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Unit- structure of atom

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The word atom is a Greek word meaning indivisible, i.e., an ultimate particle which cannot be
further subdivided. The idea that all matter ultimately consists of extremely small particles was
conceived by ancient Indian and Greek philosophers. The old concept was put on firm footing
by John Dalton in the form of atomic theory which he developed in the years 18031808. This
theory was a landmark in the history of chemistry. According to this theory, atom is the smallest
indivisible part of matter which takes part in chemical reactions. Atom is neither created nor
destroyed. Atoms of the same element are similar in size, mass and characteristics; however, atoms
of different elements have different size, mass and characteristics.
In 1833, Michael Faraday showed that there is a relationship between matter and electricity. This
was the first major break-through to suggest that atom was not a simple indivisible particle of all
matter but was made up of small particles. Discovery of electrons, protons and neutrons discarded
the indivisible nature of the atom proposed by John Dalton.
Discharge tube (Discovery of electron) It is a tube filled with low-pressure gas that glows when it
conducts electricity at a given voltage. It is used in neon & fluorescent lights.
A discharge tube is a long glass tube G closed at both ends. Two circular metal plates A & B,
called electrodes are sealed at the two ends of the tube. These are connected to a source of
electrical power such as an induction coil which can supply very high voltage. The plate A
connected to the negative terminal of the source is called cathode whereas the plate B connected to
the positive terminal of the source is called anode.
A side tube S is also fused to the tube G & can be connected to a vacuum pump to suck out the
air or gas present inside the tube to reduce the pressure inside the tube.

On applying high voltage (about 10,000 volts) between the electrodes, the results observed at
different pressures of the air or gas inside the tube are as follows
(i) at ordinary pressure, no current flows through the air between the electrodes. This is because
air or any gas at this pressure is a poor conductor of electricity.
(ii) If the air inside the tube is sucked out by the vacuum pump so that the pressure falls to about
1 mm of mercury the entire discharge tube begins to glow uniformly with magenta-red color.
(The color emitted depends upon the nature of the gas taken in the tube)
The study with different gases was made by Crookes. That is why these discharge tubes are also
called Crookes tubes.
(iii) If more air from inside the tube is sucked out so that pressure falls further the glow is
intercepted by dark bands at right angle to the axis of the tube.
(iv) When the pressure of the air or the gas inside the tube falls to about 0.001 mm, the discharge
completely disappears, i.e., there is no light emitted by the air. The tube appears completely dark.
However, the glass wall of the tube exactly opposite to the cathode glows with a greenish-yellow
fluorescent light. Some sort of invisible rays moved from the negative electrode to the positive
electrode Since the negative electrode is referred to as cathode, these rays were called cathode
(fluorescence The emission of electromagnetic radiation, especially light, by an object or substance
exposed to radiation or bombarding particles is k/as fluorescence.)
Television picture tube is a cathode ray tube in which picture is produced on the television
screen. Similarly,
Fluorescent light tubes are cathode ray tubes coated inside with suitable material (called
phosphor) which produce visible light when hit by cathode rays.
Unit- structure of atom
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Origin of cathode rays
Cathode rays are a stream of electrons emitted from a cathode in a vacuum(discharge)tube.
The cathode rays are first produced from the material of the cathode. These then hit the gas
atoms present in the discharge tube & knock out electrons (from the gas atoms). These electrons
travel towards the oppositely charged anode in the form of cathode rays. This shows that all
materials used as cathode as well as all gases contain electrons. Hence, we conclude that electrons
are constituents of all atoms.
Properties of cathode rays
1. Cathode rays travel in straight lines. A shadow of metallic object placed in the path is cast on the
wall opposite to the cathode.
2. . Cathode rays carry negative charge. When the rays are passed between two electrically charged
plates, these are deflected towards the positively charged plate. They discharge a positively charged
gold leaf electroscope. It shows that cathode rays carry negative charge.
4. They produce green fluorescence on the glass walls of the discharge tube as well as on certain
substances such as zinc sulphide.
5. Cathode rays produce heating effect. Thus, as they strike a metal foil, it becomes hot.
6. They possess kinetic energy. It is shown by the experiment that when a small pin wheel is placed
in their path, the blades of the wheel are set in motion. Thus, the cathode rays consist of material
particles which have mass and velocity. These particles carrying negative charge were called
negatrons by Thomson. The name `negatron' was changed to `electron' by Stoney.
7. Cathode rays produce X-rays. When these rays fall on material having high atomic mass like
tungsten, molybdenum etc., new type of penetrating rays of very small wavelength are emitted
which are called X-rays.
8.These rays affect the photographic plate.
9.These rays can penetrate through thin foils of solid materials and cause ionisation in gases
through which they pass.
10.The nature of the cathode rays is independent of- the nature of the cathode and the gas in the
discharge tube.
An electron can, thus,be defined as a sub-atomic particle which carries charge
coulomb, i.e., one unit negative charge and has mass 9.11 10
Kg, i.e., nearly
1/1840th of an atom of hydrogen.
As charge on the electron is l unit & mass is negligible, it is represented by the symbol O-1e.
Discovery of electron
J.J. Thomson in 1897 carried out discharge tube experiments & showed that Cathode rays were
made up of negatively charged particles called electrons. It was also found that, whatever the
nature of the gas or the material of the cathode, the electrons had the same charge to mass (e/m)
Anode rays:- (Discovery of Proton)
These are the positively charged radiations that travel from anode to cathode in a discharge tube
containing a gas under low pressure, when a high potential difference is applied between the
electrodes. They are also known as Canal rays or Positive rays.
The existence of positively charged particles (now k/as protons) in an atom was shown by
Goldstein in 1886 with discharge tube experiments.
He took a discharge tube with a
perforated cathode. On applying high
voltage b/w the anode & the cathode,
he observed that besides the
fluorescence at E due to cathode rays
coming from the cathode, fluorescence
is also observed on the glass wall of
the tube at F. This shows that some
passed through the holes or canals
(T/F also k/as canal rays) in the
cathode & struck the glass wall of the
tube at F. Since these rays are coming
from the side of the anode, therefore,
they are called anode rays.
Further, their deflection in an
Unit- structure of atom
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electric field shows that they carry positive charge. Hence they are also called positive rays.
Origin of Anode rays
Anode rays do not originate from the anode. They are produced in the space between the anode &
the cathode. It is believed that gas atoms which are bombarded have their electrons knocked out in
the form of cathode rays. The remaining parts of these atoms become positively charged particles
that travel as a beam of anode rays towards the negatively charged cathode.
Properties of anode rays
1. They travel in straight lines.
2. They are made up of material particles.
3. They carry positive charge.
4. Their charge/mass (e/m) ratio is not constant but depends upon the nature of the gas taken in
the discharge tube.
5. Mass of these positively charged particles also depends upon the nature of the gas & is found to
be nearly equal to the mass of the atom of the gas.
6. Charge on the positively charged particles constituting the anode rays is also found to depend
upon the nature of the gas & the voltage applied. However, the charge is found to be a whole
number multiple of the charge present on the electron. It may be + 1, + 2 or + 3 units depending
upon the number of electrons knocked out of the gaseous atom.
A proton is a sub-atomic elementary particle which carries one unit positive charge & has a mass
nearly equal to that of a hydrogen atom.
As charge on the Proton is +l unit & mass is 1 amu or u, it is represented by the symbol
A proton is in fact an ionized hydrogen atom, i.e., it is obtained by the removal or loss of the
only electron present in hydrogen atom.
The number of protons in the nucleus of an atom determines what kind of a chemical element it
Discovery of Neutron
The discovery of neutron was actually made about 20 years after the structure of atom was
elucidated by Rutherford. Atomic masses of different atoms could not be explained if it was
accepted that atoms consisted only of protons and electrons. Thus, Rutherford (1920) suggested
that in an atom, there must be present at least a third type of fundamental particles which should
be electrically neutral and possess mass nearly equal to that of proton. He proposed the name for
such fundamental particle as neutron. In 1932, Chadwick bombarded beryllium with a stream
of -particles. He observed that penetrating radiations were produced which were not affected by
electric and magnetic fields. These radiations consisted of neutral particles, which were called
neutrons. The nuclear reaction can be shown as:

The mass of the neutron was determined. It was 1.675 10
Kg, i.e., nearly equal to the mass of
Thus, a neutron is a sub-atomic particle which has a mass 1.675 10
Kg, approximately 1u, or
nearly equal to the mass of proton or hydrogen atom and carrying no electrical
charge.The e/m value of a neutron is thus zero.
As charge on neutron = 0 & mass = 1 u, therefore, it is represented by the symbol,
The main characteristics of the three fundamental particles, i.e., electron, proton & neutron are
given in the Table below:

d from
Unit- structure of atom
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ed that Daltons indivisible atom is composed of sub-atomic
particles carrying positive and negative charges. Different
atomic models were proposed to explain the distributions of
these charged particles in an atom.
Thomson Model of Atom
J. J. Thomson, in 1898, proposed that an atom possesses a
spherical shape (radius approximately 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. Many different names are given to
this model, for example, plum pudding, raisin pudding or
watermelon. 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.( Thomson was awarded Nobel Prize for physics in 1906, for
his theoretical and experimental investigations on the conduction of electricity by gases.)
Rutherfords Nuclear Model of Atom:
In 1911, Rutherford (and his students Hans Geiger and Ernest Marsden) performed -ray
scattering experiment to know about the position of the two fundamental particles electrons and
protons in an atom.

In the
experiment a stream of very highly energetic alpha particles from a radio active source (Ra or Po)
placed in a lead box with a hole in it was directed at a thin foil ( 100 nm thick) of gold metal. The
alpha particles coming out of the thin gold foil were then detected by scintillation s. Whenever,
alpha particles struck the screen, a tiny flash of light was produced at that point.
Rutherford noticed the following experimental observations :
1. Most of the alpha
particles (nearly 99%)
passed through the foil
without being deviated
from their paths.
2. A small fraction of the
alpha particles was
deflected by small
3. A very few alpha
particles ( 1 in
20,000) were bounced
back that is were
deflected by nearly
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Rutherford drew the following conclusions regarding the structure of atom.
1) Since most of the alpha particles passed through the foil undeflected, it indicates that the
most of the space in an atom is empty.
2) A few positively charged -particles were deflected. The deflection must be due to enormous
repulsive force showing that the positive charge of the atom is not spread through out the
atom as Thomson had presumed. The positive charge has to be concentrated in a very small
volume that repelled and deflected positively charged -particles.
3) -particles which make head on collision with heavy positive charge centre are deflected
through large angles.
On the basis of above observations and conclusions Rutherford proposed the nuclear model of
atom. According this model :
1) Most of the mass and all positive charge of an atom is concentrated in a very small region
called nucleus. Size of the nucleus is extremely small as compared with the size of the
2) The radius of the atom is of the order of 10
m whereas radius of nucleus is of the order of
3) The positive charge of the nucleus is due to protons. The magnitude of the charge of
nucleus is different for atoms of different elements.
4) The nucleus is surrounded by electrons which are revolving around it at very high speeds.
The electrostatic force of attraction between electrons and the nucleus is balanced by the
centrifugal force acting on revolving electrons.
5) Total negative charge on the electrons is equal to the
total positive charge on the nucleus so that atom on
the whole is electrically neutral.
6) Most of the space inside an atom is empty.
7) The limitations of Rutherford's model are as follows:
1) According to the 'Classical Theory of
Electromagnetism', whenever a charged body is
subjected to an acceleration around an opposite
charge, it emits radiation continuously. Hence, the
electron in Rutherford's atom will lose energy and will
not be able to stay in a circular path around the
nucleus and will ultimately go into spiral motion. Such
an electron will fall into the nucleus. This, of course,
does not happen for electrons in an atom and this
discrepancy could not be explained at that time.
8) 2) Rutherford's model could not explain the emission
of various spectral lines (Lyman, Balmer, Paschen,
Brackett, and Pfund series) in the emission spectrum of hydrogen.
9) 3) It could not suggest the discontinuous spectrum of hydrogen, which is in the form of
characteristic line wavelengths.
Atomic number ( Z )
{Moseley devised an experiment to find out positive charge on the nucleus .He calculated the
charge on the nucleus from the frequencies or wave lengths of X-rays emitted by different
elements. The number of unit-positive charges on the nucleus of the atom of the element is called
atomic number of the element. The positive charge on the nucleus is due to protons and each
proton carries one unit positive charge.
Atomic number of an element is equal to the number of protons in the nucleus of its atom. Further
in an atom the number of protons is equal to the number of electrons. Hence atomic number is
also equal to the number of electrons in an atom of the element. Thus atomic number of an
element is equal to the number of protons in the nucleus of its atom or the number of extra-
nuclear electrons. Generally it is denoted by the letter Z.
Atomic number Z = Number of protons = Number of electrons.
Mass number (A)
Mass of an atom is mainly concentrated in the nucleus. In the nucleus there are protons and
neutrons. The mass of an atom is mainly due to protons and neutrons. The number of protons and
neutrons in the nucleus is called mass number of the atom. It is generally represented by the
letter A .
Unit- structure of atom
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Mass number = Number of protons + Number of neutrons = Number of nucleons.
From the knowledge of atomic number and mass number of an element, it is possible to
calculate , the number of electrons, protons and neutrons in an atom of the element.
For example, atomic number and mass number of sodium are 11 and 23 respectively. Number of
electrons, protons and neutrons in an atom of it can be calculated as under :
Number of protons = Atomic number = 11
Number of electrons = Atomic number = 11
Number of neutrons = (Mass number) (Atomic number) = 23 11 = 12
In case of ions, the number of protons and neutrons remain the same as in atoms, however, the
number of electron changes. This is due the reason that an ion is formed either by addition or by
removal of one or more electrons from the neutral atom.
For example, Mg
ion has two electrons less than the number of electrons in Magnesium atom.
Knowing that the atomic number and mass number of Magnesium as 12 and 24 respectively, the
number of electrons , protons and neutrons in i Mg
ons may be calculated as under :
Number of protons = Atomic number = 12
Number of electrons = Atomic number 2 = 12 2 = 10
Number of neutrons = 24 12 = 12
Similarly, a negative ion is formed by a addition of one or more electrons to the neutral atom. For
example, P
ion (phosphide ion) is formed by the addition of three electrons to a phosphorus atom.
P + 3 e P

