UNIT 2 STRUCTURE OF ATOM

 All matter is composed of extremely small particles called atoms.

 The atom consists of smaller particles such as electron, proton and neutron.
 These particles are regarded as fundamental particles.
DISCOVERY OF ELECTRONS
 The electrons were discovered by conducting an experiment by using a simple
apparatus known as discharge tube or Crookes tube.
 It consists of a sealed glass tube of about 50 cm lengths.
 Two metal electrodes are fused to the ends.
 A side tube is connected to a vacuum pump.
 The discharge tube is filled with a gas under study.
 The two electrodes are connected to a source of high voltage.
OBSERVATIONS
 When the discharge tube containing the gas is at 1 atm pressure and at high
voltage, the gas remains non conducting.
 When the pressure of the gas inside the tube is less than 1 mm of mercury, a
dark space appears near the cathode.
 This is known as Crookes dark space.
 When the pressure is reduced to 0.01 mm Hg, it fills the entire tube.
 When the pressure is further reduced to 10-4 mm Hg, the electric discharge
passes between the electrodes and the tube begins to glow.
 This is due to the striking of some invisible rays from the cathode.
 These rays which start from the cathode and move towards the anode, in
straight lines.
 These rays are called cathode rays or cathode ray particles.
 These rays consist of negatively charged material particles called electrons.
PROPERTIES
OF CATHODE
RAYS
 Cathode rays travel
in straight
lines.
 Cathode rays produce mechanical effects.

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 When an electric field is applied to a stream of cathode rays, they get deflected
towards the positive plate.
 It indicates that cathode rays themselves are negatively charged.
 When a magnetic field is applied perpendicular to the path of cathode rays, they
get deflected in the direction expected for negative particles. This direction of
deflection shows that cathode rays are –vely charged.
 When cathode rays are allowed to strike a thin metal foil, it gets heated up.
 Cathode rays produce, x-rays when they strike hard metals like tungsten, copper
etc.
 Cathode rays produce fluorescence on glass walls, ZnS etc.
 Cathode rays penetrate through thin metallic foils.
 Cathode rays affect photographic plates.
DETERMINATION OF CHARGE TO MASS RATIO (e/m) OF ELECTRONS
 In 1897 J.J. Thomson determined the e/m of the electron.
 He measured the deflection of cathode rays under the simultaneous influence of
electric and magnetic fields.

 A narrow beam of cathode rays is generated by electric discharge in a gas at low

pressure.
 It produces fluorescence on the screen at the other end of the tube.
 If an electric field is applied at right angles to the beam, the beam having
negative charge is attracted to the positive plate of the field.
 The beam thus travels a parabolic path and strikes at another point on the
screen.
 A magnetic field is now applied to the beam in a direction at right angles to that
of the electric field.
 The beam undergoes deflection in the opposite direction.
 The strength of the two fields are so adjusted that the beam strikes the
screen at the original position.

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 From the strength of the two fields, the ratio e/m can be calculated.
 The e/m value is found to be 1.76 x 108 Coulombs/g.
DETERMINATION OF CHARGE OF AN ELECTRON
 The charge of an electron was determined by Robert Millikan in 1909 by oil drop
experiment.
 In this method, a spray of oil droplets is produced by an atomizer.
 The oil droplets enter the apparatus through a small hole.
 It allowed to fall in between two
charged plates.
 The motion of the droplets is
observed with a telescope.
 The space between the charged
plates is irradiated with x-rays.
 The x-rays ionize the molecules
of the air.
 One or more electrons produced may be absorbed by an oil droplet.
 The oil droplet as a result becomes negatively charged.
 By measuring the velocity of a given oil droplet as it falls freely under the
influence of gravity and then in an electric field, it is possible to calculate the
charge on the droplet.
 This charge is considered to be electronic charge.
 The charge on the electron is found to be 1.602 x 10 −19 coulombs.
CALCULATION OF MASS OF THE ELECTRON
 From the values of e and e/m, the mass (m) of the electron is calculated by
dividing e by e/m.
e  1.602x1019
e  1.76x108 C / g
m
e 1.602x1019

e 1.76x108 C / g
m
m = 9.1x10-28 g

m  9.1x1031kg / e

 An electron is a fundamental particle of atom carrying a unit negative charge.

