Discovery of Electron (Cathode Rays)

Experiment:
 A gas discharge 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 the pressure inside the
tube.
 The tube is attached to a vacuum pump that the conduction of electricity may be studied at any
value of low pressure.
Apparatus:

Results:
 It is observed that current does not flow through the gas at ordinary pressure even at high
voltage of 5000 volts.
 When the pressure inside the tube is reduced and a high voltage of 5000-10000 volts is applied,
then an electric discharge takes place through the gas producing a uniform glow inside the tube.
 When the pressure is reduced further to about 0.01 torr, the original glow disappears.
 Some rays are produced which create fluorescence on the glass wall opposite to the cathode.
These rays are called cathode rays.
 The color of the glow or the fluorescence produced on the walls of the glass tube, depends
upon the composition of glass.
Properties of Cathode Rays
1.Nature of charge:
 Cathode rays are negatively charged.
 In 1895, J Perrin showed that when the cathode rays passed between the poles of the magnet, the
path of the negatively charged particles was curved downward to point 2 by the magnetic field.
 In 1897, J. Thomson established their electric charge by the application of electric field, the
cathode ray particles were deflected upwards (towards the positive plate) to point 3.
2.Have Momentum:
These rays can drive a small paddle wheel placed in their path. This shows that these rays possess
momentum. From this observation, it is inferred that cathode rays are not rays but material particles
having a definite mass and velocity.

3.Moves in Straight Line:

Cathode rays cast a shadow when an opaque object is placed in their path. This proves that they travel
in straight line perpendicular to the surface of cathode.

4. Fluorescence Production:
They produce a greenish fluorescence on striking the walls of the glass tube. These rays also produce
fluorescence in rare earths and minerals. When placed in the path of these rays, alumina glows red and
tin stone yellow.
5. Production Of X-Rays:
Cathode rays can produce X-rays when they strike an anode particularly with large atomic mass.
6. Ionization Effect:
Cathode rays can ionize gases.
7. Reducing Effect:
They can cause a chemical change, because they have a reducing effect.
8. Penetration:
Cathode rays can pass through a thin metal foil like aluminum or gold foil.
The e/m value of cathode rays shows that they are simply electrons. J.J. Thomson concluded from his
experiments that cathode rays consist of streams of negatively charged particles.
Stony named these particles as electrons.
Discovery of Proton (Positive Rays)
 In 1886, German physicist, E. Goldstein took a discharge tube provided with a cathode having
extremely fine holes in it.
 When a large potential difference is applied between electrodes, it is observed that while
cathode rays are travelling away from cathode, there are other rays produced at the same time.
 These rays after passing through the perforated cathode produce a glow on the wall opposite
to the anode. Since these rays pass through the canals or the holes of cathode, they are called
canal rays.

Reason for the Production of Positive Rays:

These positive rays are produced, when high speed cathode rays (electrons) strike the molecules of a
gas enclosed in the discharge tube. They knock out electrons from the gas molecules and positive ions
are produced, which start moving towards the cathode.
Properties of Positive Rays:
 These rays deflected towards the negative plate of the electric filed.
 They produce flashes on ZnS.
 Their mass is 1836 times heavier than the mass of electron.
 They can ionize the gas.
 They travel in straight line opposite to the cathode rays.
 These rays suggested by Rutherford.
 The nature of canal rays depends upon the nature of gas inside the discharge tube.
 Heavier the gas lesser will be the m/e value of canal rays.
 The canal rays produced by Hydrogen gas have maximum m/e value.
Discovery of Neutron:

 Proton and electron were discovered in 1886 and their properties were completely determined
till 1895.
 Rutherford predicted in 1920 that some kind of neutral particle having mass equal to that of
proton must be present in an atom, because he noticed that atomic masses of atoms could not
 be explained
 Chadwick discovered neutron in 1932 and was awarded Nobel prize in Physics in 1935.

Experiment:
A stream of a-particles produced from a polonium source was directed at beryllium (49Be ) target. It
was noticed that some penetrating radiation were produced. These radiations were called neutrons
4
because the charge detector showed them to be neutral.
Actually a-particles and the nuclei of Be ate re-arranged and extra neutron is emitted.

