S STRUCTURE OF ATOM Y

UNIT-02 STRUCTURE OF ATOM

INTRODUCTION:
The word atom has been derived from the Greek word ‘atomio’ which means non-divisible.
In 1808 John Dalton proposed his theory ‘Dalton’s atomic theory’ in which he stated that
the “matter is made up of small indivisible particles called atoms”. However later it was
established that atoms are further subdivided into subatomic particles, namely
protons, neutrons and electrons. Even though particles which are much smaller than an
electron have been detected, our study is limited to protons, neutrons and electrons as
subatomic particles in this chapter.

DISCOVERY OF ELECTRONS:

Under normal pressure, gases do not conduct electricity but at low pressure it conducts.
William Crook took a gas in a cylindrical hard glass airtight tube called discharge tube
fitted with two metal plates (electrodes). The pressure inside the tube was reduced to 0.01
bar using a suction pump. When a very high voltage of 10,000V was applied between the
electrodes, the gas was found to conduct electricity, Light was emitted by the gas, on further
reducing the pressure a kind of particles were emitted from the cathode. When these
particles struck the walls opposite to the cathode, a flourescence (emission of visible light)
was noticed. These particles emitted from the cathode were called ‘Cathode rays’,
J.J.Thomson (Joseph John Thomson) studied the properties of cathode rays.

PROPERTIES OF CATHODE RAYS:

1. Cathode rays travel in straight lines in the absence of electric and magnetic field.
2. Cathode rays consist of negatively charged particles.
3. Cathode rays produce a heating effect when they strike metal foils.
4. Cathode rays affect photographic plates.
5. Cathode rays ionise the molecules of the gas through which they pass.
6. When cathode rays strike the surfaces of metals like tungsten, copper etc, x-rays are
produced.
7. Cathode rays pass through thin metal foils. However, they are stopped by thick metal
sheets.
8. Cathode rays are deflected even when subjected to a magnetic field.
9. The properties of the particles in cathode rays are same for all gases.
10. They are made up of material particles.

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This indicates that these particles are common constituents of all substances.
J.J.Thomson called these particles as electrons. (J.J.Thomson discovered electrons)

DETERMINATION OF CHARGE TO MASS RATIO (e/m) OF ELECTRONS:

J.J.Thomson determined the Charge of the particles of cathode rays, by simultaneously

mass
applying electric field and a magnetic field in mutually perpendicular directions, both
being perpendicular to the direction of cathode rays.
The electrons fall on the point ‘A’ in the presence of only an electric field and the
electrons fall on the point ‘C’ in the presence of only a magnetic field. In the absence of
these fields the electrons fall on the point ‘B’. By adjusting both the magnitude of the electric
and magnetic fields, it is possible to mutually nullify their effects and make the electrons fall
on the point ‘B’ itself. From the magnitude of the electric and magnetic fields so applied, it is
possible to calculate the Charge ratio of these particles and thus the value is found to be
mass
11 -1
1.7588 x 10 C kg .

The ratio of e is same for the cathode rays irrespective of the gas taken inside the
m
discharge tube. This proves that the electrons are common constituents of all the
atoms.
R.A. Millikan determined charge of the electron by 'Oil drop experiment'.

MASS OF THE ELECTRON:

By J.J. Thomson's experiment e = 1.7588 x 1011 C kg-1
m
By Millikan's oil drop experiment, charge on electron (e) = -1.6023 x 10-19 C.
-19
 Mass of the electron (me) = e = 1.6022 x 10 11  9.109 x10-31kg
em 1.7588 x 10

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DISCOVERY OF PROTONS:
Goldstein took a gas at very low pressure in a discharge tube containing a perforated metal
sheet as cathode. He found that a new type of rays moved from the side of anode towards
cathode and moved in a direction opposite to that of cathode rays. They were called 'anode
rays' or 'canal rays’

PROPERTIES OF ANODE RAYS:

1. They contain particles. (because a mica wheel rotates when kept on their path)
2. Anode rays consist of positively charged particles. (because they get deflected towards
a negatively charged plate)
3. They travel in straight lines. (because they cast shadow, if an object is kept on their
path)
4. They get- deflected by electric and magnetic fields.
5. The charge and mass of these particles depends on the gas taken in the discharge
tube. (Because the e values were different for anode rays obtained from different gases.
m
The lightest particles are obtained in the case of hydrogen gas)
The smallest and lightest positive ion was obtained from hydrogen .These positive
charges were called protons. Rutherford discovered protons.

Charge on proton (p) = +1.6023 x 10-19C.

Mass of the proton (mp) = 1.673x10-27kg.