1 th
 The mass nearly equal to of mass of an atom of hydrogen.
1837
ANODE RAYS OR CANAL RAYS

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 Goldstein in 1886 discovered the existence of a new type of rays in the discharge
tube.
 He repeated the discharge tube experiment by using a perforated cathode.
 The discharge tube is evacuated and a high voltage is applied across the
electrodes.
 He observed a new type of rays streaming behind the cathode.
 These rays were named as anode rays or canal rays.
 These rays travel in opposite directions to the cathode rays.

PROPERTIES OF ANODE RAYS

 Anode rays travel in straight lines.
 Anode rays consist of material particles.
 Anode rays are positively charged.
 When a magnetic field is applied, they get deflected in the direction expected for
positive particles.
 Anode rays produce heating effects.
DISCOVERY OF PROTON
 Protons were discovered by E. Goldstein.
 A proton is a subatomic particle having a unit positive charge and a mass nearly
equal to that of hydrogen.
 Charge of proton = 1.602 x 10−19 C
 Mass of proton = 1.672 x 10 −24 g

ORIGIN OF CATHODE
RAYS AND ANODE RAYS

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 Under the influence of high electric field, the gas in the discharge tube is ionized.
 This results in the formation of particles with positive and negative charge.
 The negatively charged particles move towards the anode at very high speeds.
 On their way they collide with the atoms of the gas producing more electrons
and positively charged particles.
 The electrons move towards the anode in the form of cathode rays.
 The positive ions move towards cathode in the form of anode rays.
EARLIER ATOM MODELS
THOMSON’S MODEL OF ATOM
 The first atom model was proposed by J.J.
Thomson.
 According to this model, an atom may be
considered as a sphere of positive charge.
 The electrons are uniformly distributed to make
the atom as a whole electrically neutral.
 Therefore, this atom model is known as plum pudding model.

RUTHERFORD’S α -PARTICLE SCATTERING EXPERIMENT

 In order to find out the arrangement of electrons and protons, Rutherford in
1911 conducted a scattering experiment.

 He bombarded a thin gold foil with a stream of fast moving +vely charged α −

particles emitting from a radioactive element.

 A movable circular screen coated with zinc sulphide was placed at the back of the

gold foil to detect whether the α −particles undergo any deviation in their path

on passing through the foil.

OBSERVATIONS

 Most of the α -particles passed through the gold foil without any deviation.
 Some of the α -particles were deflected by small angles.
 A very few α -particles bounced back.

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CONCLUSIONS

 Since most of the α -particles pass through the gold foil without any deviation, it

indicates that most of the space in an atom is empty.

 α -particles being positively charged and having considerable mass could be

deflected only by some heavy positively charged centre.

 The small angle of deflection of α-particles indicated the presence of heavy

positive centre in the atom.

 Rutherford named this +ve centre as nucleus.

 A few of the α -particles are bounced back due to the direct collision with the

nucleus.

RUTHERFORD’S NUCLEAR MODEL OF ATOM

The main features of this model are
 In an atom, the entire mass and the positive charge is concentrated in a very
small region at the centre known as nucleus.
 The magnitude of the positive
charge on the nucleus (number
of protons) is different for
different atoms.
 The nucleus is surrounded by
negatively charged electrons
which balance the positive
charge on the nucleus.
 The electrons are not stationary but are revolving around the nucleus at very
high speeds.
 Most of the space in an atom is empty.
Nuclear model of an atom can be compared with the solar system.

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 In an atom, the electrons revolve around the nucleus like planets revolve around
the sun.
 The nucleus represents the sun and the electron represents the planets.
 Therefore, this model is also referred to as planetary model of atom and the
electrons are called planetary electrons.
ATOMIC NUMBER (Z)
 The number of unit positive charges carried by the nucleus of an atom is termed
as the atomic number.
 The positive charge on the nucleus is due to the presence of protons in it and
each proton carries unit positive charge.
 The atomic number is numerically equal to the number of protons present in the
nucleus of the atom.
 The number of protons in an atom is equal to the number of electrons.
DISCOVERY OF NEUTRON
 Neutrons were discovered by Chadwick in 1932.

