Class XI

Structure of atom

Content

Sub atomic particles
Ruther fords atomic Model
Black body radiations
Planks quantum theory
Photoelectric effect
Bohrs atomic model
De-Broglies equation
Heisenbergs uncertainty principle
Quantum number





























The first atomic theory was proposed by John Dalton on the basis of the law of
conservation of mass and law of definite proportions. He regarded the atom as the
ultimate particle of matter.
J.J Thomson discovered electron and he calculated charge to mass ratio for electron
(e/m = 1.76 x 10
11
C kg
-1
). The e/m ratio is also called specific charge and was found to
be independent of the nature of gas and electrode used.
Thomson also proposed atomic model in which he assumed the atom possesses a
spherical shape radius approximately (10
10
m) in which the positive charge is uniformly
distributed. This model is also known as raisin pudding model. It explained the stability
and electrical neutrality of atom.
Goldstein discovered anode (or positive or canal) rays. The specific charge of anode
rays was found to vary with nature of gas. If H
2
is used, then these positively charged
particles are called protons.
Ruther fords Atomic model
While bombarding the gold foil with high speed, particles, Ruther ford noticed that
i. Most of the particles passed without any deflection
ii. Some of the particles were deflected from its path.
iii. A very few -particle (1 in 20,000) bounced back, i.e., were deflected by nearly
180
0
.
On the basis of the observations Rutherford drew the following conclusions regarding
the structure of atom:
i. Most of the space in atom is empty.
ii. The presence of positively charged nucleus at the centre, with all its protons.
iii. Electrons are present in the extra nuclear part of atom that moves around the
nucleus with high speed in circular orbits.
iv. Electrons and nucleus are held together by electrostatic force of attraction.
The ideal body, which emits and absorbs all frequencies is called a black body and the
radiation emitted by this body are called black body radiations. The exact frequency
distribution of emitted radiations from a black body depends upon its temperature.
According to Plancks quantum theory, the energy is emitted or absorbed only in
descrete units or packets of energy called photon (or quantum). The energy of one
photon is given by:-
E = hv
Where v = frequency and h = Plancks constant
or E =
hc

Where h = Plancks constant and has the value 6.626 x 10
-34
js
Electrons come out as soon as a beam of light falls on the surface of the metal if the
frequency of incident light is greater than threshold frequency.
h = h
o
+ K.E
Concept of Photon:
A particle travelling with the speed of light must be mass less (rest mass, m
o
= 0) or its effective
mass during motion will be infinite.
m =
2 2
o
/c 1
m
v



Note : Photoelectric effect explains the particles nature of light. But light has both wave and
particles properties i.e. it has dual nature.
Bohrs Atomic Model:
Bohrs model was given in order to remove the drawbacks of Ruther fords model. The
main postulate of the Bohrs theory are:-
i. The electron in the hydrogen atom can move around the nucleus in a circular path of
fixed radius and energy. These paths are called orbits.
ii. As long as electron stays in the same orbit, it does not radiate energy.
The emission or absorption of energy takes place only when the electron jumps from
one energy level to another. This takes place in the form of photons.
E = E
2
- E
1
= hv
iii. The angular momentum of electron in closed cell is quantized.

2
nh

= mvr
According to Bohrs theory of hydrogen atom
I. The stationary states for electron are given as n = 1, 2, 3. these integral numbers are
known as principal quantum numbers.
II. Expressions for radius, energy and velocity of electron moving in n
th
orbit of hydrogen
atom (or hydrogen like species).
1.
( )
(

=
0
2 2
2
2
4 / Ze m 4
h
n r = 0.529
Z
n
2

2.
( )
(

=
2
2
0
2 2
2
h
4 / e Z m 2
n
1
E = 21.8 10
12

2
2
n
Z
erg per atom
= 13.6
2
2
n
Z
eV per atom = 313.6
2
2
n
Z
Kcal per mol
3.
( )
nh
4 / e Z 2
0
2

= = 2.18 10
8

n
Z
cm/sec.
The expression of spectral transitions is
E = Z
2
R
h
hc
|
|

\
|

2
2
2
1
n
1
n
1

where R
H
, known as Rydberg constant,
R
H
=
( )
1 7
3
2
0
2 2
m 10 09678 . 1
c h
4 / e m 2

