Ministry of Higher Education and Scientific Research

People's Democratic Republic of Algeria

University of Algiers 1

Faculty of Pharmacy

Department of Industrial Pharmacy

General Chemistry 01

For B.Sc. First Year

By: Dr. Arrous Salah

Academic year: 2023-2024

CHAPTER

2 BOHR'S MODEL OF ATOM

 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. The main points of his theory are:
(i) Energy is not emitted or absorbed continuously. Rather, it is emitted or absorbed in a
discontinuous manner and in the form of wave packets. Each wave packet or quantum is associated
with a definite amount of energy. In case of light, the quantum of energy is often called photon.
(ii) The amount of energy associated with a quantum of radiation is proportional to the frequency
(v) of the radiation. Frequency is the number of waves passing through a point per second.
E = hv
(iii) A body can emit or absorb energy only in terms of quanta.
E = hv
The frequency ‘vo ‘ is related to the wavelength of the photon as
v=c/l
Greater the wavelength, smaller the frequency of photon
E=hc/l

v = 1/l

E=hc v

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. The relationships
of energy, frequency, wavelength, wave number about the photon of light are accepted by scientists
and used by Bohr in his atomic model.

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, can only exist in certain permitted quantized energy levels. The main
postulates of Bohr’s theory are:
(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 ΔE is given by the Planck’s equation

ΔE =E2-E1 = hv .................. (1)

Where ΔE 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. Electron can revolve only in those orbits having a fixed angular
momentum (mvr). The angular momentum of an orbit depends upon its quantum number and it
is an integral multiple of the factor h/2 π i.e.

nh
mvr= ............................ (2)
2p

Where n = 1,2,3,.............

h 2h 3h
The permitted values of angular momenta are, therefore, ..............
2p , 2p , 2p
The electron is bound to remain in one of these orbits and not in between them. So, angular
momentum is quantized.

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

Let m be the mass of electron,

the radius of the orbit and v the
velocity of the revolving electron.
According to Coulombs law, the
electrostatic force of attraction
between the electron and the nucleus
will be given by the following
formula .
 Ze+ .e- Ze2
=
4π ∈0 r2 4π ∈0 r2

∈ is the vacuum permittivity

0 and its value is 8.84 x 10-12C2J-1m-1. This force of attraction is balanced

mv 2
by the r Therefore, for balanced conditions, we can write

mv 2 Ze2
or =
r 4p ∈0 r2

Ze2
mv =
2
......................... (3)
4p ∈0 r2

Rearranging the equation (9)

Ze2
r= .......................... (4)
4p ∈0 mv 2

According to equation (10), the radius of a moving electron is inversely proportional to the square
of its velocity. 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.
The determination of velocity of electron is possible while moving in the orbit. In
order to eliminate the factor of velocity from equation (4), we use Bohr’s postulate (iv). The
angular momentum of the electron is given by.

nh
mvr =
2p
Rearranging the equation of angular momentum

nh
v=
2p mr
Taking square

n 2 h2
2
v = 2 2 2 ................... (5)
4p m r
 Substituting the value of v2 from eq. (5) into eq. (4), we get

Ze2 ×4p 2m2r2

r=
4pe 0mn2h2

Rearranging the above equation, we get

e 0 n 2 h2
=r .............................. (6)
p mZe2
For hydrogen atom Z = 1, so the equation for radius of H-atom is

e 0 n 2 h2 e 0 h2 2
=r = ( )n ............................ (7)
p me2 p me2
According to the equation (7), 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. The collection of

e 0 h2
parameters ( ) in equation (7) is a constant factor.
p me2
When we put the value of ∈0 , h2 π, m and e2 alongwith the units then the calculations show that it
o o
is equal to 0.529 x I0-10 m or 0.529 A .( 10-10 m = l A )
o
Hence r=0.529 A (n2).............................. (8)
By putting the values of na s 1,2.3,4............. the radii of orbits of hydrogen atom are
o o
n=1 r1=0.529 A n=4 r4=8.4 A
o o
n=2 r2=2.11 A n=5 r5=13.22 A
o
n=3 r3=4.75 A
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 <..........................

