Chapter 5

ATOMIC STRUCTURE

Great Entities in the Universe:

Universe is made up of three great Entities: -
i. Matter
ii. Energy
iii. Space
Matter consists of atoms of different elements. According to Daltons atomic theory: -
Atoms are considered to be ultimate particles which could not be divided further.
But now it is proved that: An atom of an element consists of a number of sub-atomic
particles.
i. Neutrons and proton lie in the center of the atom known as Nucleus.
ii. Electrons revolve around nucleus.

Experiments which led to discovery of structure of atoms are

i. Experiments of electrolysis
ii. Discharge tube experiments
iii. Rutherfords scattering experiments
iv. Radioactivity
v. Artificial disintegration (artificial radioactivity)
vi. X-rays
vii. Spectroscopic studies

Nature of Charged particles

1. An electric current is the movement of charged

particles ina conductor.
2. Oppositely charged particles attract each other
and particles having similar charges repel each other.
3. Chrged particles moving between two m_____
plates or electrodes, one of which carries of positive charge and the other a negative charge
are deflected towards oppositely charged plates.
4. Charged particles when moving in a magnetic field
(e.g.) Between the two poles of a magnet are also deflected but at right angle to the lines
joining the north and south poles of magnet.
5. A sharp beam of charged particles can be obtained
by using silts or holes to screen out all particles except those traveling in the desired

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 direction.
6. As the charged particles are not visible, their
presence and direction of movement can be revealed by using a photographic film or
fluorescent material. A fluorescent material is a chmpound which emits faint visible light by
absofbing radiant energy.
7. The force of attraction or repulsion between two
charges can be determined by coulombs law.

Discovery of Electrons (Cathode rays)

Discharge tube experiment:

The tube is fitted with two metallic electrodes
acting as cathode and anode.
The tube is filled with a gas, air or vapors of a
substance at any desired pressure.
The electrodes are connected to a source of high
voltage.
The exact voltage required depends upon the
length of the tube and pressure inside the tube.
The tube is attached to a vacuum pump by means
of a small side tube so that conduction of electricity may be studied at any vlaue of low
pressure.
A silt is placed in the tube, if necessary to get a
sharp beam of radiation.
Experiment:
William Crooks a British Scientist studied the passage of
electricity through gases taken at different pressures in the gas
discharge tube. He observed that air taken in the gas dischage
tube at ordinary pressure did not allow the electricity to flow,
even when a source of high potential of about 5000 volts was
used. However, when pressure of air was reduced by removing
most of the air from the dischage tube and high voltage of 5000 10000 volts is applied then it
allowed the current to flow and emitted light (as in neon sign). When pressure was reduced
further to about 0.01 torr, then emission of light by air ceases. But current still flows between the
electrodes and produce flurescent on stricking the glass walls opposite to the cathode. The color of
the glow of the fluorescence produced on the walls of the glass tube, depencs upon the
composition of glass. This was the result of rays emitted by cathode.
Rays emitted by cathode when electricity is passed through a gas taken in the discharge
tube at very low pressure are called Cathode Rays.
Conclusion:
The electrons were first identified in a cathode ray tube, also known as Electric discharge
tube by J.J Thomson. He calculated the mass of cathode rays. He suggested that these rays are

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matter and not electromagnetic radiations. He proposed the name corpuscles for these particles.
But as these particles were found similar to the particles present in the electricity, therefore, later
on they were named electorns. J.J. Thomson won the 1906 Nobel prize in physics for the discovery
of electron.
Emission of cathode rays does not depend on the nature of the electrodes or the gas used in
discharge tube. This indicates that cathode rays (i.e.) Electrons are constituent of all types of
matter.

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 Properties of Cathode Rays

Experiemnts show that these rays behave like particlesin motion. They possess mass, move
in straight lines and are capable of penetrating very thin metallic sheets. They are also deflected in
electric and magnetic fields in a manner that they are negatively charged.
1. Negatively Charged:
Cathode rays are fast moving negatively charged. It was
demonstrated by J. Perrin in 1895. He showed that
cathode rays are neither attracted nor repelled in a
magnetic field but are deflected perpendicular to the
line joining the two poles of magnet.

In 1897 J.J Thomson established their electric charge by

the application of electric field. When cathode ray
particles are subjected to the effect of an electric field
created by two charged metal plates inside a cathode ray
tube. The particles are deflected towards positively
charged plate.
Thomson found that be carefully controlling the cahrge
on the plates when the plates and the magnet were both
around the tube, he could make the cathode rays strike at central point again. In other
words he was able to cancel the effect of the magnetic filed by applying an electric field
that tended to bend the path of the cathode rays in the opposite direction.
These negatively charged particles were called electrons by Stoney in 1891.
2. Casting a Shadow:
Hittorf in 1869 observed that opaque objects placed in the parth of these rays inside
the tube cast shadow. This proves that they travel in a straight line perpendicular to
the surface of cathode.
3. Kinetic energy and Momentum:
Crooks in 1870 demonstrated that cathode rays are actually streams of particles which
possess kinetic energy and momentum. This is proved by the fact that these rays can
drive a small paddle wheel placed in their path. Thus cathode rays are not rays but
material particles having a difinite mass and velocity.
4. Flurescence:
They produce greenish fluorescence on striking the walls of the glass tube. These rays
also produce fluorescence in rara earth metals and minerals when placed in the parth
of these rays. Aluminia glows red and tin stone glows yellow.
5. Heating Effect:
Cathode rays can produce heat when they fall on matter (e.g.) when cathode rays from
a concave cathode are focused onplatinum foil, it begins to glow.

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 6. Production of X-rays:
Cathode rays can produce X-rays when they strike an anode, particularly with large
atomic mass.
7. Ionization:
Cathode rays can ioniz gases.
8. Reducing Effect:
Cathode rays can cause chemical change because they have reducing effect.
9. Nature of Cathode rays:
The nature of cathode rays is the same irrespective of the gas used in the tube.
10. Charge to mass Ratio:
The e/m value of cathode rays shows that they are simply electrons.
11. Cathode rays can pass through a thin metal foil like aluminum or gold foil.

Measurement of e/m value of electron

J.J. Thomson measured the e/m value of electrons in 1897 by an instrument called
Discharge tube by adjusting the electric and magnetic fields in such a way that cathode rays again
hit central point.
He found that e/m of electron is = 1.7588 x 1011 coulombs /kg
This means that 1 Kg of electrons have -1.7588 x 1011 coulombs of charge.
It was also shown that the particles (electon) had the same charge to mass (e/m) ratio and
independent of the kind of gas in the discharge tube and the materials of the electrodes. Also
electons from other sources yield the same e/m ratio. These facts indicate that the electron is the
basic constituent of all atoms.
Mass of electron:
When values of charge and e/m ratio are known then we can calculate the mass of electron
which comes to be = 9.1095 x 10-31Kg
Mass of electron compared with mass of hydrogen atom is much less.
Mass of hydrogen = 1.674 x 10-27 Kg/atom
Hydrogen atom is the Smallest and Lightest Atom
Particle Charge (C) Relative Charge Mass (Kg) Mass (amu)
Proton +1.6022 x 10-19 +1 1.6726 x 10-27 1.0073
Neutron 0 0 1.6750 x 10-27 1.0087
Electron -1.6022 x 10 -19 -1 9.1095 x 10-31 5.4858 x 10-4 (0.00055)
Our present information indicates that the dimeter of atom is some what greater than 10 -
10 m and an atom contains very tiny nucleus with a diameter less than 10 14 m or about 1/1000
that of an atoms as a whole.