Knowing the atomic number of phosphorus ( Z = 15 ) , and mass number ( A = 31 ) , the number of
electrons , protons and neutrons in phosphide ion may be calculated as under :
Number of protons = Atomic number = 15
Number of electrons = Atomic number + 3 = 18
Number of neutrons = Mass number Atomic number = 31 15 = 16
Atoms of the same element having the same atomic number but different mass number are called
For example , there are three isotopes of hydrogen having mass
numbers , 1, 2 and 3 respectively and each of them having
atomic number equal to 1. They are represented as
1 H,
1H and named as protium (H), deuterium(D)
and tritium (T)respectively. Ordinary hydrogen is protium.
Isotopes of other elements do not have special names. They are
represented by simply indicating the values of A on the symbol. For example, isotopes of chlorine
are written as
Cl and
Atoms of the different elements having the same mass number but different atomic number are
called isobars
18Ar ,
Atoms of different elements which contain the same number of neutrons are called
isotones . e.g.
These are molecules of different substances which contain the same number of atoms and same
total number of electrons which leads to similarity in their physical properties. The phenomenon is
called isosterism. For example, carbon dioxoide CO2and nitrous oxide, N2O are isosters.
Isodiapheres are the atoms having the same difference of neutron and proton or same isotopic
number. Nuclides and its decay product after the emission of an -particle are called isodiapheres.
e.g. . U -235 and Th- 231 are isodiaphers
143 - 92 and 141-90 = 51 in both

Dual nature of electromagnetic radiation
({During the period of developments of new models and to improve Rutherfords model of an
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two developments played a major role. These are:
(i) Dual character of the electromagnetic radiation which means that radiations possess both wave
like and particle like properties, and
(ii) Experimental results regarding atomic spectra which can be explained only by assuming
quantized (fixed) electronic energy levels in atoms.})
wave nature of electromagnetic radiation
Newton (17
century): - Suggested that light has a corpuscular (or particle) nature i.e. it consists of a stream of
energetic particles. The particle nature of light explained some of the experimental laws like reflection and
refraction of light. However, it failed to explain the phenomena of interference and diffraction.
James Maxwell (19
Century): - suggested that light waves are electromagnetic in nature i.e. they are
oscillations of electric and magnetic filed in space.
This theory could explain clearly optical phenomena such as interference, refraction,
diffraction, polarization etc. but failed to explain black
body radiations (radiations which are emitted by hot
bodies) and photoelectric effect (ejection of electrons
when light is incident on metal surfaces).
characteristics of electromagnetic waves
(i) The oscillating electric and magnetic fields produced
by oscillating charged particles are perpendicular to each
other and both are perpendicular to the direction of
propagation of the wave.
(ii) In vaccum all types of electromagnetic radiations,
regardless of wavelength, travel at the same speed, i.e.,
3.0 x 10
m s
(2.997925 x 10
m s
, to be precise). This
is called speed of light and is given the symbol c. The
frequency ( ), wavelength () and velocity of light (c) are
related by the equation c =
(iii) Electromagnetic waves do not require medium and can move in vacuum.



1. A particle occupies a well-defined
position in space i.e. a particle is
localized in space
2. When a particular space is occupied
by one particle, the same space cannot
be occupied simultaneously by any other
particle. In other words, particles do not
3. When a number of particles are
present in a given region of space, their
total value is equal to their sum i.e. it is
neither less nor more.
1. A wave is spread out in space. i.e,
delocalized in space.
2. Two or more waves can coexist in the
same region of space and hence
3. When a number of waves are present
in a given region of space, due to
interference, the resultant wave can be
larger or smaller than the individual
waves i.e. interference may be
constructive or destructive.

Some of the experimental phenomena such as diffraction and interference can be explained by the
wave nature of the electromagnetic radiation. However, experimental observations such as
emission of radiation from a hot body and photoelectric effect cannot be explained on this basis.
Black body radiation
The ideal body , which emits and absorbs all frequencies(which is a perfect absorber and perfect
radiator of energy), is called black body and the radiation emitted by this body is called black body
If any substance with high melting point (e.g, an iron bar) is heated, it first becomes red, then
yellow------ white and finally blue as temperature becomes very high.
According to electromagnetic wave theory, the energy is emitted or absorbed continuously. Hence,
the energy of any electromagnetic radiation is proportional to its intensity i.e. a square of
amplitude and is independent of its frequency or wavelength. Thus, according to the wave theory,
the radiation emitted by the body being heated should have the same colour, although its intensity
may vary as the heating is continued.
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In terms of frequency, it means that the radiation emitted
goes on from a lower frequency to a higher frequency as
the temperature increases. The red colour lies in the lower
frequency region , while blue colour belongs to the higher
frequency region of the electromagnetic spectrum. The
exact frequency distribution of the emitted radiation (i.e.,
intensity versus frequency curve of the radiation ) from a
black body depends upon its temperature. At a given
temperature, intensity of radiation emitted increases with
decrease of wave length, reaches a maximum value at a
given wave length and then starts decreasing with further
decrease of wave length, as shown .The above
experimental results cannot be explained on the basis of
the wave theory of light.
Explanation of Black Body Radiation. When some solid
substance is heated, the atoms of the substance are set into oscillation and emit radiation of
frequency, . Now, as heating is continued, more and more energy is being absorbed by the atoms
and they emit radiations of higher and higher frequency. As red light has minimum frequency,
yellow has higher frequency, therefore, the body on heating becomes first red, then yellow and so
When a black body is heated, it emits thermal radiations of different wavelengths or frequency. To
explain these radiations,
Planck's quantum theory of radiation
The main features of Planck's quantum theory of radiation are:
(i) Radiant energy is emitted or absorbed, not continuously but discontinuously, in discrete units
or packets of energy called quanta.
(ii) Each packet of energy or quantum has a definite amount of energy. In the case of light, the
quantum of light energy is called a photon.
(iii) The magnitude of energy (E), associated with a quantum of radiation, is proportional to the
frequency of radiation.

where the proportionality constant 'h', is a universal constant known as Planck's constant. It has a
value of 6.626 10
J s or 6.626 10
erg s. This relation was found to be valid for all types of
electromagnetic radiations.
(iv) The gain or loss of radiant energy involves discrete energy changes that must be a whole
number multiple of the quantum i.e.
E = nh ; where n is an integer such as 1, 2, 3...
Thus, a body can emit or absorb energy equal to or any other integral multiple
of . But it cannot absorb energy equal to or any other fractional value of .
Neil Bohr used this theory to explain the structure of atom.
Photoelectric Effect
In 1887, H. Hertz performed a very interesting experiment in which electrons (or electric current)
were ejected when certain metals (for example potassium, rubidium, caesium etc.) were exposed to
a beam of light . When radiations with certain minimum frequency strike the surface of a metal,
the electrons are ejected from the surface of the metal . This phenomenon is called photoelectric
effect. The electrons emitted are called photo-electrons.