NOTE:
1. Charge of proton is same as that of charge of electron but with opposite sign.
2. Mass of 1 proton is equal to mass of 1 H-atom.  1
 1.66 x10-24g = 1.66x10-27kg
6.023x1023
3. Electron mass is 1836 times lesser the mass of proton
 mass of electron is 1.66x10-27 / 1836 = 9.109x10-31kg
4. Charge carried by 1 mole of electrons =1 Faraday= 96500C
 Charge on one electron= 96500
 1.6021 x 10-11C
6.023x1023

DISCOVERY OF NEUTRONS:
In 1932, James Chadwick discovered a new particle called 'neutron', when he bombarded
a thin beryllium foil with alpha (α) particles.

9+ 4 12 + 0n1
4Be 2He 6C

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The neutron has zero charge (neutral). Its mass is approximately equal to the mass of a
proton (1.675 x 10-27 kg). Neutrons are represented as 0n1. They are present in the
atomic nucleus.
After the discovery of the neutrons, it has been established that the nucleus contains two
types of particles namely protons and neutrons (nucleons). The protons are responsible
for the positive charge of the nucleus.

 Electrons, protons and neutrons are the fundamental particles present in atoms.

SUB ATOMIC PARTICLE DISCOVERER CHARGE MASS

ELECTRON J.J Thomson - 1.6023 x 10-19C 9.109 x 10-31kg

PROTON Rutherford + 1.6023 x 10-19C 1.673 x 10-27kg

NEUTRON James Chadwick 0 (Neutral) 1.675 x 10-27kg

ATOMIC NUMBER (Z):

The number of protons present in the nucleus of an atom is known as atomic number
(Z) of the element.
However, as the atom is neutral, it should contain an equal number of positive charges
(protons) and negative charges (electrons). Hence, atomic number is also equal to the
number of electrons present in a neutral atom of the element.

MASS NUMBER (A):

The sum of the number of protons and neutrons present in the nucleus of the atom is
called mass number (A).
Thus, Z = Atomic number = No. of protons.
A = Mass number = No. of protons + No. of neutrons.
 A - Z = No. of neutrons. (In general protons and neutrons are called as 'nucleons').

ISOTOPES:
Atoms of the same element having same atomic number but different mass numbers
are called isotopes. They contain same number of protons but different number of
neutrons.

Example: 17Cl35 (containing 17 protons and 18 neutrons) and 17Cl37 (containing 17 protons
and 20 neutrons) are isotopes of chlorine. Similarly, 1H1, 1H2, 1H3 are the isotopes of
hydrogen.
In general, an atom is represented as z X A
Where X is the symbol of the element / atom, Z is the number of protons (atomic
number) and A is the sum of the number of protons and neutrons (mass number).

Problem: Calculate the number of neutrons present in 92U235 isotope.

Ans: No. of neutrons = A - Z = 235 - 92 = 143.

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ISOBARS:
Atoms of different elements having same mass number but different atomic numbers
are called isobars.
Example: 6C14 and 7N14 are isobars.

ISOTONES:
Atoms of different elements containing same number of neutrons are called isotones.
Example: 6C14 and 8O16 are isotones

DISCOVERY OF RADIOACTIVITY:

RADIOACTIVITY:
Spontaneous emission of high energy, invisible, penetrating radiations called α, β
and γ rays from the unstable nuclei of certain substances is called radioactivity.
This phenomenon was discovered by Henry Becquerel in 1896.
Three types of emissions are observed in radioactivity.

(i) α-Rays: α-rays consist of a particles which are identical to helium nucleus. They are
deflected towards a negative plate. Each α-particle consists of two protons and two
neutrons. Its charge is +2e- (i.e. +3.2 x 10-19 C) and mass is 4 a.m.u. (nearly four times
that of a proton).
α-particles ionise the molecules of the medium in which they pass. They
penetrate matter. However, their penetration power is poor.

(ii) β -Rays: A β-particle is identical to an electron. It is deflected towards a positive

plate. Charge on particle is -1e- (i.e. 1.602 x 10-19 C) and mass is 9.1 x 10-31 kg.
Their penetration power is nearly 100 times more than that of α- particles.

(iii) γ-Rays: γ rays are high energy electromagnetic radiations, even more energetic
than x-rays. They do not have any charge and are not deflected by electric or magnetic
fields.
Their penetrating power is greater than that of β rays (nearly 1000 times).
Their mass is negligible.

MODELS OF ATOM:
THOMSON MODEL OF ATOM:
J. J. Thomson, in 1898, proposed the model of an atom, An
atom is spherical in shape (radius approximately 10–10 m) in
which the positive charge is uniformly distributed, the
electrons are embedded in it in such a manner as to give
the most stable electrostatic arrangement.

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Many different names are given to this model, such as plum pudding / raisin
pudding / watermelon model. This model can be visualised as a pudding or watermelon
of positive charge with plums or seeds (electrons) embedded into it.
An important feature of this model is that the mass of the atom is assumed to be
uniformly distributed over the atom. Although this model was able to explain the overall
neutrality of the atom, but was not consistent with the results of later experiments.

NOTE: Thomson was awarded Nobel Prize for physics in 1906, for his theoretical and
experimental investigations on the conduction of electricity by gases.