 He bombarded Beryllium with α-paricles.

 The emitted radiation consists of a new particle carrying no charge.
 He called the particle, neutron.
9Be  4He  12C  1n
4 2 6 0
 A neutron is a subatomic particle having a mass equal to that of hydrogen atom
and carrying no electrical charge.
 The mass of neutron is found to be 1.675 x 10 −24 g.

MASS NUMBER (A)

 The mass of an atom is mainly due to protons and neutrons.
 Protons and neutrons are collectively known as nucleons.
 The total number of protons and neutrons in the nucleus is called mass number
of the atom.
 It is generally represented by ‘A’.
 Mass number = No. of protons + Number of Neutron
 No. of Neutrons = Mass Number − Atomic Number i.e., (A―Z)
ISOTOPES
 Atoms of an element with the same atomic number but different mass numbers
are called isotopes.
 For example, hydrogen has three isotopes.

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 They are Protium ( 11H ), Deuterium ( 21H ) and Tritium ( 31H ).
12 13 14
 Carbon has three isotopes namely, 6
C, 6
C, 6
C.

ISOBARS
 Atoms having the same mass number but different atomic numbers are called
Isobars.
40 40 40
 For example, 18
Ar , 19
K, 20
Ca are isobars.
14 14
 Similarly, 6
C and 7
N are isobars.

ISOTONES
 Atoms having the same number of neutrons but different mass numbers are
called isotones.
30 31 32
 For example, 14
Si , 15
P and 16
S are isotones.

NATURE OF ELECTROMAGNETIC RADIATION

 According to Newton’s Corpuscular theory, light is propagated as a stream of
minute particles called corpuscles of light.
 This theory of light could explain the phenomena of reflection and refraction.
 Failed to explain the phenomena of diffraction and interference.
 Therefore, the corpuscular theory was rejected.
 Later, James Clark Maxwell in 1856 suggested that light propagates through
space in the form of waves.
 These waves are associated with electric and magnetic fields.
 Therefore, these waves are called electromagnetic waves or electromagnetic
radiations.
CHARACTERISTICS OF ELECTROMAGNETIC RADIATIONS
 It propagates through space in the form of waves.
 It travels with a velocity of light.
 It requires no medium for transmission.
 The energy of electromagnetic radiation is directly proportional to its frequency
or inversely proportional to its wavelength.
CHARACTERISTIC OF A WAVE
1. Wave length (λ)
 The distance between two adjacent crests of troughs is called wavelength.
 It is denoted by the Greek letter lambda (λ)
 It is generally expressed in terms of Angstrom units.
1Å = 10−10 m or 10−8 cm.

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2. Frequency (υ)
 The number of waves which pass through a given point in one second is known
as the frequency.
 It is denoted by the Greek letter nu (υ).
 The units of frequency are cycles per second or Hertz (Hz).
1 Hz = 1 cycles / sec
3. Velocity (c)
 The distance travelled by a wave in one second is called the velocity of a wave.
 It is generally denoted by the letter (c).

4. Amplitude (a)
 It is the height of the crest or depth of the trough of a wave.
 It is generally denoted by the letter (a).

5. Wave Number (  )
 It is defined as the number of wavelengths per unit length.

 It is the inverse of wavelength. It is denoted by nu bar (  ).

 It is expressed in cm−1 or m−1.
1
wavenumber 
wavelength

1



RELATIONSHIP BETWEEN WAVELENGTH, FREQUENCY AND VELOCITY

Velocity = Wavelength x Frequency
c=λxυ
 The velocity of electromagnetic radiations is 3 x 108 m/s.
ELECTROMAGNETIC SPECTRUM
 The arrangement of different types of electromagnetic radiations according to
the increasing wavelength or decreasing frequency is known as electromagnetic
spectrum.
 The different regions of the electromagnetic spectrum are arranged as follows.
 Cosmic rays, γ-rays, x-rays, UV region, Visible region, Infrared region,
Microwaves, Radio waves etc.

