Atomic structure -

• Discovery of Electron—Discharge Tube Experiment

In 1879, William Crooks studied the conduction of electricity through gases at low
pressure. He performed the experiment in a discharge tube which is a cylindrical hard
glass tube about 60 cm in length. It is sealed at both the ends and fitted with two metal
electrodes as shown in Fig. 2.1.

The electrical discharge through the gases could be observed only at very low pressures
and at very high voltages.
The pressure of different gases could be adjusted by evacuation. When sufficiently high
voltage is applied across the electrodes, current starts flowing through a stream of
particles moving in the tube from the negative electrode (cathode) to the positive
electrode (anode). These were called cathode rays or cathode ray particles.

• Properties of Cathode Rays

(i) Cathode rays travel in straight line.
(ii) Cathode rays start from cathode and move towards the anode.
(iii) These rays themselves are not visible but their behaviour can be observed with the
help of certain kind of materials (fluorescent or phosphorescent) which glow when hit
by them.
(iv) Cathode rays consist of negatively charged particles. When electric field is applied
on the cathode rays with the help of a pair of metal plates, these are found to be
deflected towards the positive plate indicating the presence of negative charge.
(v) The characteristics of cathode rays do not depend upon the material of electrodes
and the nature of gas present in the cathode ray’tube.

• Determination of Charge/Mass (elm) Ratio for Electrons

J. J. Thomson for the first time experimentally determined charge/mass ratio called elm
ratio for the electrons. For this, he subjected the beam of electrons released in the
discharge tube as cathode rays to influence the electric and magnetic fields. These
were acting perpendicular to one another as well as to the path followed by electrons.
According to Thomson, the amount of deviation of the particles from their path in
presence of electrical and magnetic field depends upon following factors:
(i) Greater the magnitude of the charge on the particle, greater is the interaction with the
electric or magnetic field and thus greater is the deflection.
(ii) The mass of the particle — lighter the particle, greater the deflection.

(iii) The deflection of electrons from their original path increases with the increase in the
voltage across the electrodes or strength of the magnetic field.
By carrying out accurate measurements on the amount of deflections observed by the
electrons on the electric field strength or magnetic field strength, Thomson was able to
determine the value of
e/me = 1.758820 x 1011 C kg-1 where me = Mass of the electron in kg
e = magnitude of charge on the electron in coulomb (C).

• Charge on the Electron

R.A. Millikan devised a method known as oil drop experiment to determine the charge
on the electrons.
• Discovery of Proton—Anode Rays
In 1886, Goldstein modified the discharge tube by using a perforated cathode. On
reducing the pressure, he observed a new type of luminous rays passing through the
holes or perforations of the cathode and moving in a direction opposite to the cathode
rays. These rays were named as positive rays or anode rays or as canal rays. Anode rays
are not emitted from the anode but from a space between anode and cathode.

• Properties of Anode Rays

(i) The value of positive charge (e) on the particles constituting anode rays depends
upon the nature of the gas in the discharge tube.
(ii) The charge to mass ratio of the particles is found to depend on the gas from which
these originate.

(iii) Some of the positively charged particles carry a multiple of the fundamental unit of
electrical charge.
(iv) The behaviour of these particles in the magnetic or electric field is opposite to that
observed for electron or cathode rays.

• Proton
The smallest and lightest positive ion was obtained from hydrogen and was called
proton. Mass of proton = 1.676 x 10-27 kg
Charge on a proton = (+) 1.602 x 10-19 C

• Neutron
It is a neutral particle. It was discovered by Chadwick (1932).
By the bombardment of thin sheets of beryllium with fast moving a-particles he
observed • that highly penetrating rays consist of neutral particles which were named
neutrons.
• Thomson Model of Atom

(i) J. J. Thomson proposed that an atom may be regarded as a sphere of approximate

radius 1CT8 cm carrying positive charge due to protons and in which negatively charged
electrons are embedded.
(ii) In this model, the atom is visualized as a pudding or cake of positive charge with
electrons embedded into it.

(iii) The mass of atom is considered to be evenly spread over the atom according to this
model.
Drawback of Thomson Model of Atom
This model was able to explain the overall neutrality of the atom, it could not
satisfactorily, explain the results of scattering experiments carried out by Rutherford in
1911.

