Atomic theories

1
DEFINITION

First Atomic Theory

The atomic theory of matter was first proposed by John Dalton,

known as Dalton's atomic theory.
Dalton regarded that atom is the ultimate particle of matter.
2
DEFINITION

Fundamental Particles

Matter is made up of molecules and molecules are made up of

atoms.
Dalton's atomic theory proposed that atoms were indivisible. But
modern discoveries showed that atom is not indivisible and has a
complex structure.
Electrons, protons and neutrons are the fundamental particles of

atom.
Nucleons:
Protons and Neutrons are present in the nucleus and are called
Nucleons. Protons are positively charged with unit mass.
Neutrons are neutral with unit mass.
Electrons:
They are negatively charged with negligible mass.
3
DEFINITION

Cathode Ray Tube

Atomic structure was obtained from the experiments on electrical

discharge through gases. During the discharge tube experiment,
Crookes observed that rays were found to pass from
negatively charged filament (cathode) to positively charged plate
(anode). Cathode ray tube is made of glass containing two thin
pieces of metal, called electrodes, sealed in it. The electrical
discharge through the gases could be observed only at very low
pressures and at very high voltages. By maintaining low pressure
and high voltage in discharge tube, current or stream of particles
move in the tube from cathode to anode. Those rays are known
as cathode rays or cathode ray particles.
4
DEFINITION

Properties of Cathode Rays

Cathode rays starts from cathode and move towards anode.

These rays themselves are not visible but their behaviour can be
observed with the help of certain kind of materials (fluorescent or
phosphorescent) which glow when hit by them.
Rays travel in straight lines in the absence of electric and
magnetic field. In the presence of electric and magnetic field, they
are deflected which indicates that cathode rays contain
negatively charged particles known as electrons.
Cathode rays found to be independent of nature of the cathode
material and nature of the gas in the tube.
5

DEFINITION

Charge to Mass Ratio of an Electron

J.J.Thomson measured e/m ratio of the electron based on following

points. Greater the magnitude of the charge on the particle,
greater is the deflection when electric and magnetic field is
applied. Lighter the mass of the particle, greater will be the
deflection.
The deflection of electrons from its original path increases when
voltage increases from the above points, Thomson was able to
determine the value of charge to mass ratio as 1.758820 X
1011 Ckg1
6
DEFINITION

Charge of an Electron

Mullikan determined the charge of the electron by an oil drop

experiment By carefully measuring the effects of the
electrical field on the movement of many droplets. Charge on the
oildrops was always an integral multiple of 1.60 X 1019 c
me = ee/me = 1.6010191.7588201011ckg1 = 9.10941031kg
7
DEFINITION

Properties of Protons

Anode rays travel in straight line, and these are material particles.
Charge:
Anode rays are positively charged, and get deflected by external
magnetic field and affect the photographic plate.
em of Anode Rays:
em value of these rays is smaller than that of electrons.
em value of anode rays depends upon nature of the gas.
em value of anode rays is maximum when the gas present in the
tube is hydrogen.
Material in Anode Rays:
By the dissociation and ionisation of hydrogen under low pressure
discovered with charge +1 and mass 1, particles are called
proton.

8
DEFINITION

Atomic Models

Thomson's Model - J.J.Thomson, in 1898, proposed that an

atom possesses a spherical shape radius) approximately 1010m)
in which the positive charge is uniformly distributed. According to
Thomson, atom is like watermelon and electrons
are embedded like seeds in watermelon.The positive charge is
distributed like fibrous material of water melon. An important
feature of this model is that the mass of the atom is assumed to
be uniformly distributed over the atom. It cannot explain electrical
neutrality of the atom.
9
DEFINITION

Rutherford's Model of an Atom

Rutherford proposed atomic model based on - ray scattering

experiment. Scattering of a narrow beam of - particles as they
passed through a thin gold foil and it is covered with fluorescent
ZnS screen. When -particles struck the screen, then flash of
light was produced at that point.
10
DEFINITION

Observations of Rutherford's Model

Most of the - particles passes through the foil undeflected.

A small fraction of - particles were deflected by small angles.
A very few - particles bounced back were deflected by 180.
11
DEFINITION

Rutherford conclusions from his experiment

Rutherford drew the following conclusions from his experiment:

1.

Most of the space in the atom is empty.

2.