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 The wavelength of different colours constituting the visible light are as follows.
Violet Indigo Blue Green Yellow Orange Red
3700 4300 4500 4900 5500 5900 6500 7500
BLACK BODY RADIATION
 The ideal body which emits and absorbs all frequencies is known as black body.
 The radiation emitted by the black body is known as black body radiation.
PHOTOELECTRIC EFFECT
 When a light of suitable frequency strikes a metal, electrons are ejected.
 The phenomenon is known as photoelectric effect.
 The emitted electrons are called photoelectrons.
 There are three important aspects for the phenomenon.
 The ejection of electrons from the surface of a metal will take place only if the
incident radiation has a certain minimum frequency.
 The minimum frequency of light, required to cause the emission of electrons
from a metal surface is called threshold frequency (υ0).
 The kinetic energy of the ejected electrons is proportional to the frequency of the
incident radiation and is independent of its intensity.
 The number of electrons ejected from the metal surface is proportional to the
intensity of the radiation.
PLANCK’S QUANTUM THEORY
 In order to explain the phenomena of black body radiation and photoelectric
effect, Max Planck in 1900 put forward a new theory called quantum theory of
radiation.
 Radiant energy is emitted or absorbed not continuously or discontinuously in the
form of small packets of energy called quanta.
 Each packet of wave is associated with a definite amount of energy.
 In the case of light, the quantum of energy is often called a photon.
 The amount of energy associated with a quantum of radiation is proportional to
the frequency of radiation.
E
E  h
 Where h is Planck’s constant and is equal to 6.626 x 10 −34Js
c
But  

hc
E

 The energy is emitted or absorbed only in the integral multiple of quantum.
 E  nh

Page 10 of 27
DUAL NATURE OF ELECTROMAGNETIC RADIATIONS
 The particle nature of light could explain certain phenomena like photoelectric
effect and black body radiation.
 But the phenomena such as diffraction and interference can be explained only on
the basis of wave nature.
 Thus the experimental facts suggest that light has dual character.
 i.e. particle character as well as wave character.
SOLAR SPECTRUM
 When white light is passed through a prism, it splits into a series of colour bands
known as VIBGYOR.
 This indicates that sunlight is composed of a collection of electromagnetic waves
having different wavelengths.
 The prism bends the light of different wavelengths to different extents.
 The phenomenon of splitting if light into seven colours is known as dispersion
and the series of colour bands is called a spectrum.
 In this spectrum, one colour merges into the other without any gap or
discontinuity.
 Therefore, the spectrum is known as continuous spectrum.
ATOMIC SPECTRA
 The spectra of atoms are not continuous.
 The atomic spectra consist of sharp well defined lines or bands corresponding to
definite wave lengths.
 Atomic spectra are of two types.
 They are Emission Spectra and Absorption Spectra.
EMISSION SPECTRA
 The light emitted from an excited substance is dispersed by using an instrument
called spectroscope.
 The spectrum obtained is not continuous but consists of a series of sharp well
defined lines.
 Each line in the spectrum corresponds to a definite wavelength.
 Such a spectrum containing lines of definite wavelengths is called discontinuous
spectrum or line spectrum.
 The line spectrum is also known as atomic spectrum.

NOTE

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 Line emission spectra are very useful in the study of electronic structure of
atoms.
 Each element has a unique line emission spectrum.
 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.
 So line emission spectra are also called finger print of atoms.
ABSORPTION SPECTRA
 A continuous electromagnetic radiation is allowed to pass through a gas or a
solution of some salt.
 The transmitted light is analyzed in a spectroscope.
 A spectrum is obtained which contains some dark lines in an otherwise
continuous spectrum.
 Such a spectrum containing a few dark lines due to absorption of light is known
as absorption spectrum.
SPECTRUM OF HYDROGEN ATOM
LINE SPECTRUM

 The spectrum of hydrogen atoms may be obtained by passing an electric

discharge through hydrogen gas taken in a discharge tube under low pressure.
 The light emitted is analyzed by using a spectroscope.
 The spectrum consists of a large number of lines appearing in different region of
electromagnetic spectrum.
 Some of the lines are found in the visible region while others in ultraviolet and
Infra-red region.

