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ATOMIC STRUCTURE
1

Dalton, in 1808 proposed Dalton’s atomic theory and according to theory matter was made
up of extremely small, indivisible particles called atoms. However the researches done by
various scientists like J.J. Thomson, Goldstein, Rutherford, Chadwick, Bohr and others in the
later half of the 19th century and in the beginning of the 20th century have established, beyond
doubt, that atom was not the smallest indivisible particle but had a complex structure of its
own and was made up of still smaller particles like electrons, protons, neutrons etc. At
present, about 35 different subatomic particles are known.

Discovery of Electron Discharge Tube Experiment


We know that under normal condition of pressure, a gas is a poor conductor of electricity.
However, if pressure is reduced, the gas be comes conducting, i.e. electricity starts flowing
through the gas.
William Crooks, in 1879, studied the conduction of electricity through gases at low pressure.
He performed the experiment in a discharge tube which is cylindrical hard glass tube about
60 cm in length. It is sealed at both the ends and fitted with two metal electrodes as shown in
figure. High voltage
+

+
Cathode Anode

Cathode rays To vacuum pump

2
Emission of light under reduced pressure of 10− atm.

Emission of light under reduced pressure 10−2 atm.


The electrodes are connected to a source of high voltage while the tube is connected to a
vacuum pump in order to reduce the pressure inside it and the following observation are
made.
1. Under normal pressure (1 atmosphere). Nothing is observed even by applying high
voltage of 10000 volts. This means that gas does not conduct the electric current.
2. The pressure inside the tube is slowly reduced by working the vacuum pump. When
pressure is reduced to 10−2 atmosphere, the gas is found to emit light and colour of light
depend upon of the nature of gas.
3. The emission of light cease when the pressure is reduced to 10−4 atmosphere, but the
walls of the discharge tube opposite to cathode starts glowing with a faint greenish light
called fluorescence.
This experiment shows that the fluorescence is due to bombardment of the glass walls of
the tube by the rays emitted from the cathode. These rays are called cathode rays.

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Origin of Cathode Rays
Cathode rays initially originate form the metal which constitutes the cathode. These are also
formed due to bombardment of the molecules of the gas inside the discharge tube by the
high speed of particles. (electrons) which are emitted from the cathode.

Properties of Cathode rays


The properties of cathode rays were studied by J.J. Thomson and co-workers based upon
certain experiments.

These are described as follows :


(i) Cathode rays travel in straight line : When a solid object is placed in the path of the
cathode rays, its shadow is noticed immediately behind it. This shows that the cathode
rays travel in straight line.
Cathode rays Object

+
Cathode Anode

To vacuum pump
Cathode rays cast shadow of the object

(ii) Cathode rays are made up of material particles : If a light paddle wheel made from
mica are mounted on an axis is placed in the path of the cathode rays, it starts
rotating. This shows the cathode rays consists of material particle.
Light paddle
wheel

Cathode rays rotate light paddle wheel

(iii) Cathode rays consist of negatively charged particle : When electrical field is
applied on the cathode rays with the help of a pair of metal plates as shown in figure,
Cathode rays are found to be deflected towards the positive plate indicating the
pressure of negative charge. Deflection of
cathode rays
Electric plates

+
Cathode Anode
+
To vacuum pump

Deflection of cathode rays in electric field

similarly, when a magnetic field is applied, these are deflected in a direction which
shows that they carry negative charge. R.A. Millikan (1917) by its oil drop experiment
established that electron has charge = e = 1.60 × 10−19 C or 4.8 × 10−10 e.s.u.

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e ch arg e
(iv) J.J. Thomson (1897) found that = = Specific charge = 1.76 × 108 C / gm.
m mass
(v) Cathode rays produce heating effect. When these rays are made to strike on a metal
foil, the latter gets heated.
(vi) Cathode rays produce X-rays when they strike on surface of hard metals such as
tungsten copper molybdenum etc.
(vii) Cathode rays can pass through thin foils of metals like aluminium. However, they are
stopped if the foil in quite thick.
(viii) Cathode rays ionize the gas through which they pass.
(ix) Cathode rays affect the photographic plate. This is called fogging.
(x) When cathode rays strike against a glass surface or a screen coated with zinc
sulphide, they produce. fluorescence (glow).

Mass of Electrons :
By using the Thomson’s value of e/m and the Milikan’s value of e , the absolute mass of an
electron can be termed
e/m = −1.76 × 108 coulomb/g. (THOMSON)
e = −1.60 × 10−19 coulomb. (MILIKAN)
e 1.6 × 10 −19
∴ e
= 8
q
m 1.76 × 10
m = 9.1 × 10−28 gm.
= 9.1 × 10−31 kg.

Mass of Electron Relative to Hydrogen :


Avogadro number , the number of atoms in one gram atom of any element is 6.023 × 1023
From this we can find the absolute mass of hydrogen atom 6.023 × 1023 atoms of Hydrogen
1.008
= 1.008 a.m.u. = gm
6.023 × 10 23
= 1.67 × 10 −24 g
But the mass of electron = 9.1 × 10−28 g.
mass of H atoms 1.67 × 10 −24
∴ =
−28
= 1,835 × 103 = 1835
mass of electron 9.1× 10
Thus a H atom is 1835 times as heavy as an electron.
1
In other words, The mass of an electron is th of the mass of hydrogen.
1835
An electron is a negatively charged subatomic particle which bears charge 1.6 × 10−19
coulombs and has mass 9.1 × 10−28 gm or 9.1 × 10−31 Kg.
Alternatively, an electron may be defined as, A particle which bears one unit negative charge
and mass 1/1835th of a hydrogen atom.

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ATOMIC STRUCTURE
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Anode Rays :
How are Anode rays produced ?
When high speed of electrons (cathode rays) strike molecules of a gas placed in the
discharge tube, they knock out one or more electrons from it and results positive ions.

m → m+ + e−
Positive
R
− −
+
+ + + +
ANODE
− −

− Perforated
Cathode Fluorescent
Screen
Production of Positive rays

These positive ions pass through the perforated cathode and appears as positive rays. When
electric discharge is passed through the gas under high electric pressure, its molecules are
dissociated in to atoms and the positive atoms (ions) constitute the positive rays.

Properties of Anode Rays :


(i) They travel in a straight line in a direction opposite to cathode.
(ii) They are deflected by electric as well as magnetic field in a way indicating that they
positively charged.
(iii) The charge to mass ratio (e/m) of positive particles varies with the nature of the gas
placed in the discharge tube.
(iv) They possess mass many times the mass of an electron.
(v) They cause fluorescence in zinc sulphide.

Proton (Goldstein-1886) :
E-Goldstein discovered protons in the discharge. Tube containing hydrogen.
H ⎯⎯→ H + + e −
Proton
It was J.J. Thomson who studied their nature. He showed that
(1) The actual mass of the proton is 1.672 × 10−24 gram. On the relative scale, proton has
mass 1 atomic mass unit. (a.m.u.)
(2) The electrical charge of protons is equal in magnitude but opposite to that of the electron.
Thus proton carries a charge+1.6×10−19 coulombs or +1 elementary charge unit .
Since proton was the lightest positive particle found in atomic beams in the discharge tube. It
was taught to be a unit present in all other atoms. protons were also obtained in a Variety of
nuclear reaction indicating further that all atoms contains protons.

Thus a proton is defined as a subatomic particle which has a mass of 1.a.m.u. and
charge +1 elementary charge unit or simplifying.

A proton is a subatomic particle which has one unit mass and one unit positive charge.

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ATOMIC STRUCTURE
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Neutrons (James Chadwick-1932):


James chadwick discovered the third subatomic particle − He directed a stream of alpha
particle 42 He at a beryllium target. He found that a new particle was ejected. It has almost the
same mass (1.674×10−24 gm) as a proton and has no change.
4 9 12 1
2 He + 4 Be ⎯⎯→ 6 c + 0 n

α-Particle

Neutrons
Beryllium Charge Detector
Indicates no charge
(α-particles directed at beryllium sheet eject neutrons
whereby the electric charge detector remains unaffected)

(α-particle directed at beryllium sheet eject neutrons where by the electric charge detector
remains unaffected.)
The assigned relative mass of a neutron is approximately one atomic mass unit. (a.m.u.)
Thus, A neutron is a subatomic particle, which has mass equal to that of proton and
has no charge.

SUBATOMIC PARTICLE
Particle Symbol Nature Charge Mass(a.m.u) in kg Discover
Electron −1eo or e Negatively charged −1.6 × 10−19 0.000549 9.1×10−31 J.J.
particle Coulombs or one unit Thomson
negative charge or
4.8 × 10−10 e.s.u
Proton P or 1H1 Hydrogen nucleus +1.602 ×10−19 c or 1.00758 1.672×10−27 Goldstein
one unit positive
charge
1
Neutron on Neutral particle Zero Charge 1.00893 1.674×10−27 Chadwick
Positron +1eO one unit positive 0.000549 9.1×10−31 Anderson
charge i.e. +1
O
Neutrino Oe Zero charge less than the Fermi
Antineutri−No mass of electron
0.00002
Antiproton −1p Negative charge 1.00758 Chamber
Lain
Meson π Positive (π+) +ve charge 273 times heavier Yukawa
0
Neutral (π ) No charge than the mass of
Negative (π−) −ve charge electron.

Alpha Particle : Alpha particle are shot out from radioactive elements with vary speed for e.g.
They come from radan atoms at a speed of 1.5× 107 m/sec. Rutherford identified them to be
di-positive helium ions He 2+ or 42 He . Thus an α−particle has charged +2 and mass + 4 a.m.u.
α−particle are also formed in the discharge tube that contains helium
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2+ −
He ⎯⎯→ He + 2e
It has twice the charge of a proton and about 4 times its mass.

Conclusion :
Through α−particles is not a fundamental particle of the atom (or subatomic particle) but
⎛1 ⎞
because of its high energy ⎜ mv 2 ⎟ . Rutherford thought of firing them like bullets at atoms
⎝2 ⎠
and thus obtain information about the structure of the atom.
(1) He bombarded nitrogen and other light elements by α−particles when H+ ions or protons
were produced. This showed the pressure of protons in atoms other than hydrogen atom.
(2) He got a clue of the presence of a positive nucleus in the atom as a result of the
bombardment of thin foils of metals.

