STRUCTURE OF ATORM

John Dalton put forward atomic theory in 1803 known as Daltons Atomic theory. According to
this theory an atom is defined as simplest indivisible particle of matter that takes part in a
chemical reaction.

However modern researches show that atom can be divisible, atoms can be broken in to smaller
fragments like electrons, protons and neutrons.

Sub atomic particles:

Discovery of electrons: (cathode rays)

J. J. Thomson discovered electrons in 1859 during his discharge tube experiment.
A discharge tube is a long glass tube, it is fitted with metal electrodes
on both ends. The gas pressure inside the tube is reduced to 10-4 atmosphere.
High voltage of 5000 – 10000V is applied between the electrodes.
An invisible rays start emitting from the cathode and move towards the anode.
These rays were called cathode rays.

Properties of cathode rays:

1. Cathode rays travel in straight line with high speed.

2. Cathode rays are negatively charged particles.
3. Cathode rays deflected by electric and magnetic fields.
4. Cathode rays can penetrate thin sheets of materials.
5. Cathode rays ionize gas through which they pass.
6. Cathode rays affect the photographic plate. And produce fluorescence with ZnS screen.
7. Cathode rays produce x-rays when they are focused on the heavy metals.
8. Cathode rays have definite e/m ratio ( 1.76 x 1011C/Kg)
9. Nature of these rays does not depend upon the nature of the gas and nature of the
cathode material.
Hence electrons are common universal constituents of all atoms.
Mass of electron = 9.109 x 10-31kg
Charge of electron = - 1.602 x 10-19C

Determination of e/m ratio of electron: J.J.Thomson studied the deflection of cathode rays
under the simultaneous application of electric and magnetic field perpendicular to each other.
Cathode rays deflect in electric and magnetic fields. It is possible to adjust the strength of
electric and magnetic fields so that the cathode rays strike the same spot as they do when
neither field is applied. From the magnitude of electric and magnetic fields thus applied, it is
possible to calculate the e/m ratio of electron.
𝑒 𝑋
𝑚
= 𝐻2𝑟
= 1.76 x 1011C/kg

X= strength of electric field. H = strength of magnetic field. r = radius of curvature of path

described by stream of electron in magnetic field.

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Charge of an electron:Millican discovered the oil drop method to determine the charge of an
electron. The charge of electron to be – 1.60 x 10-19C.

Mass of an electron: It is possible to calculate the mass of an electron by combining results of

both Thomson and Millican.

𝑒 1.602 𝑥 10−19 𝐶
Mass of electron = 𝑒⁄ =1.76 𝑥 1011 𝐶 𝑘𝑔−1 = 9.109 x 1031kg.
𝑚

Discovery of protons: Protons were discovered by Gold Stein in 1886. He performed a

cathode ray experiment by using perforated cathode. He observed that new types of ray were
produced from the anode simultaneously with the cathode rays. These rays move towards the
cathode and passed through the canals of cathode are called canal rays or anode rays.

Properties of anode rays:

1. They travel in straight line.

2. They have positively charged particles since they bend towards the –ve plate
3. They consists of material particles
4. They have kinetic energy
5. They affect the photographic plate
6. They produce fluorescence on ZnS screen
7. They ionize gas through which they pass
8. They have very small e/m ratio, the e/m ratio value depends on the nature of the gas
taken. These particles are different for different gas.
Mass of proton is 1.672 x 10-27kg
Charge of proton is 1.602 x 1019C

Discovery of neutrons: Neutrons were discovered by James Chadwick in 1932. He bombarded

a thin sheet of beryllium with high energy α- particals, an electrically neutral particle having
mass slightly greater than that of proton was emitted. He named these particles as neutrons.
4
2𝐻𝑒 + 49𝐵𝑒→ 126𝐶 + 10𝑛

Mass of a neutron = 1.675 x 10-27kg and charge of a neutron is zero(0)

Thomson model of an atom: (Plum pudding model or water melon model)

After the discovery of electrons and protons,J.J.Thomson (1898)proposed

watermelon model for an atom. According to this, an atom has a positively charged sphere in
which negatively charged electrons are embedded in it. Mass of an atom is uniformly distributed
over the atom.