The second orbit is four times away from the nucleus than first orbit, third orbit is nine times
away and similarly fourth orbit is sixteen times away.
Energy of Revolving Electron

The total energy of an electron in an orbit is composed of two parts, the kinetic energy which
is equal to 1
mv 2
and the potential energy. The value of potential energy can be calculated as follows.
2

Ze2
The electrostatic force of attraction between the nucleus and the electron is given by .
4pe 0r2
If the electron moves through a small distance dr, then the work done for moving electron is given
by

Ze2
dr because work=(force x distance)
4pe 0r2

In order to calculate the potential energy of the electron at a distance r from the nucleus, we
calculate the total work done for bringing the electron from infinity to a point at a distance r from
the nucleus. This can be obtained by integrating the above expression between the limits of infinity
and r.

r r r
Ze2dr Ze2 dr Ze2  -1  Ze2  -1  Ze2
∫∞ 4p ∈0 r2 = 4p ∈0 ∫∞ r2 = 4p ∈0  r ∞ = 4p ∈0  r  = - 4p ∈0 r
The work done is the potential energy of electron, so

Ze2
Work done = Epotential = - ............................... (9)
4pe 0r

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
any thing 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. The quantity
less than zero is negative. For this reason, the potential energy given by equation (9) is negative.
The total energy (E) of the electron, is the sum of kinetic and potential charges.
So, =E Ekinetic + Epotential

1 Ze2
= 2
mv - .............................. (10)
2 4pe or

Now, we want to eliminate the factor of velocity from equation (10). So, from equation (3),
substitute the value of mv2 in eq. (16)

Ze2
Since mv =
2
................................... (3)
4p ∈0 r
Ze2 Ze2
=E -
8p ∈0 r 4p ∈0 r

Ze2
Simplifying it, E= - ...................................... (11)
8p ∈0 r

Now substitute the value of r from eq (6) into eq (11) we get

∈ n 2 h2
Since .............................. (6)
mZe
-mZ2e4
En = 2 2 2 .............................. (12)
8 ∈0 n h

Where En is the energy of nth orbit.

For hydrogen atom , the number of protons in nucleus is one, so ( Z = 1).

me4  1 
En = - ................................ (13)
8 ∈20 h2  n2 
 Eq.(13) gives the energy of electron revolving around the nucleus of hydrogen atom.
The factors outside the brackets in equation (19) are all constants. When the values of these
constants are substituted along with their units, then it comes out to be 2.178 x 10 -18 J. The equation
(13) can be written as,

1
En = -2.178x10-18  2  J ............................. (14)
n 
This equation (14) gives the energy associated with electron in the nth orbit of hydrogen atom.
Its negative value shows that electron is bound by the nucleus i.e. electron is under the force of attraction of
the nucleus. Actually, the electron has been brought from infinity to distance r from the nucleus.
The value of energy obtained for the electron is in joules/atom. If, this quantity is multiplied
by Avogadro’s number and divided by 1000, the value of En will become

6.02 × 1023 × 2.18 × 10-18  1 

En = - ×  2  kJmol-1
1000 n 
1313.315
En = - 2
kJmol-1 .................................... (15)
n

This energy is associated with 1.008g of H-atoms i.e. with Avogadro’s number of atoms of
hydrogen.
Substituting, the values of n as 1,2,3,4,5, etc. in equation (15), we get the energy associated
with an electron revolving in 1st, 2nd, 3rd, 4th and 5th orbits of H-atom.

1313.31
E1 = - 2
= -1313.31 kJmol-1
1

1313.31
E2 = - 2
= -328.32 kJmol-1
2

1313.31
E3 = - 2
= -145.92 kJmol-1
3
 1313.31
E = - = -82.08 kJmol-1

1313.31
E5 = - 2
= -52.53 kJmol-1
5

1313.31
E∞ = - = 0 kJmol-1 (electron is free from the nucleus)
∞ 2

The values of energy differences between adjacent orbits can be calculated as follows
E2-E1 = (-328.32)-(-1313.31) = 984.99 kJmol-1
E3-E2 = (-145.92)-(-328.32) = 182.40 kJmol-1
E4-E3 = (-82.08)-(-145.92) = 63.84 kJmol-1
The differences in the values of
energy go on decreasing from lower
to higher orbits.