Thomson Model (J.J. Thomson)


Atom is a hard solid sphere, the positive
charge of the atom is uniformally distributed,
the negative charged electrons are embedded
with in atom.
This model failed to explain the scattering of a
particles by heavy atoms and the spectral
Thomson model of atom
series obtained even in the simplest cases.
Flash of
Light

Rutherford’s Atomic Model The Nuclear Atom:


They directed a stream of very highly energetic
Gold
α-particles from a radioactive source against a Source of Foil
α-Particles
thin gold foil provided with a circular
fluorescent zinc sulphide screen around it. SLIT

Whenever α-particle struck the screen. A tiny ZnS Screen

flash of light was produced at the point. Rutherford and Marsden’s α-particle scattering

α-Particle
Undeflected
+ Particle
Large
Rutherford and Marsden notice that most of the Deflection
Nucleus

α-particles passed straight through the gold foil +


+
and thus produced a flash on the screen +
behind it. Slightly
Deflected
Particle
How nuclear atom causes scattering of α-particles
Observation
(i) Most of the α-particles (99.9%) passed through the foil without undergoing any deflection.
(ii) Few α-particles underwent deflection through small angles.
(iii) Very few (only one in 20,000) were deflected back i.e. through an angle greater than 90o.

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Conclusion
(1) Atom has a tiny dense central or the nucleus which contains practically the entire mass of
the atom of the nucleus is about 10−13 cm. as compared to that of the atom 10−8 cm. If the
nucleus were the size of a football, the entire atom would have a diameter at about 5
miles. It was this empty space around the nucleus which allowed the α-particles to pass
through undeflected. −
(2) The entire positive charge of the atom is
located on the nucleus, while electrons
were distributed in vacant space around it. + −
It was due to the presence of the positive
charge on the nucleus that α- particles −
(He2+) were repelled by it and scattered in
Rutherford’s model of atom ;
all directions. electrons orbiting around nucleus
(3) The electrons were moving in orbit or closed circular paths around the nucleus like
planets around the sun.

What is mass number ?


The total number of protons and neutrons in the nucleus of an atom is called the mass
number; it is represented by A. These elementary particles are collectively referred to as
nucleons. Obviously, the mass number of an atom is a whole number. Since electrons have
practically no mass, the entire atomic mass is due to the protons and neutrons, each of which
has a mass almost exactly one unit.
Therefore, the mass number of an electron can be obtained by rounding off the experimental
value of atomic mass (or atomic weight) to the nearest whole number.
Composition of Nucleus :
Knowing the atomic number (Z) and mass number (A) of an atom, we can tell the number of
protons and neutrons contained in the nucleus; By-definition.
Atomic Number, Z = Number of protons = No. of electons.
Mass Number , A = Number of protons + Number Of Neutrons
∴ The number of neutrons is given by the express ion
N=A−Z
Isotopes : These are the atoms of the same element which have the same atomic number
but different mass number
1
e.g 1
H (Protium), 12 H (Deuterium), 13 H (Tritium)
O-atom is also having three isotopes
16 17 18
8 O 8 O 8 O
Isotopes arises because of different number of neutrons and same number of protons.
Cl-atom is having two Isotopes
35 37
17
Cl & 17
Cl
Isobars : The atoms which have the same mass number but different atomic number are
called Isobars. The word isobar meaning ‘Equally heavy’

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40 40 40
iso = equal and barys = heavy For e.g. 18 Ar, 19 K, and 20 Ca are isobaric atoms . Similarly
235 235 235
92 U, 93 Np and 94 Pu are isobars.
Isotones :
Atoms which have different atomic numbers and different atomic masses but the same
numbers of neutrons are called Isotones. For e.g. 146 C, 157 N and 168 O are isotones since
each contains eight neutrons.
Isoelectronic : The species which have the same number of electrons are called Isoelectronic.
e.g. O2−, Ne, Na+, F−
Size of Isoelectronic species is inversely proportional to its nuclear charge.
i.e. Order of their size is O2− > F− > Ne > Na+ > Mg2+
Isosters : These are the molecules of different substances which contains the same number
of atoms and the same number of electrons which leads to similarity in their physical
properties. e.g. CO2 & N2O.
Nuclear Isomers : The radioactive elements having same atomic number and same mass
number but different radioactive properties are called nuclear Isomers.
U – X2 and U – Z
Nature of Light and Electromagnetic Spectrum:
According to Newton, light was regarded as a stream of particles also known as the
corpuscles of light. The particle nature could explain certain phenomena such as refraction
and reflection associated with light. But at the same time, it failed to explain two other
important phenomena called interference diffraction. The corpuscular theory of light was,
therefore , replaced by wave theory given by Huygens. In 1856, James Clark Maxwell stated
that light, X-rays, γ-rays and heat etc. emit energy continuously in the form of radiations or
waves and the energy is called radiant energy. These waves are associated with electric
and magnetic fields and are, therefore, known as electromagnetic waves (or radiations).

Electromagnetic Wave Theory Crest Crest


A few important characteristics of these waves λ
are listed :
(i) They emit energy continuously in the form of
radiations or waves.
(ii) The radiations consists of electric and λ
magnetic fields which oscillate perpendicular to Trough Trough
each other and also perpendicular to the Propagation of waves

direction in which the radiations propagate.


(iii) All the electromagnetic waves travel with the velocity of light (3.0 × 108 ms−1).
(iv) These rays do not require any medium for propagation.

Some important Characteristics of a Wave


(a) Wavelength (λ or lamda). The electromagnetic waves propagate as crests and Troughs.
Wavelength may be defined as the distance between any two consecutive crests or
troughs.

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Wavelength may expressed in different units such as Angstron , micron, millimicron,
nanometre, picometre etc. All of them are related to S.I . unit i.e. metre as follows :
1A = 10−10 m; 1 micron(µ) = 10−6 m, 1 milli micron (mµ) = 10−9 m
1 nm = 10−9 m; 1 pm = 10−12 m.
(b) Amplitude (a) is the height of the crest or depth of the trough and is also expressed in
the units of length.
(c) Frequency (ν or nu) is the number of the wavelengths which passes through a point in
one second. The units of the frequency are cycles per second (or sec−1) or Hertz (Hz)
1 Hz = 1 cycle per second
It may be noted that a cycle is complete when a wave consisting of one crest and one
trough passes through a point. The electromagnetic waves differ in their frequency and
wavelength.
(d) Velocity (c) of a wave is the linear distance travelled by the wave in one second. It is
measured in ms-1.
_
(e) Wave number ( ν ) may be defined as the number of wavelengths which can be
_
accommodated one cm length along the direction of propagation. The SI unit of ν is m−1.
But the units cm−1 is also commonly used.
_ 1
Wave number ( ν )=
Wavelength (λ )
Electromagnetic spectrum :
Different types of electromagnetic waves (or radiation) differ with respect to wavelength and
frequency. The wavelength of electromagnetic waves increase in the order: wavelengths
increase in the following order :
Cosmic rays < γ-rays < X-rays < Ultra violet rays < Visible < Infrared < Microwaves < Radiowaves.
The complete range of the electromagnetic waves is known as electromagnetic spectrum.
It may be defined as : The arrangement of different electromagnetic radiations in order of
increasing wavelength or decreasing frequency . It may be shown as follows.

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Increasing wave length

Decreasing frequency

10−16 10−14 10−12 10−10 10−8 10−6 10−4 10−2 100 102
) )
Infra red Micro Radio
Cos γ-rays x-rays Ultra violet
waves

Visible
waves
mic

v(Hz)
1024 1020 1016 1012 108 104

7.6x10−7
3.8 x 10−
7
V I B G Y O R
Indigo

λ(m)
Violet Blue Green Orange
Yellow red

v(Hz) Electromagnetic Spectrum 3.85 x 1014


Ultraviolet
Light
Metal
Limitations of Electromagnetic Wave Theory
PHOTOELECTRIC EFFECT − + e

When a beam of light of sufficiently high


e−
frequency is allowed to strike a metal surface
Stream of Ammeter to
in vacuum, electrons are ejected from the electrons measure
metal surface. This phenomenon is known as current
Photoelectric effect. e− e−

Apparatus for measuring the photoelectric effect

When ultraviolet light strikes on the metal, the emitted electrons flow to the anode and the
circuit is completed with the help of this photoelectric effect. The following observations can
be made : −
1. An increase in the intensity of incident light does not increase the energy of
photoelectrons. It merely increase their rate of emission.
2. The kinetic energy of the photoelectrons increases linearly with the frequency of incident
light. If the frequency is decreased below a certain critical value. (Threshold frequency vo)
no electrons are ejected at all.
The classical physics predicts that the kinetic energy of the photoelectrons should
depend on the intensity of light and not on the frequency. Thus it fails to explain the
above observations.

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Black Body Radiation


An ideal black body is that which is a perfect absorber and a perfect emitter of radiations.
When radiant energy is allowed to fall on a carbon black or a blackened metallic surface the
energy is almost completely absorbed. When such a body is heated, it becomes first of all
red, then orange, then yellow and last of all white at a very high temperature.
It emits radiations more than any other body on heating and hence it is also a perfect
radiator.

Planck’s Quantum theory of Radiations:


Max Planck in 1900 , put forward a theory known as Planck’s Quantum Theory. This was
further extended by Einstein in 1905. The main points of the theory are :
(1) The radiant energy is emitted or absorbed discontinuously in the form of small energy
packets called Quanta. In case of light, these energy packets are known as photons.
(2) The energy of each quantum is directly proportional to the frequency of the radiation
c
E∝ν or E = hν = h
λ
Here h is a constant known as Planck’s constant. Its value is 6.62 × 10−34 J sec or
3.99 × 10−13 kJ sec mol−1.
(3) The total amount of energy emitted or observed by a body is some whole number or
integral multiple of quantum i.e.
E = nhν
(Here n is an integer)
The energy associated with Avogadro’s number of quanta is called Einstein energy (E).
Its value may be given as
N hc
E=
λ
Thus, Planck’s for the first time has given a relationship between the frequency (or
wavelength) of the radiations since they have very high frequency.
At the same time, microwaves and radiowaves with small frequency are regarded as low
energy radiations.