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 Measurement of Charge on Electron

Knowing the values of m and e/m, one can calculate the cahrge of the particle(e). The
calculated value of e is 1.602 x 10-19C. This value agrees with the calculated electronic charge
basedon Faradays Discoveries.
Coulomb (C):
It is the charge passed at a given point when a current of one ampere flows for one second.
Millikans Oil Drop Method:
Millikan determined charge to mass ratio by his oil drop experiment. He found that
charge of an electron is = 1.6022 x 10-19 coulombs
He stated that all electrons bear the same charge. This smallest charge on any droplet is the
charge of one electorn. The other drops having more than one electron on them, have double or
triple the amount of this charge. The charge present on an electron is the smallest charge of
electricity that has been measured so far.
Charge on electron can be deduced from the known value of Faradays Constant and
Avogadros number.
One Faraday equals 96.485 x 104C as was note earlier by Faraday from his Laws of
electrolysis. Also one Faraday is the charge carried by one mole of electrons. The charge on one
electron may be calculated by dividing one Faraday by Avogadros number (i.e.).

Discovery of Proton (Positive rays or Canal rays)

As the atom was considered neutral, therefore, soon after the discovery of negatively
cahrged particles (i.e.) Electrons, scientists tried to discover a positively charged constituent of
atom.
In 1886, Eugene Goldstein used a discharge tube with
perforated cathode. When a large potential difference is
applied between electrodes, it is observed that while cathode
rays are traveling away from cathode, there are other rays
produced at the same time. He observed a glow in the region
behind the cathod. This glow was due to rays which were
striking the glass wall after passing through the holes of cathode. The rays were named canal rays
because they pass through the canal or opening into cathode. These rays are known as Positive
rays.
Reason for the Productionof +ve rays:
Canal rays of positive rays are the cations which move towards the cathode and these were
produced when high speed cathode rays (electrons) struck the molecules of a gas enclosed in the

6
discharge tube. The knocked out electrons from the gasmolecules and positive ions were produced
whtih started moving toward the cathode.
M + e- M+ + 2e-
Ne(g)Ne+(g) + e-
The above-discussed experiments established the electrical character of matter, electrons
and protons are constituents of all atoms. Atoms and molecules however are electrically neutral
particles.thus each atom must somehow contain a positively charged portion to balance its
negatively charged electrons.

Properties of Positive rays

Experiments showed that unlike electrons, the properties of a positive ion are
characteristic of the gas in the discharge tube.
1. They are deflected by electric as well as a magnetic field in such a way that they are
positively charged.
2. These rays travel ina straight line in a direction opposite to the cathode rays.
3. They produce flashes on ZnS plate.
4. The e/m ratio for the positive rays is always smaller than that of electrons.
5. The positive ion produced by ionization of an atom are by no means equal in mass. Infact
the relative mass of the electron is so small that the mas of the positive ion is almost equal
to that of the atom from which it was formed. E/m ratio of positive rays depend upon the
nature of gas used in the discharged tube. Heavier the gas, smaller the e/m value. When
hydrogen gas is used in the discharge tube then e/m value is found to be the maximum in
comparison to any other gas because value of mass is lowest for positive rays obtained
from the hydrogen gas.
6. Hence the positive particles obtained from the hydrogen gas is lightest among all the
positive particles. This positive particle carries a cahrge equal to that of an electrons but
opposite in sign. Hydrogen atom strapped off its electron is lightest particle proton (H+)
e/m ratio of positive ions of other gases was found to be some simple multiple of e/m ratio
of the atom of hydrogen. Similarly the removal of two electrons from a helium atom (He)
produces an alpha particle (He2+).
7. This particle is called proton, a name suggested by Rutherford. The mas sof the positive
particle is never less than that of a proton.
8. The mass of a proton (Hydrogen) is 1836 ______ more than that of an electron.

Discovery of Neutron

The proton and electron were discovered in 1886 and their properties were completely
determined till 1895. It is very strange to know that upto 1932, it was thought that an atom was
composed of only electrons and protons. Rutherford predicted in 1920 that some kind of neutral

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particles having mass equal to proton must be present in an atom because he noticed that atomic
masses of atoms could not be explained if it were supposed that atoms had only electrons and
protons. Chadwick discovered neutron in1932.
Experiment:
A stream of aprticles produced from polonium source was directed at beryllium (94Be)
target. It was notieced that some penetrating radiations were produced. These radiations were
called neutrons because the charge deector showed them to be neutral. The nuclear reactionis as
follows:
42He + 94Be 126C + 10n

Actually particles and the nuclei of Be are rearranged and extra neutron is emitted.
Neutron has a mass of 1.0087 amu while the mass of proton is 1 amu.
According to the Model of the atom that resulted from Moseleys Work, the nucleus of a
hydrogen atom (Z = 1) has a charge of +1 and therefore, contains one proton. An electron that
balances the charge on the nucleus occupies the remaining volume of the atom.
Since mass of a hydrogen atom is about 1 amu and the mass of an electron is negligibly
small, the mass of a proton must be about 1 amu. Amu stands for atomic mass unit which is 1/12th
the mass of Carbon-12 atom. Its value is 1.6 x 10-27 Kg. However, this does not account for the
mass of an atom is usually at least twice as large as the mass predicted from its atomic number
except for ordinary hydrogen atom. Aluminium, for example has an atomic number of 13 but the
average mass of aluminum atom is about 27 amu. There are two possibilities.
i. Firstly we can assume that the nucleus of an aluminium (Al) atoms contains 27 protons and
14 electrons, for a net positive charge of +13. Anotehr 13 electrons that would balance the
net positive charge on the ucleus would then surround the nucleus. This assumption is not
valid as electrons are not found in nucleus.
ii. Secondly we can assume that nucleus of an Al atom contains 13 protons and 14 other
particles that have the same mas as that of a proton but are electrically neutral.

Properties of Neutron

1. Free neutron decays into a proton with the emission of an electron and a neutrino.
1on 1+1P + o-1e + oon

2. Neutrons cannot ionize gases.

3. Neutrons are highly penetrating particles.
4. They can expen high speed protons from paraffin, water, paper and cellulose.
5. When neutrons travel and have the energy 1.2 Mev then they are called fast neutrons but
with energy below 1ev are called slow neutrons. Slow neutrons are usually more
effective than fast ones for the fission purposes.
6. When neutrons are used as projectiles, they can carry out the nuclear reactions. A fast
neutron ejects an particles from the nucleus of nitrogne atom and boron is produced along
with particles.

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 147N + 1on 115B + 42He
7. When slow moving neutrons hit the Cu metal then radiations are emitted. The radioactive
Cu is converted to Zn.
8. Neutron is captured by the nubleus of 6529Cu and 6629Cu is produced. This radioactive
Copper emits an electron (beta particle) and its atomic number increases by one unit.
Because of their intense biological effects they are being used in the treatment of cancer.

