ATOMIC STRUCTURE

 Atoms are the building blocks of elements. They are the smallest parts of an element that chemically react.
The first atomic theory, proposed by John Dalton in 1808, regarded atom as the ultimate indivisible
particle of matter. The main points of Dalton's atomic theory, as it eventually developed, are:
Elements are made of extremely small particles called atoms.
Atoms of a given element are identical in size, mass and other properties; atoms of different elements
differ in size, mass and other properties.
Atoms cannot be subdivided, created or destroyed.
Atoms of different elements combine in simple whole-number ratios to form chemical compounds.
In chemical reactions, atoms are combined, separated or rearranged.
Towards the end of the nineteenth century it was proved experimentally that atoms are divisible and consist
of three fundamental particles: electrons, protons and neutrons.
 Discovery of proton: E. Goldstein (1886), using a perforated disc cathode, obtained anode rays or canal
rays in the discharge tube experiment. Canal rays were found to consist of positively charged particles
whose e/m values varied with the
nature of the gas taken in the
discharge tube. The constituent
particles of canal rays obtained on
using hydrogen gas in the
discharge tube were found to be
the lightest and carried a unit
positive charge. These particles
were named as protons. Proton is
actually an ionised hydrogen atom
and can be represented as H+.

 Discovery of electron: J.J. Thomson (1896) passed electricity through gases at very low pressures and
studied the properties of cathode rays thus obtained. He found that the cathode rays consisted of a stream
of negatively charged particles
whose e/m value did not depend
upon the nature of the gas. The
constituent particles of cathode
rays were named as electrons by
a Dutch physicist, H.A. Lorentz.
An electron was found to carry a

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 ATOMIC STRUCTURE
unit negative charge and negligible mass. Some important properties of
electron are as follows:

 Thomson’s model of atom: It is also known as plum-pudding or raisin pudding or watermelon model.
An atom possesses a spherical shape (radius
approximately 10-10 m) in which the positive charge is
uniformly distributed.
The electrons are embedded into it in such a manner
as to give the most stable electrostatic arrangement.
An important feature of this model is that the mass of
the atom is assumed to be uniformly distributed over
the atom.
Although this model was able to explain the overall
neutrality of the atom, but was not consistent with the results of later experiments.

 Rutherford’s α- particles scattering experiment

and Nuclear Model of Atom:
Construction: Rutherford (1912) bombarded
very thin gold foil with α-particles. A stream
of high energy α-particles from a radioactive
source was directed at a thin foil (thickness
100 nm) of gold metal. The thin gold foil had
a circular fluorescent zinc sulphide screen
around it. Whenever α-particles struck the
screen, a tiny flash of light was produced at
that point.

Observations: It was observed that:

1. Most of the α-particles passed through the
gold foil undeflected.
2. A small fraction of the α-particles was
deflected by small angles.

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 ATOMIC STRUCTURE
3. A very few α- particles (≈1 in 20,000) bounced back, that is, were deflected by nearly 180 o.
Conclusions: On the basis of the observations, Rutherford drew the following conclusions regarding
the structure of atom:
1. Most of the space in the atom is empty as most of the α-particles passed through the foil un-
deflected.
2. A few positively charged α-particles were deflected. The deflection must be due to enormous
repulsive force showing that the positive charge of the atom is not spread throughout the atom as
Thomson had presumed. The positive charge has to be concentrated in a very small volume that
repelled and deflected the positively charged α-particles.
3. Calculations by Rutherford showed that the volume occupied by the nucleus is negligibly small as
compared to the total volume of the atom. The radius of the atom is about 10 -10 m, while that of
nucleus is 10-15 m. One can appreciate this difference in size by realizing that if a cricket ball
represents a nucleus, then the radius of atom would be about 5 km.
Rutherford’s Nuclear Model of Atom: On the basis of above observations and conclusions, Rutherford
proposed the nuclear model of atom (after the discovery of protons). According to this model:
1. The positive charge and most of the mass of the atom was densely concentrated in extremely small
region. This very small portion of the atom was called nucleus by Rutherford.
2. The nucleus is surrounded by electrons that move around the nucleus with a very high speed in
circular paths called orbits. Thus, Rutherford's model of atom resembles the solar system in which
the nucleus plays the role of sun and the electrons that of revolving planets.
3. Electrons and the nucleus are held together by electrostatic forces of attraction.
Limitations of Rutherford’s Atomic Model
1. If electrons have to revolve around the nucleus,
they will spend energy and that too against the
strong force of attraction from the nucleus, a lot
of energy will be spent by the electrons and
eventually, they will lose all their energy and will
fall into the nucleus so the stability of atom is
not explained.
2. If electrons continuously revolve around the
nucleus, the type of spectrum expected is a
continuous spectrum. But in reality, what we see is a line spectrum.
 Discovery of neutron: Neutron was discovered by Chadwick (1932) during the study of the bombardment
of a beryllium foil by fast moving α-particles.