(Explanation of Photoelectric Effect by Planck’s Quantum Theory)


(i) A photon of incident light transmits its
hν e−
energy (hν) to an electron in the metal
Photoelectron
surface which escapes with kinetic Photon

1
energy mv 2 . The greater intensity of
2
incident light merely implies greater
e− e− e− e− e−
number of photons each of which M+ M+ M+ M+
release one electron. This increases the
1
rate of emission of electrons while the (It needs a photon (hν) to eject an electron with energy mν 2 )
2
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kinetic energy of individual photons
remains unaffected.
(ii) In order to release an electron from the metal surface, the incident photon has first to
overcome the attractive force exerted by the positive ion of the metal. The energy of a
photon (hν) is proportional to the frequency of incident light. The minimum ν which
ejects the electron from the metal surface is called νo. If ν < νo , No e− will be emitted.
For higher frequencies ν > νo a part of energy goes to loosen the electron and
remaining for imparting kinetic energy to the photoelectron, thus −
1
hν = hν o + mv 2 (i)
2
where hν is the energy of the incoming

Kinetic energy of
photon hνo is the minimum energy for an

Photoelectrons
electron to escape from the metal and
1
mv2 is the kinetic energy of the
2
photoelectron. Frequency of
incident of light
hνo is constant for a particular solid and (Kinetic energy of photoelectrons plotted
designated as w, the work function. against frequency of incident light) Fig. ii)

Rearranging equation (i)


1
mv 2 = hν − w (ii)
2
So w = hνo here w = work function
this is the equation for a straight line ( y = mx + c) that was experimentally obtained
figure (ii). Its slope is equal to h, the Planck’s constant. The value of h thus found
come out to be the same as was given by Planck himself.

Study of Emission and Absorption Spectra


A radiation which consists of one wavelength only is called Monochromatic. Light such as
sunlight which consists of radiation of different wavelength is known as polychromatic. When
a polychromatic light is passed through a prism, it splits in to radiations of different
wavelengths. This splitting of a polychromatic light in to its constituent radiation is called
dispersion. It is due to bending of radiations (of different wavelength) through different angles.
The pattern of radiations obtained due to dispersion, is called Spectrum.
The instrument used to record a spectrum is called a spectrometer or spectrograph. It was
developed by Bunsen and Kirchoff in 1859. A spectrometer consists of a prism for dispersion
of light and a photographic plate to record the spectrum. The photograph of the spectrum is
called Spectrograph.
The spectra are broadly classified into
1. Emission spectra
2. Absorption spectra

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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’. Depending
upon the source of radiation, the emission spectra are mainly of two types :
(i) Continuous spectra When white light
from any source such as sun, a bulb or White
any hot glowing body is analyzed by Light
R
passing through a prism, it is observed
O
that it splits up into seven different
Y
wide bands of colours from violet to Beam G
red, (like rainbow), as shown in fig.
B
These colours are so continuous that
I
each of them merges into the next.
V
Hence the spectrum is called
continuous spectrum. It may be noted Slit Prism Photographic
Plate
that on passing through the prism, red
Continuous spectrum of white light
colour with the longest wavelength is
deviated least while violet colour with
shortest wavelength is deviated the
most.
(ii) Line spectra When some volatile salt PLATINUM
(e.g., sodium chloride) is placed in the WIRE
o
bunsen flame or electric discharge is 5896 A
passed through a gas at low pressure BEAM
as given in fig. , light is emitted. If this
light is resolved in a spectroscope, it is o
found that no continuous spectrum is NaCl 5890 A
obtained but some isolated coloured
lines are obtained on the photographic PRISM
SLIT TWO
plate separated from each other by YELLOW
dark spaces. This spectrum is called (a) LINES
‘Line spectrum’ or simply Line BURNER

spectrum.
Line spectrum produced from a
volatile salt placed in a fame.

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Each line in the spectrum corresponds to a particular wavelength. Further it is observed
that each element gives its own characteristic-spectrum, different from those of all
other elements.
For example , sodium always gives two
yellow lines (corresponding to
o
wavelengths 5890 and 5896 A ).
BEAM
Hence the spectra of the elements are

H2 Gas
described as the finger prints of the
human beings.
Further, it will be discussed later that
SLIT PRISM PHOTOGRAPHIC
the line spectra are obtained as a PLATE
result of absorption and subsequent
emission of energy by the electrons in Line spectrum produced from a
the individual atoms of the element. light emitted by discharge tube.
Hence the line spectrum is also called
atomic spectrum.
2. Absorption spectra When white light from
any source is first passed through the
solution or vapours of a chemical DARK LINES IN YELLOW REGION
substance and then analyzed by the OF CONTINUOUS SPECTRUM.
R
spectroscope, it is observed that some White LIGHT O
dark lines are obtained in the otherwise Y
continuous spectrum. These dark lines are G
supposed to result from the fact that when B
white light (containing radiations of many NaCl
I
wavelengths) is passed through the SOLUTION
PRISM V
chemical substance, radiations of certain
SLIT
wavelengths are absorbed, depending PHOTOGRAPHIC
PLATE
upon the nature of the element. Further it is
observed that the dark lines are at the PRODUCTION OF ABSORPTION SPECTRUM
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.’
Emission spectrum of Hydrogen When
hydrogen gas at low pressure is taken in the SERIES:LYMA BALMER PASCHEN BRACKETT PFUND HUMPHREY
discharge tube and the light emitted on passing N

electric discharge is examined with a


spectroscope, the spectrum obtained is called
the emission spectrum of hydrogen . It is found
to consist of a large number of lines which are REGION:ULTR INFRARED
VISIBLE
grouped into different series, named after the AVIOLET FAR INFRARED

discoverers.* The names of these series and Emission or atomic spectrum of hydrogen

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the region in which they are found to lie are
given in fig. The wavelength of different lines I
n each of these series are given in Table.

Rydberg formula. Although a large number of lines are present in the hydrogen spectrum,
rydberg in 1890 gave a very simple theoretical equation for calculation of the wavelengths of
these lines. The equation gives the calculation of the wave numbers.
_ _ ⎛ 1 1 ⎞
v of the lines by the formula v = R ⎜ 2 − 2 ⎟ . where R is a constant , called Rydberg
⎜n ⎟
⎝ 1 n2 ⎠
constant** and has a value equal to 109,677 cm−1, n1 and n2 are whole numbers and for a
particular series n1 is constant and n2 varies.For example,
For Lyman series, n1=1, n2 =2,3,4….
For Balmer series, n1 =2, n2=3,4,5….
For Paschen series n1 =3, n2= 4,5….
For Brackett series, n1 =4, n2=5,6,7…
For Pfund series, n1 =5, n2=6,7,8…
For Humphrey, n1 = 6, n2 = 7,8,9…..
The above expression is called Rydberg formula.

Drawbacks of Rutherford’s model Instability of Atomic Structure :


According to Rutherford’s model, electrons are
removing around the nucleus in circular orbits. The
centrifugal force (which arises due to the circular +
motion of electrons) acting outwards balances the
electrostatics force of attraction (between the
positively charged nucleus and the negatively
charged electrons) acting inwards. This prevents the e−
electrons to fall the nucleus. Continuous loss of energy by revolving
electron

However, it had been shown by Clark Maxwell that a charge and accelerated particle loses
energy constantly. Electrons is a charged particle. It gets accelerated due to continuous
change in direction while moving around the nucleus. Thus an electron must, therefore, emit
radiations and lose energy constantly. As the electron loses energy, its orbit would become
smaller and smaller. Ultimately, due to electrostatic force of attraction; the electrons will fall is
to nucleus. fig. since such a collapse of the atom does not take place , therefore, Rutherford’s
model of the atom is faulty.

Failure to Explain Atomic Spectra :


Rutherford’s model could not explain the formation of line spectrum. According to
electromagnetic theory, frequency of radiation of a charged body is equal to its frequency of
revolution. Since the electron orbit is continuously changing the frequency of revolution also
changes continuously. As a result, atomic spectra of hydrogen should have been continuous
rather than line spectra. This is not in agreement with the observed facts.

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Bohr’s Atomic Model
Neil’s Bohr (1913) developed a new theory of the atomic structure on the basis of quantum
theory of radiation. The main point of his theory are −
Bohr’s Assumptions
(i) An atom consist of a dense nucleus situated at the centre around which the electrons in
circular orbit.
(ii) Of the very large number of possible circular orbits around the nucleus, the electron can
move only in certain fixed orbits known as stationary state. Stationary state does not
mean that the electrons are stationary. An electrons keeps on revolving in the same orbit
and its energy remain constant.
(iii) Each fixed or stationary state associated
with a definite amount of energy. These NUCLEUS

different energy levels are numbered as 1, + n=1K L M N


2, 3, 4 etc. (from nucleus outward) or n=2 n=3 n=4

alternatively they are designated as K, L,


M, N shell etc.
Circular orbits (energy levels /
stationary states) around the nucleus

(iv) The electron in an atom can have certain definite or discrete value of energy which are
characteristics of that atom. In other words: The electronic energy of an atom is
quantized.
(v) The electron in an atom can revolve only in those energy levels for which the angular
h
momentum of an electron is a whole number multiple i.e.

For circular motion, the magnitude of the angular momentum L of the electron is L = mvr
nh
Bohr’s quantization of the angular momentum is L = mvr = (where n = 1, 2, 3, ….)