Discovery of Nucleus (Rutherfords Model)

Lord Rutherford in 1911 performed a classic experiment. He studied the scattering of high
speed particles which were emitted from a radioactive metal (radium or polonium).
Experiment:
Alpha particle sis a helium nucleus stripped off its electrons (two positive charges and
mass of 4 amu). A beam of particles is directed on to a gold foil 0.00004cm (0.0000004m)
thickness as target through a pinhole in lead plate.
A photographic plate or a screen coated with zinc sulphide was used as detector, whenever
an particle struck the screen, a flash of light was produced at that point. It was observed that:
1. Most of the particles went throught he foil undeflected.
2. Some (one in 20000) were deflected at fairly large angles and 3). Few were deflecting
backward.
Observation:
Path 1: Majority of alpha particles pass through straight shows that lot of empty spaces in
atom.
Path 2: Alpha particles deflecting at various angles show the repulsion of Alpha particles
by a positive nucleus.
Path 3: Head on collision of an Alpha particle with something causes rebounding of alpha
particle shows the presence of central heavy portion of atom which Rutherford
called as nucleus.
Finally Results of experiments may be summarized by saying that in solids, positively
charged centers (nuclei) are evenly distributed through out solid with lot of empty space in
between (i.e) nucleus is extremely small as compared to the size of atom. We can consider the
nucleus as pont charge.
On the basis of these expereimental observations, Rutherford proposed the planetry model
(similar to the solar system) for an atom in which a tiny nucleus is surrounded by an appropriate
number of electrons. Atom as a whole being neutral, therefore, the nucleus must be having the
same number of protons as number of electrons surrounding the nucleus.
Conclusion:
In Rutherfords Model for the structure of an atom, the outer electrons could not be
stationary. If they were, they would gradually be attracted by the nucleus till they ultimately fall
into it. Therefore, to have a stable atomic structure, the electrons were supposed to be moving
around the nucleus in closed orbits. The centrifugal force kept the nuclear force of attraction

9
balanced.the nuclear atom of Rutherford was a big step ahead thwards unerstanding the atomic
structure but the behavior of electrons remained unexplained in the atom.
Planks Quantum Theory

Introduction:
In 1900, Max Plank proposed theory to explain the emission and absorption of radiations.
These radiations are given off by heated objects. According to his revolutionary hypothesis, energy
travels in a discontinuous manner and is composed of large number of tiny discrete units
called Quantu.
Main Postulates:
The main postulates of his theory are:
1. Energy is not emitted or absorbed continuously Rather it is emitted or absorbed in a
discontinuous manner and in the form of wave packets. Each wave packet or quantum is
associated with a definite amount of energy. In case of light, the quantum of energy is
often called photon.
2. The amount of energy associated with a quantum of radiation is proportional to frequency
of the radiation.

Where h is a constant known as Planks constant and it is equal to 6.625 x 1034 joule sec.
Planks Constant:
Ratio of energy and frequency is called .
Frequency:
Number of waves passing through a point per second.
3. A body can emit or absorbe energy only interms of integral of a quantum.

The frequency v is related to the wavelength of the photon as

Thus
Wavelength:
distance between the adjacent crest or troughs is called .
Units:
Ao or m or nm or pm (1Ao= 10-10m, 1nm = 10-9m = and 1pm = 10-12m)
Greater the wavelength associated with the photon, smaller is its energy.
Wave number:
Number of waves per unit length is called . It is reciprocal of wavelength.
Units:

So the energy of a photon depends up a frquency, wavelength and wave number.

Greater the wave number of photons, greater is the energy associated with them.

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 Atomic Structure

The experiments described so far in connection with electrons and nucleus may be
summarized below:
1. The electron is a particle carrying negative charge with a mass about 1/1836 that of
hydrogen atom. Electrons occupy most of the space in an atom.
2. The proton, an integral part of nucleus is positively charged with a mass equal to a H
atom. It has a very small volume like that of nucleus itself.
3. The neutron is neutral, it caries no electric charge and possesses about the same mass as
that of hydrogen. It is also part of the nucleus.
Using electrons, protons and neutrons we begin to make the picture of atoms. The mass
(Proton + Neutrons) concentrate in the nucleus while the electrons fill the empty space around.
The total umber of negative and positive charges in an atom is equal to make the atom neutral.
The structure of any atom is written down in terms of the number of electrons, protons and
neutrons it contains.
Usually mass number is written on top left hand side of the symbol and the atomic number
on bottom left hand side, thus helium with mass number 4 and atomic number 2 is writen as 42He.
A particle (He nucleus that has lost two electrons) is called Alpha particle and is written as 42He2+.
Rules:
i. The nubmer of proton is equal to the Atomic number (Z)
ii. The number of electrons in a neu________ atom is equal to the nubmer of protons.
iii. The mass number (A) of the atom is equal to the sum of the number of protons and
neutrons in the nucleus.
Mass number (A) = number of protons + number of neutrons
iv. The number of neutrons (N) is equal to the difference between the mass numbe (A)
and atomic number (Z)
Example:
Calculate nubmer of electrons, protons and neutrons in each of the following. 126C,
199F and 2412Mh2+

1. Carbon has atomic number (Z) six and mass number (A) 12, therefore, proton = 6,
electrons = 6, N = 12 6 = 6
2. Fluorine has atomic number 9, mass number 19, therefore, proton = 9, Electrons =
9, N = 19 9 = 10
3. Divalent Magnesium ion (Mg2+) has atomic number 12, mass number 24,
therefore, proton = 12, N = 24 12 = 12 but the number of electrons is 10, as Mg2+
has already lost two of its valence electrons.

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 Atomic Models

J.J Thomson Atomic Model:

The first attempt to account for the presence of electrons in atoms was made by J.J
Thomson in 1904. He pictured as a sphere of postiive electricity in which were embedded a
number of electrons equal to the positive charge. Since the number of positive charges equals the
number of negative charges (Electrons) the atom has no net charge. It is electrically neutral. But as
we mentioned above, the mass of an electron is exceedingly small compared to the mass of an
atom. This means that nearly all the mass of an atom is associated with the positive charge. This
model was no accpeted, as it did not explain the known facts associated with atom, at that time.
Rutherfords Atomic Model:
From the results of his experiment with scattering of alpha particles, Rutherford proposed
an atomic model comprising a heavy positively charged central part called nucleus and negatively
charged electrons revolving around the nucleus. This has an analogy with the solar system. Sun
being the central part and the planets revolving around it in empty space. Rutherfords work
provided a general model of the internal structure of the atom. However, his model did not explain
how the electrons are distributed and why atoms are stable? For example, why dont the electrons
fall into the nucleus or escape into space? To answer these questions, let us consider the simplest
atom, the Hydrogen atom. If the negative electron were stationary, the electrical attractive force
would cause it to fall into positive nucleus. Therefore, Rutherford suggested that the electrons
revolve about the nucleus (proton) just as the moon revolves around the earth. The electrons does
not escape into space because the attractive force acting on the electron prevents it from moving
away from its orbit (The circular path around the nucleus).
Although Rutherfords model explained the neutral character of atom and distribution of
mass but could not explain the rearrangement of electrons, chemical properties and their
periodicities. Further consideratio nof Rutherford model confronted another dilemma. We know
that the hydrogen atom consists of charged particles (an electron and a proton). According to
classical mechanics a revolving charged object, should radiate. Thus the revolving electron should
lose energy and spiral towards the proton. In doing so, it should emit energy in a continuous
fashion and for finally into the nucleus. Rutherfords theory thus incorrectly predicts a continuous
spectrum and a collapsing atom. This model could not explain the atomic spectra of hydrogen
which showed discrete spectral lines.

Bohrs Model of atom

In 1913, Neil Bohr put a new atomic model by assembling the quantum theory of plank and
solar idea of Rutherfore. He proposed that electron in hydrogen atom can only exist in cretain
permitted quantized energy levels. Bohr theory successfully explained the line spectrum of the
H-atom, was the proof of his theory. His calculated wavelengths agreed perfectly with the
experimental wavelengths. This was the begning of the classical quantum mechanics. The main
postulates of Bohrs atomic model are:
1. Electrons revolve in circular path called orbits outside nucleus. Each orbit has a fixed

12
 energy and a quantum number is assigned to it. Orbit is also called energy level or shell or
energy state.
2. The electrons present in particula orbit do not radiate energy. The energy is emitted or
absorbed only when an electron jumps from one orbit to another. These orbits with fixed
energies are called allowed enrgy state.
3. When an electron jumps, the energy, E is given by planks equation.
E = E2 E1 = hv
E is the energy difference of any two orbits with energies E1and E2.
* Energy is absorbed by the electron when it jumps from an inner orbit to an outer orbit
and is emitted when the electron jumps fromouter to inner orbit.
4. The electrons revolve in these orbits with a fixed angular momentum (mvr) which depends
upon the quantum number of the orbit. The angular momentum (mvr) is an integral
multiple of the factor h/2 (i.e.)