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 ATOMIC STRUCTURE

 Electromagnetic Wave Theory (Maxwell)

Radiations associated with electrical and magnetic fields.

When an electrically charged particle moves under acceleration, alternating electrical and magnetic
fields are produced and transmitted in the form of waves called electromagnetic waves or
electromagnetic radiations.
Oscillating electric and magnetic field are produced by oscillating charged particles. These fields are
perpendicular to each other and both are perpendicular to the direction of propagation of the wave.
These waves do not require medium i.e. electromagnetic wave can travel in vacuum.

 Characteristics of electromagnetic radiations:

Wavelength (λ) It may be defined as the distance between two

neighbouring crests or troughs of wave. It is always
measured in the direction of the propagation of wave. It
is expressed in cm, nanometer (nm), micrometer (μm),
Angstrom (Å) or picometer (pm)

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Frequency (ν) It may be defined as the number of waves which pass through a particular point in
one second. It is expressed in cycles per second (cps) or hertz (Hz)
Velocity (c) It is defined as the distance travelled by a wave in one second. In vacuum all types
of electromagnetic radiations travel with the same velocity which is 3 × 108 m/sec.
It is expressed in cm/sec or m/sec.
Velocity = frequency × wavelength, i.e., c = ν λ
Wave Wave number is defined as the number of wavelengths per unit length (usually 1
number 1
cm). It is expressed in cm-1 or m-1. =
λ
Amplitude (a) It is the height of the crest or depth of the trough of a wave. It determines the
intensity or brightness of the beam of light.
 Electromagnetic Spectrum: When these electromagnetic radiations are arranged in order to their increasing
wavelengths or decreasing frequencies, the complete spectrum obtained is called electromagnetic spectrum.

Electromagnetic spectra may be emission or absorption spectra on the basis of energy absorbed or emitted.
An emission spectra is obtained when a substance emits radiation after absorbing energy. An absorption
spectra is obtained when a substance absorbs certain wavelengths and leave dark spaces in bright continuous
spectrum. Electromagnetic wave theory was successful in explaining the properties of light such as
interference, diffraction etc., but it could not explain the following:
1. Black body radiation
2. Photoelectric effect
3. Line spectra of atoms with special reference to hydrogen
These phenomena could be explained only if electromagnetic waves are supposed to have particle nature.

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 ATOMIC STRUCTURE
1. Black Body Radiation

The ideal body, which emits and absorbs radiations of all

frequencies, is called a black body and the radiation
emitted by such a body is called black body radiation. The
exact frequency distribution of the emitted radiation (i.e.,
intensity versus frequency curve of the radiation) from a
black body depends only on its temperature. At a given
temperature, intensity of radiation emitted increases with
decrease of wavelength, reaches a maximum value at a
given wavelength and then starts decreasing with further
decrease of wavelength, as shown in the graph.