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Equipment for studying Photoelectric effect.

The results observed in this experiment were:
(i) The electrons are ejected from the metal surface as soon as the
beam of light strikes the surface, i.e., there is no time lag between
the striking of light beam and the ejection of electrons from the
metal surface.
(ii) The number of electrons ejected is proportional to the intensity
or brightness of light.
(iii) For each metal, there is a characteristic minimum frequency,
0 (also known as threshold frequency) below which photoelectric
effect is not observed. At a frequency >0, the ejected electrons
come out with certain kinetic energy. The kinetic energies of these
electrons increase with the increase of frequency of the light used. The above observations cannot
be explained by the Electromagnetic wave theory. According to this theory, since radiations are
continuous, therefore it should be possible to accumulate energy on the surface of the metal,
irrespective of its frequency and thus radiations of all frequencies should be able to eject electrons.
Similarly, according to this theory, the energy of the electrons ejected should depend upon the
intensity of the incident radiation.
. Explanation of Photoelectric effect. Einstein (1905) was able to explain the photoelectric effect
using Plancks quantum theory of electromagnetic radiation as a starting point.
Explanation of the different points of the photoelectric effect as under :
(i) When light of some particular frequency falls on the surface of metal, the photon gives its entire
energy to the electron of the metal atom. The electron will be dislodged or detached from the metal
atom only if the energy of the photon is sufficient to overcome the force of attraction of the electron
by the nucleus. That is why photo-electrons are ejected only when the incident light has a certain
minimum frequency (threshold frequency 0 ).
(ii) If the frequency of the incident light () is more than the threshold frequency (0 ), the excess
energy (h h0 ) is imparted to the electron as kinetic energy. i.e. K.E. of the ejected electron =
Hence greater is the frequency of the incident light, greater is
the kinetic energy of the emitted electron.
(iii) Increasing the intensity of light of a given frequency
increases the number of photons but does not increase the
energies of photons. Hence, when the intensity of light is
increased, more electrons are ejected but the energies of
these electrons are not altered.
If kinetic energy of the emitted photo-electrons is plotted
against the frequency of the absorbed photons, a straight
line of slope h is obtained .
Dual Behaviour of Electromagnetic Radiation
Light has been regarded as wave to explain the phenomena of interference and diffraction and as
particle to explain the phenomena of Black body radiation & photoelectric effect.
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Thus it may be concluded that light possesses both particle and wave-like properties, i.e., light has
dual behaviour.
Depending on the experiment, light behaves either as a wave or as a stream of particles. Whenever
radiation interacts with matter, it displays particle like properties in contrast to the wavelike
properties (interference and diffraction), which it exhibits when it propagates.
Various types of electromagnetic radiation having different wave lengths (or frequency). are
known. They constitute the electromagnetic spectrum.
The arrangement of different types of electromagnetic radiations in the order of increasing wave
lengths (or decreasing frequencies) is known as Electromagnetic Spectrum. The complete
electromagnetic spectrum is shown .

Different regions of spectrum
are identified by different
names .Some important
electromagnetic radiations in
the decreasing order of their
wave lengths are :
Radio waves > Microwaves >
Infrared (IR) > Visible >Ultra
violet (UV) > X-rays > Gamma
rays > Cosmic rays
Radio waves ( = 10
Hz) are
generated from alternating
electric currents of high
frequencies. These are used in
Microwaves ( = 10
Hz) are produced by special generators, e.g., Klystron tube. These are used in
telephone transmission and radar. These are also absorbed by food molecules and hence are used
to cook food.
IR radiations ( = 10
Hz) are emitted by incandescent objects. These produce high thermal effect
and is heat radiation. These are used in physiotherapy. A plot of the frequencies of IR radiations
versus the intensities of radiations absorbed is called infrared spectrum and used to identify a
substance because each substance has a characteristic infra-red spectrum.
Visible light radiations ( = 3.95 x 10
7.9 x 10
Hz ) are produced from stars, arc lamps, hot
filaments as of tungsten in an electric bulb.
Ultra-violet radiations ( = 10
Hz) are present in sun's rays. In the laboratory these can be
produced from the arc lamps containing mercury vapour, xenon or hydrogen gas.
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X-rays ( = 10
Hz) are produced when a stream of electrons strike a heavy metal target. These are
used in radiotherapy.
Cosmic rays ( = 3 x 10
Hz to infinity) originate from the outer space and continously fall on the
earth due to their great penetrating power. )}
Emission And Absorption Spectra
Electromagnetic spectrum consists of
radiations of different wave lengths and
frequencies. An instrument used to separate
the radiations of different wavelengths (or
frequencies) is called spectroscope or a
spectrograph. A spectroscope consists of a
prism or a diffraction grating for the dispersion
of radiations and a telescope to examine the
emergent radiations with the human eye.
However, if in a spectroscope, the telescope is
replaced by a photographic film, the
instrument is called a spectrograph and
the photograph (or the pattern) of the emergent
radiation recorded on the film is called a
spectrogram or simply a spectrum of the given
Depending upon the source of radiation, the spectra are broadly classified into (i) Emission spectra
and (ii) Absorption spectra. These are briefly explained below :
1. Emission spectra. When the radiation emitted from some source e.g. from the sun or by passing
electric discharge through a gas at low pressure or by heating some substance to high temperature
etc. is passed directly through the prism and then received on the photographic plate, the
spectrum obtained is called Emission spectrum.The emission spectra are mainly of two types:
(i) Continuous spectra. When white light from any source such as sun, a bulb or any hot glowing
body is analysed by passing through a prism, it is observed that it splits up into seven different
wide bands of colours from violet to red, (like rainbow), as shown in Figure. These colours are so
continuous that each of them merges into the next. Hence the spectrum is called continuous
(ii) Line spectra. When some volatile salt (e.g., sodium chloride) is placed in the Bunsen flame or an
electric discharge is passed through a gas at low pressure, light is emitted. If this light is resolved
in a spectroscope, it is found that no continuous spectrum is obtained but some isolated coloured
lines are obtained on the photographic plate separated from each other by dark spaces. This
spectrum is called Line spectrum.
Each line in the spectrum corresponds to a particular wavelength. Further it is observed that each
element gives its own characteristic spectrum, differing from those of all other elements. For
example, sodium always gives two yellow lines (corresponding to wavelengths 5890 and 5896 ).
Hence the spectra of the elements are described as their finger prints differing from each other like
the finger prints of the human beings. Several elements including Rubidium (Rb) Caesium
(Cs),thallium(Tl) Indium (In) and gallium (Ga) were discovered in this way.
Alkali metals like Na and K and alkaline earth metals like Ca, Sr and Ba are detected in qualitative
analysis by flame test.
The element helium (He) was first discovered in the sun spectroscopically.
The line spectra are obtained as a result of absorption and subsequent emission of energy by the
electrons in the individual atoms of the element. Hence the line spectrum is also called atomic
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2. Absorption spectra. when white light from any source is first passed through the solution or
vapours of a chemical substance and then analysed by the spectroscope, it is observed that some
dark lines are obtained in the otherwise continuous spectrum . These dark lines are supposed to
result from the fact that when white light (containing radiations of many wavelengths) is passed
through the chemical substance, radiations of certain wavelengths are absorbed, depending upon
the nature of the element. Further it is observed that the dark lines are at the same place where
coloured lines are obtained in the emission spectra for the same substance. This shows that the
wavelengths absorbed were same as were emitted in the emission spectra. The spectrum thus
obtained is, therefore, called absorption spectrum.