=


Hydrogen Spectra
The emission spectrum of hydrogen was first studied by Bohr in 1914. The situation in
this case being simplified by the fact that the hydrogen atom has only one electron. the
spectrum of hydrogen consists of five sets of discrete lines occurring in the ultra-violet,
visible and infra-red regions of the electromagnetic spectrum. These sets are known as
Lyman series, Balmer series, Paschen series, Brackett series and Pfund series, after the
men who detected them.
It was also found that the lines in the series were related to one another and could be
represented in a single formula
|

\
|
=
2 2
H
m
1
n
1
R

1

is the corresponding wavelength, R
H
is a constant (Rydberg constant), n and m are
whole numbers related to the series as follows:
Lyman series n = 1 M = 2, 3, 4
Balmer series n = 2 m = 3, 4, 5
Paschen series n = 3 m = 4, 5, 6
Brackett series n = 4 m = 5, 6, 7
Pfund series n = 5 m = 6, 7, 8
Bohr model failed to
i. Explain the spectra of atom containing more than one electron.
ii. Explain the fine structure in the spectrum of H atom using high resolution
spectroscopic techniques.
iii. Explain the ability of atoms to form molecules by chemical bonds
The important discoveries which results in the failure of Bohr model were:
i. Dual behavior of matter i.e., De Broglies Equation: According to which electron
has a dual character, both as a material particle and as a wave. Wavelength , of
a particle of mass m, moving with velocity V is expressed as
=
mV
h
(h = Plancks constant)
ii. Heisenberg uncertainty principle i.e., According to this principle it is not possible
to determine precisely both the position and the momentum ( or velocity) of a
microscopic moving particle. Mathematical expression is x p
4
h

In an atom, large numbers of orbital are possible which can be distinguished by size,
shape and their orientation. Each orbitalis defined by three quantum numbers, n, l and m
i. Principle quantum number (n) determines the size of atom, the number of
orbitals in a given shell (n) = n
2
and its value varies 1 to n.
ii. Azimuthal quantum number (l) defines the three dimensional shape of the
orbital. For the given value of n, l can have n values ranging from 0 to n-1.
iii. Magnetic quantum number determines the orientation of orbital in space, the
number of values of m is given by 2 l + 1. Its value varies from l to 0 to + l
iv. Spin quantum number determines the spin of an electron. It has two values. S =
1/2 (clockwise direction), s = -1/2 (anticlockwise direction)

Electrons are filled in to various orbitals in order to increasing energy. This is known as
the Aufbaus principle. The energy of orbital depends upon (n + l) value. The increasing
order of energy of orbital is 1s < 2s <2p < 3s < 3p < 4s < 3d < 4p <5s< 4d < 5p <6s < 4f
< 5d <6p <7s <5f <6d <7p
Orbitals of same energy are called degenerate orbitals (like px, py, pz)and according to
Hunds rule of maximum multiplicity no pairing of electrons starts in degenerate
orbitals until or unless each one is singly filled.
The orbital can accommodate maximum of two electrons with opposite spins and no
electrons in an atom can have same set of four quantum numbers. This is known as
Paulis Exclusion principle.
Orbital Angular Momentum of Electron:
L =

+
2
h
) 1 (l l
l = azimuthal Q.N. = 0,1,2,3 ---------, for s,p,d,f ------------ sub shells of orbitals, respectively
Z - component of orbital angular momentum of an electron in an orbital is given by
|

\
|

=
2
h
m L
Where m = l to +l including zero (only integral value)
If be the angle between Z axis and angular momentum vector then
L
2
= L cos Or |

\
|
2
h
m =

+
2
h
) 1 (l l Cos
Or m = ) 1 ( + l l cos
Since m ) 1 ( + l l , so, 0
Spin angular momentum of electron, L
s
= 1) s(s +
2
h

Number of possible spectral lines that may be emitted by a sample of one electron system
(atom or ion) containing all or some speeds excited to nth energy level =
2
1) n(n

Number of revolutions per second made by an electron in n
th
orbit =
n
n
r 2
V

= n