• Rutherford’s a-particle Scattering Experiment

Rutherford in 1911, performed some scattering experiments in which he bombarded
thin foils of metals like gold, silver, platinum or copper with a beam of fast moving
a-particles. The thin gold foil had a circular fluorescent zinc sulphide screen around it.
Whenever a-particles struck the screen, a tiny flash of light was produced at that point.
From these experiments, he made the following observations:
–

(i) Most of the a-particles passed through the foil without undergoing any deflection,
(ii) A few a-particles underwent deflection through small angles.

(iii) Very few mere deflected back i.e., through an angle of nearly 180°.
From these observations, Rutherford drew the following conclusions:
(i) Since most of the a-particles passed through the foil without undergoing any
deflection, there must be sufficient empty space within the atom.
(ii) A small fraction of a-particles was deflected by small angles. The positive charge
has to be concentrated in a very small volume that repelled and deflected a few
positively charged a-particles. This very small portion of the atom was called nucleus.
(iii) The volume of nucleus is very small as compared to total volume of atom.

• Rutherford’s Nuclear Model of an Atom

(i) The positive charge and most of the mass of the atom was densely concentrated in
an extremely small region. This very small portion of the atom was called nucleus by
Rutherford.
(ii) The nucleus is surrounded by electrons that move around the nucleus with a very
high speed in circular paths called orbits.
(iii) Electrons and nucleus are held together by electrostatic forces of attraction.

• Atomic Number
The number of protons present in the nucleus is equal to the atomic number (z). For
example, the number of protons in the hydrogen nucleus is 1, in sodium atom it is 11,
therefore, their atomic numbers are 1 and 11. In order to keep the electrical neutrality,
the number of electrons in an atom is equal to the number of protons (atomic number,
z). For example, number of electrons in hydrogen atom and sodium atom are 1 and 11
respectively.
Atomic Number (z) = Number of protons in the nucleus of an atom.
= Number of electrons in a neutral atom.

• Mass Number
Number of protons and neutrons present in the nucleus are collectively known as
nucleons. The total number of nucleons is termed as mass number (A) of the atom.
Mass Number (A) = Number of protons (p) + Number of neutrons (n).

• Isotopes
Atoms with identical atomic number but different atomic mass number are known as
Isotopes.
Isotopes of Hydrogen:

These three isotopes are shown in the figure below:

Characteristics of Isotopes
(i) Since the isotopes of an element have the same atomic number, but different mass
number, the nuclei of isotopes contain the same number of protons, but different
number of neutrons.
(ii) Since, the isotopes differ in their atomic masses, all the properties of the isotopes
depending upon the mass are different.

(iii) Since, the chemical properties are mainly determined by the number of protons in
the nucleus, and the number of electrons in the atom, the different isotopes of an
element exhibit similar chemical properties. For example, all the isotopes of carbon on
burning give carbon dioxide.

• Isobars

• Drawbacks of Rutherford Model

(i) When a body is moving in an orbit, it achieves acceleration. Thus, an electron moving
around nucleus in an orbit is under acceleration.
According to Maxwell’s electromagnetic theory, charged particles when accelerated
must emit electromagnetic radiations. Therefore, an electron in an orbit will emit
radiations, the energy carried by radiation comes from electronic motion. Its path will
become closer to nucleus and ultimately should spiral into nucleus within . 10-8 s. But
actually this does not happen.
Thus, Rutherford’s model cannot explain the stability of atom if the motion of electrons
is described on the basis of classical mechanics and electromagnetic theory.
(ii) Rutherford’s model does not give any idea about distribution of electrons around the
nucleus and about their energies.

• Developments Leading to the Bohr’s Model of Atom

Two developments played a major role in the formulation of Bohr’s model of atom.
These were:
(i) Dual character of the electromagnetic radiation which means that radiations possess
both wave like and particle like properties.
(ii) Experimental results regarding atomic spectra which can be explained only by
assuming quantized electronic energy levels in atoms.

