower value of n has lower energy.
(3) Pauli’s exclusion principle

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According to this principle “no two electrons in an atom will
have same value of all the four quantum numbers”.
(4) Hund’s Rule of maximum multiplicity
“Electron pairing in p, d and f orbitals cannot occur until each
orbitals of a given subshell contains one electron each or is
singly occupied”.

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