Hence the integer n is called principal quantum number.
where m → mass of an electron.
v → velocity
r → radius of orbit in which the electron moving
n → orbit of the electron
Electrons orbit in certain stationary states in which orbiting electrons do not continuously
radiate electromagnetic energy. The stationary states have definite total energy. This
assumption implies that classical law of electromagnetic radiation by an accelerated
charge simply do not apply to an electron in it stationary orbits.
(vi) The emission or absorption of electromagnetic radiation occurs only when there is a
transition of electrons between two stationary states. When an electron changes from a
higher energy orbit to a lower energy orbit. The excess energy is emitted as a photon.
The frequency of the emitted or absorbed radiation is proportional to the difference in
energy of two stationary states
∆E = En2 − En1 = hv

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Radiation of Radiation of
Frequency ν E n2 Frequency ν

E n1 E n2 En
+ (b +
(a

Energy is absorbed Energy is emitted when


when an electron jumps an electron jumps from a
Energy changes during electronic
jumps
where h is the Planck constant h = 6.625 × 10−27 erg-sec. En1 and En2 are the energies of a
initial and final state. The frequency of the photon is independent of the frequency of the
electrons orbital motion.
This assumption is equivalent to that of conservation of energy with the emission of photon.

BOHR’S THEORY HAS EXPLAINED THE ATOMIC SPECTRUM OF HYDROGEN ATOM


Bohr’s theory, we have studied that the electrons are distributed in different energy levels.
Normally an electron tends to be as close to the nucleus as possible or it tends to be in the
lowest energy state also called ground state.
In case, energy is made available to the electron from some outside source, it may absorb
energy is quantum (or quanta) and jump to the higher energy state known as excited state. e.g.
in hydrogen atom, the only electron is present in the K – shell (n = 1) in the ground state with
energy E n1 . If it absorbs energy equal to one quantum (hv) it jumps to first excited state with
energy equal to E n2 . Since the excited state in unstable, the electron will jump back to the ground
state by losing a quantum of energy as radiations which appear as emission spectra.
1 ν⎤
Thus, E n2 − En1 = hν = h ν c ⎡⎢ν = = , In general, if the electron jumps from a particular excited
⎣ λ c ⎥⎦
state represented as E n2 to the lower energy state (ground state) represented as E n1 , it will
emit a radiation having definite frequency and wavelength. The spectral line which
correspond to it will have specific colour.
n=8
n=7
n=6
Humphrey Series ( far Infrared)
n=5
Pfund Series
(Infrared)
n=4
Brackett Series
(Infrared)
n=3
Paschen Series
(Infrared)
n=2
Balmer Series
(Visible)

n=1
Lyman series
(Ultraviolet) Different series in the hydrogen spectrum
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From above diagram, it is evident that the Lyman series, the electrons jump from different
excited states to n = 1. In Balmer series, they jump to n = 2 similarly, in Paschen, Brackett
and Pfund series which appear in the infrared regions, the electrons drop back to energy
states represented by n = 3, 4, 5 respectively. This may be summed as follows:

Name of the Spectral Series Downward Transition


LYMAN SERIES From n = 2, 3, 4, 5….. to n = 1
BALMER SERIES From n = 3, 4, 5, 6 … to n = 2
PASCHEN SERIES From n = 4, 5, 6, 7 … to n = 3
BRACKETT SERIES From n = 5, 6, 7, … to n = 4
PFUND SERIES From n = 6, 7, 8 … to n = 5
HUMPHREY SERIES From n = 7, 8….. to n = 6
Explanation for the Simultaneous Appearance of Many Spectral Lines in the Hydrogen
Spectrum
In study of hydrogen spectrum, we have seen the appearance of many spectral lines different
series of hydrogen spectrum such as Lyman, Balmer, Paschen Brackett and Pfund series.
This appears to be some what strange because each hydrogen atom which is formed as a
result of the dissociation of hydrogen molecule in a discharge tube has only one electron. It is
expected to be excited to the some higher energy state in all the atoms of hydrogen. But in
actual practice, the electrons absorb different amounts of energy and thus, are excited to
different higher energy states depending upon the energy absorbed, since the excited states
are unstable, the electrons are to jump back to ground states. It may be noted that in the
return journey, it is not necessary for all the electrons to follow the same route.
n(n − 1)
¾ Maximum lines in H-spectrum when it exite to nth level = when an electron
2
(n − n1 ) (n 2 − n1 + 1)
returns from n2 to n1 energy level. No. of spectral lines produced = 2
2

Some results of Bohr’s Model

1. Radius of nth Bohr’s Orbit


Consider an electron of mass ‘m’ and charge e, revolving a nucleus of charge Ze
(Z → atomic number and the being the charge) on a proton.
Let v be the tangential velocity of revolving electron and r is the radius of orbit. The
electrostatic force of attraction between the nucleus and electron. (Applying Coulombs law)
Ze ⋅ e Ze 2
=
r2 r2
mν 2
The centrifugal force on the moving electron =
r
As force of attraction = centrifugal force.
Ze 2 mv 2 Ze 2
= or v2 = ….(i)
r2 r mr

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According to one of the postulates
nh
mνr =

nh
ν=
2 π mr
Putting the value of ν in equation (i)
n2 h2 Ze 2 n 2h 2
= or = Ze 2
4 π2 m2 r 2 mr 4π 2mr
n 2h 2
r= ….(ii)
4π 2mze 2
Putting the value h, π, m and e we get
0.529 × 10 −8 × n 2
r= cm
Z
0.529
r= × n2 A o
Z
for hydrogen atom Z = 1
r = 0.529 × 10−8 × n2 Å
r = 0.529 × n2 Å

2. Energy of an Electron
Let the TE is total energy of an electron in a shell, it is the sum of kinetic energy and
potential energy.
TE = P.E. + K.E.
− Ze 2
P.E. =
rn
1 Ze 2
K.E. =
2 rn
Ze 2 1 Ze 2 Ze 2
∴ TE = − + = ….(iii)
rn 2 rn 2 rn
1 P.E.
TE = P.E., and K.E. = −
2 2
Also equating (ii) and (iii), we get
− 2π 2 me 4 z 2 − 21.72 × 10 −12
TE = = erg
n 2h 2 n2
− 21.72 × 10 −19
= J
n2
− 13.6
E=
2
eV (1 Joule = 6.2419 × 1018 eV)
n

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13.6
=−× 23.05 K cal / mol (1 eV = 23.053 K cal per mol)
n2
Energy of electron (e) in terms of K cal per mol
313.6
E = − 2 K cal / mol
n
∴Energy of Electron (E) in terms of kJ per mole
− 1312
E= kJ per mole
n2
the radius of first orbit, n = 1
= 12 × 0.529 × 10−8 cm =0.529 × 10−8 cm= 0.529 × 10−10 meter.
3. Velocity of an Electron
Putting the value v in equation ….(ii)
2 2
nh 4π mZe Z 2πe 2
v= × = ×
2πm n 2h 2 n h
Putting the values of n, e, h in the above equation, we get
Z −1
v= × 2.188 × 10 8 cm sec
n
Z −1
= × 2.188 × 10 6 m sec
n
for hydrogen atom, Z = 1
2.188 × 10 6
v= cm sec−1
n
for first orbit of hydrogen atom, then v = 2.188 × 106 m sec−1 for second orbit of hydrogen
(n = 2), thus
1 −1
v= × 2.188 × 10 6 m sec
2
= 1.094 × 106 m sec−1
¾ No. of revolution made by an electron per second in an orbit.
v
¾ No. of revolution made by electron per second =
2 πr
¾ Putting the value of r and ν in the above reaction
Z2
Thus the number of revolutions = × 1.316 × 1016 sec −1
3
n
Hence the no. of revolution made by an electron per second hydrogen atom
1.316 × 1016
= sec .
n3
Limitations of Bohr’s Theory
(i) It is unable to explain the line spectra of multi electronic atoms.
(ii) It also fails to account for the multiple of fine structure of the spectral lines. Each spectral
line has been found to consist of a number of component line was observed closely in a

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spectroscope of high revolving power. This suggested the presence of sub energy level
in a main energy level, which was not suggested by Bohr.
(iii) The further splitting up of spectral lines under the influence of strong magnetic field
(Zeeman’s effect) is not explained by Bohr.
(iv) Bohr gave a flat model of the atom in which electrons are revolving in circular orbits
around the nucleus. But at present it is believed that atom has a three dimensional
model. The new model leads the concept of orbitals in place of Bohr’s definite orbits.
(v) This theory cannot explain the directional bonding between atoms in some molecules and
thus the shape of such molecules.
(vi) Bohr theory violates Heisenberg’s uncertainty principle.
Heisenberg’s uncertainty principle. According to this principle, the position and
momentum of a small particle like electron cannot be determined simultaneously with
absolute accuracy.
(vii) It violets the dual character (i.e. particle and wave) for an electron proposed by
de-Broglie. Bohr consists electron as discrete particles and it does not take in to account
its wave character.
de-Broglie concept of dual character of matter. According to this concept, an electron
behaves not only as a particle but also as a wave. Bohr, however, considered electrons
only as discrete particles.

Sommerfeld’s Modification of Bohr’s atom


Sommerfeld modified Bohr’s theory as follows:
Bohr considered electron orbits as circular but Sommerfeld postulated the presence of
elliptical orbit also.

Dual Nature of Matter


(de-Broglie Equation)
In 1924, Louis de-Broglie suggested that just as light exhibits wave and particle properties all
microscopic material particles in motion such as electrons, protons, atoms, ions, molecules
etc. have also dual character.
In Other Words : -
All material particles in motion possess wave characteristics.
According to de-Broglie, “ the wavelength associated with a particle of mass m, moving with
velocity v is given by the relation”.
h h
λ= = (p = m⋅v)
p mv
where h is the Planck’s constant and mv is the momentum of the particle. The wave
associated with material particles are called Matter waves.

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Derivation Of de-Broglie Equation
He derived a relationship between the magnitude of the wavelength associated with mass ‘m’
of a moving body and its velocity.
According to Planck, photon of light having energy E is associated with a wave of frequency ν
as –
E = hν …(i)
where h is the Planck’s constant and ν the frequency of radiation.
By applying Einstein’s mass energy relationship the energy associated with photon of mass m.
E = m⋅c2 …(ii)
where c is the velocity of light.
Combining the above two relation in equation (i) and (ii), we get :-
hν = mc2
c
Now, since νλ = c or ν=
λ
hc
∴ = mc 2
λ
h h
= mc or λ =
λ mc
The equation is valid for a photon. de-Broglie suggested that on substituting the mass of the
particle m and its velocity v in place of velocity of light c the equation can also be applied to a
material.
Thus, the wavelength of material particles, λ is
h
λ=
mv
This equation is known as de-Broglie’s equation.
h
or λ=
p
where p stands for the momentum (mv) of the particle since h is constant
1
λ∝
momentum
de-Broglie’s equation may be put in words as ----
The momentum of a particle in motion is inversely proportional to wavelength, Planck’s
constant ‘h’ being the constant of proportionality.