• Nature of Electromagnetic Radiation (Electromagnetic Wave

Theory)
This theory was put forward by James Clark Maxwell in 1864. The main points of this
theory are as follows:
(i) The energy is emitted from any source (like the heated rod or the filament of a bulb
through which electric current is passed) continuously in the form of radiations and is
called the radiant energy.
(ii) The radiations consist of electric and magnetic fields oscillating perpendicular to
each other and both perpendicular to the direction of propagation of the radiation.
(iii) The radiations possess wave character and travel with the velocity of light 3 x 108
m/sec.
(iv) These waves do not require any material medium for propagation. For example, rays
from the sun reach us through space which is a non-material medium.

• Characteristics of a Wave
Wavelength: It is defined as the distance between any two consecutive crests or
troughs. It is represented by X and its S.I. unit is metre.

Frequency: Frequency of a wave is defined as the number of waves passing through a

point in one second. It is represented by v (nu) and is expressed in Hertz (Hz).
1 Hz = 1 cycle/sec.
Velocity: Velocity of a wave is defined as the linear distance travelled by the wave in one
second.
It is represented by c and is expressed in cm/sec or m/sec.
Amplitude: Amplitude of a wave is the height of the crest or the depth of the through. It
is represented by V and is expressed in the units of length.
Wave Number: It is defined as the number of waves present in 1 metre length. Evidently
it will be equal to the reciprocal of the wavelength. It is represented by bar v (read as nu
bar).

Electromagnetic Spectrum: When electromagnetic radiations are arranged in order of

their increasing wavelengths or decreasing frequencies, the complete spectrum
obtained is called electromagnetic spectrum.

• Limitations of Electromagnetic Wave Theory

Electromagnetic wave theory was successful in explaining properties of light such as
interference, diffraction etc; but it could not explain the following:
(i) The phenomenon of black body radiation.
(ii) The photoelectric effect.
(iii) The variation of heat capacity of solids as a function of temperature.
(iv) The line spectra of atoms with reference to hydrogen.

• Black Body Radiation

The ideal body, which emits and absorbs 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 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 Fig 2.6.

• Planck’s Quantum Theory

To explain the phenomenon of ‘Black body radiation’ and photoelectric effect, Max
Planck in 1900, put forward a theory known as Planck’s Quantum Theory.
This theory was further extended by Einstein in 1905. The main points of this theory
was as follows: ,
(i) The radiant energy emitted or absorbed in the form of small packets of energy. Each
such packets of energy is called a quantum.
(ii) The energy of each quantum is directly proportional to the frequency of the radiation

where h is a proportionality constant, called Planck’s constant. Its value is equal to

6.626 x 10-34 Jsec.

• Photoelectric Effect
Hertz, in 1887, discovered that when a beam of light of certain frequency strikes the
surface of some metals, electrons are emitted or ejected from the metal surface. The
phenomenon is called photoelectric effect.

Observations in Photoelectric Effect

(i) Only photons of light of certain minimum frequency called threshold frequency (v0)
can cause the photoelectric effect. The value of v0 is different for different metals.
(ii) The kinetic energy of the electrons which are emitted is directly proportional to the
frequency of the striking photons and is quite independent of their intensity.
(iii) The number of electrons that are ejected per second from the metal surface
depends upon the intensity of the striking photons or radiations and not upon their
frequency.

Explanation of Photoelectric Effect

Einstein in (1905) was able to give an explanation of the different points of the
photoelectric effect using Planck’s quantum theory as under:

(i) Photoelectrons are ejected only when the incident light has a certain minimum
frequency (threshold frequency v0)
(ii) If the frequency of the incident light (v) is more than the threshold frequency (v0), the
excess energy (hv – hv0) is imparted to the electron as kinetic energy.
K.E. of the ejected electron

energy of the emitted electron.

(iii) On increasing the intensity of light, more electrons are ejected but the energies of
the electrons are not altered.