Properties of Neutron:
 A free neutron decays into a proton, electron and a neutrino.
0 1 −1 0
1n → 1P + 0e + 0 n

 They cannot ionize the gas.

 They are highly penetrating.
 They can expel high speed protons from paraffin, water, paper and cellulose.
 When neutrons travel with an energy 1.2 Mev (Mega electron volt 106), 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.
 When neutrons are used as projectiles, they can carry out the nuclear reactions. A fast neutron
ejects an a-particle from the nucleus of nitrogen atom and boron is produced, along with and a-
particles.
14 1 13 4
7 N + 0n → 5 B + 2 He

 When slow moving neutrons hit the Cu metal then gamma radiations are emitted.
65 1 66
29 Cu + 0n → 29 Cu +hγ
66 66 −¿¿
26 Cu → 30Zn +1 e
Actually, neutron is captured by the nucleus of 65 66
29 Cuand 29 Cu is produced. This radio active emits
an electron (alpha-particle) and its atomic number increases by one unit

Measurement of e/m value of electron:

  In 1897, J.J Thomson devised an instrument to measure the e/m value of electron. The apparatus
consists of a discharge tube shown.
 The cathode rays are allowed to pass through electric and magnetic fields. When both the
fields are of then a beam of cathode rays, consisted of electrons, produces bright luminous
spot at P1 on the fluorescent screen.

 The north and south poles of magnetic field are perpendicular to the plane of paper in the
diagram. The electrical field is in the plane of paper.
 When only magnetic field is applied, the cathode rays are deflected in a circular path and fall at
the point P3.
 When only electric field is applied, the cathode rays produce a spot at P2.
 Both electric and magnetic fields are then applied simultaneously and their strengths adjusted
in such a way that cathode rays again hit the point P1.
 In this way by comparing the strengths of the two fields one can determine the e/m value of
electrons.
 It comes out to be 1.7588 x 1011 coulombs kg-1

Measurement of Charge on Electron - Millikan's Oil Drop Method:

In 1909, Millikan determined the charge on electron by a
simple arrangement.
Experiment:
 The apparatus consists of a metallic chamber. It
has two parts. The chamber is filled with air,
the pressure of which can be adjusted by a
vacuum pump.
 There are two electrodes A and A’
 These electrodes are used- to generate an
electrical field in the space between the
electrodes.

Procedure: Calculations:
 A fine spray of oil droplets is created by an The droplet falls under the force of gravity without
atomizer applying the electric field.
 A few droplets passes through the hole in The velocity of the droplet is determined. The
the top plate and into the region velocity of the droplet (V1) depends upon its weight,
  Between the charged plates, where one of mg.
them is observed though a microscope. This
droplet, when illuminated perpendicularly v1 mg
to the direction of view, appears in the Where ’m’ is the mass of the droplet and ‘g’ is the
microscope as bright speck against a dark acceleration due to gravity.
background.
After that the air between the electrodes is ionized
by X-rays.
The droplet under observation takes up an electron
and gets charged. Now, connect A and A’ to a
battery which generates an electric field having a
strength, E.
The droplet moves upwards against the action of
gravity with a velocity (v2).
v2Ee  mg
Dividing equation (1) by (2)
V1 mg
=
V 2 E e−mg