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Significance of de-Broglie
The wave character puts some restriction on how precisely we can express the position of an
electron or any other small moving particle. This is due to the reason that unlike particles
wave do not occupy a well-defined position in space and are delocalised.
The wave nature of matter, however, has no significance for object of ordinary size because
wavelength of the wave associated with them is too small to be detected.

Justification for the Dual Nature of Electrons


1. Particle nature
An electron exhibits all the characteristics of a particle i.e. It has a definite mass, energy,
momentum and charge. When an electron is made to fall on a screen coated with zinc
sulphide, it produces a spot of light known as scintillation. It has been observed that one
electron produces only one scintillation point. This means that the scintillation and, as
such the striking electron must be localised and not spread out like wave . Moreover
black body radiation and photoelectric effect proves the particle nature.
2. Wave nature
Louis-de-Broglie’s concept of wave nature of electron was experimentally verified by
electron beam from tungsten filament is accelerated by using a high positive potential.
When this fine beam of accelerated electron is allowed to fall on a large single crystal of
nickel, the electrons are scattered from the crystal in different directions. The diffraction
pattern so obtained is similar to diffraction pattern obtained by Bragg’s experiment on
diffraction of X–rays from a target in the same way.
Diffraction pattern

Photographic plate

Incident beam
of electrons Reflected rays

Nickel crystal
Electron diffraction experiment by Davisson and Germer

Since x – ray have wave character, therefore the electrons must also have wave
character associated with them. Moreover, the wavelength of the electrons as determined
by the diffraction experiments were found to be in agreement with the values calculated
from de-Broglie equation.
So from this it is clear that an electron behaves both as a particle and as a wave.

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Experimental verification of de-Broglie concept
(a) Verification of wave character (Davission and Germer’s experiment).
The wave character of electrons was verified experimentally by Davission and Germer in
1927. They studied the diffraction of electrons by a sample of nickel crystal and found the
diffraction pattern to be similar to that produced by x-rays figure, since x-rays are
confirmed to have wave character therefore, electrons must also have a wave character
associated with them. Moreover, the values of wavelength obtained from diffraction
experiments are in agreement with those calculated from de-Broglie’s equation.
+

x-ray Tube
Sample

Diffraction
− Pattern
+
Accelerating
Electrode

Source of Sample
Electrons

Diffraction
Pattern

Thomson experiment can also be performed to verify the wave nature of electron. In this
experiment, in place of Nickel crystal a thin gold foil is taken but similar diffraction pattern
is obtained as in case of Nickel crystal which again confirms the wave nature of electron.
(b) Verification of particle character.
It is observed that when an electron strikes a zinc sulphide screen, a spot light known as
scintillation is produced. Moreover, one electron produces only one scintillation point.
Since scintillation is localised, therefore, the striking electron must also be localised and
not spread out like a wave. Since the localised character is possessed by particle,
therefore electron has particle character. Moreover black body radiation and photoelectric
effect also proves particle nature.

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Difference between Particle and Wave
Particle Wave
1. A particle is a localised point in space. 1. A wave is delocalised(spread out) in space.
2. More than one particle cannot be 2. Two or more wave can exist
present at a given position in a space simultaneously in the same region of
i.e. particle do not interfere. space i.e. waves interfere.
3. If two or more particles are present in 3 If two waves are present in a given
any region, then due to non- region, then due to interference the
interference, their total value is equal resultant wave can be larger or smaller
to their sum. than the individual waves

Derivation of Bohr’s Postulate of Quantisation of Angular Momentum from de-Broglie


Relation
de-Broglie equation helped in explaining the Bohr’s postulate regarding the quantisation of
angular momentum of an electron. Consider an electron moving around the nucleus in the
form of wave in a circular orbit of radius r. The wave train of electrons may be continuously in
phase or out of phase. If the two ends of the wave meet to give a regular series of crests and
troughs, the wave motion is said to be in phase as shown in Fig. If the two ends do not meet
to give a regular series of crests and troughs, it is said to be out of phase [Fig.]. As evident
from Fig., for wave motion to be continuously in phase, the circumference of circular orbit
must be an integral multiple of number of the wavelengths otherwise the wave would interfere
destructively and cancel each other and, thus, destroy itself. Therefore, by considering the
electron as wave, we automatically impose a limit to the number of orbits.
From the above discussion, it is clear that the circumference of the orbit must be integral
multiple of the electron wavelength i.e.,
Circumference = nλ
or 2πr = nλ
h
But, according to de-Broglie equation, λ =
mv (a) Wave in phase (b) Wave out of phase
nh Representation of electron waves and orbits
∴ 2πr = (a) in phase (b) out of phase.
mv
nh
or mvr =

Thus, the angular momentum of the electron should be an integral multiple of h/2π. In other
words, the angular momentum is quantised. This is the same as Bohr’s condition for
quantisation of angular momentum of fixed energy orbits.

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HEISENBERG’S UNCERTAINTY PRINCIPLE
According to Heisenberg’s uncertainty principle It is impossible to measure simultaneously
the exact position and exact momentum of a body as small as electron.
Heisenberg’s uncertainty principle may be expressed as :
h
∆x . ∆p ≥ where ∆x is uncertainty of position & ∆p is uncertainty of momentum

h
∆x . ∆(mv) ≥

h 6.626 × 10 −34
∆x . ∆v ≈ ≈
4π × m 4 × 3.14 × 9.1× 10 −31
Uncertainty Product ≈ 0.077 × 10−4 J sec per kg.
When ∆x = 0, ∆v = ∞
When ∆v = 0 ∆x = ∞
1
As uncertainty product ∝
m
So for macroscopic particles uncertainty product will be negligible
So Heisenberg’s principle has no sense for macroscopic particles.

Physical concept of Uncertainty Principle. Electron changes


Photon
momentum at the
The physical concept of uncertainty principle instant of Collision
becomes illustrated by considering an attempt
to measure the position and momentum of an
electron moving in Bohr’s orbit. +
Nucleus

The locate of position of the electron we should device an instrument supermicroscope to see
the electron. A substance is said to run only if it could reflect light or any other radiation from
its surface. Because the size of the electron is too small its position at any instant may be
determined by a supermicroscope employing light of very small wavelength (such as X-rays,
or ν-rays). A photon of such a radiation of small has a great energy and therefore has quite
large momentum.
As one such photon strikes the electron and is reflected it instantly changes the momentum
of electron.
Now the momentum is changed and becomes more uncertain as the position of the electron
is being determined.
Thus it is impossible to determine the exact position of an electron moving with a definite
velocity (or possessing definite energy).
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It appear clear that the Bohr’s picture of an electron as moving in an orbit with fixed velocity
or energy is completely untendable.
As it is impossible to know the position and the velocity of any one electron on account if its
small size, the best we can do is to speak of the probability or relative chance of finding an
electron with a probable velocity.
Wave Mechanical Concept of the Atom
Based upon the idea of the electron as a standing wave around the nucleus, a new model
known as wave mechanical model was developed by Erwin Schrodinger (1927). He
considered the electron as three dimensional wave in electric field of the positively charged
nucleus. To describe the behaviour of electron waves, Schrodinger developed a
mathematical equation which is popularly known after his name as Schrodinger wave
d2 ψ d2 ψ d2 ψ 8π 2 m
equation. The equation is + + + (E − P.E.)ψ = 0 . Here
dx 2 dy 2 dz 2 h2
(i) m = mass of the electron
(ii) E = Total energy of the electron
Ze 2
(iii) V = Potential energy of the electron =
r
(iv) h = Planck’s constant = 6.62 × 10−27 erg. Sec. = 6.62 × 10−34 Js.
(v) x, y and z are cartesin co-ordinates specifying direction and distance.
(vi) ψ (read psi) is a wave function which represents the amplitude of electron wave.
Significance of ψ.
(i) It is wave function which is a solution to the Schrodinger equation.
(ii) It represents amplitude of wave and describes how this amplitude varies with distance
and direction.
(iii) The Schrodinger wave equation may have different values of ψ. All values may not be
significant. The significant values of wave function, ψ, are known as EIGEN functions.
These functions give significant values of total energy (E) of the electron. These values
are called Eigen values.
Significance of ψ2
The probability of finding an electron in an extremely small volume around a point is
proportional to the square of the function ψ2 at that point. If wave function ψ is imaginary ψψ
becomes a real quantity where ψ is a complex conjugate of ψ. This quantity represents the
probability ψ2 as a function of x, y and z co-ordinates of the system and it varies from one
space region to another. Thus the probability of finding the electron in different regions is
different. This is in agreement with the uncertainty principle and gave a deathblow to Bohr’s
concept.

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Concept of Orbital
According to wave mechanical approach, we cannot say simply that the electron exists at a
particular point but we talk about certain regions in space around the nucleus where the
probability of finding the electron is maximum such regions are expressed by mathematical
expressions and are called orbital wave functions or commonly known as orbital. Therefore,
the wave equation leads to the concept of the orbitals instead of well defined circular orbits.