RUTHERFORD'S GOLD LEAF EXPERIMENT:

Gold is highly malleable metal and can be blown into extremely thin sheets. Rutherford took
an extremely thin gold leaf; α-rays from a radium piece were allowed to pass through the
gold leaf; α-particles which came out on the other side of the gold leaf were detected using
a circular thin gold foil coated with zinc sulphide. When α-particles fall on the zinc
sulphide screen, they produce scintillations (tiny flashes of light).

OBSERVATIONS:
1. About 99% of the α-particles simply passed through the gold leaf as if they did not
come across any obstruction in their path.
2. A small number of them got deflected by small angles.
3. About 1 out of 20,000 α-particles got deflected by an angle more than 90°. A few of
them even retraced their path.

CONCLUSION: Atoms inside gold are closely packed. α-particles must have passed
through the atoms.
1. Since most of the α-particles simply passed through, most part of the atom should be
empty space.
2. Since a few of the α-particles got deflected by small angles, they must have come
across a positive part which would repel them (like charges repel).
3. Since only one out of 20,000 α-particles retraced their path, the size of the positive
part in the atom should be extremely small. Only those particles which made a head
on collision with the nucleus would retrace their path.

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RUTHERFORD'S MODEL (PLANETARY/ NUCLEAR MODEL) OF AN ATOM:

Based on the α-ray scattering experiment, Rutherford proposed a model of an atom as
follows:
1. An atom contains a small portion called 'nucleus' at the centre. (Its radius is of the
order 10-15m). The entire mass and the positive charge of the atom is concentrated
in the center of the atom (nucleus).
2. The total positive charge on the nucleus (no. of protons) is equal to the total negative
charge on the electrons, such that atom is electrically neutral.
3. The electrons keep revolving around the nucleus in circular orbits. This is similar to
the motion of planets around the sun. The electrostatic force of attraction between
the nucleus and the electrons makes the atom stable.
4. Most of the space in an atom, between the nucleus and the revolving electrons is
empty (Radius of the atom is of the order 10-10 m).

DRAWBACKS OF RUTHERFORD'S MODEL:

1. When an electrically charged particle moves under the influence of electrostatic force, it
loses energy in the form of electromagnetic radiations. Thus, an electron moving around
the nucleus should lose energy and fall into the nucleus. Hence it could not explain the
stability of the atom.
2. It could not explain the atomic spectrum of hydrogen and other elements.
3. Rutherford's model does not explain how the electrons are arranged around their
nucleus and their energy distribution.

WAVE NATURE OF LIGHT:

Based on the properties such as reflection, diffraction, interference etc. HUYGEN
Suggested that light travels in the form of waves. Later, JAMES MAXWELL proposed that
light and other radiations are transmitted and propagated through space continuously
in the form of 'electromagnetic waves'. Thus, the visible light (VIBGYOR), U.V. rays, x-
rays, (I.R) infrared rays, (gamma) γ-rays etc. are called electromagnetic radiations.
These radiations are associated with electric and magnetic fields acting perpendicular
to the direction of their propagation. These have wave properties such as wavelength,
frequency, velocity and wave number.

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CHARACTERISTICS OF A WAVE:

1. CREST: Maximum upward displacement of a wave.

2. TROUGH: maximum downward displacement of a wave.
3. AMPLITUDE: Height of the crest or depth of the trough.
It is measured in ‘m’.
4. WAVELENGTH (): Distance between any two adjacent crests or troughs.
It is measured in ‘m’ (nm).
5. FREQUENCY (): Number of waves passing through a given point in one second.
It is measured in second (Hertz).
6. VELOCITY (c): It is the linear distance travelled by wave in one second.
It is 3 x 108 ms-1 (in vacuum).
7. WAVE NUMBER (  ): Number of waves per unit length.
1


Unit: m-1

RELATIONSHIP BETWEEN VELOCITY (c), WAVELENGTH () & FREQUENCY ()

OF A WAVE:

c=

ELECTROMAGNETIC SPECTRUM:
Arrangement of all the electromagnetic radiations in the increasing, order of wave
lengths or decreasing order of frequencies is called electromagnetic spectrum.
Different electromagnetic radiations have different wavelengths. The wavelength of
the electromagnetic radiations increase in the order
Cosmic rays < Gamma rays < x-rays < U.V rays < Visible rays < IR rays < Microwaves
< Radio rays.

ELECTROMAGNETIC RADIATION - Maxwell's Wave Theory:

Light is the form of radiation with an electric and a magnetic field acting in mutually
perpendicular directions both being perpendicular to the direction of propagation.

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According to James Maxwell's wave theory of light,

1. Oscillating electrically charged particles produce electric (E) and magnetic (H)
waves acting in mutually perpendicular directions, both being perpendicular to the
direction of propagation.
2. Electromagnetic waves do not require a medium and can travel in vacuum.
3. There are many types of electromagnetic waves like radiofrequency waves, micro
waves, infrared rays, visible radiations, ultraviolet rays, x-rays, γ-rays etc.
They differ in their energies, wavelengths, frequencies and wave numbers.
4. All these radiations travel with the same velocity. (Velocity of light is 3 x 108 ms-1 in
vacuum).