The smallest charge which he found was 1.59 x 10-19 coulombs, which is very close to the recent value of
1.6022 x 10-19 coulombs.
Mass of Electron:
The value of charge on electron is 1.602 x 10-19 coulombs, while e/m of electron is 1.7588 x 1011 coulombs kg-1.
e 11
=1.7588 × 10
m
−19
1.6022 ×10 coulumb
Mass o f electron= 11 −1
1.7588 × 10 Coulumb kg
−19
Mass of electron=9.1095× 10 kg
Rutherford's Model of Atom (Discovery of Nucleus)
In 1911, Lord Rutherford performed a classic experiment. He studied the scattering of high
speed alpha-particles which w e r e e m i t t e d from a radioactive metal (radium or polonium)
Experiment:
A beam of a-particles was directed onto a gold foil of 0.00004 cm thickness as target through a pin-
hole in lead plate.
A photographic plate or a screen coated with zinc sulphide was used as a detector. Whenever, an a-
particle struck the screen, flash of light was produced at that point.
Observations:
 It was observed that most of the particles went through the foil undeflected.
 Some were deflected at fairly large angles and a few were deflected backward.
 Results:
1. An atom in which a tiny nucleus is surrounded by an appropriate number of electrons.
2. Atom as a whole being neutral, therefore, the nucleus must be having the same number
of protons as there are number of electrons surrounding it.
3. The atom has a central hard and dense part which is called nucleus by him.
4. Except electron all the fundamental particles are found in the nucleus.
5. Deflection of few particles shows that the nucleus is very small sized.
6. The electron revolves around the nucleus.
7. Maximum volume occupied by atom is empty it was shown by the passing of maximum
alpha particles remaining undeflecetd through the foil.
Defects in Rutherford Model:
According to this model atom should give continues spectrum but line spectrum of atom is
observed.
The radius of the orbiting electron should become smaller and smaller and the electron should fall into
the nucleus. Thus, an atomic structure as proposed by Rutherford would collapse it is due to loss of
energy.

PLANCK'S QUANTUM THEORY:

Max Planck proposed the quantum theory in 1900 to explain the emission and absorption of radiation.
According to his revolutionary’ theory, energy travels in a discontinuous manner and it is composed of
large number of tiny discrete units called quanta.
Assumptions:
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.
2. The amount of energy associated with a quantum of radiation is proportional to the frequency
(v) of the radiation.
Frequency
 Frequency is the number of waves passing through a point per second.
E  v
E = hv

Where ’h’ is a constant known as Planck’s constant and its value is 6.626x10-34 Js. It is, in
fact, the ratio of energy and the frequency of a photon.
A body can emit or absorb energy only in terms of quanta.
E = hv

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

v=c/
Greater the wavelength, smaller the frequency of photon
E=hc/
Wavelength:
Wavelength is the distance between the two adjacent crests or troughs and expressed in A , nm or pm.
(1 A =10 -10’m’, lnm = 10-9m, lpm=10-12m)
Greater the wavelength associated with the photon, smaller is its energy.
Wave Number:
Wave number (v) is the number of waves per unit length, and is reciprocal to wavelength.
ν = 1/

E=hc ν

So, the energy of a photon is related to frequency, wavelength and wave number. Greater the wave
number of photons, greater is the energy associated with them.
BOHR’S MODEL OF ATOM:
Bohr made an extensive use of the quantum theory of Planck and proposed that the electron, in the
hydrogen atom.
(i) Electron revolves in one of the circular orbits outside the nucleus. Each orbit has a fixed
energy and a quantum number is assigned to it.
(ii) Electron present in a particular orbit neither emits nor absorbs energy while moving in the
same fixed orbits. The energy is emitted or absorbed only when an electron jumps from one orbit
to another.

(iii) When an electron jumps, the energy change Δ E is given by the Planck’s equation
Where Δ E is the energy difference of any two orbits with energies E1 and 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 from outer to inner orbit.
Δ E=E2 −E1
(iv). Electron can revolve only in those orbits having a fixed angular momentum (mvr).
The angular momentum of an orbit depends upon its quantum number.
nh
mvr=
2π
Where n = 1,2,3,.............

Derivation of Radius and Energy of Revolving Electron in nth Orbit:

By applying these ideas, Bohr derived the expression for the radius of the nth orbit in hydrogen atom.
For a general atom, consider an electron of charge ‘e’ revolving around the nucleus having charge Ze +.
Z being the proton number and e+ is the charge on the proton.
If “m” is the mass of electron and “r” is the radius of electron then,
The force of attraction between electrons and nucleus can be explained by Coulombs law.
According to Coulombs law the force attraction
between two charges is given as:

2
Ze
Force of attraction= 2
4 π ∈° r

°
ε Is vacuum permittivity and its value is 8.84 x 10-12C 2 J -1m-1.
This force of attraction is balanced by the mv2/r Therefore, for balanced conditions, we can write.
2 2
mv Ze
= 2
r 4 π ∈° r
2
2 Ze
mv = −−−(1)
4 π ∈° r
By rearrange the above equation:
2
Ze
r= 2
−−−(2)
mv 4 π ∈°
According to equation (2), the radius of a moving electron is inversely proportional to the square of its velocity.
NOTE: It conveys the idea, that electron should move faster nearer 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.
In order to eliminate the factor of velocity from equation (2), we use Bohr’s postulate.
The angular momentum of the electron is given by.
nh
mvr=
2π
Rearranging the equation:
nh
v=
2 πmr
Taking square on both side:
2 2
2 n h
v= 2 2 2
4π m r
Substituting the value of v2.
2
Ze
r= 2 2
n h
m 4 π ∈° 2 2 2
4π m r

2 2 2 2
Z e .4 π m r
r= 2 2
m 4 π ∈° n h
 2 2
Z e . mπ r
r= 2 2
∈° n h
2 2
2 Z e . mπ r
2
∈° n h =
r
2
2 2 Z e . mπr
∈° n h =
1
2 2
∈° n h
2
=r
Z e . mπ
2 2
∈° n h
r= 2
Z e . mπ
For hydrogen atom Z = 1, so the equation for radius of H-atom is:

( )
2 2 2
∈° n h ∈° h 2
r= 2
= 2
n
e . mπ e . mπ
According to the above equation the radius of hydrogen atom is directly proportional to the square of number of
orbit (n). So, higher orbits have more radii and vice versa.
° 2
ε h
2 is constant factor whose value calculated by putting the values of m, π , ε °, e and h in the equation.
e . mπ

( )
2
8.84 ×10−12 C 2 j−1 m−1 × ( 6.626 × 10−34 Js )
r= 2
n2
( 1.6022 ×10 −19
C ) × 9.1095× 10
−31
kg ×3.14
r=0.529 Ao (n2 )
n=1 r1 =0.529 Ao
n=4 r4 =8.4 Ao
n=2 r2 =2.11 Ao
n=5 r5 =13.22 Ao
n=3 r3 =4.75 Ao
The comparison of radii shows that the distance between orbits of H-atom goes on increasing as we move from 1st
orbit to higher orbits. The orbits are not equally spaced;
r2 –r1 <r3 –r2 <r4 –r3 <r5 –r4 < ……………………
 Energy of Revolving Electron:
The total energy of an electron in an orbit is equal to sum of kinetic and potential energy.
E= EKinetic + EPotential
1 2
K.E = mv
2
The value of potential energy can be calculated as follows:
2
Ze
The force of attraction between the nucleus and revolving electron is Force of attraction= 2
4 π ∈° r
If electron moves from a small distance “dr” then the work done for moving electron is given as:
In order to calculate the potential energy at a distance from the nucleus we calculate the total work done for
electron bringing from infinity to a point at distance “r” from the nucleus.
W = Force X Distance
2
Ze
W¿ 2
x dr
4 π ∈° r
By integrating the above equation.
2
−Z e
Work Done = Potential Energy=
4 π ∈° r
The minus sign indicates that the potential energy of electron decreases, when it is brought from infinity to a
point at a distance ’r’ from the nucleus. At infinity, the electron is not being attracted by anything and the
potential energy of the system is zero. Whereas at a point nearer the nucleus, it will be attracted by the
nucleus and the potential energy becomes less than zero.
E= EKinetic + EPotential

( )
2
1 2 −Z e
E= mv +
2 4 π ∈° r
2
1 2 Ze
E= mv − ---------- (1)
2 4 π ∈° r
We know that:
2
2 Ze
mv =
4 π ∈° r
By putting the value of mv2 in equation 1.