 Planck's quantum theory

A body can emit or absorb energy not continuously but discontinuously in the form of small packets of
energy called quanta. A quantum of light is called a photon.

i.e., E ∝ v or, E = hv
The energy of each quantum is directly proportional to the frequency of the radiation,

Where, h is a proportionality constant, called Plank's constant. Its value is approximately equal to
6.626 x 10-27 erg sec or 6.626 x 10-34 joule sec.
The total amount of energy emitted or absorbed by a body will be some whole number quanta. Hence,
E = nhv, where n is any integer.
The energy possessed by one mole of quanta (or photons), i.e., Avogadro's number (N A) of quanta is
c
called one Einstein of energy. i.e., 1 Einstein of energy (E) = NA hv = NA h
λ
With this theory, Planck was able to explain the distribution of intensity in the radiation from black body as a
function of frequency or wavelength at different temperatures.
2. Photoelectric effect: H. Hertz performed a very interesting experiment in which electrons (or electric
current) were ejected when certain metals (for example potassium, rubidium, caesium etc.) were exposed to a
beam of light as shown in the diagram. The phenomenon is called Photoelectric effect.

(Light of a particular frequency strikes a clean metal

surface inside a vacuum chamber. Electrons are ejected
from the metal and are counted by a detector that
measures their kinetic energy)

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 ATOMIC STRUCTURE

The results observed in this experiment were:

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 from the metal
surface.
The number of electrons ejected is proportional to the intensity or brightness of light.
For each metal, there is a characteristic minimum frequency, v0 (also known as threshold frequency)
below which photoelectric effect is not observed. At a frequency v > v0 , the ejected electrons come out
with certain kinetic energy. The kinetic energies of these electrons increase with the increase of
frequency of the light used.
Einstein’s explanation (using Planck's quantum theory of electromagnetic radiation):
Shining a beam of light on to a metal surface can, therefore, be viewed as shooting a beam of particles,
the photons. When a photon of sufficient energy strikes an electron in the atom of the metal, it
transfers its energy instantaneously to the electron during the collision and the electron is ejected
without any time lag or delay.
Greater the energy possessed by the photon, greater will be transfer of energy to the electron and
greater the kinetic energy of the ejected electron. In other words, kinetic energy of the ejected
electron is proportional to the frequency of the electromagnetic radiation.
Since the striking photon has energy equal to hv and the minimum energy required to eject the
electron is hv0, (also called work function, W0), then the difference in energy (hv - hv0) is transferred as
the kinetic energy of the photoelectron. Following the conservation of energy principle, the kinetic
1
energy of the ejected electron is given by the following equation: hv = hv0 + mev2. Where, me is the
2
mass of the electron and v is the velocity associated with the ejected electron.
Lastly, a more intense beam of light consists of larger number of photons, consequently the number of
electrons ejected is also larger as compared to that in an experiment in which a beam of weaker
intensity of light is employed.
The x-intercept is the threshold frequency of
the material. This makes sense, since the
electron will have zero kinetic energy when it
has received a photon at the threshold
frequency. The electron has just enough
energy to be knocked off the surface, but
that’s it!
The y-intercept is the work function of the
material. For any frequency less than the
threshold frequency, it’s like the electron is in
a deep hole. As the frequency goes from zero
to higher values, the electron is lifted higher
out of the hole, until finally at its threshold frequency it’s out. When there are no photons hitting it

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 ATOMIC STRUCTURE
(frequency = 0 Hz), it is completely attached to the material. This is why they appear as negative values
on the graph.

From the formula for work function (W = hvo)

we know that the bigger the work function, the
bigger will be the threshold frequency.
Therefore, the lines are...
Sodium (2.30 eV)
copper (4.80 eV)
selenium (5.11 eV)

 Dual behaviour of
electromagnetic
radiations: Photoelectric effect shows particle nature of light. Diffraction and interference explain wave
nature of light.

Particle Wave
Particle is localised. Wave is delocalised.
Two particles cannot occupy the same position in Particle of two or more waves can exist in the same
space. region of space.
Two particles do not interfere. Particle of two waves may interfere constructively
or destructively.