This model explains the electrical neutrality of an atom. It could not explain the many
experimental facts.

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Rutherford nuclear model of an atom:

Rutherford in 1911 carried out α-particle scattering experiment. A stream of high energy
α-particles were directed against a thin gold foil(100nm). The gold foil is surrounded by
circular fluorescent ZnS screen.

Observations: On the basis of the above experiment the following observations were made.

1. Most of the α-particle(99%) passed through the foil straight un deflected.

2. A few α-particles deflected through small angle
3. A very few α-particles deflected to a large angle or even turned back.

Conclusion:

1. Most of the space inside the atom is empty hence most of the α-particles pass
through the foil un deflected.
2. A small heavy positively charged portion inside the atom is called nucleus (10-15nm)
hence the few α-particles deflected to a large angle.
3. Whole mass of an atom concentrated in the nucleus. Hence few particles deflected back or
to a large angle.

Postulates of Rutherford model of an atom:

1) An atom consists of heavy positively charged portion called nucleus, it consists of protons
2) The region of space around the nucleus consists of negatively charged electrons
3) Electrons and nucleus are held together by electrostatic force of attraction.
4) Total number of positively charged protons is equal to total number of negatively charged
electrons, hence an atom is electrically neutral.
5) Volume of the nucleus is very small when compared to the volume of the atom.
Radius of nucleus is ≈ 10-15 Radius of atom is ≈ 10-10
6) Electrons revolving around the nucleus with very high speed in circular paths called
orbits.

Atomic numbers and Mass numbers:

Atomic number(Z): The number of protons present in the nucleus of an atom is called atomic
number

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It is denoted by the symbol ‘ Z’ A neutral atom consists of equal number of protons and electrons. Atoms of
different elements contain different protons. Eg: Atomic number of sodium atom is 11 that is nucleus of sodium
atom consists of 11 protons.

Mass number(A): The total number of protons and neutrons present in an atom is called mass
number or number of nucleons.

It is denoted by the symbol ‘A’. Eg: A sodium atom consists of 11 protons and 12 neutrons hence
its mass number is 23.
An atom of an element ‘ X’ having atomic number ‘Z’ and mass number ‘A’ are represented as 𝐴𝑍𝑋

Isotopes: Atoms of same elements have same atomic number but different mass number are
called isotopes.
12 13 14 1 2 3
Eg: 6𝐶 6𝐶 6𝐶 , 1𝐻 1𝐻 1𝐻

Isotopes of an element have same number of protons but different number of neutrons. Isotopes
of an element have same chemical properties.

Isobars: Atoms of different elements have same mass number but different atomic numbers are
called isobars.Eg: 146𝐶 147𝑁

Limitations of Ruther ford model:

1) This model fails to explain stability of the atom. According the classical theory a moving
charged particle continuously loses its energy in the form of EM radiations. Due to this
electrons lose energy in every turn and move closer and closer to the nucleus and finally
fall into the nucleus makes the atom unstable.
2) If the electron loses energy continuously, the observed spectrum should be continuous,
but the spectrum obtained is discontinuous. That is electron lose energy discontinuously.
3) It could not explain the line spectra of hydrogen.
4) It fails to explain distribution of electrons around the nucleus and the energies of these
electrons.

Development leading to the Bohr’s model of an atom:

Nature of light and electromagnetic radiations: In 1856 James Clark Maxwell proposed that light and other form of
radiations propagate through space in the form of waves. These radiations associated with electrical and magnetic
fields oscillating perpendicular to the direction of propagation. These radiations are called electromagnetic
radiations. Eg. Cosmic rays, √- ray, X-ray, UV-ray Visible light, IR-ray, Microwave, radio waves are the
electromagnetic radiations.

Characteristics of electromagnetic radiations: Electromagnetic radiations have following characteristics.

