1.

STRUCTUREOF ATOM
1. Discovery of Electron by cathode ray discharge tubes

In 1879, William Crooks studied the conduction of electricity through gases at low pressure. A cathode ray
tube is made of glass containing two thin pieces of metal, called electrodes, sealed in it. The electrical
discharge through the gases could be observed only at very low pressures and at very high voltages. 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) The cathode rays start from cathode and move towards the anode.
(ii) These rays themselves are not visible but they produce fluorescence on ZnS screen.
(iii) In the absence of electrical or magnetic field, these rays travel in straight lines
(iv) In the presence of electrical or magnetic field, the behavior of cathode rays are similar to that expected
from negatively charged particles, suggesting that the cathode rays consist of negatively charged particles,
called electrons.
(v) The characteristics of cathode rays(electrons) do not depend upon the material of electrodes and the
nature of the gas present in the cathode ray tube.
Charge to Mass Ratio of Electron
J.J. Thomson measured the ratio of electrical charge (e) to the mass of electron (me ) by using cathode ray
tube and applying electrical and magnetic field perpendicular to each other as well as to the path of
electrons .
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).

Discovery of proton anode ray

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 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 behavior 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: 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.

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 Nuclear Model of Atom
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.

The important observations are:

(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°.
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
Drawbacks of Rutherford Model
(i) 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.
Atomic Number: The number of protons present in the nucleus is equal to the atomic number (z). In
order to keep the electrical neutrality, the number of electrons in an atom is equal to the number of protons
(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.
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: protium, deuterium and tritium.
Isobars :Isobars are the atoms with same mass number but different atomic number for Example

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 –
(i) 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.
(ii) 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:
(iii) 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.
(iv) 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.
(v) 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

Planck’s Quantum Theory

The main points of this theory was as follows:
i. Atoms and molecules could emit (or absorb) energy only in discrete quantities and not in a continuous
manner.
ii.The smallest quantity of energy that can be emitted or absorbed in the form of electromagnetic radiation
is called quantum.
The energy (E ) of a quantum of radiation is proportional to its frequency (ν ) and is expressed by equation
(2.6).
E = nhν , ‘h’ is known as Planck’s constant = 6.626×10–34 J s.
Photoelectric effect
It is the phenomenon of ejection of electrons by certain metals (like potassium, rubidium, caesium
etc.) when light of suitable frequency incident on them. The electrons ejected are called photoelectrons.
This phenomenon was first observed by H.Hertz.
The important characteristics of photoelectric effect are:
1. 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.
2. 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.
3. 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.
(iii) On increasing the intensity of light, more electrons are ejected but the energies of the electrons are not
altered.
Following the law of conservation of energy principle, the kinetic energy of the ejected electron is given by
K.E = hν - hν0
hν = hν0 + 1/2mev2
Dual Behaviors of Electromagnetic Radiation
Light possesses both particle and wave-like properties, i.e., light has dual behaviour.
The particle nature of light could be explained the black body radiation and photoelectric effect. The wave
behavior of light could be explained by the phenomena of interference and diffraction.
Atomic spectrum
When a ray of white light is passed through a prism, we get a series of colored bands called
spectrum. This spectrum is called continuous spectrum, because here violet merges into blue, blue into
green and so on.
Emission and Absorption Spectra
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.
The emission spectra of atoms in the gas phase do not form a continuous spectrum.
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.
Each element has a unique line emission spectrum. So line emission spectra are also called finger
print of atoms.
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: 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 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) = (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).
vi. The radius of orbits can be given by the equation: rn= a0 n2 where a0 = 52.9 pm.
Thus the radius of the first stationary state is 52.9 pm (called the Bohr radius). As n increases, the value of r
will increase.
vii. It is also possible to calculate the velocities of electrons moving in these orbits. Qualitatively the
magnitude of velocity of electron increases with increase of positive charge on the nucleus and decreases
with increase of principal quantum number
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.
Limitations of Bohr Atom Model
Bohr atom model could explain the stability and line spectra of hydrogen atom and hydrogen like ions (e.g.
He+,Li2+, Be3+ etc). But it has the following limitations:
1. It could not explain the fine spectrum of hydrogen atom.
2. It could not explain the spectrum of atoms other than hydrogen.
3. It was unable to explain the splitting of spectral lines in the presence of electric field (Stark effect) and
in magnetic field (Zeeman effect).
4. It could not explain the ability of atoms to form molecules by chemical bonds.
5. It did not consider the wave character of matter and 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.