E2 -E1 >E3 -E2 >E4 -E3 >..........................

The energy difference between

first and infinite levels of energy is
calculated as:
E„ - E1 = 0 - (-1313.31) = 1313.31
kJmol-1
1313.31 kJmol-1 is the ionization
energy of hydrogen. This value
is the same as determined
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 splitted up into radiations of
different wavelengths.
The colours 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,
X-rays, y-rays and cosmic rays are
towards the lower wavelength end
of the spectrum and they possess
the photons with greater energies. On the other side of the visible region, there lies infrared,
microwave and radio frequency regions. The figure shows the continuity of wavelengths for
all types of regions of spectrum. Hence, a visual display or dispersion of the components of
white light, when it is passed through a prism is called a spectrum.
Spectrum is of two types.
(i) Continuous spectrum (ii) Line spectrum

Continuous Spectrum

In this type of spectrum, the boundry line between the colours cannot be marked. The colours
diffuse into each other. One colour 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. For example, line spectrum of
sodium contains two yellow coloured lines separated by a definite distance. Similarly, the spectrum
of hydrogen consists of a number of lines of different colours 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

Atomic Emission Spectrum

When solids are volatilized or elements in their gaseous states are heated to high temperature or
subjected to an electrical discharge, radiation of certain wavelengths are 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.
 Atomic absorption spectrum

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.

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 (1.1).
It is seen from the Table (1.1) that as we proceed from Lyman series to Pfund series, the wave
numbers (m-1) of spectral lines decrease. The lines of Balmer series have been
given specific names as H α, H β ........, etc.

Table (1.1)Wave numbers (m-1) of various series of hydrogen spectrum.

Lyman series Balmer series Paschen series Brackett series Pfund series
(U.V. region) (Visible region) (I.R. region) (I.R. region) (I.R. region)

82.20 x 105 5.30 x 105 2.46 x 105 1.34 x 105

15.21 x 105 (H á line)
97.20 x 105 7.80 x 105 3.80 x 105 2.14 x 105
20.60 x 105 (H â line)
102.20 x 105 9.12 x 105 4.61 x 105
23.5 x 105 (H ã line)
105.20 x 105 9.95 x 105
24.35 x 105 (H ä line)
106.20 x 105 25.18 x 105
107.20 x 105

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.

Electronic transitions in hydrogen atom and series of spectral lines, justified by Bohr's model atom

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

The wavelength ( l ) 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 n, and emits a photon of light.
According to Bohr’s equation of energy
 -Z2me4
E1 = 2 2 2
8 ∈0 n 1 h

-Z2me4
E2 =
8 ∈20 n2 2 h2

E1 and E2 are the energies of electrons in n1 and n2 respectively. The energy difference between the

Z2me4  1 1 
two can be calculated as follows: ∆
= =
E E2 -E - Joules .......................... (16)
8 ∈20 h2  n12 n22 
1

For H-atom; Z - 1

me4
and = 2.18 x 10-18 J (by putting the values of constants)
8 ∈0 h
2 2

1 1
∆E = 2.18x10-18  2 - 2  Joules ...................................... (17)
 n1 n2 
With the help of equation (17), the energy difference between any two orbits of Hatom can be
calculated where nt is the lower level and n2 is higher level. It is not necessary that n1 and n2 are
adjacent orbits.
Since ∆E = hv

me4  1 1 
Therefore hv = 2 2  2 - 2 
8 ∈0 h  n1 n2 

me4  1 1 
v= - Hz ............................... (18)
8 ∈20 h3  n12 n22 
 Frequency (v) has the units of the cycles s-1 or Hz. (1 Hz = 1 cycle s-1)
Equation (18) gives us the frequency of a photon emitted, when electron jumps from higher orbit
to lower orbit in H-atom. The frequency values go on decreasing between adjacent levels.