Wave length:

It is the distance between the any two adjacent crests or troughs of a wave. Unit of wave
length is meter. Eg: Wavelength if visible light is 400nm to 750nm

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Frequency: it is defined as the number of wavelengths passing through the given point in one second.
𝑐
ν= Unit of frequency is hertz (Hz) or s-1
𝜆

Wave number: It is the number ofwavelengths in unit length of a wave.

1
𝜈̅ = 𝜆
Unit of wave number is m-1

Velocity: It is the distance travelled by a wave in one second. Electromagnetic radiations travels
with the velocity of light ( c = 3 x 108ms-1).

Electromagnetic spectrum: The arrangement of different electromagnetic radiations in the

order of increase in wavelength or decrease in frequency is called electromagnetic spectrum.

λ = 10-16 10-14 10-1210-10 10-8 10-6 10-4 10-2 1 102

Cosmic ray X-ray 𝛾- ray UV- ray Visible IR- ray

Micro wave Radio wave

V I B G Y O R
400nm
750nm

A very small portion of electromagnetic radiation is visible.

Problems: 1. TheVividhBharati station of all India radio Dehli broad cast on a frequency of
1368kHz calculate the wave length of radiation emitted by transmitter. Which part of the
electromagnetic spectrum does it belongs?

2) The Wave length range of the visible spectrum extended from violet =400nm to red=750nm.
Express these wavelengths in frequencies.(Hz)

3) Calculate wave number and frequency of yellow radiation having wavelength 5800A 0

Particle nature of electromagnetic radiations:

Some experimental phenomenon such as diffraction and interference can be explained by the
wave nature of the light.
Electromagnetic theory fails to explain emission of radiation by black body, Photoelectric effect,
Line spectra of hydrogen and variation of heat capacity of solid as a function of temperature. In
order to explain these Max Planck in 1900 proposed the theory called Quantum theory.

Panck’s quantum theory:According to this theory

1) The radiant energy is emitted or absorbed discontinuously in the form of small energy packets
called quanta or photon(in light).

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2) The energy of each quanta is directly proportional to the frequency of radiation. E ∝ ν or E =
hν
3) The energy is emitted or absorbed by a body is integral multiple of quanta. E = nhν
Where n = 1,2,3,4………………………

h= planck’sconstant = 6.626 x 10-34JS

Photoelectric effect: (Hertz in 1817)

When a beam of light of certain frequency strikes the surface of some metals, electrons are
emitted from the metal surface; this phenomenon is called photoelectric effect, (K, Rb, Cs metals)
Defination: “ Ejection of electrons from the surface of a metalunder the influence of striking
photons is called photoelectric effect.”

Observations: 1) Electrons are ejected from the metal surface only with the photons of certain
minimum frequency, this is called threshold frequency (ν0 ) This is also called work function.
Threshold frequency depends on the nature of the metal used.

2) There is no time-lag between the light striking the metal surface and the emission of
electrons.

3) The number of electrons ejected per unit time depends upon the intensity of striking photon
and not on the frequency of photon.

4) The kinetic energy of the emitted electron is directly proportional to the frequency of photon
but not on the intensity of photon.

Based on the above experimental observation Einstein was able to explain photoelectric effect
using Planck’s quantum theory.

Einstein suggested that: 1) Light consists of stream of particles called photons, which move with
the speed of light.

2) Greater the energy of photon, greater will be the transfer of energy to the electron and greater
will be the kinetic energy of ejected electron.

Kinetic energy of photo electron = ½ mev2 = (hν – hν0) = h(ν – ν0)

Where ν = frequency of incident photon
ν0 = threshold frequency of photon.

3) A more intense beam of light consists of large number of photons hence large number of
electrons ejected.

Duel nature of electromagnetic radiations:

From the study of wave like and particle like characteristics of light. Scientists came to
conclusion that light and other electromagnetic radiations have duel nature(wave and particle
nature)

(Wave nature can be explained by phenomenon like interference and diffraction. Particle nature
can be explained by phenomenon like black body radiation and photoelectric effect)
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This duel nature of radiation formed the basis of the modern picture of atomic model.

problems: 1) calculate the energy of one mole of photons of radiation whose frequency is 5 x
1014Hz

2) A 100 Watt bulb emits monochromatic light of wave length 400nm. Calculate the number of
photos emitted per second. ( 100W = 100JS-1)

3) The threshold frequency ν0 for a metal is 7 x 1014S-1. Calculate the kinetic energy of an
electron emitted when radiation of frequency emitted when radiation frequency ν = 1 x 10 15 S-1
hits the metal.