V I B G Y O R

LIMITATIONS OF WAVE THEORY:

Maxwell's electromagnetic wave theory explains 'diffraction' and 'interference' of light.
However, it does not explain the following experimental observations.
1. Black body radiation: Emission of radiations from black bodies.
2. Photoelectric effect: Emission of electrons from a metal surface when light falls on the
surface.
3. Variation of heat capacity of solids with temperature.
4. Line spectrum of hydrogen: Emission of light of particular wavelength by hydrogen, at
high temperatures and low pressures.

BLACK BODY RADIATION:

An ideal body that emits and absorbs radiations of all frequencies is called a black
body. The radiation emitted by such a body on heating is called black body radiation.

Example: Surface of Iron rod is heated, it first turns to dull red and then progressively
becomes more and more red as temperature increases. As this is heated further, the
radiation emitted becomes white and then becomes blue as the temperature increases.

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CONCLUSION: Frequency of the emitted radiation increases as the temperature

increases (red colour lies in lower frequency range while blue colour in higher frequency
range).

PHOTOELECTRIC EFFECT: [Discovered by Heinrich Hertz, in 1887]

Ejection of electrons from the surface of a metal when exposed to a beam of light
having suitable frequency is called photoelectric effect.

EXPERIMENTAL OBSERVATIONS:
1. The electrons are ejected out of the metal surface as soon as a beam of light strikes the
surface of the metal. i.e. there is no time lag. Thus photo electric effect is instantaneous.
2. Each metal has a characteristic frequency called threshold frequency ( 0 ) which is
minimum frequency (  ) of incident light, below which photoelectric effect is not
observed.
3. Kinetic energy of the emitted electrons increases with increase in frequency of the
incident radiation. It does not depend on the intensity of the radiation.
4. The number of the photoelectrons emitted is directly proportional to the intensity
of the incident light and not on its frequency.

PLANCK’S QUANTUM THEORY OF RADIATIONS:

In order to explain the nature of electromagnetic radiations, Max Planck proposed a
theory in 1900 which is called as Planck’s Quantum theory.

POSTULATES OF PLANCK’S QUANTUM THEORY:

1. Electromagnetic radiations are emitted, absorbed and propagated discontinuously
in the form of small packets of energy. Each packet of energy is called a 'photon' or
'quantum' of radiation (quantum means 'bundle').
2. Energy associated with a quantum of radiation is given by E = h υ
[ where ‘h’ is a constant called Planck's constant, h = 6.627 X 10-34 J s. It is a universal
constant. Its value is same for all types of electromagnetic radiations under all
conditions.]
3. A body emits or absorbs radiations only in integral multiples of the quantum (h υ ).
i.e. E = nh υ where n = 1, 2, 3, 4, 5………..

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BOHR’S ATOMIC THEORY OR BOHR’S ATOMIC MODEL:

In order to explain the formation of lines in hydrogen spectrum based on quantum theory,
Neil Bohr theory was proposed.

POSTULATES OF BOHR’S ATOMIC THEORY:

1. The electrons revolve around the nucleus in circular paths called shells or orbits or
stationary states (The shells are designated by K, L, M, N shell)
2. As long as electron revolve in the same shell, the electron does not gain or lose energy.
3. Quantization rule: Around the nucleus, only those shells are possible in which the
h
angular momentum of electron is an integral multiple of
2
nh
i .e . mvr 
2
where, m = mass of electron
V = Velocity of electron
R = Radius of the orbit
n = 1, 2, 3 …..Etc
h = Planck’s constant
4. Bohr’s frequency rule: When an electron jumps from outer shell to inner shell, the
energy difference is emitted in the form of photons. When an electron jumps from inner
shell to outershell, the energy difference is absorbed. E2 - E1 = ΔE = h υ
5. Each shell is associated with a definite amount of energy. Hence shells are called
energy levels. Shells closer to the nucleus have low energy and shells away from
the nucleus have high energy.

SPECTRUM:
Pattern of arrangement of different colors obtained when a light is subjected to
dispersion and analysed using a spectroscope or photographic plate is called
spectrum.
Example: The spectrum obtained by the dispersion and analysis of light emitted by the sun
is called continuous spectrum. It consists of radiations of all kinds of wavelength.

ATOMIC SPECTRUM:
When an element is strongly heated, it emits radiations. When these radiations are
subjected to dispersion and analysed using a photographic plate. A pattern of array of
colours is obtained which is called as atomic spectrum
Atomic spectrum is also called as line spectrum because it consists of closely
spaced lines, with dark space between them.
The spectra are classified into TWO types.
1) Emission spectrum
2) Absorption spectrum.

