CHAPTER 2

STRUCTURE OF ATOM

• Atom is the smallest indivisible particle of the matter. Atom is made of electron,
proton and neutrons.
PARTICLE ELECTRON PROTON NEUTRON
Discovery Sir. J. J. Thomson Goldstein (1886) Chadwick (1932)
(1869)
Nature of charge Negative Positive Neutral
-19 -19
Amount of charge 1.6 x 10 Coloumb 1.6 x 10 Coloumb 0
Mass 9.11 x 10-31kg 1.672614 x 10-27kg 1.67492 x10 -27kg
Electrons were discovered using cathode ray discharge tube experiment.
Nucleus was discovered by Rutherford in 1911.
Cathode ray discharge tube experiment: A cathode ray discharge tube made
of glass is taken with two electrodes. At very low pressure and high voltage,
current starts flowing through a stream of particles moving in the tube from
cathode to anode. These rays were called cathode rays. When a perforated
anode was taken, the cathode rays struck the other end of the glass tube at the
fluorescent coating and a bright spot on the coating was developed
Results:
a. Cathode rays consist of negatively charged electrons.
b. Cathode rays themselves are not visible but their behavior can be
observed with
help of fluorescent or phosphorescent materials.
c. In absence of electrical or magnetic field cathode rays travel in
straight lines
d. In presence of electrical or magnetic field, behavior of cathode rays
is similar to that shown by electrons
e. The characteristics of the cathode rays do not depend upon the
material of the electrodes and the nature of the gas present in the cathode ray
tube.
Charge to mass ratio of an electron was determined by Thomson. The charge
to mass ratio of an electron as 1.758820 x 1011 C kg-1
Charge on an electron was determined by R A Millikan by using an oil drop
experiment. The value of the charge on an electron is -1.6 x 10-19C.
The mass on an electron was determined by combining the results of
Thomson’s experiment and Millikan’s oil drop experiment. The mass of an
electron was determined to be 9.1094 x 10-31kg.
Discovery of protons and canal rays: Modified cathode ray tube
experiment was carried out which led to the discovery of protons.
Characteristics of positively charged particles:
a. Charge to mass ratio of particles depends on gas from which these originate
 b. The positively charged particles depend upon the nature of gas present in the
cathode ray discharge tube
c. Some of the positively charged particles carry a multiple of fundamental of
electrical charge.
d. Behavior of positively charged particles in electrical or magnetic field is
opposite to that observed for cathode rays
Neutrons were discovered by James Chadwick by bombarding a thin sheet of
beryllium by α- particles. They are electrically neutral particles having a mass
slightly greater than that of the protons.
Atomic number (Z) : the number of protons present in the nucleus
(Moseley1913).
Mass Number (A) :Sum of the number of protons and neutrons present in
thenucleus.
Thomson model of an atom: This model proposed that atom is considered as
a uniform positively charged sphere and electrons are embedded in it.An
important feature of Thomson model of an atom was that mass of atom is
considered to be evenly spread over the atom. Thomson model of atom is also
called as Plum pudding, raisin pudding or watermelon model. Thomson model
of atom was discarded because it could not explain certain experimental results
like the scattering of α- particles by thin metal foils.
Observations from α- particles scattering experiment by Rutherford:
a. Most of the α- particles passed through gold foil un deflected
b. A small fraction of α- particles got deflected through small angles
c. Very few α- particles did not pass through foil but suffered large deflection
nearly180o
Conclusions Rutherford drew from α- particles scattering experiment:
a. Since most of the α-particles passed through foil undeflected, it means most
of the space in atom is empty
b. Since some of the α-particles are deflected to certain angles, it means that
there is positively mass present in atom
c. Since only some of the α-particles suffered large deflections, the
positively charged mass must be occupying very small space
d. Strong deflections or even bouncing back of α-particles from metal foil
were due to direct collision with positively charged mass in atom
Rutherford’s model of atom: This model explained that atom consists of
nucleus which is concentrated in a very small volume. The nucleus comprises
of protons and neutrons. The electrons revolve around the nucleus in fixed
orbits. Electrons and nucleus are held together by electrostatic forces of
attraction.
Drawbacks of Rutherford’s model of atom:
a. According to Rutherford’s model of atom, electrons which are negatively
charged particles revolve around the nucleus in fixed orbits. Thus,
b. The electrons undergo acceleration. According to electromagnetic theory
of Maxwell, a charged particle undergoing acceleration should emit
electromagnetic radiation. Thus, an electron in an orbit should emit
radiation. Thus, the orbit should shrink. But this does not happen.
c. The model does not give any information about how electrons are
distributed around nucleus and what are energies of these electrons.
Isotopes: These are the atoms of the same element having the same atomic
number but different mass number. e. g 1H1,1H2,1H3
Isobars: Isobars are the atoms of different elements having the same mass
number but different atomic number .e g 18Ar40 , 20Ca40
Isoelectronic species: These are those species which have the same number of
electrons.
Electromagnetic radiations: The radiations which are associated with
electrical and magnetic fields are called electromagnetic radiations. When an
electrically charged particle moves under acceleration, alternating electrica
land magnetic fields are produced and transmitted. These fields are transmitted
in the form of waves. These waves are called electromagnetic waves or
electromagnetic radiations.
Properties of electromagnetic radiations:
a. 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.
b. They do not need a medium to travel. That means they can even travel in
vacuum.
Characteristics of electromagnetic radiations:
a. Wavelength: It may be defined as the distance between two
neighbouring crests or troughs of wave as shown. It is denoted by λ.
b. Frequency (ν): It may be defined as the number of waves which
pass through a particular point in one second.
c. Velocity (v): 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. Its value is 3 X108m sec-1. It is denoted by v
d. Wave number: Wave number is defined as the number of wavelengths
per unit length.
Velocity = frequency x wavelength c = νλ
Planck's Quantum Theory-
o The radiant energy is emitted or absorbed not continuously but
discontinuously in the form of small discrete packets of energy called
‘quantum’. In case of light , the quantum of energy is called a ‘photon’
o The energy of each quantum is directly proportional to the frequency of
the radiation, i.e. E α υ or E= hυ where h= Planck’s constant =
-27
6.626 x 10 Js
o Energy is always emitted or absorbed as integral multiple of this
quantum. E=nhυ Where n=1,2,3,4,.....
Black body: An ideal body, which emits and absorbs all frequencies, is called
a black body. The radiation emitted by such a body is called black body
radiation.
Photoelectric effect: The phenomenon of ejection of electrons from the
surface of metal when light of suitable frequency strikes it is called
photoelectric effect. The ejected electrons are called photoelectrons.
Experimental results observed for the experiment of Photoelectric effect-
o When beam of light falls on a metal surface electrons are
ejected immediately.
o Number of electrons ejected is proportional to intensity or brightness of
light
o Threshold frequency (υo): For each metal there is a characteristic
minimum frequency below which photoelectric effect is not
observed. This is called threshold frequency.
o If frequency of light is less than the threshold frequency there is no
ejection of electrons no matter how long it falls on surface or how
high is its intensity.
Photoelectric work function (Wo): The minimum energy required to
eject electrons is called photoelectric work function. Wo= hυo
Energy of the ejected electrons :