A few positively charged alpha particles were deflected. The

deflection must be due to enormous repulsive forces showing that
the positive charge of the atom is not spread out of the atom.
3.
Main postulates in Rutherfords model.

All the positive charge and mass of the atom is present in a

very small region at the centre of the atom. It is called nucleus.

The size of the nucleus is very small in comparison to the

size of the atom.

Most of the space outside the nucleus is empty.

The electrons revolve round the nucleus like planets revolve

round the sun.

The centrifugal force arising due to fast moving electrons

balances the coulombic force of attraction of the nucleus and
the electrons.

Rutherford's atomic model is comparable with the solar

system. So, it is called planetary model.
12
DIAGRAM

Defects of Rutherford's Atomic Model

It is against the law of electrodynamics.

It fails to explain the atomic spectrum or line spectrum.
13
DEFINITION

Atomic Number

A neutral atom contains equal number of electrons and protons.

The number of electrons or protons present in an atom of an
element is called its atomic number. Atomic number is denoted by
Z. Atomic number is equal to the nuclear positive charge of an
element.
14
DEFINITION

Mass Number

The sum of protons and neutrons in the atom of an element is

called its mass number. It is denoted by A. Mass number is always
a whole number. Number of neutrons = A - Z

15
DEFINITION

Isotopes

Atoms with identical atomic number but different mass numbers

are known as isotopes. Isotopes exhibit similar chemical
properties
Eg :
Isotopes of hydrogen:
Protium (1H1)
Deuterium (1H2) or D
Tritium
(1H3) or T
Isotopes of chlorine:
17Cl35 and 17Cl37
It is evident that difference between the isotopes is due to the
presence of different number of neutrons present in the nucleus.
For example, considering of hydrogen atom again, 99.985% of
hydrogen atoms contain only one proton. This isotope is
called protium (11H).
Rest of the percentage of hydrogen atom contains two other
isotopes, the one containing 1 proton and 1 neutron is
called deuterium (D, 0.015% ) and the other one possessing 1
proton and 2 neutrons is called tritium (T). The latter isotope is
found in trace amounts on the earth.
Isotopes of an element have the same number of protons and
electrons but differ in the number of neutrons.
16
DEFINITION

Isobars

Atoms with same atomic mass number with different atomic

number are known as isobars.
Eg : 146Cl , 147N
17
DEFINITION

Wave Length( )

The distance between two neighbouring troughs or crests in wave

is known as wave length.
The units of wave length are m, cm, A , nm,m.
1A =108 cm =1010 m
1nm = 1m = 10 A

Electromagnetic radiation

1
DEFINITION

Nature of Electromagnetic Radiaition

Cosmic rays, - rays, X - rays, UV light,visible light, Infrared light,

micro waves, TV waves and radio waves are
called electromagnetic radiation because they are made up
of electric and magnetic fields propagating in
perpendicular directions in one another. Electromagnetic
radiations have wave characteristics and no medium is required
for their propagation. They can travel through the vacuum. All
electro-magnetic radiations have same velocity.
2
DEFINITION

Frequency(v)

The number of waves that pass through a given point in one

second is called frequency.
The units of frequency are sec1, cycles per second (cps) or Hertz
(Hz).
1 cps = 1 Hz= sec1
3
DEFINITION

Wave Number(v)

The number of wavelengths per centimeter or the reciprocal of

wavelength is called wave number.
The unit of wave number is cm1 or m1
4
DEFINITION

Amplitude(A)

The height of the crest or depth of the trough of a wave is called

amplitude. Amplitude is a measure of the intensity or brightness
of a beam of light.
5
DEFINITION

Velocity(v)

The distance travelled by a wave in one second is called its

velocity.
The units of velocity are m/sec or cm/sec.
All types of electromagnetic radiations have the same velocity
which is equal to 3x1010 cm/ sec or 3x108 m/ sec
6
FORMULA

Relationship between Wave Characteristics

v = C or = Cv .......... (1)
v = 1 = vc ...........(2)
Where v = frequency in sec1
= wavelength in cm
C = velocity of light = 3x1010 cm/ sec
v = wave number in cm1
The wave length of UV light is 1800 - 3800 A
The wave length of visible light is 3800 - 7600 A
The wave length of IR radiation is 7600 - 31060 A
7
DEFINITION