Line Spectrum of Hydrogen
When an electric discharge is passed through gaseous hydrogen, the H2 molecules dissociate and
the energetically excited hydrogen atoms produced emit electromagnetic radiation of discrete
frequencies. The hydrogen spectrum consists of several series of lines named after their
discoverers. Balmer showed in 1885 on the basis of experimental observations that if spectral lines
are expressed in terms of wavenumber ( ), then the visible lines of the hydrogen spectrum obey the
following formula :

where n is an integer equal to or greater than 3 (i.e., n = 3,4,5,.)
The series of lines described by this formula are called the Balmer series. The Balmer series of lines
are the only lines in the hydrogen spectrum which appear in the visible region of the
electromagnetic spectrum. The Swedish spectroscopist, Johannes Rydberg, noted that all series of
lines in the hydrogen spectrum could be described by the following expression :

where n1 = 1,2..
n2 = n1 + 1, n1 + 2..
The value 109,677 cm
is called the Rydberg constant for hydrogen. The first five series of lines
that correspond to n1 = 1, 2, 3, 4, 5 are known as Lyman, Balmer, Paschen, Bracket and Pfund
series, respectively, Of all the elements, hydrogen atom has the simplest line spectrum. Line
spectrum becomes more and more complex for heavier atom. There are however certain features
which are common to all line spectra, i.e., (i) line spectrum of element is unique and (ii) there is
regularity in the line spectrum of each element.

Unit- structure of atom
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Bohrs model of atom:-
To overcome the shortcomings of Rutherfords model
and to account for the line spectra of hydrogen. Neil
Bohr (Danish physicist) in 1913 put forward his
model of atom. Bohr proposed his model on the
basis of Plancks quantum theory. The main
postulates of the Bohr's model are: -
1) The electrons in an atom revolve around the
nucleus in certain specific orbits. These
orbits are associated with definite amounts
of energy and are called energy levels or
energy shells. These orbits are arranged
concentrically around the nucleus. The
energy levels are designated as K, L, M, N, O,
P, Q or numbered as 1, 2, 3, 4, 5, 6, 7
starting from the nucleus.
2) The electron can revolve around the nucleus only along those circular orbits for which the
angular momentum of an electron is an integral multiple of the quantity h/2t. That is
mvr = nh/2t

m = mass of the electron
v = velocity of the electron
r = radius of the orbit
n= an integer (1, 2, 3,----)
h = Plancks constant.
This postulate implies that the angular momentum of an electron revolving around the nucleus
is quantised.
3) The energy of an electron revolving in a particular orbit is given by the expression
En = - Z

where m = Mass of the electron
e = charge of the electron
h = Plancks constant
n = number of orbit
0 = permitivity constant
When values are substituted in the above expression, the energy of an electron in the nth
orbit comes out i.e be
En = -1312 kjmol


Thus an electron cannot radiate energy if no lower energy level is available.
4) As long as the electron stays in a particular orbit, its energy remains constant i.e. electron
can have acceleration and yet not radiate energy.
5) Energy given out or absorbed is not continuous but is quantized i.e. in separate packets of
energy called quanta represented by hv where h is
Plancks constant and v is the frequency of radiation.
6) When an electron accepts a quantum of energy, it
jumps from a lower energy level to higher energy
level. The excited electron being unstable jumps
down quickly to lower energy level by emitting energy
in the form of light of suitable wavelength and
frequency. The difference in the energies of two levels
is given as follows
AE = E2 E1 = hv
E1=Energy of the electron in lower energy level
E2=Energy of the electron in higher energy level
{* At the time, this view was proposed there was no reason for
the quantization of momentum in terms of h/2 units except that
correct results were obtained by this postulates}.
En = - Z

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AE = Energy difference between the two levels.
a) The stationary states for electron are numbered n = 1,2,3. These integral numbers are
known as Principal quantum numbers.
b) The radii of the stationary states are expressed as r n = 0.529 x 10
) m
As n increases , r n also increases indicating greater separation between the orbit and the nucleus.
The radius of first orbit r 1 , is called Bohr radius ( n= 1) is 52.9 pm.
The radius for ions such as He
, Li
the radius is given as :

where Z is the atomic number and has values 2 and 3 for He
, Li
c) The most important property associated with the electron, is the energy of its stationary state. It
is given by the expression.
En = RH(1/n
) n=1,2,3..
where RH is called Rydberg constant and its value is 2.1810
J. The energy of the lowest state,
also called as the ground state, is E
= -2.1810
) = -2.1810
The energy of the stationary state for n = 2, will be : E2 = -2.1810
J ( 1/2
) = = -0.54510
Bohrs theory can also be applied to the ions containing only one electron, similar to that present
in hydrogen atom. For example, He
, Be
and so on. The energies of the stationary states
associated with these kinds of ions (also known as hydrogen like species) are given by the
En = -2.18 x 10
) J
d) Velocity of an electron in nth orbit =2.18

Z/n ms

Bohrs explanation of line spectrum of hydrogen:
According to Bohrs model of an atom the solitary electron of H-atom keeps on rotating in the first
energy level in the ground state. In general, when atoms of a substance are exposed to conditions
under which energy absorption that is excitation is possible, for example by the use of high
temperature or an electrical discharge, the electron will take up energy and various jumps from
lower to upper energy levels i.e from inner to outer orbit will occur. The return of the electrons from
the various upper levels to the lower levels will result in the liberation of definite amounts of energy
and each transition corresponds to a line of definite frequency in the emission spectrum. Since a
number of different energy levels are possible in every atom, there will be a number of transitions
and hence a series of lines will be observed in spectrum.
In the case of hydrogen the various possibilities by which the electrons fall back from
various excited states (higher energy levels) to lower energy levels are depicted in the energy level