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 The different series are Lymann Series, Balmer Series, Paschen Series, Brackett
Series and Pfund Series.
 Lymann series appear in the ultraviolet region.
 Balmer series appear in the visible region.
 The other three series appear in the infra-red region.
 Rydberg gave a general expression which is applicable to all series of lines in the
 
1 1 1 
hydrogen spectrum. The equation is    R 
 n 2 n 2 
 1 2 

 where R is Rydberg constant.

 The value of R is 109677 cm─1.
 The expression is known as Rydberg Equation.
 Lymann Series: Lies in the ultraviolet region. n1 = 1 n2 = 2, 3, 4, 5, 6, ……
 Balmer Series: Lies in the visible region. n1 = 2 n2 = 3, 4, 5, 6, 7 ……
 Paschen Series:Lies in the near IR region. n1 = 3 n2 = 4, 5, 6, 7 ……
 Brackett Series: Lies in the middle IR region. n1 = 4 n2 = 5, 6, 7 ……
 Pfund Series: Lies in the far IR region. n1 = 5 n2 = 6, 7, 8, ……

FAILURE OF RUTHERFORD’S MODEL

 Failed to explain the stability of atoms.
 Failed to explain the existence of certain definite lines in the Hydrogen
spectrum.
BOHR’S MODEL OF THE ATOM
The important postulates of Bohr’s theory are
1. The electrons in an atom revolve around the nucleus in certain selected
circular paths called orbits.
 These orbits are associated with definite
energies and are therefore known as energy
levels.
 These are numbered as 1, 2, 3, 4 etc starting
from the nucleus or designated as K, L, M, N etc.
2. As long as an electron revolves in a
particular orbit, it does not lose or gain
energy.
 This means that energy of an electron in a particular orbit remains constant.
Therefore, these orbits are also called stationary orbits.

Page 13 of 27
3. Only those orbits are permitted in which the angular momentum (mvr) of the
h
electron is an integral multiple of where h is the Planck’s constant.
2
nh
 i.e., mvr  where m is the mass of electron, v is the velocity of electron; r is
2
the radius of the orbit. n = 1, 2, 3, …….
4. When an electron jumps from one orbit to another, it will absorb or emit
radiation of a definite frequency.
 For example, when an electron jumps from a lower level to a higher level, it
absorbs energy equal to E2 − E1.
 When the electron jumps back to the lower level, it emits the same amount of
energy.
 This amount of energy absorbed or emitted is given by the difference in energies
of the two levels concerned.
E  E2  E1  h
E2  E1

h
MERITS OF BOHR MODEL
1. Could explain the stability of an atom.
 According to the Bohr model, an electron cannot lose energy as long as it
revolves in a particular orbit. This explains the stability of the atom.
2. Helped in calculating the energy of the electron in a particular orbit of
hydrogen atom.
 The energy of an electron in the nth energy level of hydrogen atom is given by
the expression
22me4
En  n2h2
2.18x1018
En  J / atom
n2
13.6
En  n2 eV / atom
1312
En  n2 kJ / atom
 Bohr’s theory is also applicable to hydrogen like species such as He +, Li2+ etc.
 The energy of the electron is given by the expression
2.18x1018 xZ2
En  n2
J / atom

 Where Z is the atomic number and has values 2 for He + and 3 for Li2+.

3. Helped in calculating the radius of each circular orbit by using the

Page 14 of 27
 expression rn = 0.529 x n2 where n = 1, 2, 3, …….