It shows that light possesses both particle and wave like properties, i.e., light has dual behaviour. Depending
on the experiment, we find light behaves either as a particle (when interacts with matter) or like wave
(interference and diffraction) which it exhibits when it propagates.
3. Line Spectrum of Hydrogen: When an electric discharge is passed through gaseous hydrogen, the H 2
molecules dissociate and the energetically excited hydrogen atoms produced, emit electromagnetic radiation
of discrete frequencies. The hydrogen spectrum consists of several series of lines named after their
discoverers. Balmer showed in 1885 on the basis of experimental observations that if spectral lines are
expressed in terms of wavenumber, then the visible lines of the hydrogen spectrum obey the following
formula:

The series
of lines described by this formula are called the Balmer series. The Balmer series of lines are the only lines in
the hydrogen spectrum which appear in the visible region of the electromagnetic spectrum.
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 ATOMIC STRUCTURE
These observed spectral lines are due to the electron making transitions between two energy levels in an
atom. The Swedish spectroscopist, Johannes Rydberg, noted that all series of lines in the hydrogen spectrum
could be described by following the expression.

Where, n1 and n2 have integral values as follows:

n1 n2 Spectral Series Spectral region

1 2, 3, 4… Lyman UV

2 3, 4, 5… Balmer Visible

3 4, 5, 6… Paschen IR

4 5, 6, 7… Brackett IR

5 6, 7, 8… Pfund IR

 Postulates of Bohr’s model of an atom: The main postulates of Bohr’s theory proposed by Niels Bohr
(1913) are as follows:

1) An atom consists of a small, heavy positively

charged nucleus in the centre and electrons revolve
around it in circular orbit.

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 ATOMIC STRUCTURE
2) The electrons revolve only in those orbits which have a fixed value of energy. These orbits are called energy
levels or stationary states.

The energy of the electron revolving in a particular orbit is fixed and does not change with time. The different
energy levels are numbered as 1, 2, 3, 4…. or designated as K, L, M, N, O….. starting from the shells closest to
the nucleus.

a) The energies of the different stationary states in case of hydrogen atom are given by the expression

The first energy level (n=1) which is closest to the nucleus has lowest energy. The energy of the levels
increases as we move outwards starting from the first level i.e., K< L<M<N<O…..

b) The radii of the stationary states of the hydrogen atom are given by the expression:

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 ATOMIC STRUCTURE
3) Since the electrons revolve only in those orbits which have fixed value of energy, hence electrons in an
atom can have only certain definite or discrete values of energy and not any value of their own. The energy of
an electron is quantized.

4) Like energy, the angular momentum of an electron in an atom can have certain definite or discrete values
and not any value of its own. The only permissible values of angular momentum are given by the expression:

Where m is the mass of the electron, v is the tangential velocity of the revolving
electron, r is the radius of the orbit, h is the Planck’s constant and n is any Integer.

The angular momentum of an electron in an atom is also quantized.

5) When the electrons in an atom are in their lowest energy state, they keep on revolving in the respective
orbits without losing energy because energy can neither be lost nor gained continuously. This state of atom is
called normal or ground state.

6) Energy is emitted or absorbed only when the electron jumps from one orbit to the other. When energy is
supplied to an atom, an electron in the atom may jump from its normal energy level to some high energy level
by absorbing a definite amount of energy. This state of atom is called excited state. Since the lifetime of the
electron in the excited state is short, it immediately jumps back to the lower energy level by emitting energy in
the form of light of suitable frequency or wavelength. The amount of energy emitted or absorbed is given by
the difference of energies of the two energy levels concerned i.e., ΔE = E2 – E1
Where E2 and E1 are the energy of the electron in the higher and lower energy levels ΔE is the difference in
energies of the two levels.

Energy is always emitted or absorbed in certain discrete quantities called quantas or photons and not any
value.