Atomic spectra: (evidence for the quantized electronic energy levels)

Atomic emission spectra: when atoms are heated to high temperature, the atoms gets
exited(energized), these exited atoms returns to the ground state by emitting electromagnetic
radiations of definite frequency these emitted
radiation produce a series of bright lines
separated from each other by dark space is
called atomic spectra.

Line spectra of every element are different from the other element; hence an atomic spectrum is
the figure print of an element. It is used to identify elements. The study of emission and
absorption spectrum is calledspectroscopy.

Line spectra of hydrogen:

When an electric discharge is passed through the hydrogen gas, the H2 molecules dissociate and
hydrogen atoms gets exited, the exited hydrogen atoms emit electromagnetic radiations of
discrete frequency. The hydrogen spectrum consists of several series of lines and they are named
after their discoverer.

The wave number of each line in different series can be

calculated using Rydberg’s equation.
1 1 1
𝜈̅ = 𝜆
= RH(𝑛2 − 𝑛2 )
1 2

Where RH = Rydberg’s constant = 10967800 cm-1 n1 lower energy level n2 = higher energy
level.

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Bohr’s Model of an atom:Neils Bohr in 1913 proposed atomic model based on the quantum
theory. According to this theory,

1) In an atom the electrons revolving around the nucleus in certain definite circular paths
called orbits.
2) Each orbit is associated with definite amount of energy are called energy levels or
stationary states or shells, they are numbered as 1, 2, 3, 4, etc., or Labeled as K, L, N,
O, P etc., shells.
3) As long as the electron remains in a particular energy level(orbit), it neither emit not
absorb energy.
4) Energy(frequency) emitted or absorbed only the electron makes transition from one state
to another state.
𝐸2−𝐸1
hν= 𝛥𝐸 =
ℎ
5) The angular momentum of an electron is quantized, that is electrons can move only in
those orbits in which the angular momentum is always integral multiple of h/2π
mevr = nh/2π where n= 1, 2, 3, 4, ………..

Bohrs model for hydrogen atom:

1) The stationary states are numbered as 1,2,3,4,….. are known as principal quantum
numbers.
2) The radius of stationary states are given by r = n2α0α0 = 52.9pm it is also called Bohr’s
radius
1
3) The energy of the stationary state in a hydrogen atom are given by En = -Rh( 2 ) where n =
𝑛
1,2,3… Rh = 2.18 x10-18J
E1 = -2.18 x 10-18J E2 = - 0.545 x 10-18J
The energy of the lowest state is called ground state.
Due to the attractive interaction of electrons and nucleus a certain amount of energy is
released, hence the energy of the electron is less than zero or negative.
4) Bohrs theory can also applicable to the ions containing only one electron. Eg. He +, Li2+,
Be3+ etc.,

Explanation of hydrogen spectrum using Bohr’s theory:

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When energy is supplied to hydrogen atoms, different hydrogen atoms absorb different amount
of energy as result, electrons in different atoms gets promoted to different higher energy states.
The electrons in the higher energy state are unstable and they return back to the lower energy
states by emitting energy in the form of radiation of certain frequency. This resulting in the line
spectra of hydrogen.

The wave number and wave length of each spectral line in each series can be calculated by
using the equation
1 1 1
𝜈̅ = = RH( − ) Rh = 1.09678 x 107m-1
𝜆 𝑛12 𝑛22

Lyman series: The spectral lines in the Lyman series produced when the electrons jumps from
2nd, 3rd, 4th and higher energy levels to 1st energy level. This series appears in UV region of EM
spectrum. For
Lyman series n1= 1 and n2= 2, 3, 4, …….