Dual behavior of electromagnetic radiation- The light possesses both particle

and wave like properties, i.e., light has dual behavior . whenever radiation
interacts with matter, it displays particle like properties.(Black body radiation
and photoelectric effect) Wave like properties are exhibited when it
propagates(interference an diffraction)
When a white light is passed through a prism, it splits into a series of coloured
bands known as spectrum.
Spectrum is of two types: continuous and line spectrum
a. The spectrum which consists of all the wavelengths is called
continuous
spectrum.
b. A spectrum in which only specific wavelengths are present is known
as a line
spectrum. It has bright lines with dark spaces between them.
Electromagnetic spectrum is a continuous spectrum. It consists of a range of
electromagnetic radiations arranged in the order of increasing wavelengths or
decreasing frequencies. It extends from radio waves to gamma rays.
Spectrum is also classified as emission and line spectrum.
o Emission spectrum: The spectrum of radiation emitted by a substance
that has absorbed energy is called an emission spectrum.
o Absorption spectrum is the spectrum obtained when radiation is
passed through a sample of material. The sample absorbs radiation
 of certain wavelengths. The wavelengths which are absorbed are
missing and come as dark lines.
The study of emission or absorption spectra is referred as spectroscopy.
Spectral Lines for atomic hydrogen:

Rydberg equation

R = Rydberg’s constant = 109677 cm-1

Bohr’s model for hydrogen atom:
a. An electron in the hydrogen atom can move around the nucleus in a circular
path of fixed radius and energy. These paths are called orbits or energy
levels. These orbits are arranged concentrically around the nucleus.
b. As long as an electron remains in a particular orbit, it does not lose or gain
energy and its energy remains constant.
c. When transition occurs between two stationary states that differ in
energy, the frequency of the radiation absorbed or emitted can be
calculated.
E2−E1 ∆𝐸
𝑣= =
ℎ ℎ

d. An electron can move only in those orbits for which its angular
momentum is an integral multiple of h/2π.
𝑛ℎ
𝑚𝑣𝑟 = n=1,2,3…..
2π
The radius of the nth orbit is given by rn =52.9 pm x n2
Z
energy of electron in nth orbit is :

Limitations of Bohr’s model of atom:

a. Bohr’s model failed to account for the finer details of the hydrogen
spectrum.
b. Bohr’s model was also unable to explain spectrum of atoms containing
more than one electron.
Dual behavior of matter: de Broglie proposed that matter exhibits dual
behavior i.e. matter shows both particle and wave nature. de Broglie’s relation
is
 Heisenberg’s uncertainty principle: It states that it is impossible to
determine simultaneously, the exact position and exact momentum (or
velocity) of an electron. The product of their uncertainties is always equal to
or greater than h/4π.