The permitted values of angular momentum are therefore , , ,

The electron is bound to remain in one of these orbits and not in between them. So angular
momentum is quantized.
By virtue of his postulates, Bohr was able to introduce quantization, quite arbitararily.
Let us consider how Bohr might have developed his model.
First, Bohr recognized that his first assumption violated the principles of classical
mechanics, but he also knew that it was impossible to solve this problem within the limits of
classical physics. For that reason, he was willing to assume that one or more of the principles
fromclassicle physics that operate on matter at the macroscopic scales might not be valid on the
microscopic (atomic) scale.
Second, he assumed that there were only a fixed numbeer of orbits or energy states in
which electrons can reside. He based this assumption on the fact that there are only limited
number of lines in the spectrum of the hydrogen atom and on his belief that these lines were the
result of light emitted or absorbed as an electron moved from one orbit to another into atom.
Third, Bohr restricted the number of orbits in the hydrogen atom by limiting the values of
the angular momentum of the electron. Any object moving along a straight line has a momentum
(mv). An objectmoving in a circular orbit has a angular momentum equal to the mass(m) times the
linear velocity(v) times the radius of the orbit(r) (i.e.) mvr. Bohr assumed that the angular
momentum of the electron could only take certain values given by the expression.

Based on these assumption, Bohr calculated the distance (radius) of the orbits and the
energy that an electron possess when placed in that orbit. When an electron (negatively charged
particle) revolves around the nucleus (positively charged part of the atom), two types of forces,
Centripetal and Centrifugal acts upon electron. The nucleus being heavy is supposed to be
stationary (rotation around the center of mass).

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 Derivation of Radius for nth Orbit

Bohr derived the expression for the radius of the orbit in hydrogen or ion like He+, Li+ etc.

Is the vacuume permittivity and its value is 8.84 x 10-12C2J-1m-1.

According to this equation:
Radius of an orbit is inversely proportional to square of its velocity.
It means that electron should move faster nearly to the nucleus in an orbit of smaller
radius. It also tells that if hydrogen atom has many possible orbits then the promotion of electron
to higher orbits makes it move with less velocity.
According to another equation, the radius of hydrogen atomis directly porpotional to the
square of number of orbit(n). So higher orbits have more radii and vice versa.
Final equation for radius of nth orbit is: r = 0.529Ao (n2)
By putting the values of n as 1, 2, 3, 4, The radii of orbits atom are: -
When n = 1 then r1 = 0.529Ao (Radius of first orbit is called Bohr Radius)
N = 2 then r2 = 2.11Ao n = 3 then r3 = 4.75Ao
N = 4 then r4 = 8.4Ao n = 5 then r5 = 13.22Ao
This shows that the distance between orbits of H-atom goes on increasing. The orbits are
not equally spaced. (i.e.) r2 r1< r3 r2< r4 r3< ..
a. The second orbit is four times away from the nucleus than first orbit.
b. Third orbit is nine times away and similarly
c. Fourth orbit is 16 times away from the nucleus.
Example:
Calculate the radius of 3rd orbit of electron in hydrogen atom.
Using formular = 0.529Ao (n2) therefore, r3 = 0.529Ao (3)2
r3 = 0.529Ao (9) = 4.76Ao

Energy of Revolving Electron in nth orbit of hydrogen

The total energy of an orbit is composed of two parts; the kinetic energy and potential
energy. Final equations for energy of nth orbit comes to be

This equation gives the energy associated with electron in the nth orbit of hydrogen atom.
Its negative value shows that electron is bounded by the nucleus (i.e) electron is under the force of
attraction of nucleus.

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The value of energy obtained for the electron is in joules/atom. If this quantity is multiplied by
Avogadros number and divided by 1000 the value of En will become

Thus E1< E2< E3

The value of energy difference between adjacent orbits can be calculated as follows
E2 E1= (-328.32) (-1313.31) = 984.99 KJ/mole
E3 E2= (-145.92) (-328.32) = 182.40 KJ/mole
E4 E3= (-82.08) (-145.92) = 63.84 KJ/mole
The difference in the values of energy go on decreasing from lower to higher orbits.
E2 E1> E3 E2> E4 E3>
The energy difference betweenfirst and infinite levels of energy is calculated as
E E1 = 0 (-1313.31) = 1313.31 KJ/mole
1313.31 KJ/mole is the ionization energy of hydrogen. This value is the same as
determined experimentally.
These values show that the energy difference between adjacent orbits of Bohrs model of
hydrogen atom go on decreasing sharply. Keep in mind that distances between adjacent orbits
increase.
The first energy level, when the principal quantum number of the electron is one (n=1) is
known as the ground state of hydrogen atom. All other energy levels are known as excited state.
This is called Energy level diagram. Except ground state energy, the electronin anyother state is
called to be in excited state.
Energy Difference Between Levels:
We can claculate the energy difference between two given energy states of electrons in
hydrogen atom. It is common experience that, energy difference between two staed is worked out
by subtracting initial state from final state. E = Final Initial
When the electrongains energy it jumps to higher energy states, the atomis said to be in
excited state.

Spectrum

15
 A visual display or dispersion of components of white light, when it is passed through a
prism is called .
Explanation:
When a radiation of light is passed through a prism, the radiation undergoes refraction or
bending or dispersion. Light is dispersed into different colors. Each color has a characteristic
wavelength called a Spectral line. Each wavelength can be seen on screen, or photographed or
detected by an appropriate electronic device. This pattern of spectral lines is called spectrum. The
device or experimental setup to study the dispersion of radiation is called spectroscope. The
extent of bending/dispersion of light depends upon the wavelength of photon.
* A radiation of longer wavelengthis bent to smaller degree then the radiation of a shorter
wavelength.
* Ordinary white light consists of radiations of all wavelengths, So after passing through the
prism, white light splits up into radiations of different wavelengths.
* The colors of visible spectrum are:
i. Violet
ii. Indigo
iii. Blue
iv. Green
v. Yellow
vi. Orange
vii. Red
The range from 400nm to 750nm (1nm = 10-9m)
In addition to visible region of the spectrum there are other seven regions of the spectrum.
Ultraviolet, x-rays, Gamma () rays, cosmic rays are towards lower wavelength end of the
spectrum and they possess photon with greater energy.
On the other side of the visible region, there lies infrared, Microwave, and radio frequency
regions are towards longer wavelength end of the spectrum and they posses photon with less
energy.