Balmer series: The spectral lines in the Balmer series are produced when the electrons jumps
from 3rd, 4th, 5th and higher energy levels to 2nd energy level. This series appears in the visible
region of EM spectrum.
For Balmer series n1= 2 and n2= 3, 4, 5 ……

Paschen series, Bracket series, and pfund series: When the electrons jumps from any other
higher levels to 3rd, 4th and 5th energy levels gives Pachen, Bracket and Pfund series lines
respectively. These spectral series appears in the IR region of EM spectrum.
For Paschen series n1= 3 and n2= 4, 5, 6,……For Bracket series n1= 4 and n2= 5, 6, 7, ……
For Pfund series n1= 5 and n2= 6, 7, 8, ……

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Limitations of Bohr’s theory: Bohr’s theory fails to explain the following facts.

1) Line spectra of atoms containing more than one electrons, Eg: He, Li, Be, atoms
2) Splitting up of spectral lines in presence of electric field(Zeeman effect) and magnetic field
(Stark effect)
3) Why angular momentum of electron is always integral multiple of h/4π?
4) Fine spectra of line spectra of hydrogen.
5) Heisenberg’s uncertainty principle.
6) Why atoms combine to form chemical bonds and molecules are stable than atoms?

PROBLEMS:

1) Calculate the wavelength of a spectral line in Lyman series in which electrons jumps from
3rd energy level.
2) Calculate the wavelength of radiation emitted when an electron in a hydrogen atom
makes a transition from an energy level with n2 = 3 to a level with n1= 2
3) Calculate the wavenumber for the longest wavelength and shortest wavelength transition
in the Balmer series of hydrogen spectra.

TO WARDS THE QUANTUM MECHANICAL MODEL OF ATOM:

Duel nature of Particle: Louis de-Broglie in 1024 proposed that moving material particles have
wave character. That is moving particles like electrons, protons, neutrons, etc,.associated with
wave like properties(duel nature)

According to Einstein E = mc2………(1) and According to Planck’s E = hν……………..(2)

ℎ𝑐 ℎ ℎ
Combine equations (1) and (2) mc2 = λ = = Where p = momentum
𝜆 𝑚𝑐 𝑝

The above equation is called de-Broglie equation for matter -wave. The wavelength associated
with a material particle is commonly called as de-Broglie wavelength.

Heisenberg’s Uncertainty principle:Werner Heisenberg state that“ It is impossible to determine

simultaneously the exact position and exact momentum of an electron.”

According to Heisenberg, the product of uncertainty in position and uncertainty in momentum is

greater than or equal to h/4π.Δx xΔp = h/4π or Δx x Δmv = h/4π Δx x Δv =
h/4πm

If the velocity of the electron is known accurately the position of the electron will be uncertain.
(to observe an electron we must use light having wavelength smaller than the dimension of an
electron. The high momentum of light photon would change the energy of an electron and its
velocity)

PROBLEM: 1) Calculate the uncertainty in the position of an electron if the uncertainty in its
velocity is 5.7 x 105ms-1( h= 6.6 x 10-34kg m2s-1,me = 9.1 x 10-31kg)

According to Heisenberg’s uncertainty principle, it is not possible to know the exact position and
momentum of electron.(microscopic particles). Hence it is impossible to describe the exact

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position of an electron in an atom at a given instant, so it is not correct to talk of an electron
moving with a fixed velocity around the nucleus in a fixed orbit of definite radius.

Thus the uncertain principle suggests that, in an atom, an electron does not always remain at a
fixed distance from the nucleus. It keeps moving in the whole space around the nucleus within a
given volume.

Reasons for the failure of the Bohr’s model:

1) The wave nature of electrons is not considered by Bohr’s theory

2) Uncertainty principle is not considered.

Quantum mechanical model of an atom (Wave Mechanical model of an atom ):

In 1926 Erwin schrodinger developed an atomic model based on de-Broglies wave- particle
nature of the electron. This is called quantum mechanical model.

It describes the electron as a three dimensional wave in the electronic field of the positively
charged nucleus.