Compton Effect

The increase in wave length or decrease in energy of the X - rays

after scattering from an object is called the Compton effect.
8
FORMULA

Planck's Quantum Theory

Substances absorb or emit light discontinuously in the form of

small packets or bundles.
The smallest packet of energy is called quantum.
The smallest particle of energy is called is called photon.
The radiation is propagated in the form of waves.
The energy of a quantum is directly proportional to the frequency
of the radiation - Ev
The energy of a quantum is
E = hv = hc = hcv
Where E = Energy in ergs
h = Planck's constant
= 6.625 x 1027 ergsec
= 6.625 x 1034 Joulesec
C = Velocity of light = 3 x 1010 cm/ sec
= 3 x 108 m/ sec
v = Frequency of radiation in sec1
= Wave length in cm
v = Wave number in cm1
A body can absorb or emit in whole number of
quantum (E=n(hv))
9
DEFINITION

Photo-Electric Effect

In 1887, H.Hertz performed a very interesting experiment that is

photo electric effect.
E = 12375 Where E = Energy in eV
= wavelength in A
The radiation is propagated in the form of photons. Planck's
equation determines both wave nature and particle nature of
light.
When light is exposed to clean metallic surface, electrons are
ejected from the surface. This effect is called photo electric
effect.
The electrons are ejected from the metal surface as soon as the
beam of light strikes the surface,i.e., there is no time lag between
the striking of light beam and the ejection of electrons.
Conditions for Photo-electric Effect:.

Ejection of electrons from the surface of a metal by irradiating it

with light of suitable frequency.
The photo electric effect is readily exhibited by alkali metals like K
and Cs.
A part of the energy of photon is used to escape the electron from
the attractive forces and the remaining energy is used in
increasing the kinetic energy of electron.
hv = W+KE
K.E. = 12meV2 , W = hvo
hv = hvo + 12meV2
me= mass of the electron, V = velocity of the ejected
electron, vo= Threshold frequency
Effect of Intensity and Frequency of Light:
In photo electric effect, the number of photo electrons emitted is
proportional to intensity of incident light.
Kinetic energy of photo electrons depends only on the frequency
of incident light and not on the intensity of light.
The minimum energy required for emission of photo
electrons is called threshold energy or work function.
For each metal, there is a characteristic
minimum frequency vo (also known as threshold
frequency) below which photoelectric effect is not observed. At a
frequency v > vo then photoelectric effect is observed.

Bohr's atomic model

1
DEFINITION

Spectra

Spectrum formed by rays and its properties:

1.

Sun light or light from an incandescent filament lamp gives a

continuous spectrum.
2.
When a gas or a vapour of a metal is kept in a discharge
tube and higher potential is applied, a line spectrum is formed.
3.
Each element has its own characteristic line spectrum.

4.

The characteristic lines in atomic spectra can be used in

chemical analysis to identify unknown atoms in the same way as
finger prints are used to identify people.
5.
The spectra obtained by the emission of energy by the
excited atoms are called emission spectra.
6.
These spectra consist of bright lines on the dark background.
7.
When white light is passed through a gas and the emergent
beam of light is allowed to fall on a photographic plate, the
spectrum obtained is called absorption spectrum.
8.
As the substance absorbs certain portion of white light, dark
lines appear on bright background.
9.
For a given element, dark lines in the absorption spectrum
coincides with the bright lines in the emission spectrum.
10.
An absorption spectrum is like the photographic negative of
an emission spectrum.
11.
German chemist, Robert Bunsen(1811-1899) was one of the
first investigators to use line spectra to identify elements.
2
DEFINITION

Hydrogen Spectra

The source of radiation here is a hydrogen discharge tube. The

discharge tube contains hydrogen gas at low pressure and high
potential difference. The bright light emitted from the discharge
tube is passed through a prism to cause dispersion. The emergent
beam of light falls on a photographic plate and is recorded as the
atomic spectrum of hydrogen. The hydrogen spectrum is the
simplest of all the atomic spectra. It contains a number of groups
of lines. They can be classified into various series.
Only one such series is visible to the naked eye and is termed as
the visible region of hydrogen spectrum. As it was discovered by
Balmer, it is called Balmer series.
3
DEFINITION

Balmer Series

The wavelength or wave number of various lines in the visible

region can be expressed by an equation.