Types of Spectrum

1. Continuous Spectrum
2. Line Spectrum
1. Continuous Spectrum:
The spectrum in which boundary lines between the colors can not be marked because the
colors are diffused into each other is called .
Solids, liquids and dense gases glow at high temperature. If emitted light is examined with a
spectroscope, it willconsist of a continuous band of colors as observed in a rainbow. One
color merges into another without any dark space.
Example:

16
 i. The best example of continuous spectrum is Rainbow
ii. Light emitted by sun
iii. Light emitted from incandescent solids (electric light)
Thus Continuous spectrum is characteristic of matter in bulk. This kind of Emission
spectrum is typical of matter in which the atoms are closely together.
2. Atomic or Line Spectrum:
When an element or its compound is volatilized on a flame and the light emitted is seen
through a spectrometer, we see distinct lines separated by dark spaces. This type of
spectrum is called .
Gases at low pressure, as in neon sign, behave quite differently. If the light from neon sign
is examined with spectroscope, the resulting emission spectrum does not look like a
rainbow. Instead it consists of several isolated colored lines. This kind of emission
spectrum is called a line spectrum.
1. The number of lines and the distance between them depends upon the elements
volatilized (e.g.).
a. If a salt such as sodium chloride or sodium bromide, is sprayed on a flame, golden
yellow light is emitted. When this light is examined in a spectroscope, a line
spectrum is observed. Line spectrum of sodium is obtained from metallic socium,
socium chloride and sodium bromide.
b. Line spectrum of hydrogen consists of a number of different lines of different colors
having different distances from each other.
2. Line spectrum is charateristic of an atom, thus line spectrum of an element is
characteristic of that element regardless of its source. Sodium always yields the
same line spectrum, differing from that of all other elements. It is thus the atoms of the
element that emit the line spectrum. There the study of the spectra of elements are
important is determining the structure of atoms.
3. It has also been observed that distance between the lines decreases with the decreasein
wavelength and spectrum becomes continuous after a certain value of wavelength.
4. Atomic spectrum can also be observed when elements in gaseous state are heated at
high temperature or subjected to an electric discharge.
5. Atomic spectra are highly ordered. The frequencies of the lines in the hydrogen atom
spectrum, for example can be represented by a relation involving whole numbers.

Where v is the frequency of line in sec-1, 3.2898 x 1015 sec-1is a constant for hydrogen
known as Redberg constant a and b are two numbers such that b > a. Thus when a = 1, b may be
any whole numbers greater than 1 and each value of b yields a frequency (v) corresponding to a
line in the spectrum of hydrogen. When a = 2, b may be any whole number greated than 2, each
value yielding a frequency corresponding to a line in the hydrogen spectrum. This relationship for
atoms more complex than hydrogen is more complicated but each frequency can still be

17
represented as a difference of two frequency terms. The atoms therefore emit or absorbed only
photons of definite, characteristic frequencies, or energies depending upon the values of whole
numbers a and b. this restriction means that the energy absorbedor emitted by atoms is
quantized. Unlike an automobile that can accelerate continuously so that it passes through all
speeds from zero km/h to say 90km/h. An atom cannot emit photons over a continuous range of
energies (Frequencies). Spectra can be explained only by quantum mechanics.
There are two ways in which an atomic spectrum can be viewed.
1. Atomic emission spectrum
2. Atomic absorption spectrum
Atomic Emission spectrum:
When light emitted from a source is analyzed, the spectrum obtained is called Emission
spectrum.
When solids are volarilized or elements in their gaseous states are heated to high
tempearture or subjected to an electrical discahrge, radiation of certain wave lengths is emitted.
The spectrum of this radiation contained bright lines against a dark background. This is called
Emission Spectrum. This is a kind of specrum observed when the light from a neon lamp or a
sodium vapor street lamp is examined in a spectroscope. For example, the emission spectrum
obtained fromsodium vapor consists of two yellow lines on a black background.
Atomic Absorption Spectrum:
Spectrum obained after light from some source has pased through a substanceis known as
an Absorption spectrum.
When a beam of white light is passed through a gaseous sample of an element, the elements
absorbs certain wavelengths while rest of wavelengths pass through it. The spectrum of this
radiation is called Atomic Absorption Spectrum. The wavelengths of the radiation that have
been absorbed by the element appear as dark lines and the back ground is bright.
It is intresting to note that the positions of the wavelengths of lines appearing in both
emission and absorption spectral are exactly the same. In emission spectra the lines appear bright
because the corrsponding wavelengths are being emitted by the element. Where as they appear
dark in absorption spectra because the wavelengths are being absorbed by the element.
Differences between Contineous and Line Spectrum
Properties Contineous Specrum Line Specrum
1. Definition Such a spectrumin which one Such a spectrum in which
color merges into another distinct lines are separated by
without any dark space is dark spaces is called .
called .
2. Formation This spectrum is obtained This spectrum is obtained
fromlight emitted by sund or from eleemnts or its
incandescent solids (Electric compounds whtn volatized on
light). flame.
3. Visual Scene This spectrum is seen through This spectrum is seen through
naked eye. spectrometer.
4. Characteristi This specrum is charactristic This spectrum is
c of matter characteristic of atom.

18
 5. Types This spectrum has no special This spectrum is of two types.
type. i. Emission spectrum
ii. Absorption spectrum
6. Examples Rainbow Line spectrum of sodium
contains two yellow colored
lines separated by definite
distance.

Hydrogen Spectrum

Hydrogen spectrum is an important example of atomic (Line) spectrum. Hydrogen is filled

in a discharge tube at a very low pressure. A bluish light is emitted from the dischage tube. This
light when viewed through spectrometer, shows several isolated sharp lines.
These are called Spectral lines. The wavelength of these lines lie in visible, ultraviolet and
infrared regions. These spectral lines can be classifies into five groups called Spectral series.
These series are named after their discoverers as given below:
1. Lyman series (Ultraviolet Region)
2. Balmer series (Visible Region)
3. Paschen series (Infrared Region)
4. Brackett series (Infrared Region)
5. Pfund series (Infrared Region)
The first four series were discovered before Bohrs Atomic model (1913).
Wave number (m-1) of spectral lines fromLymen series to pfund series decreases.
The lines of Balmer sereis have been given specific names as H line, H line, H line, H$ line.
Lymen Series Balmer Series Paschen Series Bracket Series Pfund series
82.20 x 105 15.21 x 105 (H 5.30 x 105 2.46 x 105 1.34 x 105
line)
97.60 x 105 20.60 x 105 (H 7.80 x 105 3.80 x 105 2.14 x 105
line)
102.70 x 105 23.5 x 105 (H line) 9.12 x 105 4.61 x 105
105.20 x 105 24.35 x 105 (H 9.95 x 105
line)
106.20 x 105 25.18 x 105 (H
line)
107.10 x 105

Origin of Hydrogen Spectrum on the basis of Bohrs Model

Accroding to Bohr, Electrons inhydrogen atom may revolve in any orbit depending upon its
energy.
1. When hydrogen gas is subjected to electric discahrge, its electrons move from one of the
lower orbits to higher orbits absorbing particular wavelength of energy.

19
 2. Subsequently when it comes back, the same enegy is released. This energy is observed as
readiation of particular wavelengths in the form of birght lines seen in the emission
spectrum of hydrogen gas.
3. The energy of the light emitted or absorbed is equal to the difference between the energies
of the two orbits.
E = Final state - Iitial state
Since the energy of the electron is quantized, the hydrogen atom can emit or absorb only
photons whose energy is equal to the difference between two energy levels. A spectral line thus
originates when the electron Jumps or Frops from one energy level to another.
The spectral lines of Lymans Series are produced when the electron jumps from n = 2, 3, 4,
to n = 1.
Similarly spectral lines of Balmer series discovered in 1887 originated when an electron
jumps from n = 3, 4, 5 etc to n = 2 orbit.
In the same way Paschen, Brackett and Pfund series of lines are produced as the result of
electronic transition from higher orbits to 3rd, 4th and 5th orbits respectively.the spectral series
are:
Series n1 n2 Region
Lymen 1 2, 3, 4 ----- to UV
Balmer 2 3, 4, 5, ----- to Visible
Paschen 3 4, 5, 6, ----- to IR
Bracket 4 5, 6, 7, ----- to Far IR
Pfund 5 6, 7, 8, ----- to Far IR
General Formula of Wave number:

Here RH is called Rydberg Cosntant and its value is 1.097 x 107 m-1.
Lymen Series:

First Line:
P = 1 (lower orbir) n = 2 (Higher orbit)
Putting values in formula we get.