• Dual Behaviour of Electromagnetic Radiation

From the study of behaviour of light, scientists came to the conclusion that light and
other electromagnetic radiations have dual nature. These are wave nature as well as
particle nature. Whenever radiation interacts with matter, it displays particle like
properties in contrast to the wavelike properties (interference and diffraction) which it
exhibits when it propagates. Some microscopic particles, like electrons, also exhibit this
wave-particle duality.
• Spectrum
When a ray of white light is passed through a prism the wave with shorter wavelength
bends more than the one with a longer wavelength. Since ordinary white light consists
of waves with all the wavelengths in the visible range, array of white light is spread out
into a series of coloured bands called spectrum. The light of red colour which has
longest wavelength is deviated the least while the violet light, which has shortest
wavelength is deviated the most.

Continuous Spectrum
When a ray of white light is analysed by passing through a prism it is observed that it
splits up into seven different wide bands of colours from violet to red (like rainbow).
These colours are so continuous that each of them merges into the next. Hence, the
spectrum is called continuous spectrum.

Emission Spectra
Emission Spectra is noticed when the radiations emitted from a source are passed
through a prism and then received on the photographic plate. Radiations can be emitted
in a number of ways such as:
(i) from sun or glowing electric bulb.
(ii) by passing electric discharge through a gas at low pressure.
(iii) by heating a substance to high temperature.

Line Spectra
When the vapours of some volatile substance are allowed to fall on the flame of a
Bunsen burner and then analysed with the help of a spectroscope. Some specific
coloured lines appear on the photographic plate which are different for different
substances. For example, sodium or its salts emit yellow light while potassium or its
salts give out violet light.

Absorption Spectra
When white light is passed through the vapours of a substance and the transmitted light
is then allowed to strike a prism, dark lines appear in the otherwise continuous
spectrum. The dark lines indicate that the radiations corresponding to them were
absorbed by the substance from the white light. This spectrum is called absorption
spectrum.
Dark lines appear exactly at the same positions where the lines in the emission spectra
appear.
• Line Spectrum of Hydrogen
When electric discharge is passed through hydrogen gas enclosed in discharge tube
under low pressure and the emitted light is analysed by a spectroscope, the spectrum
consists of a large number of lines which are grouped into different series. The
complete spectrum is known as hydrogen spectrum.
On the basis of experimental observations, Johannes Rydberg noted that all series of
lines in the hydrogen spectrum could be described by the following expression:

Rydberg in 1890, and has given a simple theoretical equation for the calculation of
wavelengths and wave numbers of the spectral lines in different series of hydrogen
spectrum. The equation is known as Rydberg formula (or equation).

This relation is valid for hydrogen atom only. For other species,

where Z is the atomic number of the species.

Here RH = constant, called Rydberg constant for hydrogen and n1 , n2 are integers (n2 >
n1)
For any particular series, the value of n1 is constant while that of n2 changes. For
example,
For Lyman series, n1= 1, n2= 2, 3, 4, 5………..
For the Balmer series, n1 = 2, n2 = 3, 4, 5, 6………..
For the Paschen series, n1= 3, n2 = 4, 5, 6, 7………..
For the Brackett series,n1 = 4, n2 = 5, 6, 7, 8………..
For the Pfund series, n1 =5, n2 = 6, 7, 8, 9………..
Thus, by substituting the values of n1 and n2 in the above equation, wavelengths and
wave number of different spectral lines can be calculated. When n1 = 2, the expression
given above is called Balmer’s formula.

• Bohr’s Model of Atom

Niels Bohr in 1913, proposed a new model of atom on the basis of Planck’s Quantum
Theory. The main points of this model are as follows:
(i) In an atom, the electrons revolve around the nucleus in certain definite circular paths
called orbits.
(ii) Each orbit is associated with definite energy and therefore these are known as
energy
levels or energy shells. These are numbered as 1, 2, 3, 4……….. or K, L, M, N………..
(iii) Only those energy orbits are permitted for the electron in which angular momentum
of the electron is a whole number multiple of h/2π
Angular momentum of electron (mvr) = nh/2π (n = 1, 2, 3, 4 etc).
m = mass of the electron.
v = tangential velocity of the revolving electron.
r = radius of the orbit.
h = Planck’s constant.
n is an integer.
(iv) As long as electron is present in a particular orbit, it neither absorbs nor loses
energy and its energy, therefore, remains constant.
(v) When energy is supplied to an electron, it absorbs energy only in fixed amounts as
quanta and jumps to higher energy state away from the nucleus known as excited state.
The excited state is unstable, the electron may jump back to the lower energy state and
in doing so, it emits the same amount of energy. (∆E = E2 – E1).