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EMISSION SPECTRUM:
The spectrum of radiation emitted by a substance that has absorbed energy is called
emission spectrum.

CAUSE FOR EMISSION SPECTRUM:

When Electromagnetic radiations interact with matter or when the substance is
heated strongly, the electrons in the atoms & molecules absorb energy & jump to higher
energy states called excited states. While returning to the normal or ground state, they emit
radiations having frequency in various regions of electromagnetic spectrum.

Emission spectrum is of 2 types:

a) Continuous spectrum:
b) Line spectrum / Atomic spectrum:

a) CONTINUOUS SPECTRUM:
The emission spectrum of white light that consists of all kinds of wavelengths in a
particular range, without any gap in between & one colour merges into another
gradually is called continuous spectrum.
Example: Spectrum of the light emitted by the sun.

b) LINE SPECTRUM / ATOMIC SPECTRUM:

The emission spectrum of atoms in their gaseous phase has bright lines
corresponding to specific wavelength with dark spaces in between them is called line
spectrum.
Example: Emission spectrum of hydrogen has 4 prominent lines corresponding to red,
green, blue & violet colour.
Emission spectrum of sodium has two yellow lines called D1 & D2 lines.

CHARACTERSTICS OF LINE SPECTRUM:

1) Each element has its own characteristic line spectrum & it is unique like finger prints.
2) The colour of the light emitted depends on nature of the substance.
3) Atomic spectrum has applications in identifying the element.
4) Robert Bunsen was the first person to use line spectrum to identify the elements.
5) The elements Rubedium (Rb), Caesium (Cs), Thallium (Tl), Indium (In), Gallium (Ga),
Scandium (Sc) were identified using their spectra.
6) Helium was also discovered in the sun by spectroscopic methods.

ABSORPTION SPECTRUM:
When white light is passed through the vapours of the substance (or solution of the
substance), the transmitted light when passed through prism, have a few dark lines in
other wise continuous spectrum. It is called absorption spectrum.
Note:
 The radiations of certain wavelengths have been absorbed by the substance.

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 The wavelengths absorbed are same as the wavelengths corresponding to bright lines in
the emission spectrum of the substance.
 Absorption spectrum is like photographic negative of emission spectrum.
 In the absorption spectrum of Na, 2 dark lines appear corresponding to 589.6 nm & 589
nm

DIFFERENCE BETWEEN EMISSION SPECTRUM AND ABSORPTION SPECTRUM:

EMISSION SPECTRUM ABSORPTION SPECTRUM

Emission spectrum is obtained when a
source of radiation is analysed directly.
It has bright coloured lines on dark
background.
Absorption spectrum is obtained when white
light is passed through the substance & the
transmitted light is analysed.
It has dark lines in otherwise continuous
spectrum.

It can be continuous or discontinuous. It is always discontinuous.

Atomic spectrum of hydrogen is the simplest, as hydrogen atom has one

electron, it has minimum number of lines. The line spectrum of hydrogen could not be
explained by Rutherford’s atomic model.
Hence, a Danish Physicist Neils Bohrs in 1913 proposed a New Atomic
Model based on Quantum Theory.

LINE EMISSION SPECTRUM OF HYDROGEN:

When hydrogen gas under low pressure (10-3 mm of Hg) is heated strongly in an electric
discharge tube by applying potential, the gas gets heated up and begins to glow by emitting
light. When this light is subjected to dispersion and analysis using a photographic plate. A
spectrum consisting of a group of sharp lines are obtained.

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The groups of sharp lines found in the hydrogen spectrum are

1. Lyman series –U-V region
2. Balmer series –Visible region
3. Paschen series – IR region
4. Bracket series - IR region
5. Pfund Series – IR region
The wave number and wavelength of each line in the spectral series is calculated by
1  1 1
Rydberg equation, given by    R 2  2 
  n1 n2 
Where υ = Wave number
λ = Wavelength
R = Rydberg constant i.e. 10967800m-1 =1.09678x107m-1.
n1 is integer 1, 2, 3, 4, 5 for Lyman, Balmer, Paschen, Brackett, Pfund series
respectively.
n2 is integer greater than n1

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EXPLANATION FOR THE FORMATION OF SPECTRAL LINES IN THE

HYDROGEN SPECTRUM USING BOHR’S THEORY:
When hydrogen gas is heated strongly in a electric discharge tube by applying potential the
electrons present in the H2 gas absorbs energy and jumps to the higher energy levels.
Within a short interval of time. The excited electrons return back to their ground level either
by directly or jumping to intermediate energy levels. During this, they emit radiations in the
form of photons. These transition of electrons forms different groups (i.e. 5 groups) of lines in
the spectrum.

LYMAN SERIES:
When electrons jumps from higher energy levels to first energy level, they emit
energy in the form of photon corresponding to UV region, these transition of
electrons form Lyman series.
The wave number and wavelength is calculated using Rydberg’s formula.
1 1 1  where, R = 1.09678x107m-1.
  R 2  2 
  1 n2  n2 = 2, 3, 4, 5, …..

