STRUCTURE OF ATOM

• Charge on the Electron

R.A. Millikan devised a method known as oil drop experiment to determine the charge on the electrons.

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

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(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.
• Isotopes
Atoms with identical atomic number but different atomic mass number are known as Isotopes.
Isotopes of Hydrogen:
11H,12H &13H are isotopes of Hydrogen.1735Cl &1737Cl are isotopes of Chlorine.
• 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 . 10-8s. But actually this does not happen.
(ii) Rutherford’s model does not give any idea about distribution of electrons around the nucleus and
about their energies..
• 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 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 10 8m/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.
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).

• 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.
• 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 -34Jsec.
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 Balmer series, n1 = 2, n2 = 3, 4, 5, 6………..
For Paschen series, n1= 3, n2 = 4, 5, 6, 7………..
• 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) Each atom consists of two parts. i. Nuclear part and ii. Extra nuclear part.
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,

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
multielectron atoms.
(ii) Bohr’s 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.
According to Einstein E= mc2----(i)
And according Planck, E=hν ----(ii)

From equations (i) and (ii) mc2= hν

Or mc2= h x c/ λ
Or λ= h/mc

For electron like microscopic particles c = v & hence;

• Heisenberg’s Uncertainty Principle:

It states that, “It is impossible to determine simultaneously, the exact position and exact momentum (or
velocity) of an electron”. If the position of electron is measured with absolute accuracy then momentum
becomes uncertain and vice versa.
 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.
• Quantum Numbers
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 represents 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.
Azimuthal or Subsidiary or Orbital Angular Quantum Number (l):
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.
(iii) The shapes of the various subshells present within the same principal shell.
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 &1.
Subshells corresponding to different values of l are represented by the following symbols:
value of l 0 1 2 3 4 5 ……………..17
Magnetic Orbital Quantum Number (m):
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):

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.
The probability of s 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:
Thus, there are three orbitals in the p-subshell which are designated as p x, 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.

• 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 all 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.