• Achievements of Bohr’s Theory

1. Bohr’s theory has explained the stability of an atom.
2. Bohr’s theory has helped in calculating the energy of electron in hydrogen atom and
one electron species. The mathematical expression for the energy in the nth orbit is,
• Limitations of Bohr’s Model
(i) The theory could not explain the atomic spectra of the atoms containing more than
one electron or multielectron atoms.
(ii) Bohr7s theory failed to explain the fine structure of the spectral lines.
(iii) Bohr’s theory could not offer any satisfactory explanation of Zeeman effect and
Stark effect.
(iv) Bohr’s theory failed to explain the ability of atoms to form molecule formed by
chemical bonds.
(v) It was not in accordance with the Heisenberg’s uncertainty principle.

• Dual Behaviour of Matter (de Broglie Equation)

de Broglie in 1924, proposed that matter, like radiation, should also exhibit dual
behaviour i.e., both particle like and wave like properties. This means that like photons,
electrons also have momentum as well as wavelength.
From this analogy, de Broglie gave the following relation between wavelength (λ) and
momentum (p) of a material particle.

• Heisenberg’s Uncertainty Principle

It states that, “It is impossible to determine simultaneously, the exact position and exact
momentum (or velocity) of an electron”.
• Significance of Uncertainty Principle
(i) It rules out existence of definite paths or trajectories of electrons and other similar
particles.
(ii) The effect of Heisenberg’s uncertainty principle is significant only for microscopic
objects and is negligible for macroscopic objects.

• Reasons for the Failure of Bohr Model

(i) The wave character of the electron is not considered in Bohr Model.
(ii) According to Bohr Model an orbit is a clearly defined path and this path can
completely be defined only if both the position and the velocity of the electron are
known exactly at the same time. This is not possible according to the Heisenberg’s
uncertainty principle.

• Quantum Mechanical Model of Atom

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

Important Features of Quantum Mechanical Model of Atom

(i) The energy of electrons in atom is quantized i.e., can only have certain values.
(ii) The existence of quantized electronic energy level is a direct result of the wave like
properties of electrons.
(iii) Both the exact position and exact velocity of an electron in an atom cannot be
determined simultaneously.
(iv) An atomic orbital has wave function φ. There are many orbitals in an atom. Electron
occupy an atomic orbital which has definite energy. An orbital cannot have more than
two electrons. The orbitals are filled in increasing order of energy. All the information
about the electron in an atom is stored in orbital wave function φ.
(v) The probability of finding electron at a point within an atom is proportional to square
of orbital wave function i.e., |φ2|at that point. It is known as probability density and is
always positive.
From the value of φ2 at different points within atom, it is possible to predict the region
around the nucleus where electron most probably will be found.