The three-dimensional region within which


there is higher probability that an electron
having a certain energy will be found, is called
an orbital.
(a) Orbital (b) Orbit
Representation of (a) orbital and (b) orbit.
(The orbital is indicated by dotted figure representing electron cloud. The intensity of dots
gives the relative probability of finding the electron in that particular region.)
If a boundary is drawn which encloses a region where there is high probability (about 90-
95%) of finding the electron, the figure obtained gives the general picture of an orbital.
However, it is difficult to draw the real picture of an orbital. For the sake of simplicity, it may
be represented as shown in figure.
Differences between ORBITS and ORBITALS

Orbits Orbitals
(i) It is well-defined circular path It is a region in three dimensional space
around the nucleus in which the around the nucleus where the probability of
electron revolves. finding electron is maximum
(ii) It is circular in shape s, p and d-orbitals are spherical dumbell and
double dumbell in shape respectively.
(iii) It represents that an electron moves It represents that an electron can move
around the nucleus in one plane around nucleus along three dimensional
space along x, y and z axis
(iv) The maximum number of electrons The maximum number of electrons in an
in an orbit is 2n2 where n is the orbital is two
number of the orbit
(v) It represents that position as well as It represents that position as well as
momentum of an electron can be momentum of an electron cannot be known
known simultaneously with simultaneously with certainty it is in
certainty. It is against Heisenberg’s accordance with Heisenberg’s uncertainty
uncertainty principle principle.

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The coordinates x, y, z of electrons w.r.t. nucleus in terms of polar coordinates are given by −
x = r sin θ cos φ
y = r sinθ sin φ
z = r cosθ
And solution of schrodinger wave equations gives −
ψ nlm = R (r)(n, l), θ (θ) (l , m) φ (φ)(m)

QUANTUM NUMBERS
Quantum numbers are the index numbers, which are used to specify the position and energy
of an electron in an atom. The word quantum is used to signify that all the energy levels,
which are available to an electron are governed by the laws of quantum mechanics.
There are four quantum numbers. Each of these can have only specific values, which are
inter-related. The values assigned to these numbers determine specific energies that an
electron can have. Each quantum number refers to a particular character of the electron. In
order to specify completely the position and energy of an electron in an atom, it is necessary
to state the values of each of the four quantum numbers. Just as a person is identified by his
address, an electron in an atom is completely known by specifying four quantum numbers.
Thus, quantum numbers are complete address of the electrons.
The significant aspects of the four quantum numbers are described below :
1. Principal Quantum Number (n). This quantum number is designated as ‘n’ and gives
the number of major energy level (shell or orbit) to which the electron belongs. It can
have any positive whole number value excluding zero i.e., n = 1, 2, 3, 4 …..∞.
Thus n can have infinite value and it has been called principal quantum number by Bohr.
Information given by n values
The value of n represents the shells which are designated by capital letters K, L M, N……
Thus,
Value of n 1 2 3 4
Letter designation K L M N
of shells (First shell) (Second shell) (Third shell) (Fourth shell)
(i) The principal quantum number also helps to determine the average distance of the
electron from the nucleus. In terms of quantum mechanics, it gives the effective
volume of the electron cloud.
In case of hydrogen atom, the approximate distance from the nucleus is given
n 2h 2
by rn = .
4π 2 me 2

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Lower value of ‘n’ represents that the electron is nearer to the nucleus. Thus, n
represents the size of the electron orbits. Higher is the value of n, larger is the size of
the electron orbit of atom.
(ii) ‘n’ also determines the energy of the electron in an orbit. For hydrogen like particles,
it is given by :
2π 2me 4 z 2
En = −
n 2h 2
Where z is the atomic number, m and e are the mass and charge of the electron
respectively, h is the Planck’s constant and n is the number of the orbit.

Substituting the value of m, e, z, n and h, we get


1312 313.6
En = − kJ mol − = − kcal mol − [Q 1 kcal = 4.184 kJ]
2 2
n n
The above relation shows that largest negative value of energy −1312 kJ mol−1 (i.e.
maximum stability) is obtained when n = 1. Thus n = 1 gives the lowest energy state
(E1) of an electron in H-atom. This state is called the ground state or stationary
state of an electron in atom.
From above, it is clear that +1312 kJ mol−1 energy (called ionisation energy) is
needed to knock out an electron from H-atom.
− 1312
for n = 2, E= kJ mol −1 = −328 kJ mol −1
4
This reduced negative value indicates that the atom is less stable as compared to the
ground state. Similarly, all states with higher value of ‘n’ are also less stable. All
states with n values greater than one are called excited states. When energy called
excitation energy (which is equal to the energy difference between two states) is
provided, an electron makes a transition from the ground state to one of the excited
states.
The difference (∆E) in energy between the two states is given by ∆E = E n2 − E n1 or a
transition from ground state (n1 = 1) to the first excited state (n2 = 2).
∆E = E2 – E1 = (− 328 kJ mol−1) − (−1312 kJ mol−1) = 984 kJ mol−1
The various energy states in an atom are commonly called its energy levels.
With the increase in the value ‘n’, energy associated with an electron increases and
the energy difference between two successive energy states goes on decreasing.
When n becomes infinity, energy becomes zero.
(iii) ‘n’ value can also be used to calculate the maximum number of electrons that a shell
can hold. Maximum number of electrons in an orbit with principal quantum number n
can have 2n2 electrons.

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Thus :
The maximum number of electrons in K-shell (n = 1) = 2 × 12 = 2
The maximum number of electrons in L-shell (n = 2) = 2 × 22 = 8
The maximum number of electrons in M-shell (n = 3) = 2 × 32 = 18
The maximum number of electrons in N-shell (n = 4) = 2 × 42 = 32.
2. Azimuthal, subsidiary, orbital or angular quantum number (l). This quantum number
is given by sommerfield. When hydrogen spectrum was observed by means of a
spectroscope of high resolving power, the individual spectral lines were found to consist
of a group of closely spaced lines. Such a spectrum consisting of closely spaced spectral
lines is called fine structure. The fine structure of a spectral line is explained by
assuming that all electrons of a shell do not have same energy and each shell is
composed of a number of subshells which are specified by a secondary quantum
number, designated as ‘l’.
The value of ‘l’ depends on the value of ‘n’. For a given value of n, l can have values
from zero to (n – 1) where n is the value of the principal quantum number.

Information given by l values


(i) This quantum number determines the angular momentum of the electron. The
angular momentum is given by the relation :
Angular momentum (mvr) = l(l + 1) ⋅ h / 2π or l(l + 1) h

(ii) The values of l for a given value of n determine the number of subshells in a shell.
For example, when n = 1, the largest (and only) value of l is zero. Therefore, K-shell
consists of only one subshell. When n = 2, l = 0 and 1. Hence, L-shell is made up of
two subshells. For n = 3, l = 0, 1, 2, therefore, M-shell consists of three subshells.
(iii) Different values of l represent different subshells which are designated by small
letters s, p, d, f…..
For example,

Value of l 0 1 2 3 4 5
Designation of sub-shell s p d f g H
For the same value of ‘n’, the energies of sub-levels are determined by the value of ‘l’ for
them. A sub-level with a higher value of ‘l’ is associated with higher energy. Thus,
s < p < d < f (for same value of n)
(l = 0) (l = 1) (l = 2) (l = 3)
(iv) The shape of an orbital is also related to its l value. When l = 0, the orbital is
spherically symmetrical and is known as s-orbital. When l = 1, the orbital is dumbell
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shaped and is called p-orbital. Similarly, orbitals having l = 2 and 3 are known as d
and f-orbitals respectively. The d-orbitals are double dumbell shaped whereas the f-
orbitals have more complex shape.
The letters s, p, d and f find origin in the atomic spectra of the alkali metals. In these
spectra, four series of lines were observed and were termed the sharp, principal,
diffuse and fundamental series, hence the letters s, p, d and f.
To specify a subshell within a given shell, we write the value of n for the shell followed
by the letter designation of the subshell. For example, s-subshell of the first shell
(n = 1, l = 0) is known as 1s-subshell. Similarly, the p-subshell of the second shell
(n = 2, l = 1) is known as 2p-subshell. The designations of subshells for n = 1 to n = 5
are given below.
n l subshell designation No. of subshells in a shell
1 0 1s One
2 0 2s ⎫ Two
1 ⎬
2p⎭
3 0 3s ⎫ Three

1 3p⎬
2 3d⎪⎭

4 0 4s ⎫ Four
1 4p⎪⎪

2 4d⎪
4f ⎪⎭
3
5 0 5s ⎫ Five

1 5p⎪

2 5d⎬
5f ⎪
3 ⎪
5g⎪⎭
4
(v) l-values also enable us to calculate the total number of electrons in a given subshell
(s, p, d and f subshell). The total number of electrons in a given sub-shell with a given
l value is equal to 2(2l + 1). For example,
Value of l 0 1 2 3 4 5
sub-shells s p d f g h
No. of electrons in a sub- 2 6 10 14 18 22
shell = 2(2l + 1) = 4l + 2

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3. Magnetic quantum number (m or ml). It has been observed that a moving electron in a
subshell is associated with a magnetic field. When an atom is placed in an external
magnetic field, the orbitals of same kind (e.g. px, py and pz orbitals) are no longer identical
in energy because some of them are parallel to the magnetic field while others are not.
As a result, electrons get excited from one of these orbitals to another and give additional
lines. In other words, the finer lines of spectrum further split up. This phenomenon was
first of all studied by Zeeman and is called Zeeman effect. In order to correlate these
energy changes, magnetic quantum number (m or ml) was suggested.
Under the influence of external magnetic field, electrons in a sub-shell adjust themselves
in different orientations. The orientations (or preferred regions in space) are called
orbitals. Thus each sub-shell is composed of orbitals. Each orbital is designated by a
different value of m.
The values of m range from −l to zero to + l and maximum values of m = 2l + 1. For
example
When l = 0 (s-subshell), m = 0 (Only one value)
When l = 1 (p-subshell), m = −1, 0, +1 (Three values)
When l = 2 (d-subshell), m = −2, −1, 0, +1, +2 (Five values)
When l = 3 (f-subshell), m = −3, −2, −1, 0, 1, 2, 3 (Seven values)
Information gives by m values. m values for a given value of l are used to calculate the
number of orbitals in a sub-shell. For a given value of l, the number of m values is equal
to the number of orbitals in a subshell. In terms of l values, the number of orbitals in a
sub-shell is equal to 2l + 1. For example,
(i) When n = 1, l = 0 (s-subshell), m = 0 (−l to 0 to +l), i.e. only one value of ‘m’ is
permitted. Hence, s-subshell is composed of only one orbital.
(ii) When n = 2, l = 0, 1. When l = 0, m = 0 but when l = 1, m = −1, 0, +1. Therefore, for
l = 1, (p-subshell), there are three permitted values of m. Hence, p-subshell is
composed of three orbitals known as px, py and pz orbitals.
(iii) When n = 3, l = 0, 1, 2. For l = 2 (d-subshell) m = −2, −1, 0, +1, +2. Thus, d-subshell
is composed of five different orbitals.
(iv) When n = 4, l = 0, 1, 2, 3. For l = 3 (f-subshell) m = −3, −2, −1, 0, +1, +2 and +3. fore,
f-subshell is composed of seven orbitals.
Maximum number of orbitals in a shell = n2. For example, maximum number of orbitals in:
(i) first shell = 12 = 1 (1s)
(ii) second shell = 22 = 4 (2s, 2px, 2py, 2pz)
(iii) third shell = 32 = 9 (3s, 3px, 3py, 3pz, 3dxy, 3dyz,
3dzx , 3d , 3dz2
x2 −y2