( )
2 2
1 Ze Ze
E= −
2 4 π ∈° r 4 π ∈° r
2 2
Ze Ze
E= −
8 π ∈° r 4 π ∈° r
2 2
Z e −2 Z e
E=
8 π ∈° r
2
−Z e
E= −−−−−(2)
8 π ∈° r
Since
2 2
∈° n h
r= 2
Z e . mπ
By putting the value of “r” in equation 2.
2
−Z e
En = 2 2
∈n h
8 π ∈° ° 2
Z e . mπ
2 2
−Z e . Z e . m
En = 2 2 2
8 ∈° n h
2 4
−Z e m
En = 2 2 2
8 ∈° n h
For hydrogen atom Z = 1
4
−e m
En = 2 2 2
8 ∈° n h

[ ]
4
−e m 1
En = 2 2
× 2
8 ∈° h n
The factors outside the brackets are all constants.
4
e m −18
2 2
=2.178 ×10 j
8 ∈° h

En =−2.178 ×10−18
[ ]
1
n
2
j

It is for joul per atom to convert it kJ/mol.

Multiplying by Avogadro’s number and divided by the 1000.

[ ]
−18
−2.178 × 10 23 1
En = ×6.02 ×10 2
j
1000 n

−1313.315
En = 2
kJ /mol
n
−1313.315
As mole of H=1.008g so energy associated to the 1.008g of hydrogen is 2
kJ /mol
n
Substituting, the values of n as 1,2,3,4,5, etc. in above equation we get the energy associated with an electron
revolving in 1st, 2nd, 3rd, 4th and 5th orbits of H-atom.
−1313.315 −¿¿
E 1= 2
=−1313.315 kJ mol
( 1)
−1313.315 −¿¿
E 2= 2
=−328.32 kJ mol
( 2)
−1313.315 −¿¿
E3 = 2
=−145.92kJ mol
( 3)
−1313.315 −¿¿
E 4= 2
=−82.08 kJ mol
(4 )
−1313.315 −¿¿
E5 = 2
=−52.53 kJ mol
( 5)
The values of energy differences between adjacent orbits.
E2− E1=(−328.32 )− (−1313.315 )
−¿ ¿
E2− E1=−328.32+1313.315=984.99 kJ mol

E3 −E2=(−145.92 ) −(−328.32 )
−¿¿
E3 −E2=−145.92+328.32=182.40 kJ mol

E 4−E3 =(−82.08 )− (−145.92 )

−¿ ¿
E 4−E3 =−82.08+145.92=63.84 kJ mol
The differences in the energy values are decreasing.
E2− E1> E3−E 2> E 4 −E3 … … … … … .

SPECTRUM:
The arrangement of electromagnetic radiations on the basis of increasing wavelength and decreasing energy is
known as spectrum.
 When a radiation of light is passed through a prism, the radiation undergoes refraction or bending.
 The extent of bending depends upon the wavelength of the photons.
 A radiation of longer wavelength is bent to a smaller degree than the radiation of a shorter
wavelength.
 Ordinary, white light consists of radiation of all wavelengths, and so after passing through the
prism, white light is split up into radiations of different wavelengths.
 The colors of visible spectrum are violet, indigo, blue, green, orange, yellow and red and their
wavelengths range from 400 nm to 750 nm.
 In addition to the visible region of the spectrum, there are seven other regions.
 Ultraviolet rays, X-rays , Y-rays and cosmic rays are towards the lower frequency in the spectrum and have
greater energy. While on the other side of the visible region there are larger wavelength containing rays like
microwaves, infrared radiation and radio waves having very lower energy.
 Spectrum is of two types.
(i) Continuous spectrum (ii) Line spectrum
Continuous Spectrum:
 In this type of spectrum, the boundary line between the colors cannot be marked.
 The colors diffuse into each other.
 One color merges into another without any dark space. The best example of continuous spectrum is
rainbow
 It is obtained from the light emitted by the sun or incandescent (electric light) solids.
 It is the characteristic of matter in bulk.
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 line
spectrum or atomic spectrum.
 This is characteristic of an atom.
 The number of lines and the distance between them depend upon the element volatilized.
Example:
 Line spectrum of sodium contains two yellow colored lines separated by a definite distance.
 Similarly, the spectrum of hydrogen consists of a number of lines of different colors having
different distances from each other.
 It has also been observed that distances between the lines for the hydrogen spectrum decrease with the
decrease in wavelength and the spectrum becomes continuous after a certain value of wavelength