Electronic energy as negative energy: When the electron is at distance Infinity from the nucleus, there is no
force of attraction on the electron by the nucleus. Hence, the energy of the electron at distance infinity from
the nucleus is taken as zero. As the electron move towards the nucleus, it experiences a force of attraction by
the nucleus. As a result some energy is given out. Since its value was already zero, hence now it becomes
negative. As the electrons come more and more close to the nucleus, the attraction increases and more
energy is released. Hence, the energy of the electron becomes less and less. This explains why the energy
decreases as we move from outer to inner shell.

Quantization of Electronic energy: Quantization means that a quantity cannot change gradually and
continuously to have any arbitrary value but changes only abruptly and discontinuously to have certain
definite or discrete value. Electron revolve around the nucleus in certain fixed circular orbits in which they can
continue revolving without gaining or losing energy. The energy of the electron cannot change continuously
but can have only definite values. Thus, we can say that energy of an electron is quantized.

Usefulness of Bohr’s Model

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 ATOMIC STRUCTURE
It explains the stability of the atom: An electron cannot lose energy as long as it stays in a particular
Orbit.
It explains the line spectrum of hydrogen: An electron neither emits nor absorbs energy as long as it
stays in a particular orbit. When an atom is subjected to electric discharge or high temperature, an
electron in the atom may jump from the normal energy level i.e., ground state to some higher energy
level i.e., excited state. Since the lifetime of the electron in the excited state is short, it returns to some
lower energy level or even to the ground state in one or more jumps. During each such jump, energy is
emitted in the form of a photon of light of a definite wavelength of frequency. Corresponding to the
frequency or wavelength of each Photon emitted, there appears a line in the spectrum.

The frequency of the photon of light emitted depends upon the energy difference of the two energy level
concerned and is given by:

Limitations of Bohr’s model of atom

Inability to explain line spectra of multi-electron atom: When spectroscope with better resolving
power were used, it was found that even in case of hydrogen spectrum, each line was split up into a
number of closely spaced lines which could not be explained by Bohr’s model of an atom.
Inability to explain splitting of lines in the magnetic field (zeeman effect) and in the electric field
(stark effect): If the source emitting the radiation is placed in a magnetic field or in an electric field, it is
observed that each spectral line splits up into a number of lines. The splitting the spectral line in
magnetic field is called zeeman effect while the splitting of spectral lines in magnetic electric field is
called stark effect.
Inability to explain the three dimensional model of atom.
Inability to explain the shapes of molecules.
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 ATOMIC STRUCTURE
Inability to explain de Broglie concept of dual nature of matter and Heisenberg Uncertainty Principle.

 de Broglie hypothesis

Louis de Broglie (1924), a French physicist, suggested that just as light has both wave-like and particle-like
properties (as suggested by Einstein), electrons also have wave-like properties. Therefore, if we look at every
moving particle whether it is microscopic or macroscopic it will have a wavelength.

de Broglie Equation Derivation and de Broglie Wavelength

Plank’s quantum theory relates the energy of an electromagnetic wave to its wavelength or frequency.

c
E = hν = h …….(1)
λ

Einstein related the energy of particle matter to its mass and velocity, as E = mc2 ..…..(2)

As the smaller particle exhibits dual nature, and energy being the same, de Broglie equated both these
relations for the particle moving with velocity ‘v’ as,

c h h h h
E = h = mv2 Then, = mv or, λ = = = where ‘h’ is the Plank’s constant.
λ λ mv p momentum

This equation relating the momentum of a particle with its wavelength is de Broglie equation and the
wavelength calculated using this relation is de Broglie wavelength.