n series
t series
Formation of emission spectra of atomic hydrogen
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(1) Lyman series( T. Lyman.)
When the electrons jump from the energy levels n2 equal to 2,3,4,5,6 etc to the energy level n1
equal to 1, the group of lines obtained is called Lyman series. The frequency of these lines is given
1/ = v- = RH [1/n1
1/ n 2
Where n2 = 2, 3, 4, 5, 6 etc
These lines were found in the ultraviolet region of the electromagnetic spectrum.
(ii)Balmer series:(J. J. Balmer.)
When the electrons jump from the energy level n2 equal to 3,4,5,6, etc to the energy level n1
equal to 2, the group of lines obtained is called Balmer series.
The frequency of these lines is given by
1/ = v- = RH [1/(2)
where n2 = 3,4,5,6 etc
These lines were found in the visible region of the electromagnetic spectrum.
(3) Paschen series (F.Paschen.)
When the electrons jump from the energy level n2 equal to 4,5,6 etc to the energy level n1 equal to
3, the group of lines obtained is called Paschen series. The frequency of these lines is given by
v- = RH [1/(3)
-1/ n2
Where n2 = 4, 5, 6 etc
These lines were found in the infrared region of electromagnetic spectrum
(4) Brackett series: (F. S. Brackett.)
When the electrons jump from the energy level n2 equal to 5,6 etc to the energy level n1 equal to 4,
the group of lines is called Brackett series.
The frequency of these lines is given by
v- = RH [1/ (4)
- 1 /n2
Where n2 = 5, 6,7 etc
These lines were found in the 1R region of electromagnetic spectrum.
(5) Pfund series(A. H. Pfund.)
n2 = 6,7,8
n1 = 5
The group of lines is called Pfund series.
The frequency of these lines is given by
1/ = v- = RH [1/(5)
1/ n2
Where n2 = 6,7,8 etc
These lines were found in the IR region of the electromagnetic spectrum.
Bohr's theory and Absorption spectrum
If hydrogen is exposed continuously to a strong source of light ( e.g. an arc light ), then according
to Bohr's theory, the electron present in the atom of the element may pass from a lower energy to a
higher energy level. Suppose the electron pass from a lower energy associated with energy E1 to a
level associated with a higher energy E2 . Then an energy equal to (E2 - E1) will be absorbed from
the light falling on it. As a result of this the spectral line of frequency corresponding to energy (E2 -
E1) will be missing from the spectrum of the light falling on the element. This gives rise
to absorption spectrum .
Limitations of Bohrs model: -
The main limitations of Bohrs model of atom are:
1) This model could hardly explain the line spectrum of hydrogen like atoms e.g. He+, Li2+ etc. it failed
to explain the spectra of atoms having more than one electron. When the spectral lines of hydrogen
atom are observed very closely with the help of highly refined spectroscopes, each line is found to be
made up of two closed lines. The existence of such lines could not be explained by Bohrs model.
2) It failed to explain Zemann effect and stark effect i.e. splitting up of spectral lines under the influence
of the strong magnetic field and the electrostatic field respectively.
3) It could not explain that why angular momentum (mvr) of an electron should be integral multiple of
The main objection against Bohrs model came from two sources:
(i) In 1924, Louis de-Broglie suggested that like light electron also displays wave-particle dualism. But the
wave nature of electron is not accounted by Bohrs model.
(ii)In 1927, Heisenberg suggested that it is not possible to determine simultaneously the exact
position and momentum of a micro particle like electron. It out rightly rejects that electrons revolve
in definite orbit

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Dual nature of matter: -
Einstein had suggested ( 1905 ) that light has dual nature, that is wave nature as well as
particle nature. de Broglie ( 1923 ) proposed that like light, matter also has dual character. It
exhibits wave as well as particle nature. He derived a relationship for the calculation of wave length
() of the wave associated with a particle of mass m' moving with a velocity v' as given below:
= h / m v
or, = h / p
where h ' is Planck's constant and p the momentum of the particle.
de-Broglie equation: -
Light which consists of electromagnetic radiations exhibits both corpuscular (particle) and
wave properties based on this analogy, a French physicist, Louis de Broglie (1924) suggested that
all material particles such as electrons, protons, neutrons, atoms, molecules etc exhibit wave as
well as particle nature. The wave associated with a particle is called a matter wave or pilot wave or
de Broglie waves.
Derivation of de-Broglie equation: -
By employing Maxwell Plancks quantum theory of radiation and Einsteins mass energy
equation,de-Broglie derived his equation as follows:
According to plancks quantum theory
E = hv ----------(1)
Where E is the energy, h is the Plancks constant and v is the frequency of radiation
According to Einsteins mass and energy equation
E = mc
Where E is the energy ,m is the mass and c is the velocity of light,
From eq(1) and (2) we get,
hv = mc
but v = c/
substituting the value in eq (3), we get
h c/ =mc

de Broglie pointed out that the above equation is applicable to any material particle. The mass of
the photon is replaced by the mass of the material particle and the velocity c of the photon is
replaced by the velocity v of the material particle.
Thus for any material particle, we may write
= h/mv
or =h/p
Where p is the momentum (mv) of the particle, the de Broglies equation was experimentally verified
by Davision and Germer (1927) and independently by G. P. Thomson (1928).
Significance of de_Broglies equation: -
The de_Broglies equation has significance in case of material objects having small mass but
it has no significance for objects of relatively larger size because wave length of the wave associated
with them is too small to be detected. This can be illustrated by the following examples.
Suppose we consider an electron of mass 9.1 x 10
kg and moving with a velocity of 10
m /s. Its
de_Broglie wave length will be
= h/mv= 6.62 x 10

9.1 x 10
x 10

= 0.727 x 10
= 7.27 x 10
This value can be measured experimentally.
Let us now consider a ball of mass 10
kg moving with a velocity of 10
. Its de_Broglie wave
length will be

6.62 x 10

= 6.62 x 10

x 10

This wavelength is too small to be measured. Thus de_Broglie equation has no significance
for such a large object.
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The wave nature of electron was verified experimentally by Davison and Germer , by carrying out
diffraction experiments with a beam of fast moving electrons. This wave nature of electrons is
utilised in construction of electron microscope.
Derivation of Bohrs postulate of angular momentum from de Broglie equation.
According to Bohrs model, the electron revolves around the nucleus in circular orbits. According
to de Broglie concept, the electron is not only a particle but has a wave character. Thus in order
that the wave may be completely in phase (Fig. (a), the circumference of the orbit must be equal to
an integral multiple of wavelength ( ) i.e.,

Heisenbergs uncertainty principle: -
One of the important consequences of the dual nature of matter is the uncertainty principle
developed by Werner Heisenberg in 1927. This principle is an important feature of wave mechanics
and discusses the relationship between the position and momentum (velocity) of a moving particle.
The uncertainty principle states as follows
It is impossible to determine simultaneously both the position and movement (velocity) of
a moving particle like electron.
Explination of uncertainty principle: -
To locate the position of an
electron, a supermicroscope and a light of
short wave length (i.e. -rays and x-rays) is
required. In order to locate the exact
position of the electron, the wavelength of
the radiation used should match with the
size of the electron. In other words, it
should be small. The photons of short
wave length are associated with large
momentum according to de_Broglie
equation =h/p. When such photons
strike an electron, an unknown amount of
momentum is transferred to the electron
at the time of collision. This changes the
velocity and hence the momentum of the electron.
If the photons of longer wavelength are used which are associated with low momentum, the
momentum of the electron is not so appreciably changed but its position will be correspondingly
less accurately known.
Thus it is clear that the position and the momentum of an electron cant be determined
This principle can be stated mathematically as
Ax Ap > h/4t
Ax mAv > h/4t
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Where Ax is the uncertainty in the determination of position and Ap is the uncertainty in the
determination of momentum.
The consequences of the uncertainty principle are far reaching and probably take the place
of exactness in at.theory. That is why the principle is also known as probability principle.
This principle is important only for the motion of small particles like electrons, protons,
atoms, molecules etc. its effect is negligible for the motion of objects like balls, planets etc.
Why electron cannot exist in the nucleus? On the basis of Heisenbergs uncertainty principle, it can be
shown why electrons cannot exist within the atomic nucleus. This is because the diameter of the atomic
nucleus is of the order of 10
m. Hence if the electron were to exist within the nucleus, the maximum
uncertainty in its position would have been 10
m. Taking the mass of electron as 9.1 10
kg, the
minimum uncertainty in velocity can be calculated by applying uncertainty principle as follows:

This value is much higher than the velocity of light (viz 3 108 ms--1) and hence is not possible.
Quantum mechanics is a theoretical science which deals with the study of the motions of the
microscopic objects that have both observable wave like and particle like properties. Erwin
Schrodinger , in 1926, gave a wave equation to describe the behaviour of electron waves in atoms
and molecules. In Schrodinger wave model of atom, the discrete energy levels or orbits proposed by
Bohr are replaced by mathematical function , which are related with probability of finding
electrons at various places around the nucleus.
Schrodinger put the wave model or quantum mechanical model of atom forward. The behavior of
an electron is defined by the mathematical representation:

= (psi) is a wave function of space coordinates 'x', 'y', 'z' and represents the amplitude of the
electron wave.
m = mass of the electron
E = the total permissible energy level, which the electron can have.
V = potential energy of the electron given by ze
h = Planck's constant having the value 6.626 x 10
J s.
= (delta)stands for infinitesimal change.
Above equation may be rearranged to produce the eq.

where is a mathematical operator called Hamiltonian. Schrdinger gave a recipe of constructing
this operator from the expression for the total energy of the system. The total energy of the system
takes into account the kinetic energies of all the sub-atomic particles (electrons, nuclei), attractive
potential between the electrons and nuclei and repulsive potential among the electrons and nuclei
individually. Solution of this equation gives E and .
Important Features of the Quantum Mechanical Model of Atom
Quantum mechanical model of atom is the picture of the structure of the atom, which emerges
from the application of the Schrodinger equation to atoms. The following are the important features
of quantum mechanical model of atom.
1) The energy of electrons in atoms is quantised ( i.e., can have certain specific values).
2) The existence of quantised electronic energy levels is a direct result of the wave like
properties of electrons.
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3) Both exact position and exact velocity of an electron in an atom cannot be determined
simultaneously (Heisenberg uncertainty principle). The path of the electron in an atom can,
therefore, be never determined or known.
4) An atomic orbital is the wave function for an electron in an atom. Whenever an electron
is described by a wave function, we say that the electron occupies that orbital. Since many
such wave functions are possible for an electron, there are many atomic orbitals in an
atom. These orbitals form the basis of the electronic structure of atoms. In each orbital
electron has a definite energy. An orbital cannot contain more than two electrons. In multi-
electron atom, the electrons are filled in various orbitals in the order of increasing energy
For each electron of multi-electron atom, the electrons are filled in various orbitals in the
order of increasing energy. For each electron of multi-electron atom, there shall, therefore,
be an orbital wave function characteristic of the orbital it occupies. All the information
about the electron in an atom is stored in its orbital wave function Y and quantum
mechanics makes it possible to extract this information out of .
5) The probability of finding an electron at a point within an atom is proportional to the square
of the orbital wave function i.e., | |
at that point . | |
is known asprobability
density and is always positive. From the value of
| |
at different points within an atom , it is possible to predict the region around the
nucleus where electron will most probably be found .
Orbit and orbital are synonymous. An orbit , as proposed by Bohr , is a circular path around the
nucleus in which an electron moves. A precise description of this path of electron is impossible
according to Heisenberg's uncertainty principle. Bohr's orbits, therefore, have no real meaning and
their existence can never be demonstrated experimentally.
An orbital is a quantum mechanical concept and refers to the one electron wave function in
an atom. It is characterized by three quantum numbers (n , l and ml) and its values depends upon
the three coordinates of the electron. has , by itself, no physical meaning. Its square of the wave
function | |
which has a physical meaning. | |
at any point in the atom gives the value of
probability density at that point. Probability density | |
is the probability per unit volume and a
small volume (called a volume element) yields the probability of finding the electron in that volume
(the reason for specifying a small volume element is that | |
varies from one region to another
in space but its value can be assumed to be constant within a small volume element). The total
probability of finding electron in a given volume can be calculated by the sum of all the products
of | |
and the corresponding volume elements. It is thus possible to the probable distribution of
electron in an orbital.
An orbital may be defined as a region in space around the nucleus where the probability of
finding the electron is maximum.

The main difference between orbit and orbital are summed up below.
Orbit Orbital
1 It is a circular path around the
nucleus in which an electron
It is a region of space around the nucleus,
where the electron is most likely to be
2 It represents planar motion of
an electron.
It represents three-dimensional motion of
an electron around the nucleus.
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3 The maximum number of
electrons in an orbit is 2 n 2 ,
where 'n' stands for the
number of orbit.
An orbital cannot accommodate more than
two electrons.
4 Orbits are circular in shape. Orbitals have different shapes, e.g. s-
orbitals are spherically symmetrical,
whereas, p-orbitals are dumb-bell shaped.
5 Orbits are non-directional in
character and hence they
cannot explain shapes of
Orbitals(except s-orbitals) have directional
character and hence they can account for
shapes of molecules.
6 Concept of well-defined orbit is
against Heisenberg's
uncertainty principle.
Concept of orbitals is in accordance with
Heisenberg's uncertainty principle.
Quantum numbers:
The set of four index numbers required to define the state of an electron in an atom are called
quantum numbers. The Bohrs model introduced a single quantum number n to describe an orbit.
The quantum mechanical model uses three quantum numbers (n,l,m) to describe an orbital. The
three quantum numbers are the results of Schrodinger wave equation.
Principal quantum number:
It is designated by n and gives the number of principal shell to which an electron belongs. It
designates the average distance of the electron from the nucleus; hence this quantum number
represents the size of the electron orbit. The energy of the electron also depends upon this
quantum number.
The energy of different energy levels is given by the equation.
En = -1312 kJ mol


Where En represents the energy of the electron in nth level and n can have integral values
theoretically ranging from 1 to but practically only from 1 to 7. The energy levels are designated
as K, L, M, N, O, P, Q or 1,2,3,4,5,6,7
The maximum number of electrons in n shell is given by 2n
Azimuthal quantum number:
This quantum number is also known as the second, subsidiary, the lesser or the orbital quantum
number. It is designated by l.
Each shell is made up of number of sub-shells. The azimuthal quantum number describes
the subshell to which the electron belongs and also describes the shape of the orbital. For a
particular value of n , l can have values ranging from 0 to n-1. Since each value of l represents a
different subshell. Therefore l = 0 (s-subshell) l =1 (p-subsehll), l = 2 (d-subshell) and l = 3 (f-
The letters s,p,d and f have been derived from the names of the spectral lines sharp,
principal, diffused and fundamental respectively.
In a particular energy level the energies of its sub shell are in the order s, < p, < d< f. This is
attributed to the shielding effect of electrons.
Magnetic quantum number:
It is designated by m. This quantum number has been introduced to account for the Zemann
effect (i.e, splitting of spectral lines under the influence of an applied magnetic field)
A shell is made up of number of subshells and each shell is made of various orbitals. The
number of these orbitals is given by n