Atomic spectrum can also be observed when elements in gaseous state are heated at high
temperature or subjected to an electric discharge.
There are two ways in which an atomic spectrum can be viewed.
(i) Atomic emission spectrum
(ii) Atomic absorption spectrum
Atomic Emission Spectrum:
When solids are volatilized or elements in their gaseous states are heated to high temperature or subjected to
an electrical discharge, radiations o f c e r t a i n w a v e l e n g t h s a r e emitted. The spectrum of this radiation
contained bright lines against a dark background. This is called atomic emission spectrum.
Atomic Absorption Spectrum:
When a beam of white light is passed through a gaseous sample of an element, the element absorbs certain
wavelengths while the rest of wavelengths pass through it. The spectrum of this radiation is called an atomic
absorption spectrum.
 The wavelengths of the radiation that have been absorbed by the element appear as dark lines and the
background is bright.

 It is interesting to note that the positions or the wavelengths of lines appearing in both
emission and absorption spectra are exactly the same.
 In emission spectrum, these lines appear bright because the corresponding wavelengths are
being emitted by the element, whereas they appear dark in absorption spectrum because the
wavelengths are being absorbed by the element.
5.1.1 Hydrogen Spectrum
Hydrogen-spectrum is an important example of atomic spectrum. Hydrogen is filled in a discharge
tube at a very low pressure a bluish light is emitted from the discharge tube. This light when viewed through a
spectrometer shows several isolated sharp lines.
These are called spectral lines. The wavelengths of these lines lie in the visible, ultraviolet and
infrared regions. These spectral lines can be classified into five groups called spectral series. These series are
named after their discoverers as shown below.
(i) Lyman series (U.V region) (ii) Balmer series (visible region)
(iii) Paschen series (LR region) (iv) Brackett series (I.R region)
(v) Pfund series (I.R region)

The first four series were discovered before Bohr’s atomic model (1913). The wave numbers (m-1) of the series
of lines in hydrogen spectrum are given in Table.
Lyman series (U.V. Balmer series Paschen series Brackett series (I.R. Pfund
 region) (Visible region) (I.R. region) region) series (I.R.
region)
5 5 5 5
82.20 x 10 15.21 x 105 (H line) 5.30 x 10 2.46 x 10 1.34 x 10
á
5 5 5 5
97.20 x 10 7.80 x 10 3.80 x 10 2.14 x 10
20.60 x 105 (H âline)
5 5 5
102.20 x 10 9.12 x 10 4.61 x 10
23.5 x 105 (H ãline)
5 5
105.20 x 10 24.35 x 105 (H line) 9.95 x 10
ä
5
106.20 x 10 25.18 x 105
5
107.20 x 10

Origin of Hydrogen Spectrum on the Basis of Bohr’s Model:

According to Bohr, electron in hydrogen atom may revolve in any orbit depending upon its energy. When
hydrogen gas is heated or subjected to an electric discharge, its electron moves from one of the lower orbit
to higher orbit, absorbing particular wavelength of energy. Subsequently, when it comes back, the same
energy is released. This energy is observed as radiation of particular wavelengths in the form of bright lines
seen in the certain region of the emission spectrum of hydrogen gas.

The spectral lines of Lyman series are produced when the electron jumps from n2= 2, 3,4,5, to, n,
= 1 (Lyman did not know this reason). Similarly, spectral lines of Balmer series discovered in 1887
originated when an electron jumps from n2 = 3, 4, 5, 6,.........................................................to n1= 2orbit.
In the same way, Paschen, Brackett and Pfund series of lines are produced as a result of
electronic transitions from higher orbits to 3rd, 4th and 5th orbits, respectively.