BALMER SERIES:
When electrons jumps from higher energy levels to second energy level, they emit
energy in the form of photon corresponding to visible light; these transitions of
electrons form Balmer series.
The wave number and wavelength are calculated using Rydberg’s formula.
1 1 1 where, R = 1.09678x107m-1.
  R 2  2 
  2 n2  n2 = 3, 4, 5, …..

PASCHEN SERIES:
When electrons jump from higher energy levels to third energy level, they emit energy
in the form of photon corresponding to infra-red light. These transitions of electrons
form Paschen series.
The wave number and wavelength are calculated using Rydberg’s formula.
1 1 1 where, R = 1.09678x107m-1.
  R 2  2 
  3 n2  n2 = 4, 5, 6, …..

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BRACKETT SERIES:
When electrons jump from higher energy levels to fourth energy level, they emit
energy in the form of photon corresponding to infra-red light. These transitions of
electrons form Brackett series.
The wave number and wavelength are calculated using Rydberg’s formula.
1 1 1 where, R = 1.09678x107m-1.
  R 2  2 
  4 n2  n2 = 5, 6, …..

PFUND SERIES:
When electrons jump from higher energy levels to fifth energy level, they emit energy
in the form of photon corresponding to infra-red light. These transitions of electrons
form Pfund series.
The wave number and wavelength are calculated using Rydberg’s formula
1 1 1 where, R = 1.09678x107m-1.
  R 2  2 
  5 n2  n2 = 6, 7…..

MERITS OF BOHR THEORY:

1. This theory explains the spectra of all mono electron species like H, He2+, Li2+, etc.
2. The value of Rydberg’s constant calculated using Bohr’s theory is in good
agreement with its experimental value of 1.09678 x107 m-1.
3. The experimental values of wave number of each spectral line are in good
agreement with values calculated using Bohr’s theory.
4. It could explain the stability of an atom.

DE-MERITS OF BOHR’S THEORY:

1. This theory does not explain the spectra of multi electron species.
2. This theory cannot explain the fine spectrum of Hydrogen.
3. This theory cannot explain why the angular momentum of an electron is an integral
h
multiple of .
2
4. This theory cannot explain Zeeman and Stark effect.
5. This theory is against the Heisenberg's uncertainty principle (position and energy).
6. It could not explain the 3-D model of an atom.

ZEEMAN EFFECT:
Splitting of a spectrum line into several components by the application of a magnetic
field is called Zeeman Effect.

STARK EFFECT:
Splitting of a spectrum line into several components by the application of an electric
field is called Zeeman Effect.

DEPARTMENT OF CHEMISTRY 16 SKCH PU COLLEGE

 S STRUCTURE OF ATOM Y

WAVE PARTICLE NATURE OF ELECTRON OR DUAL NATURE OF ELECTRON:

According to Einstein light possess both wave and particle nature.
Later, Louis de Brogle extended this concept for all moving particles. According to him a
moving particle is associated with a wave called “matter wave”.
Finally, he proposed that moving electron possess both wave and particle nature. This
is called dual nature of electron.

DERVATION OF DE-BROGLIE EQUATION OR MATTER-WAVE EQUATION:

According to Einsten,
Energy of a photon is given by
E = mc2 ----------(1) Where, m = mass of photon
c = velocity of light (3×108 ms-1)
According to Planck,
Energy of a photon is given by
E = h ν but ν  c
λ
hc
E -----------------(2) Where, h = plank’s constant
λ
c = velocity of light (3 × 108 m s-1)
λ = wavelength
Comparing equation (1) and (2)
hc
We get,  mc2
λ
h
  This equation is called De-Broglie equation
mc
mc = mass (m) x velocity (c) = momentum (p)
h

p

h
NOTE: De-Broglie’s equation is also given by   Where, v = velocity of the moving body.
mv

DIFFERENCE BETWEEN WAVE AND PARTICLE:

WAVE PARTICLE

The energy of wave depends upon amplitude of Energy of a particle depends on mass
the wave and velocity of the particle

It is delocalized in the space It is localized point in the space

Two or more waves can exist simultaneously in Two or more particle cannot exist
a region of space simultaneously in region of space
Waves undergo interference Particles do not undergo interference.

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HEISENBERG UNCERTAINTY PRINCIPLE:

It is not possible to determine the exact position and exact momentum of a moving
subatomic particle like electron simultaneously at a given instant of time.

MATHEMATICALLY:
 If x is the error (uncertainty) in determination of position
 If p is the error (uncertainty) in determination of momentum
 Then according to Heisenberg
h
x . p 
4
 If the exact position of the electron is determined then it is not possible to
determine the momentum accurately.
 This principle leads to the failure of Bohr’s theory on position of electrons
 Further, Bohr’s theory was modified by Born, Heisenberg, Schrodinger and others
using a new mechanics (Mathematical expressions), this concept is called Quantum
Mechanics.
 Based on Quantum mechanics they proposed a model for an atom which is called as
Quantum mechanical model.
 According to this model the position of electrons in an atom is explained by using
probabilistic description.

