Structure of Atom

• Discovery of Electron J. J. Thomson

• Determination of Charge/Mass (elm) Ratio for Electrons J. J. Thomson
• Charge on the Electron R.A. Millikan
• Discovery of Anode Rays Goldstein
• Discovery of Proton Rutherford
• Discovery of Neutron J Chadwick

• Atomic Number:- The number of protons present in the nucleus is equal to the atomic number (z).

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.

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:

• Isobars
Isotones and Isoelectronic species (Do Yourself)

• Drawbacks of Rutherford Model

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 with in. 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.
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.

• Electromagnetic Radiation (Electromagnetic Wave)

The radiations consist of electric and magnetic fields oscillating perpendicular to each other and
both perpendicular to the direction of propagation of the radiation.
The radiations possess wave character and travel with the velocity of light 3 x 10 8 m/sec.
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. 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 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 (v 0) 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 (v 0), the excess
energy (hv – hv0) is imparted to the electron as kinetic energy.
K.E. of the ejected 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 coloured 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 Balmer series, n1 = 2, n2 = 3, 4, 5, 6………..
For Paschen series, n1= 3, n2 = 4, 5, 6, 7………..
For Brackett series,n1 = 4, n2 = 5, 6, 7, 8………..
For 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 designated by 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,

3. Bohr’s theory has explained the atomic spectrum of hydrogen atom.

• Limitations of Bohr’s Model

(i) The theory could not explain the atomic spectra of the atoms containing more than one electron
or multi electron atoms.
(ii) Bohr’s theory could not offer any satisfactory explanation of Zeeman effect and Stark effect.
(iii) Bohr’s theory failed to explain the ability of atoms to form molecule formed by chemical bonds.
(iv) It was not in accordance with the Heisenberg’s uncertainty principle and dual behaviour of
matter.

• 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.

• 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

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

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, 4d, 5p, 6s, 4f, 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 wayFor 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.