 The radius of the first orbit r1 is 0.529Å

 For hydrogen like species, the expression for the radius is given as

0.529Åxn2
rn  where Z is the atomic number.
Z
4. Bohr model could explain the line spectrum of hydrogen.
 Whenever an electron jumps from higher energy levels to the first energy level,
the lines in the Lymann series appear.
 When the excited electron jumps from higher energy levels to the second energy
level, the lines in the Balmer series appear.
 Similarly, Bracket, Paschen and Pfund series appear when the excited electron
jumps from higher energy levels to 3rd, 4th and 5th energy levels respectively.
5. Could explain the simultaneous appearance of a large number of lines
in the hydrogen spectrum.
DEMERITS OF BOHR MODEL
 It could not explain the line spectrum of multi electron atoms.
 It could not explain the splitting of spectral lines under the influence of electric
and magnetic field.
 It could not explain the shape of molecules formed by the combination of atoms.
 Bohr model could not explain the fine structure of the spectral lines produced by
hydrogen.
NOTE
 The splitting of spectral line under the influence of electric field is called Stark
Effect.
 The splitting of spectral line under the influence of magnetic field is called
Zeeman Effect.
De-BROGLIE EQUATION
 According to de-Broglie, the wave length (λ) associated with a particle of mass
‘m’ moving with velocity (v) is given by the relation
h h
 or   [P = mv]
mv P
 Where ‘λ’ is the wavelength, ‘h’ is Planck’s constant, ‘P’ is the momentum.
DERIVATION OF De-BROGLIE RELATIONSHIP
 Consider a photon of light energy, E. According to Max Planck,
E  h.....................(1)

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 where υ is the frequency, h is the Planck’s constant.
c


hc
E .....................(2)

 According to Einstein’s mass energy relationship
E  mc2....................(3)

 Combining equations (2) and (3), we get

hc
 mc2

h
 mc

h

mc
h

mv
h
Or 
p
 Where P = mv is the momentum.
 This equation is known as de-Broglie equation and λ is called de-Broglie wave
length.
HEISENBERG’S UNCERTAINTY PRINCIPLE
 Heisenberg in 1927, pointed out that we cannot measure accurately both the
position and velocity of a particle as small as electron.
 Heisenberg’s uncertainity principle states that it is impossible to measure
simultaneously both the position and velocity of a microscopic particle in motion
with absolute accuracy.
h
 Mathematically it can be expressed as x.p 
4
 Where ∆x is the uncertainity in position and ∆p is the uncertainity in
momentum.

QUANTUM MECHANICS
 Quantum mechanics was developed independently in 1926 by Werner
Heisenberg and Erwin Schrodinger.
 The branch of science that takes into account, the dual behaviour of matter is
called Quantum mechanics.

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 Quantum mechanics is a theoretical science that deals with the study of the
motions of the microscopic objects that have the observable wave like and
particle like properties.

SCHRODINGER WAVE EQUATION

 On the basis of de-Broglie concept of matter waves and Heisenberg’s uncertainity
principle, a new model of atom was developed.
 It is known as quantum mechanical model.
 In this model, the behaviour of the electron in an atom is described by an
equation known as Schrodinger Wave Equation.
 Schrodinger equation is represented as

2 2 2 82m

   (E  V)  0
x2 y2 z2 h2

 Where x, y and z are three Cartesian coordinates, E is the total energy, V is the
potential energy, m is the mass of the electron, h is Planck’s constant and  is

the amplitude of the electron wave.

 For a system such as an atom or a molecule whose energy does not change with
time, the Schrodinger equation is written as H  E

 Where H is a mathematical operator called Hamiltonian Operator.

SIGNIFICANCE OF (Ψ)
 Ψ is the amplitude of the electron wave.
 Ψ has no physical significance but its square
 i.e., Ψ2 has a physical significance.
 Ψ2 gives the intensity of the electron at any point.
 Ψ2 gives the probability of finding an electron in a given region around the
nucleus.
 Thus, Ψ2 is termed as probability density and Ψ is called probability amplitude.

ORBITAL
 An orbital may be defined as the region of space around the nucleus where the
probability of finding the electron is maximum.
 Each orbital has definite amount of energy.