Calculations of Wave Numbers of Photons of Various Spectral Series By Bohr’s Theory

The wavelength ( λ ) or wave number ( v ) of a spectral line depends on the quantity of energy emitted by the electron.
Suppose, an electron jumps from n2 to n1, and emits a photon of light.
According to Bohr’s equation of energy:
Energy of electron on n1 orbit:
 2 4
−Z e m
E 1= 2 2 2
8 ∈° n1 h
Energy of electron on n2 orbit:
2 4
−Z e m
E 2= 2 2 2
8 ∈° n2 h
The difference of energy between two orbits:
Δ E=E2 −E1

[ ][ ]
2 4 2 4
−Z e m −Z e m
Δ E= 2 2 2
− 2 2 2
8 ∈° n 2 h 8 ∈° n1 h
2 4 2 4
−Z e m Z e m
Δ E= 2 2 2
+ 2 2 2
8 ∈° n2 h 8 ∈° n1 h

[ ]
2 4
Z e m 1 1
Δ E= 2 2 2
− 2
8 ∈° h n1 n 2
For “H” atom Z=1

[ ]
4
e m 1 1
Δ E= 2 2 2
− 2
8 ∈° h n 1 n2

[ ]
4
e m 1 1
2 2 It is constant factor whose value is =2.18x10
-18
2
− 2 joule
8 ∈° h n 1 n2
Frequency:
Since Δ E=hυ

[ ]
2 4
Z e m 1 1
Δ E= 2 2 2
− 2
8 ∈° h n1 n 2

[ ]
2 4
Z e m 1 1
hυ= 2 2 2
− 2
8 ∈° h n1 n2

[ ]
2 4
Z e m 1 1
υ= 2 3 2
− 2 Hz
8 ∈ ° h n1 n 2
Z is equal to 1 for “H”

[ ]
4
e m 1 1
υ= 2 3 2
− 2 Hz
8 ∈° h n 1 n2
The unit of frequency unit cycle per second or Hz.
Wave Number:
υ=c υ

[ ]
2 4
Z e m 1 1
c υ= 2 3 2
− 2
8∈° h n1 n2

[ ]
2 4
Z e m 1 1
υ= 2 3 2
− 2
8 ∈° c h n1 n2
Z is equal to 1 for “H”

[ ]
4
e m 1 1
υ= 2 3 2
− 2
8 ∈° c h n1 n2
4
e m 7 -1
All the terms in 2 3 are constant have been calculated to be 1.09678x10 m . This is called Rydberg constant.
8 ∈° c h
 So υ=1.09678 ×10
7
[ 1 1
2
− 2
n1 n2 ]
Defects Of Bohr’s Atomic Model:
1- Origin of Spectrum:
 Bohr’s theory can only successfully explain the origin of spectrum in monoelectron
(one electron system) system like H, He+,Li2+ , Be+3 etc.
 Bohr’s theory failed to successfully explain the origin of spectrum of multi-electron or
poly- electron system like He, Li and Be.
2. Fine Structure or Multiple Structure of Spectral Line
 The splitting of spectral line into component lines while passing through high power
resolving spectrometer is called Multiple or fine structure.
 Bohr failed to explain the multiple structure of spectral line.
Example: The H-line in the Balmer series is found to consist of 5-component lines.
Note:Actually, appearance of several lines in single line suggest that only one quantum number is
not sufficient to explain the origin of various spectral lines.
3. Atomic Model is not Flat:
 Modern researches have shown that motion of electron is three-dimensional instead of a
single plane.
 In contrary to that, Bohr suggested circular orbits of electron and flat atomic model.
4. Zeeman Effect
The splitting of spectral line into number of closely spaced lines in the presence of magnetic field is
called Zeeman Effect.