Second Line:
P=1 n=3
Putting values in formula we get.

Limiting Line:
P=1 n = (infinity)
Putting values in formula we get.

These all radiation lie in Ultraviolet region.

20
Balmer Series:

First Line:
P=2 n=3
Putting values in formula we get.

21
 Second Line:
P=2 n=4
Putting values in formula we get.

Limiting Line:
P=2 n = (infinity)
Putting values in formula we get.

The limiting line of Balmer series lies in U.V region where as all over lines fall in visible
region. Similarly we can calculate wave numbers for all the lines of Paschen, Brackett series and
Pfund series.

Defects of Bohr Model

1. Bohrs Theory can successfully explain the origin of the spectrum of H-atom and ions like
He+1, Li+2 and Be+3 etc. These are all one electron systems. But this theory is not able to
explain the origin of the spectrum of multi-electrons system like He, Li and Be etc.
2. Why are there only fixed number of orbits in which an electron can reside in a hydrogen
atom.
3. Why cant this model be extended to many electron atoms?
4. When the spectrum of hydrogen gas is observed by means of a light resolving power
spectrometer the individual lines are replaced by several very fine line (i.e.) Original lines
are seen to be divided into other lines. The H line in Balmer series is found to consist of
five component lines. This is called fine structure or multiple structure. Actually the
apperance of several lines in a single line suggests that only one quantum number is not
sufficient to explain the origin of various spectral lines.
5. Bohr suggested circular orbits of electrons around the nucleus of hydrogen atom, but
research has shown that the motion of electron is not in a sircle plane but takes place
inthree dimensional space. Actually the atomic model is not flat.
6. When the excited atoms of hydrogen which give an emission of line spectrum are placed in
a magnetic field, its spectral lines further split up into closely spaced lines. This type of
splitting of spectral lines is called Zeemans Effect. So if the source which is producing the
Na-spectrum is placed in a weak magnetic field, it causes the splitting of two lines of Na into
component lines. Similarly when the excited H-atom is placed in a electrical field, then
similar splitting of spectral line takes place which is called Stark Effect. Bohrs Theory does
not explain eithe Zeeman effect or Stark Efect.
The theory of Wave-particle duality developed by de Broglie eventually explained the
success of the Bohr model with atoms or ions that contained one electron and provided a
basis for understanding why this model failed for more complex systems.

22
 Summerfields Modification of Bohrs atomic Model

In 1915, Summerfield suggested that the moving electrons might

describe, in additions to the circular orbits, elliptical orbits as well, with
the nucleus situated at one of the foci of Ellipse. The elliptical paths of
moving electron go on changing their position in space and the nucleus
is buried by the electronic cloud from all the sides thus nucleus cannot be
seen from any side.

Elliptical orbits of Hydrogen atom

Radioactivity and Structure of Atom

Radioactivity:
It is the spontaneous disintegration of atoms of certain
elements into atoms of other elements with the emission of
smaller sub-atomic particles.
Discovered in 1897 by H. Bacqueral, radioactivity played an important role in determining
the structure of the atom. Some elements and compounds such as radium, uranium, thorium
spontaneously emit radiation owning to changes occurring in the nucleus and thus cause
fogging of photographic plates. Elements which emits such radiations are called radioactive
elements. It has been observed that three types of radiation are called radioactive elements. It has
been observed that three types of radiation are emitted during radioactivity. These are called
alpha (), Beta () and gamma () rays.
When passed through electric field, these rays behave as shown. Gamma rays are
undeflected while alpha rays are deflected towards negtive plate and beta rays towards the
positive plate. This clearly shows that gamma rays are neutral high energy light rays
(Electromagnetic radiations) capable of penetrating layer of mater opaque to ordinary light. While
alpha and beta rays are streams of charged particles. Alpha rays are positive charged helium
nuclei and Beta rays are negatively charged electrons. As shown in the figure alpha particles due
to larger mass are deflected relatively to a leasser extent than the beta particles.

Name Alpha rays Beta rays Gamma rays

Symbol
Nature Helium nuclei (He2+) Electrons High energy photons
Mass 6.65 x 10-27Kg (4amu) 9.11 x 10-31 Kg 0
Charge +2 -1 0 (No charge)
Velocity 1/10th velocity of light (3 x 107 m/sec) Velocity of light Velocity of light
Relative Being relatively heavy they can only Due to smaller size they On the account of non-
penetrating pass through thin layers of solids or a can penetrate a few mm meterial nature and high
power few centimeters of gas at atmospheric into metals. Their velocity, they are more
pressure. Its penetration power is low penetration power is 100 penetrating than and
(i.e.) 1 or 102 times greater than particles. 104
that of alpha rays.
Relative They are good ionizers of gases (i.e.) Their power of ionizing 1
ability to 104 the gaseous molecules is

23
 ionize air much less thanthat of
alpha particles (i.e.) 102
Deflection Deflected by electric and magnetic Deflected by Electric and Not deflected at all by
field magnetic field any of the field

Artificial Radioactivity:
Emission of radiation from nuclei of lighter atoms due to bombardment of moving particles
is known as Artificial radiactivity.
Example:
4Be9 + 2He46C12 + 0n1

7N14 + 2He48O17 + 1H1

In these nuclear reactions we have bombarded stable isotopes of 4Be9 and 7N14 with helium
nuclei or alpha aprtiles. As a result of this bombardment the nuclei of thse atoms are broken, new
atoms are produced and some radiations is emitted. This is artificial disintegration and it clearly
shows that atoms are divisible.

X-rays and atomic Number

X-rays:
The rays which are produced when rapidly moving electrons collide with heavy metal
anode in the discharge (Cathode ray) tube are called X-rays.
1. They were discovered by W.C Roentgen therefore,they also called Roentgen rays.
2. They are highly penetrating radiations.
3. They have very high frequency and very low wavelength.
Explanation:
Energy is released in the form of electromagnetic waves when the electrons are suddenly
stopped. In discharge tube, the electrons produced by a heated tungsten filament are accelerated
by high voltage. It gives them sufficient energy to bring about the emission of x-rays on striking
the metal target. X-rays are emitted from the target in all directions but only a small portion of
them is used for useful purposes through the windows. The wavelength of X-rays produced
depends upon the nature of target metal. Every metal has its own characteristic X-rays.

Comprehensive Study of X-rays by Mosley

Mosley in 1913 1914 studied x-rays emitted from38 different elements from Al to gold
which were used as target in x-ray tube. His research covered a range of wavelengths of 0.04 8
Ao and discovered discrete spectral lines of X-rays. These are grouped into K-series, L-series and M
series etc. Each series has various line as K, K, L, L, M, M etc.
Conclusions Drawn by Mosley:

24
 The spectral lines could be classified into two distinct groups. One of shorter wavelengths
is identified by K-series and the other of comparatively longer wavelengths are identified by L-
series.
If the target element is of higher atomic number the wavelength of x-rays becomes shorter.
Frequescies of the emitted X-rays depend upon the material of th etarget and that the
Frequency increases with theincreasein positive charges (number of proton) in the nuclei
of the target material. The results showed that the frequency of emitted X-rays increases by
one unit for an increase of positive charte (number of protons in the nucleus) by one unit.
Relationship between frequency of x-rays and atomic number of element emitting it is:

Here a and b are the constants characteristics of metal under consideration. This linear
equation is known as Mosleys Law. a is proportionality constant and b is called Screening
constnt of the metals.
Mosleys Law:
It states that The frequency of a spectral line in X-ray spectrum varies as the square of
atomic number of an element emmiting.
This convinces us that it is the atomic number and not the atomic mass of the element
which determines its both physical and chemical properties. If value of for K-series are plotted
against Z (atomic number) a straight line number.
i. Mosley arranged K and Ar, Ni and Co in a proper way in a Mendeleev periodic table.
ii. This law has led to the discovery of many new elements like Tc (43), Pr(61), Rh(45)
iii. The atomic number of rare earths have been determined by this law.