v = 1 = R[1n211n22]
where n1 = 2 which is constant for all the lines in Balmer series.
n2 = 3, 4, 5......
R is Rydberg constant and its value for hydrogen is 1,09,677
cm1 (or) 1.09677 x 105 cm1
Ryedberg constant value is not same for all the elements.
The first line in Balmer series is called H line and its wavelength
is 6563 A. The second line is called H line and its wavelength is
4861 A
The spectral lines get closer when the n2 value is increased. If
n2 is taken as infinity the wavelength of the limiting line in the
series is obtained.
v = 1 = R[12212] = R4 = 27,419 cm1
The other series in the hydrogen spectrum are invisible.
The wavelength or wave numbers of all the lines in all the series
can be calculated by using Rydberg's equation
v = 1 = 1,09,678 (1n211n22 )
Maximum number of lines produced when an electron jumps from
nth level to ground level
= n(n1)2
4
DEFINITION

Series of Hydrogen Spectrum

The value of R = 1,09,678 cm1 is valid only for the lines in the
hydrogen spectrum.
For a spectral line of any one electron species like He+, Li2+ the
value of R = RHZ2
5
DEFINITION

Postulates of Bohr's Model

Energy Levels:
The electrons in an atom revolve around the nucleus in definite
circular orbits or shells or energy levels.
Stationary States:
So far an electron revolves in a certain orbit, its energy remains
constant and does not radiate energy. These orbits are called
stationary orbits or stationary states.
Angular Momentum of Electron in an Orbit:
Electrons can revolve only in those stationary orbits in which their
angular momentum is equal to integral multiple of h2
mvr = nh2
where m = mass of electron
v = velocity of electron, r = radius of orbit
n = 1 , 2 , 3 ,4 ......
h = Planck's constant
Just as linear momentum is the product of mass (m) and linear
velocity (v), angular momentum is the product of moment of
inertia (I) and angular velocity (). For an electron of mass m,
moving in a circular path of radius r around the nucleus, angular
momentum = I
Since I = mer2, and = v/r where v is the linear velocity,
angular momentum = mr2v/r = mvr
Difference in Energy Levels:
When an electron drops from a higher orbit to a lower orbit,
energy is released. When an electron jumps from a lower orbit to
a higher orbit,energy is absorbed. The absorbed or
evolved energy is equal to the difference in energies of two orbits,
which is equal to quanta.
E = E2 - E1 = hv
The line spectrum is obtained due to the electronic transition from
one orbit to another orbit.
Force of Attraction:
The force of attraction between the nucleus and the electron
= Ze2r2
The centrifugal force of the electron due to revolving around the
nucleus = mV2r
6

DEFINITION

Radius of Bohr's Orbit

Expression for the radius of Bohr's orbit

r = n2h24mZe2
where r = radius of orbit
n = 1, 2, 3, 4 ......
h = Planck's constant
m = mass of electron
Z = atomic number
e = charge of electron
Radius of Hydrogen atom,
r = 0.529 x 108 x n2 cm
= 0.529 x n2 A
Radius of orbits in H atom like ions
r = 0.529n2ZA
7
FORMULA

Velocity of an Electron in Hydrogen Atom

Velocity of electron in hydrogen atom

V = 2Ze2nh = 2.188108n cm/sec
where V = velocity of electron
e = charge of electron
n = 1, 2, 3, 4 .......
h = Planck's constant
For hydrogen atom,
Vn = V1n
where Vn = Velocity of electron in nth orbit
V1 = Velocity of electron in first orbit
n = 1, 2, 3, 4 ........
For H atom like ions.
Vn = ZV1n
where Vn = Velocity of electron in nth orbit
V1 = Velocity of electron in first orbitof H-atom
n = 1, 2, 3, 4 .......
Z = Atomic number
8