ATOMIC ORBITAL: This concept of atomic orbital was introduced by Quantum theory.
Atomic orbital is a three dimensional region in the space around the nucleus where
there is maximum probability of finding electrons.

SHELLS:
The circular paths in which electrons are revolving around the nucleus of an atom is
called shells.
 The concept of sub shell is introduced to explain fine structure of hydrogen
 Each shell consist of sub shells, each sub shell consist of orbitals: Subshells undergoes
orientations. These orientations are orbitals.
Ex: - K shell has s sub shell; s sub shell has s orbital.

SHAPE OF s-ORBITAL:
s- orbital has spherical shape. s-sub shell consists of only 1 – orbital, in which electrons
are distributed in symmetrical spherical shape.
z
y

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 S STRUCTURE OF ATOM Y

SHAPE OF p -ORBITALS:
p- orbital has dumb bell shape. p-sub shell consists of 3 – orbitals i.e. px, py, pz
z z z
y y y

x x x

px py pz

SHAPE OF d – ORBITALS:
d-orbitals have double dumb bell shape. d-sub shell consists of 5 orbitals i.e.
d x-y , d y-z , d z-x , d x2 - y 2 ,d z 2
y z z y z

x y x x x

dx-y dy-z dx-z dx2-y 2 dz2

Quantum mechanical 3D model of atom.

DEPARTMENT OF CHEMISTRY 19 SKCH PU COLLEGE

 S STRUCTURE OF ATOM Y

DIFFERENCE BETWEEN ORBIT AND ORBITAL:

ORBIT
It is a circular path in which electrons are
revolving around the nucleus.
An orbit can accommodate a maximum of
2n2 electrons.
They have spherical shape.
The position and momentum of electron in an
orbit can be determined simultaneously.
ORBITAL
It is a three dimensional region in space where
there is maximum probability of finding electrons.
An orbital can accommodate a maximum of 2
electrons with opposite spin.
They have different 3-dimensional shapes.
The position and momentum of electrons in an
orbital cannot be determined simultaneously.

QUANTUM NUMBERS:
The numbers used to define the state of an electron in an atom are called Quantum
numbers.
The position of an electron in an atom is defined by using four quantum numbers

a) PRINCIPAL QUANTUM NUMBER (n):

The quantum number that indicates the main shell to which an electron belong is
called as principal quantum number.
It is represented by ‘n’ where, n = 1, 2, 3, 4, …….
This quantum number also represents the energy of electron and size of the orbital
If n = 1 K shell 1st energy level
If n = 2 L shell 2nd energy level
If n = 3 M shell 3rd energy level
If n = 4 N shell 4th energy level

b) AZIMULTHAL OR ORBITAL or ANGULAR MOMENTUM QUANTUM NUMBER (l):

The quantum number that indicates the sub shell to which electron belongs is called
as azimuthal quantum number.
It is represented by ‘l’, for given value of ‘n’ the possible values of ‘l’ are 0, 1, 2, 3,…….(n-1)
A total of ‘n’ values are possible.
This quantum number also indicates the angular momentum of the electron and shape
of the subshell or orbital.
If l = 0 s – sub shell spherical orbital
If l = 1 p – sub shell dumbbell shaped
If l = 2 d – sub shell double dumbbell shaped
If l = 3 f – sub shell complex

c) MAGNETIC QUANTUM NUMBER (m):

The quantum number that indicates the orientation of the orbitals is called as
magnetic quantum number.
It is represented as ‘m’. For a given value of azimuthal quantum number, the possible values
‘m’ are -l,….., 0,……., +l i.e. ( - l to + l including 0)

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 S STRUCTURE OF ATOM Y

A total of (2l + 1) values are possible.

If l = 0 m=0 s-orbital
If l = 1 m = - 1, 0, +1 px, py, pz -orbitals

If l = 2 m = - 2, - 1, 0, +1, +2 d x-y , d y-z , d z-x , d x2 - y 2 ,d z 2 -orbitals

d) SPIN QUANTUM NUMBERS (s):

The quantum number that indicates the direction of spin of electron is called as spin
quantum number.
 An electron spins on its own axis in clockwise or in anticlockwise direction hence the
values for spin quantum number are + ½ and – ½ respectively.
 An orbital contains maximum of two electrons with opposite spin.

ENERGY LEVEL DIAGRAM:

The diagram which shows the relative energies of various atomic orbitals is
1s < 2s < 2p < 3s < 3p < 4s < 3d< 4p < 5s< 4d< 5p < 6s < 4f etc.

E
n
e
r
g
y
Note:
 The state of an atom in which all the electron are present in the available orbitals in the
increasing order of their energies is called ground state of an atom.
 The state of an atom in which the electrons in atom are distributed in higher energy
orbitals instead of distributing in lower energy orbitals is called excited state.