Wave Particle Nature of Matter (Dual Nature of Matter)

According to the planks quantum theory of radiations light shows a dual character (i.e.) it
behaves both as a material particle and as a wave. This idea was extended to matter particles in
1924 by Louis De-Broglie. According to de-Broglie all matter particles in motion have dual
character. It means that electrons, protons, neutron, atoms and molecules possess the
characteristic of both the material particles and a wave. This is called Wave particle duality. De-
Broglie derived a mathematical equaltion which relates the wavelength () of the electron to the
momentum of electrons.
De-Broglies Equation:

This equation shows that:

Wave length associated with an electron is inversely proportional to its momentum.
Example:

25
 1. Consider an electron which is moving with a velocity of 2.188 x 106 m/sec then the
wavelength associating with it, can be calculated from above equation which is:

This value of wavelength of electron while moving in 1st orbit of H atom is comparable to
the wavelength of X-rays and can be measured.
2. If we imagine that a proton moving in a stranght line with the same velocity as mentioned
for electron, its wavelength will be 1836 times smaller than that of electron.
3. Similarly and particles moving with the same velocity as electron should have a
wavelength 7344 times smaller as compared to that of electron.
4. Now consider a stone of mass 1gm moving with a velocity of 10 m/sec then its wavelength
will be:

This wavelength is so smaller that it cannot be measured by any method. It means that
heavy material particles have the waves but they cannot be captured and we say the
macroscopic bodies do not show wave motion.
Experimental Verification of Dual nature of Matter:
In 1927, two American Scientists, Davission and Germer did an experiment to verify the
wave nature of moving electron.
Davission and Germer proved that accelearated electrons undergo diffraction like waves
(X-rays) when they fall on nickel Crystal. In this way the wave nature of electrons got verified.

Heisenbergs Uncertainty Principle

According to Bohrs Theory, an electron a material particles and its position as well as
momentum can be measured with great accuracy. But with the advent of the concept of wave-
nature of electron, it has not been possible for us to measure simultaneously the exact position
and velocity of electron. This was suggested by Heisenberg in 1927.
Principle:
Suppose that x is the uncertainty in the measurement of position and p is the
uncertainty of momentum of an electron. Then

This relationship is called uncertainty principle.

* This equation shows that if x is small then p will be large and vice versa.
Comptons Effect can help us to understand the uncertainty principle. Suppose we wish to
determine the position of electron. Visible light cannot help us because the wvelength of visible
light is million times large as compared to diameter of electron. For this purpose we have to use X-
rays which have very short wavelength as compared to that of visible light. When this photon of X-
rays strikes an electron the momentum of electron willchange. In other words uncertainty of

26
momentum will appear due to change of velocity of electron. Smaller he wavelength of X-rays
greater will be the energy of the photon. Hence collision of X-rays with electron will bring about
greater uncertainty in momentum. When we use the photon of longer wavelength to avoid the
change of momentum, the determination of position of photon of electron will be impossible.
Concept of Orbital

The volume of space in which ther is 95% chance of finding an electron is called . OR
The region in space round the nucleus in which an electron with a specific energy is most
probably located is called Atomic Orbital.
The orbital can regardd as a spread of charge surrounding the nucleus. This is often called
the Electron cloud.
Electrons of different energies are likely to be found in different regions.
Explanation:
In Bohrs atomic picture the electrons are moving with specific velocities in orbits of
specified radii and accoridng to uncertainty principle both these quantities cannot be measured
experimentally. So Bohrs Atomic model does not appear to be satisfactory. A theory involving
quantities with cannot be measured does not solve this difficulty.
In order to solve this difficulty Schrodinger, Heisenberg and Dirac worked out wave
theories of the atom. The best known treatment is that of Schordinger.
He set up wave equation for hydrogen atom. According to schrodinger, although the
position of an electron cannot be found exactly. But there is probability of finding an electron at a
certain position.
The maximum probability of finding the electron is at a distance of 0.053nm. It is the same
radius as calculated for the Bohrs first orbit. There is a possibility that the electron is either closer
to the nucleus or outside the radius of 0.053nm where probability of finding electron decreases
sharply.

Quantum Number

Set of numerical values which specify the address (location) of electron in an atom is
termed as .
Explanation:
You know that a complete address of a person is decribed by his name, city in which he
lives, the block, street and the house number. On the similar basis, quantum number serve as
identification numbers or labels which completely describe an electron. These quantum number
specify position of electron in an atom.
* Quantum number describe the behavior such as energy of electron, shape of orbital and
orientation etc.

Types of Quantum Number

27
 1. Princi;e Quantum number(n)
2. Azimuthal Quantum number (l)
3. Magnetic Quantum number(m)
4. Spin Quantum number(s)
1. Principle Quantum number:
It gives us information about shell in which electron is revolving around nucleus.
2. Azimuthal Quantum number:
It has already been mentioned in the defect of Bohrs model that a spectrometer of high
resolving power shoes that an individual line in the spectrum is further divided into several
very fine lines. This thing can be explained by saying that each shell is divided into sub-
shells. So only principle quantum number (n) is not sufficient to explain the line spectrum.
There is another quantum number called Azimuthal quantum number and is used to
represent the sub-shells.
3. Magnetic Quantum Number:
In the defects of Bohrs Model, it has been mentioend that strong magnetic field splits the
spectral lines further. In order to explain this splitting, a third quantum number called
magnetic quantum number is required.
It shows orientation of orbital so it is also called orbital orientation quantum number.
S sub shell:
S sub shell is spherical and probability of finding the electron in all the directions from the
nucleus is the same. Thus s-sub shell is not subdivided into anyother orbitals.
P sub shell:
For P sub shell there are three orbitals which are oriented perpendicular to each other and
named as Px, Py and Pz. They have egg shaped lobes which touch each other at the origin.
They are disposed symmetrically alone one of the three axes called orbital axes.
In the absence of magnetic field all the three p-orbitals have the same energy and are
called degenerate orbital. Since they are three in number so these are said to be 3 fold
degenerate or triply degenerate.
d sub shell:
For d sub shell there are five degenerate orbitals. All these five d-orbitals are not identical
in shape. In the absence of a magnetic field all five d-orbital have the same energy and they
are said to be five fold degenerate orbitals.
f sub shell:
For f sub shell there are seven degenerate orbitals.
4. Spin quantum Number(s):
Alkali metals have one electron in their outermost shell. We can record their emission
spectra when the outermost electron jumps from an excited state to a ground state. When
the spectra are observed by means of high resolving power spectrometer, each line in the
spectrum is found to consists of a pair of lines, this is called Doublet line structure. We
should keep it in mind that doublet line structureis different from the fine spectrum of

28
hydrogen. Because doublet lines are widely separated from each other, while those of fine
structrue are closely spaced.
In 1925, Goudsmit and Yhlenbech suggested that an electron while moving in an orbital
around the nucleus also rotates or spins about its own axis either in a clock wise or
anticlockwise direction. This is called Self rotation. This spinning electron is associated
with a magnetic field and hence a magnetic moment. Hence opposite magnetic fields are
gnerated by the clockwise and anticlickwise spins o electrons. The spin motion of
electrons is responsible for doublet line structure in the spectrum.