FORMULA

Energy in Bohr's orbit

Kinetic energy of electron = 12mV2

= Ze22r
Potential energy of electron = Ze2r
Total energy of electron
= KE+PE = Ze22rZe2r = Ze22r
Expression for the energy of Bohr's orbit
E = 22mZ2e4n2h2
where E = energy of orbit
m = mass of electron
e = charge of electron
n = 1, 2, 3, 4 ........
h = Planks constant
Effect of Kinetic,Potential and Total Energies
as n Increases:
As we go to higher orbits, kinetic energy decreases, potential
energy increases and the total energy increases.
Energy of orbits in hydrogen atom ( Z = 1 )
Energy Expressions in Different Units:
E = 2.1791011n2 ergs
= 2.1791018n2 joules
= 13.6n2 eV = 313.6n2 Kcal/mole
= 1312.6n2 KJ/mole
1eV = 1.6021019 J
The energy of the electron in a hydrogen atom has a negative
sign for all possible otbitals because the energy of the electrons in
the atom is lower than the energy of a free electron at rest.
Energy of orbits in H atom like ions
E = 2.1791011n2Z2 ergs
En = E1n2
where En = Energy of nth orbit in hydrogen atom
E1 = Energy of first orbit in hydrogen atom
n = 1, 2, 3, 4 .........
For Hydrogen atom like ions.
En = Z2n2E1
where En = Energy of nth orbit in other ions like H - atom
Z = Atomic number

n = 1, 2, 3, 4 ........
E1 = Energy of first orbit in hydrogen atom
Ionisation of Electron:
Ionisation Potential is the energy required for removal of electron
from the outermost orbit.
For hydrogen atom, Ionization potential = E1n2
For H atom, like ions, Ionisation potential = E1Z2n2
Ionisation potential of an atom or ion = 13.6 [Z2n2] eV
9
DEFINITION

Rydbergs constant

R = 22mZ2e4h3C = 109680cm1
Difference of energy between two Bohr orbits of hydrogen
atom
E = Rhc[1n211n22]
where E = Energy difference
R = Rydberg constant
h = Planck's constant
c = Velocity of light
n1 = lower orbit,
n2 = higher orbit
As the value of n increases, the difference of energy becomes
smaller. After a certain stage, the energy becomes nearly equal
and this position of continuum is called critical energy. If
energy is slightly greater than this given value, then the electron
will be completely removed from the atom.
Difference of energy between two orbits in H atom like ions.
E = Z2Rhc[1n211n22]
where Z = atomic number.
10
DEFINITION

Merits of Bohrs model

It successfully explains the hydrogen spectrum and spectra of

ions having one electron.
The experimental values of the energies and radii of possible

orbits in hydrogen atom are in good agreement with that

calculated on the basis of Bohr's theory.
The experimental value of Rydberg constant for hydrogen is in
good agreement with that calculated from Bohr's theory. The
calculated value of ionization energy of hydrogen using Bohr's
theory is very close to the experimental value.
11
DEFINITION

Limitations of Bohr's Model

1.

It failed to explain the spectra of atoms or ions having more

than one electron. The fine structure of spectral lines cannot
be explained by Bohr's theory.
2.
It failed to explain Zeeman effect and Stark effect.
3.
Bohr model of the hydrogen atom, not only ignores dual
behavior of matter but also contradicts Heisenberg uncertainty
principle.
Zeeman Effect:
The splitting of spectral lines of an atom into a group of fine lines
under the influence of a magnetic field is called Zeeman effect.
Stark Effect:
The splitting of spectral lines of an atom into group of fine lines
under the influence of an electric field is called Stark effect.

de-Broglie's hypothesis

1
DEFINITION

de-Broglie Wave Theory:

The wave nature of electron was first proposed by de Broglie.

According to de Broglie theory, all moving particles have wave
properties.
Wave properties are important only for particles of small mass
and high velocity.
de Broglie equation is = hmv = hp
where = wave length
h = Planck's constant = 6.625 x 1034 J.sec
v= Velocity of the particle

m = mass of the particle

p = Momentum of the particle
According to de Broglie's theory, electrons revolve around the
nucleus in atomic orbits with stationary waves.
Electrons revolve in those orbits, whose circumference must be
equal to integral multiple of wave length 2r = n
where r = radius of the orbit
n = 1, 2, 3, 4 .....
= wavelength
Number of waves in an orbit = n
Number of revolutions of an electron per second in an orbit
= Velocityofelectroncircumference
2
DEFINITION

Bohr's Theory and de-Broglie's Concept

According to de Broglie, an electron behaves as a standing or

stationary wave which extends around the nucleus in a circular
orbit.
If the two ends of the electron wave meet to give a series of
crests and troughs, the electron wave is said to be in phase. In
other words, there is constructive interference of electron waves
and the electron motion has a character of standing wave or nonenergy radiating motion.
To be an electron wave in phase, the circumference of the Bohr's
orbit should be an integral multiple of the wavelength of the
electron wave.
n = 2r
Explanation of de Broglie's Concept:
In case, the circumference of the Bohr's orbit (2r) is bigger or
smaller than n, the electron wave is said to be out of phase.
Then, destructive interference of waves occurs causing radiation
of energy. Such an orbit cannot possibly exist.
The wavelengths associated with ordinary objects are so short
(because of their large masses) that their wave properties cannot
be detected.