Heisenberg’s uncertainty principle rules out the existence of definite paths or

trajectories of electrons and other similar particles
Failure of Bohr’s model:
a. It ignores the dual behavior of matter.
b. It contradicts Heisenberg’s uncertainty principle.
Classical mechanics is based on Newton’s laws of motion. It successfully
describes the motion of macroscopic particles but fails in the case of
microscopic particles.
Reason: Classical mechanics ignores the concept of dual behavior of matter
especially for sub-atomic particles and the Heisenberg’s uncertainty principle.
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 mechanics is based on a fundamental equation which is called
Schrodinger equation.
Schrodinger’s equation: For a system (such as an atom or a molecule
whoseenergy does not change with time) the Schrödinger equation is written
as:
𝐻Ψ =EΨ

Where, H is the hamiltonial operator

E is the total energy of the system
Ψ represents the wave functions which is the amplitude of the
electron wave

When Schrödinger equation is solved for hydrogen atom, the solution gives
the possible energy levels the electron can occupy and the corresponding wave
function(s) of the electron associated with each energy level .Out of the
possible values, only certain solutions are permitted. Each permitted solution
is highly significant as it corresponds to a definite energy state. Thus, we can
say that energy is quantized.
ψ gives us the amplitude of wave.Value of ψ has no physical significance.
Ψ2gives us the region in which the probability of finding an electron is
maximum. It is called probability density.
Orbital: The region of space around the nucleus where the probability of
finding an electron is maximum is called an orbital.
Quantum numbers: There are a set of four quantum numbers which specifythe
energy, size, shape and orientation of an orbital. To specify an orbital only
three quantum numbers are required while to specify an electron all four
quantum numbers are required.
Principal quantum number (n):It identifies shell, determines sizes and
energy of orbitals

Azimuthal quantum number (l): Azimuthal quantum number. ‘l’ is also

known as orbital angular momentum or subsidiary quantum number. It
identifies sub-shell, determines the shape of orbitals, energy of orbitals in
multi-electron atoms along with principal quantum number and orbital angular
ℎ
momentum, i.e.,√𝑙(𝑙 + 1) .The number of orbitals in a subshell = 2l + 1.
2𝜋
For a given value of n, it can have n values ranging from 0 to n-1. Total
number of subshells in a particular shell is equal to the value of n.
Subshell S p d f g
notation
Value of ‘l’ 0 1 2 3 4
Number of 1 3 5 7 9
orbitals
Magnetic quantum number or Magnetic orbital quantum number (ml): It
gives information about the spatial orientation of the orbital with respect to
standard set of co-ordinate axis. For any sub-shell (defined by ‘l’ value) 2l+1
values of ml are possible .For each value of l, ml = – l, – (l –1), – (l–2)... 0,1...
(l – 2), (l–1), l
Electron spin quantum number (ms): It refers to orientation of the spin of
the electron. It can have two values +1/2 and -1/2. +1/2 identifies the
clockwise spin and -1/2 identifies the anti- clockwise spin.
The region where this probability density function reduces to zero is called
nodal surfaces or simply nodes.
Radial nodes: Radial nodes occur when the probability density of wave
function for the electron is zero on a spherical surface of a particular radius.
Number of radial nodes = n – l – 1
Angular nodes: Angular nodes occur when the probability density wave
function for the electron is zero along the directions specified by a particular
angle. Number of angular nodes = l, Total number of nodes = n – 1
 Degenerate orbitals: Orbitals having the same energy are called degenerate
orbitals.
Shape of p and d-orbitals
Shielding effect or screening effect: Due to the presence of electrons in
the inner shells, the electron in the outer shell will not experience the
full positive charge on the nucleus.
So, due to the screening effect, the net positive charge experienced by the
electron from the nucleus is lowered and is known as effective nuclear
charge. Effective nuclear charge experienced by the orbital decreases with
increase of azimuthal quantum number (l).
Aufbau Principle: In the ground state of the atoms, the orbitals are filled in
order of their increasing energies.
n+l rule-Orbitals with lower value of (n+l) have lower energy. If two orbitals
have the same value of (n+l) then orbital with lower value of n will have lower
energy.
The order in which the orbitals are filled is as follows:
1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 4f, 5d, 6p, 7s...
Pauli Exclusion 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 spin.
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.
Electronic configuration of atoms: Arrangement of electrons in
different orbitals of an atom. The electronic configuration of different
atoms can be represented in two ways.
a. sapbdc...... notation.
b. rbital diagram:, each orbital of the subshell is represented by a box and the
electron is represented by an arrow (↑) a positive spin or an arrow (↓) a negative
spin.
Stability of completely filled and half filled subshells:
a. Symmetrical distribution of electrons- the completely filled or half filled
sub-shells have
symmetrical distribution of electrons in them and are more stable.
b. Exchange energy-The two or more electrons with the same spin present in
the degenerate orbitals of a sub-shell can exchange their position and the
energy released due to this exchange is called exchange energy. The
number of exchanges 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.