λ= =

Heisenberg’s Uncertainty Principle

It states that, “It is impossible to determine simultaneously, the exact position and exact momentum (or
velocity) of an electron”.
 Δx.Δp ≥ , Δx.mΔv ≥ Δx.Δv ≥

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.
The principal quantum number gives us the following information:
The following information’s are obtained from n.
1. It gives the size the orbit.
2. It gives the energy of electron in an orbit.
3. It gives the shell in which the electron is found.
4. It also gives the average distance between the electron and the nucleus. As the value of n increases, the
distance between the electron and the nucleus also increases.
The possible values of n are 1, 2, 3, 4, 5 etc.
If n = 1 the electron is in K shell
n = 2 the electron is in L shell
n = 3 the electron is in M shell and so on.
5. The maximum number of electrons in the shell with principal quantum number n is equal to 2n2.
Azimuthal or Subsidiary or Orbital Angular Quantum Number (l)
The following information’s are obtained from Ɩ.
1. It gives the shape of the orbital.
2. It gives the sub shell or sub level in which the electron is located.
3. It also gives the orbital angular momentum of the electron.
4. the values of l = 0 to (n-1)
The number of sub shells in a principal shell is equal to the value of n. For example,
When n = 1, Ɩ= 0. i.e. K shell contains only one sub shell - s sub shell
when n = 2, Ɩ = 0 and1. i.e. L shell contains two sub shells - s and p sub shells
when n = 3, Ɩ = 0, 1 and 2. i.e. M shell contains three sub shells – s, p and d sub shells
when n = 4, Ɩ = 0, 1, 2 and 3. i.e. N shell contains four sub shells – s, p,d and f sub shells
4. the number of electrons that can be accommodated in sub-energy level is equal to 2(2l+1).
If l = 0 for s orbital then= 2(2*1+1)=2 electrons
If l =1 for p orbital then= 2(2*2+1)=6 electrons
If l = 2 for d orbital then= 2(2*3+1)=10 electrons
if l = 3 for f orbital then= 2(2*3+1)=14 electrons

Magnetic Orbital Quantum Number (m or m1)

1. The magnetic orbital quantum number determines the number of preferred orientations of the electrons
present in a sub-shell.
2. The magnetic quantum number is denoted by letter m 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-sub-shell), m can have only one value i.e., m = 0.
This means that s-sub-shell 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 micro-magnet 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 with only one orientation has a spherical shape with uniform electron
density along all the three axes.
The plots of probability density (ψ2) against distance from the nucleus (r) for 1s and 2s atomic orbitals are
as follows:

The probability of 1s 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.
Number of radial nodes = n - Ɩ – 1
Number of angular nodes = Ɩ
Total number of nodes = n-1
• Shapes of d-orbitals
For d-orbitals, Ɩ = 2 and mƖ = -2, -1, 0, +1 and +2. i.e., there are five possible orientations for d orbitals. So
there are 5types of d-orbitals. They are dxy, dxz, dyz, dx2-y2 and dz2. . The shapes of the first four d-
orbitals are double dumb-bell and that of the fifth one, dz2, is dumb-bell having a circular collar in the XY-
plane. The five d-orbitals have equivalent energies. For d orbitals the number of radial nodes is 2 and the
total number of nodes is n-2. Boundary surface diagrams for d-orbitals are as follows.

f-orbitals:
For f-orbitals, Ɩ = 3 and mƖ = -3, -2,-1.0.+1,+2 and +3. i.e., there are seven possible orientations for f
orbitals.so there are 7 types of f-orbitals. They have diffused shapes.
Electronic Configuration of Atoms
The distribution of electrons into orbitals of an atom is called its electronic configuration. The electronic
configurationis explained based on Aufbau principle, Hund’s rule, Pauli’s exclusion principle and stability
concept.
1. 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.
This rule has two sub rules:
a) The various orbitals are filled in the increasing order of their (n+l) value.
b) If two orbitals have the same (n+l) values, the orbital with the lower n value is filled first.The increasing
order of orbitals is as follows.
Pauli Exclusion Principle
According to this principle, no two electrons in an atom can have the same set of
four quantum numbers. Only two electrons may exist in the same orbital and
these electrons must have opposite spins.If 2 electronshave same values for n, Ɩ
and m, they should have different values for s. i.e. if s = +1/2. for the first
electron, it should be -1/2. for the second electron.
3. Hund’s rule of maximum multiplicity
It states that: pairing of electrons in the orbitals belonging to the same sub-shell
(p, d or f) does not take place until each orbital belonging to that sub-shell has
got one electron each with parallelspin. For examplethe electronic configuration
of N is 1s2 2s2 2p 1p 1p 1 and notx 1sy2 2sz 2 2p 2p 1. x y

Stability of Completely Filled and Half Filled Subshells

For atoms having half filled or completely filled electronic configurations have
extra stability compared to other atoms. This is due to their symmetrical
distribution of electrons and greater exchange energy. For example, the
electronic configuration of Cr is [Ar] 3d54s1 and not 3d44s2. This is because d5
represents a half filled configuration and has extra stability. Similarly for Cu the
electronic configuration is [Ar] 3d104s1and not 3d94s2.

Cr(24) = [Ar] 3d5

4s1 not [Ar] 3d4
4s2Similarly
Cu(29) = [Ar] 3d10 4s1 not [Ar] 3d94s2