Heisenberg's uncertainty principle

1
DEFINITION

Heisenberg's Uncertainty Principle

It is impossible to determine accurately and simultaneously the

position and momentum of a particle in an atom. It is
called Heisenberg's uncertainty principle.
The uncertainty principle equation is
x . p h4
x . m v h4
where x = uncertainty in position
p = uncertainty in momentum
v = uncertainty in velocity
m = mass of the particle
h = Planck's constant
The uncertainty principle is mainly applicable for microscopic
particles.
Explanation for Heisenberg's Uncertainty Principle:
To observe an electron we can illuminate it with light or
electromagnetic radiation. The light used must have a wavelength
smaller than the dimesions of an electron. The high
momentum photons of such light (p=h) would change the energy
of electrons by collisions. In this process we, no doubt, would be
able to calculate the position of the electron, but we would
know very little about the velocity of the electron after the
collision.
If one of tries to find the exact location of the electron, say to an
uncertainty of only 108 m,then the uncertainty v in velocity
would be
104m2s1108m10+4ms1

which is so large that the classical picture of electrons moving in

Bohr's orbit (fixed) cannot hold good.

Orbitals and Quantum numbers

DEFINITION

Radial Probabilty Distribution

The probability of finding an electron at a certain distance from

the nucleus is calledradial probability.
The curves obtained by plotting probability
function D = 4r2dr2 and radial distance (r) are called radial
probability distribution curves.
Number of peaks obtained in a curve = n - l
where n = principal quantum number
l = Azimuthal quantum number
The nodal surface of 2s orbital exists at a distance of 2ao from
the nucleus. Where ao is the Bohr radius 0.529 A
The curve for 2s orbital has two peaks, the curve passes through
lower maximum at 0.53 A and higher maximum at 2.6 A radial
distance.
2
DEFINITION

Orbitals

The space around the nucleus of an atom in which there is

a maximum probability of finding an electron is called an
orbital.
The maximum probability of finding an electron in an orbital is 95
%.
The plane where the probability of finding the electrons is
zero (2=0 ) is called a nodal plane.
Number of nodal planes in an orbital = l.
3
DEFINITION

s orbital

The shape of s orbital ( l = 0 ) is spherical.

s - orbital is a non directional orbital.
4
DEFINITION

p orbital

In a p - sub shell, the three orbitals are represented as px, py, and
pz. These are degenerate orbitals.
The shape of a p - orbital ( l = 1 ) is dumbbell.
p - orbitals are oriented along the axes. So they are directional
orbitals.
Orbital : px py pz
m
: 1
1 0
5
DEFINITION

d orbital

In a d - sub shell, the five orbitals are represented as dxy, dyz,

dzx, d{x2y2} and d2z.
These are degenerate orbitals.
The shape of a d - orbital ( l = 2 ) is double dumbbell.
dxy, dyz and dzx orbitals are oriented in between the axes
dx2y2 and d2z orbitals are oriented along the axes.
Orbital : dxy
dyz
dzx
dx2y2
d2z
m
: 2
1 1 2 0
6
DEFINITION

No. of nodal planes

When the number of nodal planes increases, the energy of the

orbital increases.
So the energy order of the orbitals is s < p < d < f
Number of radial nodes = nl1
where n =principal quantum number
l = Azimuthal quantum number
7
DEFINITION

Quantum Numbers

A set of numbers used to provide a complete description of an

electron in an atom are called quantum numbers.
There are four quantum numbers required for a complete
explanation of electrons in an atom.
The quantum numbers are
n-Principal quantum number
l-Azimuthal quantum number

m- Magnetic quantum number

s-Spin quantum number
8
DEFINITION

Principle Quantum Number(n)

It was proposed by Niels Bohr.