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3d 3d (five)
The number of subshells and orbitals in the n = 3 or M 3p 3p (three)
Shell
first three shells (K, L, M) are shown in Fig. 3s
3s (one)
2p
2p (three)
n = 2 or L
Shell
2s
2s (one)
n = 1 or K 1s
1s (one)
Shell Subshell
Orbital
Number of subshells and orbitals in first
three shells (K, L and M)
4. Spin Quantum Number (s). This quantum number is given by Gold Schmidth. In 1921, the
German physicists Otto Stern and Walter Gerlach passed a beam of neutral silver atoms
(obtained from the vaporisation of silver) between the poles of a specially designed magnet.
The beam was found to split into two separate beams (Fig.) i.e. half the atoms were
deflected in one direction, and the rest in the opposite direction. This means that half of the
silver atoms are acting like magnets pointing in one direction and the other half in the
opposite direction. To explain this magnetic behaviour, it was assumed that an electron spins
around its own axis and this spin creates a small magnetic field. Thus, an electron acts like a
tiny magnet. An electron can spin either clockwise or anticlockwise. Thus, it can have two
1 1
possible values + or − . These values depend upon the direction of the spin. As a rule,
2 2
when two electrons are present in an orbital, these have opposite spins (↑ ↓). By convention −
1 1
+ (clockwise rotation ) and − (anticlockw ise rotation)
2 2
Shapes of Atomic Orbitals or Boundary Surface Diagrams
The probability of finding the electron does not become zero even at large distances from the
nucleus. Therefore, it is not possible to draw any sort of geometrical figure that will enclose a
region of 100% probability.

Radial Wave Functions


The shapes of orbitals are obtained from the variation of wave function ψ as a function of r
(distance from the nucleus). This is also called radial dependence or radial wave function.
This can be shown in a simple method by plotting a graph between wave function (ψ) and
distance (r) from the nucleus.
These graphs are shown for 1s, 2s and 2p orbitals in figure. It is clear from figure(a) that
wave function for 1s-orbital continuously decreases with increase in r. However, for 2s-orbital
fig (b), the wave function decreases in the beginning with increase in r.

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2s – Orbital
2p orbital
1s – Orbital
ψ
ψ Node ψ

r
Distance from the r
nucleus (b)
(a) (c)

This point at which radial wave function becomes zero is called radial nodal surface or simply
node. At the node, the value of wave function changes from positive to negative. In general, it
has been found that ns orbitals have (n −1) nodes. Similarly, np orbitals have (n − 2) nodes
and so on. In all cases, ψ approaches zero as r approaches infinity.

Probability Density (ψ2) Graphs

According to the German physicst, Max, Born, the square of the wave function, ψ2 at a point
gives the probability density of finding the electron at that point. These variations of ψ2 as a
function of r are obtained by plotting ψ2 against r.
These plots for 1s, 2s and 2p orbitals are shown in figure. These graphs are called probability
density graphs. It may be noted that for s-orbitals (1s and 2s), the maximum electron density
is at the nucleus and for p-orbitals (2p), it has zero electron density at the nucleus. It may be
noted that all orbitals except s-orbitals have zero electron density at the nucleus.

1s – Orbital 2s – Orbital 3s – Orbital


2p orbital

ψ2 ψ2 Node Nodes ψ2
ψ2

Distance from the Distance from the Distance from the r


nucleus nucleus nucleus

Radial Probability Functions ( 4πr2 ψ2)


In order to determine the total probability in an infinitesimally small region, we have to multiply
probability density (ψ2) by the volume of region, i.e.
Probability = ψ2 × dV
where dV is the volume of the region. Since the atoms have spherical symmetry, it is more
useful to discuss the probability of finding the electron in a spherical shell between the
spheres of radius (r + dr) and r.
This gives the total probability of finding the electron at a particular distance (r). This is called
radial probability. The plots of probability (4πr2 ψ2] as a function of distance from the nucleus
(r) are called radial probability distribution function (r.d.f.) graphs.
It is clear that the radial probability distribution graphs depend not only upon the probability
density but also on the volume of the shell. The probability density (ψ2) for 2s is maximum
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near the nucleus and it goes on decreasing with distance. However, the volume of the shell
goes on increasing with increase in distance. The product of probability density and volume
of shell gives the radial probability (4πr2ψ2) and is plotted against the distance from the
nucleus.
The graph for 1s-orbital shows that the probability of finding the electron is zero at nucleus, it
keeps on increasing and becomes maximum at a particular distance from the nucleus and
then gradually decreases. This is called the radius of maximum probability.
The radial probability functions versus distance r from the nucleus for 1s, 2s and 2p orbitals
are shown in figure.

Node
4πr2drψ2

4πr2drψ2
4πr2drψ2

r rr r
1s- orbital 2s- orbital 2p- orbital

Shapes of s-orbitals
s-orbitals are non-directional and spherically symmetrical. This means that the probability of
finding the electron is same in all directions at a particular distance from the nucleus.
There is a spherical shell within 2s-orbital where the probability of finding the electron is
practically zero. This is called a node or a nodal surface.

Nodal Sphere
Nodal Sphere

1S 2S 3S

Shapes of p-orbitals :– On the basis of probability circulation, it has been found that the
probability of finding the p-electrons is maximum in two lobes on the opposite side of the
nucleus, thus giving rise to a dumb-bell shape for the p-orbital. Further, the probability of
finding a particular p-electron is equal in both the lobes. There is a plane passing through the
nucleus on which the probability of finding the electron is almost zero. This is called a nodal
plane.

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For p-subshell, l = 1. Hence m = –1, 0, + . Thus p – orbitals have three orientations. These
are designed as px, py and pz depending upon whether the electron density is maximum
along the X – axis, Y – axis and Z – axis respectively.
There is no probability of finding a p-electron right at the nucleus. Directional nature of p-orbitals
help us in predicting the shapes of the molecules
z

z z

xz +
– Nodal Plane

X Nodal Plane

+ y +
yz Nodal Plane X
X y
PX y
PX Pz

Shapes of d – Orbitals
There are five degenerate d-orbitals corresponding to l =2 in each d – subshell corresponding to
m = –2, –1, 0, +1, +2. These are double dumb bell shaped four of these 5 orbitals have the same
shape but differ in orientation in space. They have four lobes of electron density and two nodal
planes. One of these four lobed d – orbitals, has maximum density along X and Y axes. It is
called d x 2 − y 2 . For the other three, the directions along which the electron density is maximum lie
at 45o to the coordinate axis. These are dxy, dyz and dxz orbitals.
The fifth d – orbital ( d 2z ) has two lobes of electron density directed along the Z – axis and a
ring of electron density (called a doughnut) centred in XY plane. The shape of this orbital
( d 2z ) quite similar to baby soother. dxy, dxz and dyz orbitals having their greatest electron
densities in the region between the axes are called t2g or d∈. The other two namely d 2z and
d 2 2 have their greatest electron densities in the directions that lie along the axes and also
x −y

known as eg or dy.

Y Z Z Z Z

X Y X X X

2 2 2
dxy dyz dxz dz dx y

t2g or de eg or dr

Shapes of f-orbitals
There are seven degenerate ƒ – orbitals with l = 3 and m = –3, –2, –1, 0, +1, +2, +3 in each
ƒ – subshells. These orbitals are complicated in shape. They possess 8 lobes with three
nodal planes.

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Nodes and Nodal planes


As we have learnt nodes are the positions where radial wave function passes through zero.
These are also called radial nodes.
Beside radial nodes, the probability density functions for np and nd orbitals are zero at the
planes passing through the nucleus. For example as shown in figure, in case of 2p3 orbital, xy
plane is a nodal plane. This is called Angular Node or Nodal Plane. Similarly, for of the 3d
orbitals (3dxy, 3dyz, 3d3x and 3d 2 2 ) have two perpendicular nodal planes that intersect in a
x −y
line passing through the nucleus. For example, 3dxy orbital have two nodal planes, passing
through the origin and bisecting the xy plane containing z-axis. The number of angular nodes
or given by ‘l’ i.e, one angular node for p orbitals, two angular nodes for d-orbitals and so on.
In general, in an orbital :
Total number of nodes = n − 1
Angular nodes = l
Radial nodes = n − l − 1.
Pauli’s Exclusion Principle
Wolfgang Pauli (1925) studied atomic spectra of elements and discovered the principle called
Pauli’s exclusion principle. According to this principle, “No two electrons in an atom can have
all the four quantum numbers alike.”
Applications
1. An orbital cannot have more than two electrons. Consider three electrons e1, e2, e3
(having spin values ‘s’ as shown against each) present in one orbital.
Electrons e1 e2 e3
1 1 1 1
Values of ‘s’ + − + or −
2 2 2 2
(i) Two electrons, e1, e2 of the same orbital will have same values of n, l and m. Spin
1 1
value can be either + or − so that exclusion principle is obeyed.
2 2
1
(ii) For the electron, e3, let value of s = + . In this case, the value of four quantum
2
numbers for e1 and e3 will be same
1
(iii) For the electrons e3, let value of s = − . In this case, the value of four quantum
2
numbers for e2 and e3 will be same. The (ii) and (iii) possibilities are denied by Pauli
exclusion principle. Hence an orbital can not accommodate more than two electrons.
2. Maximum number of electrons in a sub-shell. Pauli’s exclusion principle can be used to
calculate the number of electrons in different subshells. For s-subshell (l = 0), m = 0 i.e. s-
subshell has only one orbital and hence can accommodate only two electrons. For p-subshell
(l = 1), m = 1, 0 and −1 i.e. a p-subshell has three orbitals, so that it can have 2 × 3 or six
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electrons. For d-subshell (l = 2), m = 2, 1, 0, −1, −2 i.e. a d-subshell has five orbitals and
hence 5 × 2 or 10 electrons. For f-subshell (l = 3), m = 3, 2, 1, 0, −1, −2, and −3 i.e. a f-
subshell can have seven orbitals and hence 2 × 7 or 14 electrons.
3. Maximum number of electrons in a shell. The number of orbitals in a shell = n2.
Therefore, maximum number of electrons in an orbit = 2n2. Thus, maximum number of
electrons in first shell = 2 × 12 = 2. Maximum number of electrons in second shell = 2 × 22
= 8 and so on. The maximum number f electrons in different sub levels and shells are
shown in table.
Subdivisions of main energy levels
Main energy level (n) 1 2 3 4 5
Number of sublevels (n) 1 2 3 4 5
Type of sublevels s s, p s, p, d s, p, d, f s, p, d, f, g
Number of orbitals per sublevel 1 1,3 1, 3, 5 1, 3, 5, 7 1, 3, 5, 7, 9
Maximum number of electrons per 2 2, 6 2, 6, 10 2, 6, 10, 14 2, 6,10,14,18
sublevel (4l + 2)
Maximum number of electrons per 2 8 18 32 50
main level (2n2)