Examples:
(i) The two lines in the emission spectrum of sodium split up into component lines in
magnetic field.
(ii) The spectral line of Hydrogen spectrum splits up into component lines in the presence
of magnetic field.
5. Stark Effect:
The splitting of a spectral line, into number of closely spaced lines in the presence of electric field is
called stark effect.
Example:
The spectral line of Hydrogen spectrum splits up into component lines in the presence of electric
field.
X-RAYS AND ATOMIC NUMBER:
 X-rays are produced when rapidly moving electrons collide with heavy metal anode in the
discharge tube.
 Energy is released in the form of electromagnetic waves when the electrons are suddenly
stopped.
 In the 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 the target metal. Every metal
 has its own characteristic X-rays.
 The X-rays are passed through a slit in platinum plate and then emerged through aluminum
window.
 This is thrown on a crystal of K4[Fe(CN)6], which analyses the X-ray beam.
 The rays are difracted from the crystal and are obtained in the form of line spectrum of X-
rays.
 This is allowed to fall on photographic plate. This line spectrum is the characteristic of target
material used.
 This characteristic X-rays spectrum has discrete spectral lines.
 These are grouped into K-series, L-series and M-series, etc. Each series has various line as K
α, K β, L α, L β, M α, M β etc.
A systematic and comprehensive study of X-rays was undertaken by Moseley in 1913-1914. His researches
covered a range of wavelengths 0.04 - 8 A.

Conclusions:
(i) The spectral lines could be classified into two distinct groups. One of shorter wavelengths are
identified by K-series and the other of comparatively longer wavelengths are identified by L-series.
(ii) If the target element is of higher atomic number the wavelength of X-rays becomes shorter.
(iii) A very simple relationship was found between the frequency (v) of a particular line of X-rays and the
atomic number Z of the element emitting it.
√ v =a(Z−b)
Here ‘a’ and ‘b’ are the constants characteristic of the metal under consideration.
‘a” is proportionality constant and ‘b’ is called screening constant of the metals.
Moseley Law:
This law states that the frequency of a spectral line in X-ray spectrum varies as the square of atomic
number of an element emitting it.
This law convinces us that it is the atomic number and not the atomic mass of the element which
determines its characteristic properties, both physical
and chemical. If value of v for K-series are plotted against Z, then a straight line is obtained.
Importance of Moseley Law:
(i) Moseley arranged K and Ar, Ni and Co in a proper way in Mendeleev’s periodic table.
(ii) This law has led to the discovery of many new elements like Tc(43), Pr(59), Rh(45).
 (iii)The atomic number of rare earths have been determined by this law.

WAVE-PARTICLE NATURE OF MATTER (DUAL NATURE OF MATTER)

Planck’s quantum theory of radiation tells us that light shows a dual character.
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 a dual character.
It means that electrons, protons, neutrons, atoms and molecules possess the characteristics of both the material
particle and a wave.
This is called wave-particle duality in matter.
de-Broglie derived a mathematical equation which relates the wavelength (  ) of the electron to the
momentum of electron.
h
λ=
mv
λ is the wavelenght of photon
m Is the mass of photon
v Is the frequency of photon
According to this equation, the wavelength associated with an
electron is inversely proportional to its momentum (mv).
According to planks equation:
E=hν
According to the Einstein mass energy relationship.
2
E=m c
By comparing both equations:
2
hν=mc
c
ν=
λ
c 2
h =m c
λ

h
=mc
λ
h
=λ … … …..(1)
mc
According to equation (1), the wavelength of photon is inversely proportional to the momentum of
photon. Considering that nature is symmetrical, we apply this equation (1) to the moving electron of
mass m’ and velocity V. This idea gives us the de-Broglie’s equation.
h
=λ … … … ..(2)
mv
According to equation (2), the wavelength of electron is inversely proportional to momentum of
electron. Now, consider an electron which is moving with a velocity of 2.188x106 ms-1 in the first
orbit of Bohr’s model of hydrogen atom.
−34
6.626 ×10
λ= −31 6
9.1095 ×10 x 2.188 x 10

 =0.33x10-9m (10-9m=1mm)

 =0.33 nm
 This value of wavelength ()of electron while moving in the first
orbit of H-atom is comparable
to the wavelength of X-rays and can be measured.
Now, consider a stone of mass one gram moving with a velocity
of 10 ms-1, then its wavelength will be:

6.626 1034 Js

=
103kg 10ms-1

= 6.626x10-30 m

This wavelength is so small, that it cannot be measured by any

conceivable method. It means that heavy material particles have
waves associated with them, but they cannot be captured and we
say that the macroscopic bodies don’t have the waves.