Calculation of Wave Number

Since v=cv
Putting in equation (18)

Z2me4  1 1 
Therefore cv = 2 3  2 - 2 
8 ∈0 h  n1 n2 

Z2me4  1 1  -1
v= - m .............................. (19)
8 ∈20 h3c  n12 n22 
me4
The value of the factor in eq. (19) has been calculated to be 1.09678 x 107m-1
8 ∈0 h c
2 3

This is called Rydberg constant. Putting Z = 1 for hydrogen atom, the equation (19)becomes.

1 1
=v 1.09678 × 107  2 - 2  m-1 .......................... (20)
 n1 n 2 
Equation (20) gives the values of wave number of photons emitted or absorbed when the electron
jumps between n1 and n2 orbits.
Let us calculate, the wave numbers of lines of various series.
Lyman Series:

Fitrst line n1 = 1(lower orbit), n2 = 2 (higher orbit)

1 1
v=
1.09678 × 107  2 - 2  =
82.26x105m-1
1 2 

Second line n1 = 1 n2 = 3

1 1
v=
1.09678 × 107  2 - 2  =
97.49x105m-1
1 3 

Limiting line n1 = 1 n2 = ∞

1 1 
v=
1.09678 × 107  2 - 2  =
109.678x105m-1
1 ∞ 
Limiting line is developed, when electron jumps from infinte orbit to, n = 1
The values of all these wave numbers lie in the U.Y region of the spectrum. It means that
when electron of H-atom falls from all the possible higher levels to n = 1, then the photons of
radiation emitted lie in the range of U.V region.

Balmer Series:

Fitrst line n1 = 2, n2 = 3

1 1
v=
1.09678 × 107  2 - 2  =
15.234x105m-1
2 3 
Second line n1 = 2 n2 = 4

1 1
v=
1.09678 × 107  2 - 2  =
20.566x105m-1
2 4 
Third line n1 = 2 n2 = 5

1 1
v=
1.09678 × 107  2 - 2  =
23.00x105m-1
2 5 

Limiting line n1 = 2 n2 = ∞

1 1 
v=
1.09678 × 107  2 - 2  =
27.421x105m-1
2 ∞ 
The limiting line of Balmer series lies in U.V region, while other lines fall in visible region.
Similarly, we can calculate the wave numbers for all the lines of Paschen, Brackett and Pfund series.
These three series of lines lie in the infrared region.

Defects of Bohr’s Atomic Model

1. Bohr’s theory can successfully explain the origin of the spectrum of H-atom and ions like
He+1, Li+2 and Be+3, etc. These are all one electron systems. But this theory is not able to explain the
origin of the spectrum of multi-electrons or poly-electrons system like He, Li and Be, etc.
2. When the spectrum of hydrogen gas is observed by means of a high resolving power
spectrometer, the individual spectral lines are replaced by several very fine lines, i.e. original lines
are seen divided into other lines. The Hα- line in the Balmer series is found to consist of five -
component lines. This is called fine structure or multiple structure. Actually, the appearance of
several lines in a single line suggests that only one quantum number is not sufficient to explain the
origin of various spectral lines.
3. Bohr suggested circular orbits of electrons around the nucleus of hydrogen atom, but
researches have shown that the motion of electron is not in a single plane, but takes place in three
dimensional space. Actually, the atomic model is not flat.
4. When the excited atoms of hydrogen (which give an emission line spectrum) are placed in a
magnetic field, its spectral lines are further split up into closely spaced lines. This type of splitting
of spectral lines is called Zeeman effect. So, if the source which is producing the Na - spectrum
is placed in a weak magnetic field, it causes the splitting of two lines of Na into component lines.
Similarly, when the excited hydrogen atoms are placed in an electrical field, then similar splitting
of spectral lines takes place which is called “Stark effect”. Bohr’s theory does not explain either
Zeeman or Stark effect.
However, in 1915, Sommorfeld suggested the moving electrons might describe in addition to
the circular orbits elliptic orbits as well wherein the nucleus lies at one of the focii of the ellipse.

MAIN BOHR'S MODEL EQUATIONS