Relation between de Broglie Equation and Bohr’s Hypothesis of Atom

Bohr postulated that angular momentum of an electron revolving around the nucleus as quantized. Hence, the
angular momentum will only be an integral multiple of a constant value and suggested the following
nh
expression. Angular momentum of electron in orbit, mvr = where ‘n’ is an integer with values of 1, 2, 3…..
2π
Bohr did not give any reason for such a proposal. But, de Broglie equation gives a scientific validation for such
an imaginative proposal.

h
By, de Broglie, equation λ =
mv

The electron wave in an orbit must be in phase and so, Circumference of an orbit = integral multiple of the
h nh
wavelength, hence 2πr = n λ or, 2πr = n or, mvr =
mv 2π

h
Hence the angular momentum of electron (mvr) is an integral multiple of a constant ( ).
2π

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 Heisenberg uncertainty principle

Heisenberg uncertainty principle (1927) states that for particles with the dual nature of particle and wave
nature, it will not be possible to accurately determine both the position and velocity at the same time.
If, ∆x is the error in position measurement and ∆p is the error in the measurement of momentum, then

Since momentum, p = mv, Heisenberg’s uncertainty principle formula can be

alternatively written as

Where, ∆v is the error in the measurement of velocity and assuming mass remaining constant during the
experiment. Accurate measurement of position or momentum automatically indicates larger uncertainty
(error) in the measurement of the other quantity.

[NOTE: Why can’t electrons exist inside the nucleus? We can explain this by heisenberg's uncertainty
principle.

Now if electron is in the nucleus then Δx = 10-15 m (size of nucleus), m= 9.1 x 10-31 kg,
h= 6.626x 10-34 joule sec. If we substitute all the values and just observe the power on ten
we get, Δv ≥ …. x 1011, that is an electron cannot have velocity greater than the velocity
of light. Hence, electrons can’t exist inside the nucleus.]

 Quantum mechanical model

Quantum mechanics is based on Schrödinger’s wave equation and its solution.

The solution of the wave equation brings the idea of shells, sub-shells and orbitals. The probability of finding
an electron at a point within an atom is proportional to the |ψ|2 at that point, where ψ represents the wave-
function of that electron.

Application of Schrödinger’s equation to multi-electron atoms present’s some difficulty: Schrödinger’s wave
equation cannot be solved exactly for a multi-electron atom. This difficulty was overcome by using
approximate methods.

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 ATOMIC STRUCTURE
The application of Schrödinger wave equation in determining the structure of an atom led to the formation of
the quantum mechanical model of an atom.

Features of quantum mechanical model:

1. The energy of an electron is quantized i.e. an electron can only have certain specific values of energy.

2. The quantized energy of an electron is the allowed solution of the Schrödinger wave equation and it is
the result of wave like properties of electron.

3. As per Heisenberg’s Uncertainty principle, the exact position and momentum of an electron cannot be
determined. So the only probability of finding an electron at a position can be determined and it is |ψ|
2
at that point where ψ represents the wave-function of that electron.

4. An atomic orbital is the wave-function (ψ) of an electron in an atom. Whenever an electron is

described by a wave-function, it occupies atomic orbital. As an electron can have many wave-functions,
there are many atomic orbitals for electron. Every wave-function or atomic orbital have some shape
and energy associated with it. All the information about the electron in an atom is stored in its orbital
wave function ψ and quantum mechanics makes it possible to extract this information out of ψ.

5. The probability of finding an electron at a point within an atom is proportional to the square of the
orbital wave function i.e., | ψ |2 at that point. | ψ |2 is known as probability density and is always
positive.

[NOTE: Significance of ψ and ψ2: The wave function ψ used in the above equation represents the amplitude of
the electron wave. The square of the wave function, i.e., ψ2 gives the probability of finding an electron at
various places in a given region around the nucleus.]
 Concept of orbitals: The three dimensional region in the space around the nucleus in which the probability
of finding an electron is maximum is called an orbital.
Characteristics of orbitals:
An orbital can accommodate maximum of two electrons only.
In the absence of a magnetic field, all the orbitals belonging to the same subshell possess the same
energy and are said to be degenerate.
In the presence of a magnetic field, different orbitals belonging to the same subshell acquire slightly
different energies and are said to be non-degenerate orbitals.
The orbitals of the same subshell differ in their direction of orientation in space.
The number of orbitals belonging to a principal shell is equal to n2, where n represents the principal
quantum number.
Differences between Orbit and Orbitals
Orbit Orbitals
An orbit is the simple planar representation of an An orbital refers to the dimensional motion of an