ELECTRONIC CONFIGURATION:
Distribution of available electrons in an atom in different orbitals in the increasing
order of their energy is called as electronic configuration.

RULES FOR FILLING ATOMIC ORBITALS:

1. AUFBAU RULE (building):

“In the ground state of an atom the electron enters into various atomic orbitals in the
increasing order of their energy”.

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 S STRUCTURE OF ATOM Y

In an atom the electron first enters into the orbital having less energy. The increasing
order of energy of different orbitals is 1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p …..etc.

2. (n + l) Rule:
“This rule is used to compare the relative energies of different orbitals in an atom”.
i. Among two orbitals, the orbital having greater value for (n + l) has more energy.
Example:
Orbital n l n+l
 energy of 4s < 3d
4s 4 0 4
3d 3 2 5

ii. If the atomic orbitals have same (n + l) values, then the orbital with higher principal
quantum number has more energy.
Example:
Orbital n l n+l
 energy of 4f < 5d
4f 4 3 7
5d 5 2 7

3. PAULI’S EXCLUSION PRINCIPLE:

“No two electrons of the same atom can have the same set of value for all the four
quantum numbers”.
Example: The electrons present in the 1s orbital have same values for n, l, m quantum
numbers but spin quantum number (s) have different values i.e. + 1/2 , - 1/2 hence an
orbital has maximum of two electrons.

4. HUND’S RULE OF MAXIMUM MULTIPLICITY:

“In the orbitals having same energy, the pairing of electrons does not take place until
all the orbitals are filled with one electron”.
This rule is applicable only for p, d, f orbitals [degenerate orbitals (orbitals having same
energy)]

5. EXTRA STABILITY RULE OF HALF – FILLED OR COMPLETELY FILLED ORBITALS:

“A set of orbitals with same energy are more stable when they are either completely
filled or half filled”.
Reason: An atom possessing half-filled or completely filled atomic orbitals in the outermost
shell is more stable due to symmetry.
Example: Nitrogen gains extra stability due to presence of half-filled orbitals, nitrogen is
more stable than oxygen, because oxygen does not contain either half-filled orbitals or
completely filled orbitals.

*********

DEPARTMENT OF CHEMISTRY 22 SKCH PU COLLEGE

 ELECTRONIC CONFIGURATION OF ATOMS UP TO ATOMIC NUMBER 54:
At. ELECTRONIC S STRUCTURE OF ATOM Y
ELEMENT SYMBOL BOX DIAGRAM
No. CONFIGURATION
1 Hydrogen H 1s1
1s

2 Helium He 1s2
1s

3 Lithium Li [He] 2s1 [He]

2s

4 Beryllium Be [He] 2s2 [He]

2s

5 Boron B [He] 2s2 2p1 [He]

2s 2p

6 Carbon C [He] 2s2 2p2 [He]

2s 2p

7 Nitrogen N [He] 2s2 2p3 [He]

2s 2p

8 Oxygen O [He] 2s2 2p4 [He]

2s 2p

9 Fluorine F [He] 2s2 2p5 [He]

2s 2p

10 Neon Ne [He] 2s2 2p6 [He]

2s 2p

11 Sodium Na [Ne] 3s1 [Ne]

3s

12 Magnesium Mg [Ne] 3s2 [Ne]

3s

13 Aluminium Al [Ne] 3s2 3p1 [Ne]

3s 3p

14 Silicon Si [Ne] 3s2 3p2 [Ne]

3s 3p

15 Phosphorous P [Ne] 3s2 3p3 [Ne]

3s 3p

16 Sulphur S [Ne] 3s 3p2 4 [Ne]

3s 3p

17 Chlorine Cl [Ne] 3s 3p2 5 [Ne]

3s 3p

18 Argon Ar [Ne] 3s 3p2 6 [Ne]

3s 3p

19 Potassium K [Ar] 4s 1 [Ar]

4s

20 Calcium Ca [Ar] 4s 2 [Ar]

4s

21 Scandium Sc [Ar] 3d 4s1 2 [Ar]

3d 4s

22 Titanium Ti [Ar] 3d 4s2 2 [Ar]

3d 4s

23 Vanadium V [Ar] 3d 4s3 2 [Ar]

3d 4s

24 Chromium Cr [Ar] 3d 4s5 1 [Ar]

3d 4s

25 Manganese Mn [Ar] 3d 4s5 2 [Ar]

3d 4s

26 Iron Fe [Ar] 3d 4s6 2 [Ar]

3d 4s

27 Cobalt Co [Ar] 3d 4s7 2 [Ar]

3d 4s

28 Nickel Ni [Ar] 3d 4s8 2 [Ar]

3d 4s

29 Copper Cu [Ar] 3d 4s10 1 [Ar]

3d 4s

30 Zinc Zn [Ar] 3d 4s10 2 [Ar]

3d 4s

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