Page 17 of 27
DIFFERENCES BETWEEN AN ORBIT AND AN ORBITAL

Orbit Orbital
An orbit is a well-defined circular An orbital is a region of space
1 path followed by the revolving 1 around the nucleus of an atom
electron around the nucleus. where there is a high probability of
finding an electron.
It represents the planar motion of It represents the three dimensional
2 an electron 2 motion of an electron around the
nucleus.
The maximum number of An orbital cannot accommodate
3 electrons in an orbit is 2n2 3 more than 2 electrons.

Orbitals have different shapes.

4 Orbits are circular in shape 4 s orbitals are spherical, p orbitals
are dumbbell shaped.
Concept of well-defined orbits is Concept of orbital is in accordance
5 against Heisenberg’s uncertainity 5 with Heisenberg’s uncertainity
principle principle.

QUANTUM NUMBERS
 In an atom, the orbitals are designated by a set of numbers known as quantum
numbers.
 In order to specify energy, size, shape and orientation of the electron orbital,
three quantum numbers are required.
 In order to designate the electron, an additional quantum number, called spin
quantum number is required.
 Thus, each orbital in an atom is designated by a set of three quantum numbers
and each electron is designated by a set of four quantum numbers.

1. PRINCIPAL QUANTUM NUMBER (n)

 Principal quantum number is denoted by the letter ‘n’.
 It represents the main shell.
 It determines the energy of an electron.
 This quantum number tells us in which principal energy level, the electron is
present.
 It can have any whole number value such as 1,2,3,4 ……… corresponding to K, L,
M, N…
 As the value of ‘n’ increases, the electron gets farther away from the nucleus.
 Principal quantum number also determines the size of the orbital.

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2. Angular Momentum Quantum Number or Azimuthal Quantum
Number(l )

 Angular Momentum Quantum Number is denoted by ‘ l ’.

 This quantum number determines the angular momentum of the electron.

 The value of ‘l ’ gives the sub shell in which the electron is located.

 It also determines the shape of the orbital in which the electron is located. ‘ l ’

may have all possible whole number values from 0 to (n─1) for each principal
energy level.
 The various sub shells are designated as s, p, d, f depending upon the value of
‘l’’.

 For n = 1, ‘l ’ can have only one value. i.e., 0.

 It means that electron present in the first energy level can be present only in the
s sub shell. i.e., 1s.
 For n = 2, ‘l ’ can have only two values. i.e., 0 and 1.

 It means that electron present in the second principal energy level may be
located either in the s sub shell or p sub shell. i.e., 2s and 2p.
 For n = 3, ‘l ’ can have only three values. i.e., 0, 1and 2.

 It means that electron present in the third principal energy level may be located
either in the s sub shell, p sub shell or d sub shell. i.e., 3s, 3p and 3d.
MAGNETIC QUANTUM NUMBER (m)
 Magnetic Quantum Number is denoted by ‘m’.
 It represents the different orientations of electron cloud in a particular sub shell.
 These different orientations are called orbitals.
 Magnetic quantum number represents the number of orbitals present in the sub
shell.
 The possible values of ‘m’ ranges from ― l to + l including zero or ‘m’ can have

(2l + 1) values.

 For l =0, m can have one value, m = 0.

 It implies that s sub shell has only one orbital.

 For l =1, m can have three values, m = −1, 0, +1.

 It implies that p sub shell has three orbitals.

 For l =2, m can have five values, m = −2, −1, 0, +1, +2.

 It implies that d sub shell has five orbitals.

 For l =3, m can have seven value, m = −3, −2, −1, 0, +1, +2, +3.

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 It implies that f sub shell has seven orbitals.
4. SPIN QUANTUM NUMBER (s)
 Spin Quantum Number is denoted by ‘s’.
 It tells us about the direction of spin of the electron.
 i.e., clockwise or anticlockwise.
 The spin quantum number can have only two values, +½ and −½.
 The value +½ indicates clockwise spin and the value −½ indicates anticlockwise
spin.

SHAPES OF ORBITALS
s-Orbitals
 For s-orbitals, l = 0 and hence m can have only one value i.e., m = 0.