The wave nature of the electron is described by Schrodinger equation

𝜕2 𝛹 𝜕2 𝛹 𝜕2 𝛹 8𝜋2 𝑚
+ + + (𝐸 − 𝑉)𝛹 = 0
𝜕𝑥 2 𝜕𝑦 2 𝜕𝑧 2 ℎ2

Where x, y and z are the space coordinates. m = mass of electron. E = total energy of electron.
𝑍𝑒 2
V= total potential energy of the electron (- 𝑟
). Ψ = wave function of the electron (amplitude of
electron wave). h = Planck’s constant.

Hydrogen atom and the schrodinger wave equation:

On solving the Schrodinger wave equation for hydrogen atom we get three possible energy levels,
these are quantized and the corresponding Wave functions are characterized by set of three
quantum number( n, l, m)Ψ is a wave function of the electron, it has no physical significance, Ψ 2
is the probability of finding electron at a point with in an atom.

Atomic Orbital:

Atomic orbital is the region of space around the nucleus where the probability of finding
the electron is maximum.

Orbital is three dimensional, orbital have directional characteristics except s- orbital, an orbital
accommodate only two electrons with opposite spin.

Differences between Orbit and Orbital:

Orbit Orbital
An orbit is a well defined circular path An orbital is the region of space around the
around the nucleus in which electrons nucleus where the probability of finding the
revolves K,L,M,N,Oetc,. electron is maximum
It represent the movement of electron in
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It represent the movement of electron three dimensional region around the
around the nucleus in one plane. nucleus.

In an orbit the position and momentum of In an orbital the position and momentum of
the electron can be known with certainty. electron cannot be known with certainty.

Orbits are non directional. Orbitals are directional characteristics

except s- orbital.
An orbit can accommodate 2n2 number of An orbital can accommodate only two
electrons electros with opposite spin.

Quantum numbers: The state of an electron in an atom is described by set of four numbers are
called quantum numbers. These quantum numbers gives complete information about energy,
shape, orientation of orbital and spin of electron.

The quantum numbers are 1)

Principal quantum number(n) 2) Azimuthal quantum
number or angular or subsidiary quantum number(l) 3) magnetic quantum number(m) 4) spin
quantum number(s)

Significance of quantum numbers:

Principal quantum number (n): This quantum number gives the energy and size of the orbital.
It identifies the shell. It is denoted by the symbol ‘n’

Where n = 1,2,3,4,5……… represent K, L, M, N, O, …….. shells respectively.

Azimuthal OR angular OR Subsidiary quantum number (l): This quantum number gives the
shape of the orbital. And sub shell in which the electron is present. It is denoted by the symbol
‘l’. For each value of n, l can have all integer values from 0 to n-
1

Principal quantum NO. Azimuthal quantum NO. (l) Type of sub shell
(n)
1 0 s- sub shell
2 0 s- sub shell
1 p- sub shell
0 s-sub shell
3 1 p-sub shell
3 d-sub shell

Magnetic quantum number(m): This quantum number gives the special orintation of orbital
and number orbitals in each sub shell, it is denoted by the symbol ‘m’

For each value of ‘l’, m can have 2l+1 values. That is all integer values from –l to +l including 0

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l = 0 then m has one value that is 0 that is one orbital (no orientation)
l = 1 then m has three values that is = -1, 0, +1 that is 3 orbitals ( 3 orientations)
l = 2 then m has five values that is -2, -1, 0, +1, +2 that is 5 orbitals ( 5 orientations)

Spin quantum number(s): This quantum number gives the spin of electron that is electrons
spins about its own axis it is denoted by the symbol ‘s’

Spin quantum number has only two values +1/2 and -1/2 corresponding to clockwise(↑) and
anticlockwise(↓) spins.

n l m s No. of No. of
Main sub shell/s orientations spin electrons electrons
shell In sub shell In the
shell=2n2
1 0 (s- 0 1 2 2
±
orbital) 2
0 (s- 0 2
2 orbital) 8
-1, 0, +1 6
1 (p-
orbital)
0 (s- 0 2
3 orbital) -1, 0, +1 6 18
1 (p- -2, -1, 0, +1, +2 10
orbital)
2 (d-
orbital)
0 (s- 0 2
4 orbital) -1, 0, +1 6
1 (p- -2, -1, 0, +1, +2 10 32
orbital) -3, -2, -1, 0, +1, +2 14
2 (d- +3
orbital)
3 (f-
orbital)

Problems: 1) What are the n, l, and m values for 2s, 2p and 3d electrons.
2) What designations are given to the orbitals having i) n = 2 and l = 1 ii) n = 2, and l = 0 iii) n
= 4, and l = 2 iv) n = 3 and l = 1

3) what are the possible values of l and m for n = 3.