Where n represents the principal quantum number.
For a given value of l, there are 2l + 1 permitted values of m ranging from l through 0 to +l.
Thus for l = 0, m = 0 l = 1, m = -1, 0, +1; l = 2, m = -2, -1, 0, +1, +2; l = 3, m = -3, -2, -1, 0, +1, +2,
This means that s-sub shell will have 1, p-sub shell will have 3, d-sub shell will have 5 and
7 sub shell will have 7 values of m i.e. orbitals.
Spin quantum number:-
It is designated by s. This quantum number arises from the spectral evidence that an electron in
its motion around the nucleus in an orbit also rotates or spins about its own axis. This quantum
number gives the direction in which the electron is spinning clockwise (|) or counter clockwise (+).
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The values associated with clockwise and anticlockwise spins of the electron are +1/2 and 1/2

Aufbau Principle:
The word Aufbau is a German word which means building up. The building up means filling up of
orbitals with electrons. The principle states that in the ground state of the atom, orbitals belonging
to different sub shells are filled with electrons in the order of increasing energies. In simple words,
the orbitals of lower energy are filled first followed by the orbitals of higher energy. To decide about
energy of an orbital, the following two rules are used
(n + l) rule: The rule states that the orbital having lower value of (n + l) has lower energy than the
orbital having higher value of (n + l) where n and l are principal and azimuthal quantum numbers
respectively. e.g.,
3d 4s
n = 3 n = 4
l = 2 l = 0
(n + l) = 5 (n + l) = 4
The value of (n + l) is equal to 4 for 4s-orbital and 5 for 3d orbital. Therefore, 4s orbital has lower
energy than 3d orbital and will be filled first by electrons.
(n ) rule : This rule states that if two orbitals have same value of (n + l) then the orbital with lower
value of n has lower energy e.g.
2p 3s
n = 2 n = 3
l = 1 l = 0
(n + l) = 3 (n + l) = 3
The value of n is equal to 2 for 2p orbital and 3 for 3s orbital. Therefore, 2p orbital has lower
energy than 3s orbital and will be filled first by electrons.
The increasing order of energy of various orbitals is:
1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s, 5f, 6d, 7s -----.
This sequence is represented graphically in the below given figure.
This order of electron build up holds good in various elements but fails in certain cases
especially in transition and inner-transition elements.


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(II) (III)

Mnemonic diagram for the building up order (diagonal rule)
Paulis exclusion principle:
The number of electrons to be filled in various orbitals is restricted by the exclusion principle, given
by the Austrian scientist Wolfgang Pauli in 1925. The principle states that no two electrons in an
atom can have the same set of four quantum numbers. This implies that if two electrons in an
atom have the same values for three quantum numbers, then they must have different values of
fourth quantum number. The most important consequence of this principle is that an orbital can
accommodate not more than two electrons and that too with opposite spins.
This principle is helpful to determine the number of electrons present in an orbital, subshell and
shell e.g., an orbital can accommodate at the most two electrons with opposite spins, s,p,d and f
subshells can accommodate 2,6,10 and 14 electrons respectively i.e., 2(2 + 1) electrons and first,
second, third, fourth and fifth shells can accommodate at the most 2,8,18,32 and 50 electrons
respectively i.e., 2n
Inf:-According to thermodynamics, a system having lower energy is maximum stable.Therefore, the
state with the lower energy(opposite spins) is preferred and electrons entering the same orbital
must have opposite spins.
Hunds rule of maximum multiplicity:-
This rule deals with the filling of electrons into the orbitals of same subshell (i.e. orbitals of equal
energy, called degenerate orbitals). It states as under:-
The 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 subshell has got one electron each (i.e. is singly
occupied). Moreover, the singly occupied orbitals must have the electrons with parallel spins.
For example, there are three orbitals in the p. subshell i.e. Px, Py and Pz orbitals. If three
electrons are to be filled then there are three possible ways to do it.

Px Py Pz Px Py Pz Px Py Pz

Thus, according Hunds rule the last distribution (III) is correct.
The reason for such a tendency is that the electrons are negatively changed and repel each
other. In order to minimize, the forces of repulsion, they spread out and occupy the identical
orbitals singly with spins in the same direction (clock wise or anti-clockwise). Hence the energy is
minimum and stability is maximum. Further same spin leads to lower energy state and maximum
stability state.
Pairing occurs because less energy is needed to do so than the energy required to place the
electron in the next higher empty orbital.
{* Hunds rule is called maximum multiplicity rule because, out of the various electronic
configurations only that configuration is correct for which the total spin value is maximum e.g.
total spin of the unpaired electrons in configurations (I), (II) and (III) are: -
(I) + + = 11/2 (II) + - + = (III) }
Electronic configuration of elements:
The distribution of electrons into shells, sub shells and orbitals of an atom in the ground
state is called its electronic configuration. The following steps are used to write the electronic
configuration of elements.
The main energy level or shell (1,2,3-----) is written first.
The subshell (s, p, d or f) is written next.
The number of electrons in a particular sub shell is shown as the superscript to the sub shell. The
electronic configuration of first 30 elements is given below:

Unit- structure of atom
Paper A
Class 11
23 | P a g e
B y : A l t a f

Unit- structure of atom
Paper A
Class 11
24 | P a g e
B y : A l t a f

Stability of half filled and completely filled orbitals:
According to Aufbau principle, the outer configuration of Cr(Z = 24) is 3d
and that of Cu (Z =
29) is 3d
but the experimentally supported configuration is 3d
for Cr and 3d
, 4s
for Cu.
Unit- structure of atom
Paper A
Class 11
25 | P a g e
B y : A l t a f
The reason for these deviations are attributed to the extra stability associated with half filled or
completely filled orbitals.
Cause of extra stability
Following are the reasons for extrastability of half filled and completely filled orbitals
Symmetry of orbitals:
The configurations in which all the degenerate orbitals of the same sub shell are half-filled or
completely filled have symmetrical distribution of electrons. Such configurations are more stable
than those in which the distribution is not symmetrical. As symmetry leads to stability, such
electronic configurations are preferred.
Following configurations are stable.
Ne = 10

Cr = 24

Cu = 29

Exchange Energy:
In an atom, electrons present in various orbitals of the same sub shell tend to exchange their
positions mutually and during this process small amount of energy is lost, it is called exchange
energy. Larger the exchange energy greater is the stability. Maximum exchange of energy is
possible in half filled and completely filled sub shells so that maximum amount of exchange energy
is released in these configurations. This allows for greater stability in such symmetrical
configuration than the other symmetrical configuration. Thus electronic configuration 3d
, 4s
are preferred over respective 3d
, 4s
and 3d
, 4s