 This means that the probability of finding the electron in s-orbitals is same in all
directions.
 In other words, s-orbitals are spherically symmetrical.
 In the case of 2s orbitals, there is a spherical shell where the electron density is
zero.
 This is called a node.

p-ORBITALS
 For p-orbitals, l = 1 and hence m can have 3 values i.e., m = +1, 0, −1.

 This means that there are three p orbitals in each p sub shell.

 These are designated as Px, Py and Pz.

 P orbitals are dumb bell shaped.

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d-ORBITALS
 For d-orbitals, l = 2 and hence m can have 5 values.

 i.e., m = +2, +1, 0, −1, −2.

 This means that there are five d orbitals in each d sub shell.

 These are designated as dxy, dxz, dyz, dx2−y2 and dz2.

 d orbitals are double dumb bell shaped.

RULES FOR FILLING OF ORBITALS IN AN ATOM

1. PAULI’S EXCLUSION PRINCIPLE
 Pauli’s exclusion principle states the no two electrons in an atom can have the
same values for all the four quantum numbers.
 Thus, in any atom, the two electrons may have a maximum of three quantum
numbers the same, but the fourth must be different.
 Eg:- Consider K shell where n = 1.
n=1 l=0 m=0 s = +½
n=1 l=0 m=0 s = −½

NOTE: On the basis of Pauli’s Exclusion Principle, it is concluded that an orbital can
have a maximum of two electrons and they must have opposite spins.
 s-subshell can have a maximum of 2 electrons
 p-subshell can have a maximum of 6 electrons
 d-subshell can have a maximum of 10 electrons
 f-subshell can have a maximum of 14 electrons

2. AUFBAU PRINCIPLE
 According to Aufbau Principle, the electrons are filled in various orbitals in the
increasing order of their energies.
 The increasing order of energies of various orbital is
 1s 2s 2p 3s 3p 4s 3d 4p 5s 4d 5p 6s 4f 5d 6p 7s 5f 6d 7p ……..

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(n + l RULE)

 Orbitals are filled in the order of increasing value of (n + l ).

 Eg:- 4s (n + l = 4 + 0 = 4) is filled before 3d (n + l = 3 + 2= 5)

 If two orbitals have the same (n + l ) value, the one with lower ‘n’ value will be

filled first.
 Eg:- 2p (n + l = 2 + 1 = 3) is filled before 3s (n + l = 3 + 0 = 3) because 2p

has lower value of n.

4. HUND’S RULE OF MAXIMUM MULTIPLICITY
 Hund’s Rule states that electron pairing will not take place in orbitals of same
energy until each orbital is first singly filled with parallel spin.
ELECTRONIC CONFIGURATION OF ATOMS
 The electronic configuration of atom means the distribution of electrons in the
various orbitals of the atom.
 The number of electrons in an atom will be equal to the atomic number.
 These electrons are placed in the various orbitals in the increasing order of
energy.
EXAMPLES
Atomic Electronic
Element
Number Configuration
1 Hydrogen 1s1
2 Helium 1s2
3 Lithium 1s2 2s1
4 Beryllium 1s2 2s2
5 Boron 1s2 2s2 2px1
6 Carbon 1s2 2s2 2px1 2py1
7 Nitrogen 1s2 2s2 2px1 2py1 2pz1
8 Oxygen 1s2 2s2 2px2 2py1 2pz1
9 Fluorine 1s2 2s2 2px2 2py2 2pz1
10 Neon 1s2 2s2 2px2 2py2 2pz2

STABILITY OF COMPLETELY FILLED AND HALF FILLED SUBSHELLS

 For atoms having half-filled or completely filled electronic configurations have
extra stability compared to other atoms.
 This is due to their symmetrical distribution of electrons and greater exchange
energy.

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 For example, the electronic configuration of Cr is [Ar] 3d54s1 and not 3d44s2.

This is because d5 represents a half filled configuration and has extra stability.

 Similarly, for Cu the electronic configuration is [Ar] 3d 104s1 and not 3d94s2.

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