Electronic Configuration of Elements


The electrons are distributed among the orbitals of an atom is the electronic structure or
electronic configuration. The electronic configuration of the elements are constructed by
assuming that the electrons occupy the lowest possible energy level available. The number of
electrons in any one level are determined by the four quantum numbers and the Pauli’s
Exclusion Principle.
Electronic configuration of elements is governed by the following rules :-
Aufbau Principle (German : Aufbau means building up)
According to this principle, the electrons are filled in various orbitals in order of their
increasing energies. Thus an orbital with lowest energy will be filled first. The energy content
of the two sub-shell can be compared by means of (n + l) rule as explained below.
(i) The subshell with lower (n + l) value will possess lower energy and will be filled first for
e.g. 4s subshell is filled first than 3d
(a) for 4s – subshell : n + l = 4 + 0 = 4
(b) for 3d – subshell : n + l = 3 + 2 = 5
Since (n + l) value of 4s subshell is less than 3d, the 4s subshell has lower energy and is
filled first.

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(ii) The subshell with lower value of n 8s

possesses lower energy if (n + l) values for 7 7p


both subshell are equal for e.g. 3p subshell 7s
6d
is filled than 4s 6 6p
5f
6s
5d
(a) for 3p subshell : n + l = 3 + 1 = 4 5 n+l=8
5p
4f
5s
(b) for 4s – subshell n + l = 4 to 4 4d
4 n+l=7
4p
The value of n (= 3) is less for 3p-subshell 4s n+l=6
3d
as compared to n (= 4) for 4s subshell.
3 3p
Hence 3p subshell has lower energy than 3s
n+l=5
4s-subshell and is filled first.
2 2p n+l=4
The different orbitals in the increasing 2s
order of energies are n+l=3
1
1s n+l=2
start from here
n+l=1

1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d < 5p < 6s < 4f < 5d < 6p < 7s < 5f < 6d.

The order is diagrammatically illustrated in figure.


Hund’s Rule of Maximum Multiplication
(i) Electron paring of degenerate orbitals cannot takes place until each orbital is singly
occupied and some of the spin should be maximum .
The basic of Hund’s rule is that when electrons are brought closer, they repel each other.
Hence energy of the system increases. Therefore, to have the lowest energy state. The
electron must be farthest apart i.e. in different orbitals having equivalent energy. Thus in
carbon (at. No. 6), the electron configuration will be 1s2, 2s2, 2p1x , 2p1y , 2p 0z and not 1s2
2s2 2p 2x 2p 0y 2p 0z
(ii) When different orbitals of the same energy are half or less than half filled, the electron
should parallel spin. It is because parallel arrangement of spins is more stable than
antiparallel arrangement. This rule is based upon the magnetic effect of electron spins.
1s 2s 2p
N
Z=7 ↑↓ ↑↓ ↑ ↑ ↑

O
Z=8 ↑↓ ↑↓ ↑↓ ↑ ↑

Ne
Z = 10 ↑↓ ↑↓ ↑↓ ↑↓ ↑↓

Electronic Configuration of Elements


The electrons are distributed among the orbitals of an atom is the electronic structure or
electronic configuration. The electronic configuration of the elements are constructed by
assuming that the electrons occupy the lowest possible energy level available. The number of
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electrons in any one level are determined by the four quantum numbers and the Pauli’s
Exclusion Principle.

Exceptional Configuration of Chromium and Copper


From the electronic configuration listed above, it is evident that both chromium and copper
have exception configuration. Their actual configuration are different from those as expected
for these elements.
For Cr (z = 24) 4
4s2 3d
18 2 4
Expected configuration [Ar] 4s 3d ↑↓ ↑ ↑ ↑ ↑
1 5
4s 3d
Actual configuration [Ar]184s13d5 ↑ ↑ ↑ ↑ ↑ ↑
For Cu (z = 29)
18 2 9 4s2 3d9
Expected configuration [Ar] 4s 3d
↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑
1 10
4s 3d
Actual configuration [Ar]184s13d10
↑ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓

It is based on the concept of symmetry. The stability of the atom is linked with symmetry of
the electronic configuration. The half filled and fully filled configuration are more symmetrical
and the symmetry leads to greater stability. To achieve this, in case of Chromium (Cr) an
electron gets shifted from 4s filled orbital to 3d empty orbital to make all the five 3d orbitals
half filled. Similarly, in case copper, an electron gets shifted from 4s filled orbital to 3d half
filled orbital to make all the five 3d orbitals fully filled.
The extra stability of d5 and d10 configuration can also be explained on the basis of exchange
energy.
The electrons present in the different orbitals of the same subshell can exchange their
positions mutually and exchange energy is released.
It may be noted that more the number of exchangeable positions, more will be exchange
energy released and thus, more will be the stability of the atom.
In case of the element chromium, the number of exchanges (10) for 3d5 configuration are
more compared with 3d4 configuration (6) as shown below :-
1 2 3

↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑
3 EXCHANGE BY ELECTRON 1 1 EXCHANGE BY ELECTRON
2 EXCHANGE BY ELECTRON
Total number of exchange = 3 + 2 + 1 = 6

1 2 3 4

↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑
4 EXCHANGE BY ELECTRON 1 3 EXCHANGE BY ELECTRON 2 2 EXCHANGE BY ELECTRON 3 1 EXCHANGE BY ELECTRON 4

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Total number of exchange = 4 + 3 + 2 +1 = 10
Therefore, 3d5 electronic configuration is more stable than 3d4 configuration.

Electronic Configuration of Ions


In the formation of cations, the electrons are removed from the valency shell of the atoms
while in the formation of anions, these are added to the valency shell. The number of
electrons lost or gained is equal to the numerical value of the charge on the ion.

Some Important Formula for Calculation or Numerical Problem


¾ Mass No (A) = Atomic no (z) + No. of neutrons(N)
1 v
¾ Velocity (a) = νλ and wave number ( v ) = =
λ c
¾ Increasing (λ) for electromagnetic waves cosmic rays < x rays < γ rays < u.v. rays <
visible < I.R. rays < microwaves < Radiowaves
hc
¾ Energy of photos (E) = hv =
λ
⎛ ⎞
1 ⎜ 1 1 ⎟
¾ Rydberg formula = (v) = RH z 2 ⎜ − ⎟ (RH = 109678 cm−1)
λ ⎜n 2 2 ⎟
⎝ 1 n2 ⎠
1 ⎛ 1 1 ⎞
¾ Balmer formula = ( v ) = R ⎜⎜ − ⎟ for hydrogen atom

λ ⎝ 22 n2 ⎠
¾ Angular momentum (mvr) = nh/2π
2π 2 me 4 Z 2
¾ Energy of electron (En) = −
n 2h 2
− 1312 −
¾ Energy of hydrogen electron (En) = 2
K.J. mol
n
313.6 2.18 × 10 −18 − 13.6
= − 2
k cal / mol = − 2
J / atom = eV
n n n2
n 2h 2
¾ Radius of orbit (γ) =
4π 2 mZe 2
¾ Radius of first orbit (H atm) = 0.529 A°
¾ Radius of nth orbit (H atm) = 0.529 n2 A°
2πZe 2
¾ Velocity of electron (v) =
nh
h h
¾ de Broglie’s relation (λ) = =
mv p
h
¾ Uncertainty principle ∆x.. ∆p ≥

h
¾ Angular momentum of electron = l(l + 1)

¾ No. of radial nodes is an orbital = (n – l – 1)
¾ No. of angular nodes = l
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¾ Increasing energy of electrons orbitals 1s.2s 2p 3s 3p 4s 3d 4p 5s 4d 5p 6s 4f 5d & 6s 7s
¾ Electronic energy has negative sign.
¾ The energy emitted or absorbed in the electronic transition (∆E) = E2 − E1
¾ The number of spectral line produced when an electron jumps from nth level to ground
n(n − 1)
level (n = 1) = and when an electron jumps from n2 to n1 number of spectral line
2
(n 2 − n1 ) (n 2 − n1 + 1)
produced =
2
¾ For a given value of n, l = 0 to n − 1
¾ For a given value l, m = −l to +l including zero
¾ For a given value of m, s = + ½ , −1/2
¾ No of orbitals in nth shell = n2
¾ No of electrons in nth shell = 2n2
¾ Actual mass of neutron (1.675 × 10-27 Kg) is slightly more than that of proton
(1.672 × 10−27Kg)

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