Shapes of atomic orbitals: An atomic orbital is defined as the region of space around the
nucleus in which the probability of finding the electron is maximum.

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Ѱ2 gives the probability density of the electron at a given point.
The probability density for an orbital can describe the shape of the orbital.

Shape of s- orbital:( l = 0 and m = 0)

In s-orbitals density of electron cloud distributed uniformly about the nucleus hence s-orbitals
arespherical shape.

1s-orbital has no nodal plane

2s-orbital has one nodal plane
ns- orbital has (n-1) nodal planes.
Nodelplane is the region where the probability density of electron decreases to zero.

Shape of p-orbital: (l = 1 and m = -1, 0, +1)In p- orbital the density of electron cloud
distributed in two lobes one on each side of the nucleus hence shape of the p-orbital is dumb
bell shape.Each p-orbital has 1 nodal plane. The three p- orbitals are degenerate orbitals (
orbitals of same energy) and three orientations. Px, Py, andPz The number of radial nodes are
given by n – 2 ( Eg: No. or radial nodes for 3p is 1, and for 4p is 2 etc.,)

The number of angular nodes(nodal planes) is 1 for p –orbitals and 2 for d-orbitals (l no. pf
angular nodes)

Shapes of d-orbital: (l = 2 and m = -2, -1, 0, +1, +2): In d- orbitals the density of electron cloud
distributed in four lobes hence d-orbitals have double dumb-bell shape. (Clover leaf shape) The
four d- orbitals have similar shape and other is doughnut shape. d-orbitals have two nodal
planes. The five d-orbitals are degenerate and have five orientations. dxy, dxz, dyz, dx2-y2 dz2.

Relative energy of atomic orbitals: Energy level diagram for hydrogen: hydrogen atom has
only one electron;hence all the orbitals of the particular shell have same energy.
Energy of the orbital depends on the value of ‘n’ and not on the value of ‘l’

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Energy of 1s< 2s = 2p < 3s = 3p = 3d < 4s = 4p = 4d = 4f ……..

Energy level diagram for multielectron atom:Energy of multi electron atom depends on both
‘n’ and ‘I’ values.The difference in the energy of the different subshells is due to mutual
repulsion of electrons and attraction between electrons and nucleus.

(n + l) Rule (BohrsBury’s rule): a) The orbital having lesser n+l value has lower energy. The
orbitals having higher n+l value has higher energy.

For 4s orbital n+l = (4+o) = 4,

For 3d orbital n+l = (3 + 2) = 5
4s orbital has lesser n+l value than3d orbital hence 4s-orbital has lower energy than 3d- orbital.

b) If the two orbitals have same (n + l) value then the orbital with lower ‘n’value has lower
energy.

For 4s-orbital n+l = (4 + 0) = 4

For 3p-orbital n+l = (3+1) = 4
3p-orbital has lesser n value than 4s-orbital hence 3p-orbital has lower energy than 4s-orbital.

Screening or Shielding effect:In a multi electron atom, the electrons present in the inner shell
shield the electrons in the outermost shell from the attraction of the nucleus this is known as
shielding of screening effect. Due to this electron do not experience the complete charge of the
nucleus.

The net Positive charge experienced by the outer most electron is known as effective nuclear
charge(Zeffective)

Effective nuclear charge ( Zeffe) = Total nuclear charge (Z) – Screening constant (𝜎)
More is the number of electrons in the inner shell grater will be the value of screening constant
and lesser is the effective nuclear charge. Screening effect of s- electron > p-electron > d-
electron.