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electron. electron around the nucleus in a three dimensional
motion.
It can be simply defined as the path that gets An orbital can simply be defined as the space or the
established in a circular motion by revolving the region where the electron is likely to be found the
electron around the nucleus. most.
The shape of molecules cannot be explained by The shapes of the molecules can be found out as
an orbit as they are non-directional by nature. they are directional by nature.
An orbit that is well defined goes against the An ideal orbital agrees with the theory of
Heisenberg principle. Heisenberg’s Principles.

 Quantum numbers
A set of four numbers which gives complete information about an electron in an atom.

Quantum Values Information conveyed

numbers

Principal quantum Any integer value i.e., Main shell of the electron.
number (n) 1, 2, 3, 4, etc. Approximate distance from the nucleus.
Energy of shell.
Maximum number of electrons present in the
shell (2n²).
Explains the main lines of spectrum.

Angular momentum can be calculated.

nh
mvr =
2π

Azimuthal For a particular value of n, l = No. of subshells present in the main shell.
quantum 0 to n-1 Relative energies of the subshells.
number (l ) l = 0, s-subshell Shapes of orbitals.
l = 1, p-subshell Explains the fine structure of the line spectrum.
l = 2, d-subshelI Orbital angular momentum of an electron can be
l = 3, f-subshell h
calculated as μl = √ l(l+1)
2π
Magnetic For a particular value of l , m Spatial orientation of the orbital with respect to
quantum = -l to +l including standard set of co-ordinate axis.
number (ml) Zero. No. of orbitals present in any subshell.
Explains the splitting of lines in a magnetic field.
Spin quantum 1 1 Direction of electron spin (clockwise or
+ ,-
number (ms) 2 2 anticlockwise).
Explains the magnetic properties of substances.

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 Shapes of orbitals
Shape of an orbital is given by total probability density ψ including both radial part as well as angular part.
Shape of s-orbital:
Shape of s-orbital must be spherical since probability of
finding electron is equal in all directions at a distance from
nucleus.
Shape of p-orbital:
The probability of finding p-electron is maximum in two
dumb-bell type lobes on the two opposite sides of nucleus.
Thus, p-orbital has dumb-bell shape. In the three p-orbitals, px, py and pz the probability lies maximum along x-
axis, y-axis and z-axis respectively. p-orbitals possess one nodal plane passing through the nucleus.

Shape of d-orbital:
Depending on the probability, d-orbitals have clover-leaf shape. There are five d-orbitals, d xy , dyz , dxz , dx2-y2 and
dz2 . dz2 has exceptionally doughnut shape. Each d-orbital has two nodal-planes.

[NOTE: Nodes are points of zero electron density. From the principal quantum number n and the azimuthal
quantum number ℓ, you can derive the number of nodes, and how many of them are radial and angular.
radial nodes = n− ℓ−1
angular nodes = ℓ
Mr. T.K. BOSE (M.SC. in Organic Chemistry from J.U., B.Ed.)
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 ATOMIC STRUCTURE
number of nodes = n−1
radial nodes=(number of nodes)−(angular nodes)
Distribution function (D):
It is given by D= 4 π r2 ψ2. The distribution function can be regarded as a measure of probability of finding an
electron in a spherical shell of thickness dr at various distances r from the nucleus. In other words, the
function D represents the density of the electron cloud, i.e., electron density at a particular distance r from the
nucleus.
An atomic orbital can be specified by specifying the energy and angular momentum of the electron present in
it. In an orbital, there may be regions of higher probability and regions of lower probability as is clear from the
following radial probability distribution curves for 1s, 2s- and 2p-orbitals.