Principle Quantum Azimuthal Quantum Magnetic Quantum Spin Quantum Number

Number Number Number
Definition: Definition: Definition: Definition:
Quantum number which Quantum number which Quantum number which Quantum number which
represents shell (energy represents the shape of represents orientation of represents clockwise or
level) in which electron orbitals is . orbital in magnetic field anticlockwise rotation of
revolves around nucleus is . electron in an orbital.
is .
Symbol: n Symbol: l Symbol: m Symbol: s
Mathematical value: Mathematical value: Mathematical value: Mathematical value:
N = 1, 2, 3, .. l = 0, 1, 2, 3, .. m = 0, +1, +2, +3, .. s = +1/2, -1/2
Mathematical Mathematical Formula:
Formula: m=2+1
l=n1
Number of shells: Number of shells: Number of orientation:
1st shell = K 1st sub-shell = s 1. l = 0 (s-sub shell)
2nd shell = L 2nd sub-shell = p m=0
3rd shell = M 3rd sub-shell = d 2. l = 1 (p-sub shell)
4th shell = N 4th sub-shell = f m = -1, 0, +1
5th shell = 0 Thus p sub shell has
Note: three degenerate orbitals
s = sharp 3. l = 2 (d-sub shell)
p = principal m = -2, -1, 0, +1, +2
d = diffused Thus d sub shell has five
f = fundamental degenerate orbitals
4. l = 3 (f-sub shell)
m = 0, +1, +2, +3
Thus f-sub shell has
seven degenerate orbitals
Number of e-s in Number of e-s in sub- Each degenerate orbital
shells: shells: carries a maximum of 2e-
It is determined by It is determined by: s
Bohrs Formula: 2(2l+1)
(2n2) So. So.
K = 2 e-s S = 2 e-s
L = 8 e-s P = 6 e-s
M = 18 e-s d = 10 e-s
N = 32 e-s f = 14 e-s
O = 50 e-s
Advantages: Advantages: Advantages: Advantages:
It tells us about: It tells us about: It tells us about: It tells us about doublet
1. Distance of electron Shape of sub shell Orientation of orbitals. line structurein
from nucleus. S = spherical shaped spectrum.
(Generater the value P = Dumb-bell shaped
of n, greater will be d = complicated
energy and electron f = more complicated
away from nucleus)
2. Size of shell

29
3. Energy of electron

30
 Table (5.3) quantum Numbers of Electrons
Principal Azimuthal Magnetic Quantum Spin Quantum Number of
Quantum Quantum number m number s electrons
numbeer n number l accommodated
1 K 0 s 0 + , - 2
0 s 0 + , - 2
2 L 8
1 p +1, 0, -1 + , - 6
0 s 0 + , - 2
3 M 1 p +1, 0, -1 + , - 6 18
2 d +2, +1, 0, -1, -2 + , - 10
0 s 0 + , - 2
1 p +1, 0, -1 + , - 6
4 N 32
2 d +2, +1, 0, -1, -2 + , - 10
3 f +3, +2, +1, 0, -1, -2, -3 + , - 14

Shapes of Orbitals

So far four types of robitals have been introduced depending upon the values of asimuthal
quantum number. These orbitals are:
s, p, d and f having azimuthal quantum number values as l = 0, 1, 2, 3 respectively.
Shape of s-orbital:
i. s orbital has a Spherical shape
ii. it is represented by a circle which is turn represents a cut of sphere.
iii. With the increase of value of principle quantum number(n), the size of s orbital incrases.
Example:
2s orbital is larger in size than 1s orbital.
iv. 2s orbital is further away from the nucleus.
v. The probability for finding the electron is zero between two orbitals. This place is called
nodal plane or nodal surface.
Shape of p-orbital:
There are three valuesof magnetic quantum number for p sub-shell. SO P sub-shell has
three orientations in space (i.e.) along x, y and z-axis. All the three p orbitals namely Px, Py and Pz
have dumb-bell shape. So p-orbitals have directional character which determines the geometry of
molecules. All the p orbitals of all the energy levels have similar shape but with the increase of
principle quantum number of the shell their sizes are increased.
Shapes of d-orbitals:
For the d sub-shell there are five values of magnetic quantum number. So there are five
space orientation and it can be arranged in space in five different ways along x, y and z-axis. They
are designated dxy, dyz, dxz, dx2 y2, dz2.
They are not idential in shape. Four d orbital out of these five contain four lobes while the
fifth orbital dz2 consists of only two lobs.

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 In the absence of magnetic field all the five d-orbitals are degenerate. The shape of f-
orbitals are very complicated.

Electronic Configuration

The distribution of electrons in an atom takes place according to the facts.

An orbital like s, px, py, pz and dxy etc can have at the most two electrons.
The maximum number of electrons that can be accommodated in a shell is given by 2n2
where n is principal quantum number.
Electronic Configuration:
Arrangement of electrons in shells, sub-shells and orbitals intheir ground state is called .
Atom is in the ground (most stable) state of its atom when the electrons in the atom are at
the lowest energy level.
The following rules are used to determine the ground state electronic configuration of an
elements.
1. The Auf bau principle
2. Paulis exclusion principle
3. Hunds rule
Wiswessors Rule:
The sub shells should be arranged according to (n + l) sub-shell have same (n + l) values
then the subshell is placed first whose n value is smaller. The arrangement of sub-shells in
ascending order of their energy may be as follows:
1s, 2s, 3p, 3s, 3p, 4s, 5s, 4d, 5p, 5s, 4f, 5d, 6p, 7s and so on.
Thus the single electron in a hydrogen atom must be placed in the 1s orbital.
Attangement of orbitals According to n + rule
n l n+l
1s 1 0 1+0=1
2s 2 0 2+0=2
2p 2 1 2+1=3
3s 3 0 3+0=3
3p 3 1 3+1=4
3d 3 2 3+2=5
4s 4 0 4+0=4
4p 4 1 4+1=5
4d 4 2 4+2=6
4f 4 3 4+3=7
5s 5 0 5+0=5
5p 5 1 5+1=6
5d 5 2 5+2=7
5f 5 3 5+3=8

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 6s 6 0 6+0=6
6p 6 1 6+1=7
6d 6 2 6+2=8
6f 6 3 6+3=9
7s 7 0 7+0=7

Auf Bau Principle

This principle states that:

The electrons intheir ground states occupy orbitals in order of the orbitals energy levels
(i.e.) the lowest energy orbitals are always filled first. OR
The electrons should be filled in energy sub-shells in order of increasing energy values.
The order of filling orbitals is shown in figure:

Paulis Exclusion Principle

This states that no two electrons of an atom can have the same values of the four quantum
numbers. OR
It is impossible for two electrons residing in the same orbital of a poly electron atom to
have the same value of four quantum numbers. OR
Two electrons in the same orbital should have opposite spins.

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 Hunds Rule

It states that if more then one degenerating orbitals are available the electron will prefer
to occupy different orbitals with same spins rather to occupy same orbital with opposite spin.
According to this rule the two electrons in 2p sub shell of carbon will be distributed as
follows:
6C = 1s , 2s , 2Px , 2Py , 2Pz

The three orbitals of 2P sub-shell are degenerate.

Electronic Configuration of some elements

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