• Quantum Numbers
Atomic orbitals can be specified by giving their corresponding energies and angular
momentums which are quantized (i.e., they have specific values). The quantized values
can be expressed in terms of quantum number. These are used to get complete
information about electron i.e., its location, energy, spin etc.
Principal Quantum Number (n)
It is the most important quantum number since it tells the principal energy level or shell
to which the electron belongs. It is denoted by the letter V and can have any integral
value except zero, i.e., n = 1, 2, 3, 4……….. etc.
The various principal energy shells are also designated by the letters, K, L, M, N, O, P …..
etc. Starting from the nucleus.
The principal quantum number gives us the following information:
(i) It gives the average distance of the electron from the nucleus.
(ii) It completely determines the energy of the electron in hydrogen atom and hydrogen
like particles.
(iii) The maximum number of electrons present in any principal shell is given by 2n2
where n is the number of the principal shell.
Azimuthal or Subsidiary or Orbital Angular Quantum Number (l)
It is found that the spectra of the elements contain not only the main lines but there are
many fine lines also present. This number helps to explain the fine lines of the
spectrum.
The azimuthal quantum number gives the following information:
(i) The number of subshells present in the main shell.
(ii) The angular momentum of the electron present in any subshell.
(in) The relative energies of various subshells.
(iv) The shapes of the various subshells present within the same principal shell.
This quantum number is denoted by the letter T. For a given value of n, it can have any
value ranging from 0 to n – 1. For example,
For the 1st shell (k), n = 1, l can have only one value i.e., l = 0 For n = 2, the possible value
of l can be 0 and 1.
Subshells corresponding to different values of l are represented by the following
symbols:
value of l 0 1 2 3 4 5 ……………..
Notation for subshell s p d f g h ………………..
Magnetic Orbital Quantum Number (m or m1)
The magnetic orbital quantum number determines the number of preferred orientations
of the electrons present in a subshell. Since each orientation corresponds to an orbital,
therefore, the magnetic orbital quantum number determines the number of orbitals
present in any subshell.
The magnetic quantum number is denoted by letter m or ml and for a given value of l, it
can have all the values ranging from – l to + l including zero.
Thus, for energy value of l, m has 2l + 1 values.
For example,
For l = 0 (s-subshell), ml can have only one value i.e., m1 = 0.
This means that s-subshell has only one orientation in space. In other words, s-subshell
has only one orbital called s-orbital.
Spin Quantum Number (S or ms)
This quantum number helps to explain the magnetic properties of the substances. A
spinning electron behaves like a micromagnet with a definite magnetic moment. If an
orbital contains two electrons, the two magnetic moments oppose and cancel each
other.

• Shapes of s-orbitals
s-orbital is present in the s-subshell. For this subshell, l = 0 and ml = 0. Thus, s-orbital
with only one orientation has a spherical shape with uniform electron density along all
the three axes.
The probability of Is electron is found to be maximum near the nucleus and decreases
with the increase in the distance from the nucleus. In 2s electron, the probability is also
maximum near the nucleus and decreases to zero probability. The spherical empty shell
for 2s electron is called nodal surface or simply node.
• Shapes of p-orbitals
p-orbitals are present in the p-subshell for which l = 1 and m1 can have three possible
orientations – 1, 0, + 1.
Thus, there are three orbitals in the p-subshell which are designated as px, py and pz
orbitals depending upon the axis along which they are directed. The general shape of a
p-orbital is dumb-bell consisting of two portions known as lobes. Moreover, there is a
plane passing through the nucleus along which finding of the electron density is almost
nil. This is known as nodal plane as shown in the fig.

From the dumb-bell pictures, it is quite obvious that unlike s-orbital, a p-orbital is
directional in nature and hence it influences the shapes of the molecules in the
formation of which it participates.

• Shapes of d-orbitals
d-orbitals are present in d-subshell for which l = 2 and m[ = -2, -1, 0, +1 and +2. This
means that there are five orientations leading to five different orbitals.
• Aufbau Principle
The principle states: In the ground state of the atoms, the orbitals are filled in order of
their increasing energies.
In other words, electrons first occupy the lowest energy orbital available to them and
enter into higher energy orbitals only after the lower energy orbitals are filled.
The order in which the energies of the orbitals increase and hence the order in which the
orbitals are filled is as follows:
Is, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, id, 5p, 6s, if, 3d, 6p, 7s, 5f 6d, 7p
The order may be remembered by using the method given in fig. 2.11.
• Pauli Exclusion Principle
According to this principle, no two electrons in an atom can have the same set of four
quantum numbers.
Pauli exclusion principle can also be stated as: Only two electrons may exist in the
same orbital and these electrons must have opposite spins.
• Hund’s Rule of Maximum Multiplicity
It states that: 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.

• Electronic Configuration of Atoms

The distribution of electrons into orbitals of an atom is called its electronic
configuration. The electronic configuration of different atoms can be represented in two
ways.
For example:

• Causes of Stability of Completely Filled and Half Filled Subshells

The completely filled and half filled subshells are stable due to the following reasons:
1. Symmetrical distribution of electrons: The completely filled or half filled subshells
have symmetrical distribution of electrons in them and are therefore more stable.
2. The stabilizing effect arises whenever two or more electrons with same spin are
present in the degenrate orbitals of a subshell. These electrons tend to exchange their
positions
and the energy released due to their exchange is called exchange energy. The number of
exchanges that can takes 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.