Filling of orbital in an atom:In multi electron atom electrons are filled in different orbitals
based on the Aufbau principle, pauli’s exclusion principle and Hund’s rule of maximum
multiplicity.

Aufbau principle: (Aufbau means building up):

Statemnt: “In the ground state of an atom orbitals filled by the electrons in the order of
increasing energy” That is electros first occupies lowest energy orbitals before inter into higher
energy orbitals.

The energy level sequence is given by 1s<2s<2p<3s<3p<4s<3d<4p<5s<4d

Pauli Exclusion principle:

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Statement:“No two electrons in an atom can have the same set of four quantum
numbersOR An atomic orbital can have only two electron of opposite spin.
Two electrons in an atom have same value for 3 quantum numbers but differ in other quantum
number.

Hund’s Rule of maximum multiplicity:

Statement:“ Pairing of electron not takes place in the orbitals of p, d and f –sub shells
until all the orbitals of the given set occupy one electron each with parallel spin”

↑ ↑ ↑ Filling up of degenerate p- orbitals.

↑ ↑ ↑ ↑ ↑ Filling up of degenerate d-orbitals.

Electronic configuration: The distribution of electrons to the different orbitals available in an

atom is called electronic configuration. The electronic configuration of an atom is governed by
three rules namely Aufbau rule, Pauli’s rule and Hund’s rule

Electronic configuration:

Hydrogen H 1 1s1

Helium He 2 1s2 stable

Lithium Li 3 1s2 2s1

Beryllium Be 4 1s2 2s2

Boron B 5 1s2 2s2 2p1

Carbon C 6 1s2 2s2 2p2

Nitrogen N 7 1s2 2s2 2p3

Oxygen O 8 1s2 2s2 2p4

Fluorine F 9 1s2 2s2 2p5

Neon Ne 10 1s2 2s2 2p6 stable

Sodium Na 11 1s2 2s2 2p6 3s1

Magnesium Mg 12 1s2 2s2 2p6 3s2

Aluminium Al 13 1s2 2s2 2p6 3s23p1

Silicon Si 14 1s2 2s2 2p6 3s2 3p2

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phosphorus P 15 1s2 2s2 2p6 3s2 3p3

Sulphur S 16 1s2 2s2 2p6 3s2 3p4

Chlorine Cl 17 1s2 2s2 2p6 3s2 3p5

Argon Ar 18 1s2 2s2 2p6 3s2 3p6

Potassium K 19 1s2 2s2 2p6 3s2 3p6 4s1

Calcium Ca 20 [Ar] 4s2

Scandium Sc 21 [Ar] 4s2 3d1

Titanium Ti 22 [Ar] 4s2 3d2

Vanadium V 23 [Ar] 4s2 3d3

*Chromium Cr 24 [Ar] 4s1 3d5

Manganese Mn 25 [Ar] 4s2 3d5

Iron Fe 26 [Ar] 4s2 3d6

Cobalt Co 27 [Ar] 4s2 3d7

Nickel Ni 28 [Ar] 4s2 3d8

*Copper Cu 29 [Ar] 4s1 3d10

Zinc Zn 30 [Ar] 4s2 3d10

Gallium Ga 31 [Ar] 4s2 3d10 4p1

Germanium Ge 32 [Ar] 4s2 3d10 4p2

Arsenic As 33 [Ar] 4s2 3d10 4p3

Selenium Se 34 [Ar] 4s2 3d10 4p4

Bromine Br 35 [Ar] 4s2 3d10 4p5

Krypton Kr 36 [Ar] 4s2 3d10 4p6

Electronic configuration of Cr and Cu have exceptions. Due to following resions

1) Symmetrical distribution of electrons: The half filled and fully filled orbitals are more
symmetric and the symmetry leads to stability. To achieve this in Cr and Cu electrons
shift from 4s to 3d- sub shell.

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 2) Exchange energy: Electrons in different orbitals of sub shell can exchange their position
mutually and exchange energy is released.
More the exchangeable positionsmore will be the exchange energy and more will be the
stability of atom.

↑ ↑ ↑ ↑ ↑ Number of exchanges = 4+3+2+1= 10 hence more stable.

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