The point (within an orbital) at which the probability of finding electron is zero is called a nodal point and a
plane passing through this point is called a nodal plane.
So each type of orbital (s, p, d etc.) has its own unique, fixed number of angular nodes, and then as n
increases, you add radial nodes.
Examples: First shell
For the first shell, n=1, which means the number of nodes will be 0.
Examples: Second shell
For the second shell, n=2, which yields 1 node.
For the 2s orbital, ℓ=0, which means the node will be radial.
For the 2p orbital, ℓ=1, which means the node will be angular.
Examples: Third shell
For the third shell, n=3, yielding 3−1=2 nodes.
The 3s orbital still has ℓ=0 meaning no angular nodes, and thus the two nodes must be radial.
The 3p orbital still has one angular node, meaning there will be one radial node as well.
The 3d orbital has two angular nodes, and therefore no radial nodes!
The difference between radial and angular nodes

Radial nodes are nodes inside the orbital lobes. It’s easiest to understand by looking at the s-orbitals, which
can only have radial nodes.

Mr. T.K. BOSE (M.SC. in Organic Chemistry from J.U., B.Ed.)

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 ATOMIC STRUCTURE

To see what an angular node is, then, let's examine the 2p-orbital - an orbital that has one node, and that
node is angular.

We see that angular nodes are not internal countours of zero electron probability, but rather is a plane that
goes through the orbital.

 For the 2px-orbital, the angular node is the plane spanned by the z- and y-axis.
 For the 2py-orbital, the angular node is the plane spanned by the z- and x-axis.
 For the 2pz-orbital, the angular node is the plane spanned by the x- and y-axis.]

 Filling of orbitals in an atom:

Aufbau principle: The filling up of electrons in different orbitals is based on the following rules :
 Orbitals are filled in the order of increasing energy. The subshell with lowest (n + l ) value is filled up
first. When two or more subshells have same (n + l ) value, the subshell with lowest value of 'n' is
filled up first.
 In the ground state of the atoms, the orbitals are filled in order of their increasing energies: 1s, 2s,
2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s …

Mr. T.K. BOSE (M.SC. in Organic Chemistry from J.U., B.Ed.)

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 ATOMIC STRUCTURE

Pauli Exclusion Principle:

“No two electrons in an atom can have the same set of four quantum numbers.” Or
“Only two electrons may exist in the same orbital and these electrons must have opposite spin.”

Subshell n l m s
1s 1 0 0 1
+
2
1 0 0 1
-
2

This means that the two electrons can have the same value of three quantum numbers n, l and m l but
must have the opposite spin quantum number.

Hund's Rule of Maximum Multiplicity:

“Pairing of electrons in the orbitals belonging to the same subshell (p, d or f) does not take place until
each orbital belonging to that subshell has got one electron each i.e., it is singly occupied.”
Since there are three p, five d and seven f orbitals, therefore, the pairing of electrons will start in the p,
d and f orbitals with the entry of 4th, 6th and 8th electron, respectively.

Mr. T.K. BOSE (M.SC. in Organic Chemistry from J.U., B.Ed.)

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 ATOMIC STRUCTURE

 Electronic configuration of elements

Mr. T.K. BOSE (M.SC. in Organic Chemistry from J.U., B.Ed.)

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Causes of Stability of Completely Filled and half-filled sub-shells

In certain elements such as Cu, or Cr, where the two subshells (4s and 3d) differ slightly in their energies, an electron
shifts from a subshell of lower energy (4s) to a subshell of higher energy (3d), provided such a shift results in all orbitals
of the subshell of higher energy getting either completely filled or half filled. The valence electronic configurations of Cr
and Cu, therefore, are 3d5 4s1 and 3d104s1 respectively and not 3d4 4s2 and 3d94s2.

The completely filled and half-filled sub-shells are stable due to the following reasons:

Symmetrical 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.

Mr. T.K. BOSE (M.SC. in Organic Chemistry from J.U., B.Ed.)

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 ATOMIC STRUCTURE

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.

Mr. T.K. BOSE (M.SC. in Organic Chemistry from J.U., B.Ed.)

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