Possible Values of Principle Quantum Number:
The values of n =1, 2, 3, 4 ..... or K, L,M, N ....... respectively.
It indicates the size and energy of the orbit.
The maximum number of electrons in an orbit = 2n2
Total number of orbitals = n2
where n = no.of the orbit
Angular momentum of an electron in an orbit = nh2
9
DEFINITION

Azimuthal Quantum Number(l)

It was proposed by Sommerfield.

Possible Values of Azimuthal Quantum Number:
The values of l = 0, 1, 2, .....( n -1 ).
The values of l represents various sub shells. When l = 0, 1, 2,
3 ...... etc are called s, p, d, f ....... sub shells respectively.
Energies are in the order of s < p < d < f .
It indicates the shape of orbit or orbital and angular momentum of
electron.
Number of sub shells in an energy level = n
where n = no.of the orbit
Angular momentum of the electron in an orbital = h2l(l+1)
= hl(l+1)

(h=h2 )
where h = Planck's constant
l = Azimuthal quantum number
10
DEFINITION

Magnetic Quantum Number (m)

It was proposed by Lande.

Possible Values of Magnetic Quantum Number:
The values of m = +l ..... 0 ..... -l.
The total m values = 2l + 1
The total number of m values indicates the total number of
orbitals in the subshell.
The number of orbitals in s, p,d and f sub shells are 1, 3, 5 and 7
respectively.
It indicates the orientation of orbitals in space.
The number of orbitals in an energy level n2
The number of orbitals in a sub shell = 2l + 1
Maximum number of electrons in a subshell 2(2l + l)
where l = Azimuthal quantum number.
11
DEFINITION

Spin Quantum Number (s)

It was proposed by Goudsmit and Uhlenbeck.

Possible Value of Spin Quantum Number:
The values of s = +12 and 12
The clock wise direction spin is represented by +12 and anticlock
wise direction spin is represented by 12
For each value of m, there can be two values.
It indicates the direction of the spin of the electron.
Maximum number of electrons in an orbital = 2.
The maximum number of electrons present in s, p, d and f shells
are 2, 6, 10 and 14 respectively.

Important Principles

1
DEFINITION

Pauli's Exclusion Principle

No two electrons in the same atom can have the same values for
all the four quantum numbers.
Two electrons in a given orbital have same values of n, l and m.

Electrons in the same orbital differ in their spin quantum number

and they spin in opposite directions.
Consequence of Pauli's Exclusion Principle:
An orbital can not accommodate more than two electrons.
2
DEFINITION

Aufbau Principle

Electron filling follows energy ranking.

The orbitals are successively filled in the order of their increasing
energy.
Among the available orbitals, the orbitals of lowest energy are
filled first.
Energy of the Orbital in terms of n+l:
The energy value of an orbital increases as its (n+l) value
increases.
If two orbitals have the same value for (n+l), the orbital having
lower n value is first filled.
3
DEFINITION

Hund's Rule

Orbitals of the same kind should be half filled before electron

pairing takes place.
Degenerate Orbitals:
Orbitals having the same values for n and l are called degenerate
orbitals.
Unpaired electrons have parallel spin.
Half filled and completely filled degenerate orbitals give greater
stability to atoms.
Example:
Chromium (Z = 24) and copper (Z = 29) have anomalous
electronic configuration due to this reason.

Electronic configuration of chromium atom

is 1s2 2s2 2p6 3s23p6 3d5 4s1 but not 1s2 2s2 2p6 3s23p6 3d4 4s2.
4
DEFINITION

Stability of Completely Filled and Half Filled Sub-Shells

The valence electronic configurations of Cr and Cu are 3d54s1 and

3d10 4s1 respectively and not 3d4 4s2 and 3d94s2.
Reasons:
The completely filled and completely half filled sub-shells are
stable due to the following reasons.
Symmetrical distribution of electrons:
It is well known that symmetry leads to stability. The completely
filled or half filled subshells have symmetrical distribution of
electrons in them and are therefore more stable.
Exchange Energy:
The stabilizing effect arises whenever two or more electrons with
the same spin are present in the degenerate orbitals of a
subshell. These electrons tend to exchange their positions and the
energy released due to this exchange is called exchange energy.
The number of exchanges that can take place is maximum when
the subshell is either half filled or completely filled. As a result the
exchange energy is maximum and so is the stability.