NOTES

C H E M I S T R Y

ATOMIC STRUCTURE
BOHR’S MODEL

What you already know

• Discovery of subatomic particles • Black-body radiation

• Properties of electromagnetic waves • Photoelectric effect

What you will learn

• Variation of photocurrent with potential difference • Ground state

• Variation of photocurrent with frequency of radiation • Ionisation energy
• Bohr’s postulates • Ionisation potential
• Radius of the orbit • Excited state
• Velocity of electron • Excitation energy
• Energy of electron • Excitation potential
• Time period of electron • Bindng energy or Separation energy
• Energy difference between two energy levels

BOARDS MAIN ADVANCED

Variation of Photocurrent with Frequency of
Radiation and Potential Difference

Variation of photocurrent with retarding potential

When a retarding potential is applied, less electrons will reach the electrode, therefore, the
photocurrent will decrease. The retarding potential at which the current becomes zero is known as
the stopping potential. This stopping potential is maximum for the highest frequency of radiation
since these electrons have maximum kinetic energy.

Variation of photocurrent with the frequency of radiation

Greater the frequency of radiation, greater will be the kinetic energy of the electron. At high
frequencies, more electrons have enough kinetic energy to reach the electrode. Hence, the
photocurrent is the highest when the incident photons have high energy

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 02

Variation of photocurrent with accelerating potential

When an accelerating potential is applied for all the frequencies of radiations, more and more
electrons tend to have enough kinetic energy to reach the other electrode (plate). At a certain
accelerating potential, all the electrons will reach the electrode and produce a saturation current.
This saturation current is the same for all the frequencies since it depends only on the number of
electrons released/emitted per unit area per unit time.

Saturation current

The highest (maximum) value of the photocurrent Photocurrent

is known as saturation current. The saturation
current depends on the intensity of the light for a
given frequency. Saturation
𝜈3 current
In figure 1, stopping potential depends on incident
frequency. Therefore, when the frequency of the 𝜈2 𝜈
1
incident light increases, then the kinetic energy -V03 -V02 -V01 Collector plate potential
of the emitted electrons also increases. Thus, a
greater stopping potential is required to stop the Retarding Accelerating
movement of the emitted electrons. potential potential
𝜈3 > 𝜈2> 𝜈1 Fig. 1: Variation of photocurrent with
frequency and potential difference

•  Saturation current : The maximum value of current is known as saturation current.

• Retarding potential : It is the reverse potential at which kinetic energy of the ejected electron
is zero.
•  Collector plate potential : Potential difference between emitter plate and collector plate.

No. of Photons 1000 1000 1000

900 electrons
Energy/Photon (eV) 10 12 14
10: 8 eV
Photocurrent

90: [7, 8) eV
700: (1, 7) eV
90: (0, 1] eV
10: 0 eV

Retarding potential Accelerating potential

Fig. 2: Variation of photocurrent with frequency of radiation and potential difference

We are assuming that 900 electrons are emitted (K.E. of the photoelectrons are mentioned in
the above box)

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 03

10 electrons are emitted at maximum K.E. = 8 eV

90 electrons are emitted at K.E. = [7, 8) eV
700 electrons are emitted at K.E. = (1, 7) eV
90 electrons are emitted at K.E.= (0, 1] eV
10 electrons are emitted at K.E. = 0 eV
When a light radiation is incident on a metal
surface some photoelectron collides with
Photocurrent
surface atom. Hence, emission of electron takes
place at a range of zero to maximum kinetic I 3 > I2 > I1
I3
energy. I2
In figure 3, I3 > I2 > I1 means the intensity order. Stopping I1
The greater intensity of incident light merely potential
implies a greater number of photons per unit
area per unit time each of which releases one
-V0 0
electron.
Retarding Collector plate
Here, kinetic energy is the same for all the potential potential
three cases because we are not changing the
Fig. 3: Variation of photocurrent with
frequency. As more photons incident, more
intensity of radiation and potential difference
electrons are emitted. Since more electrons are
emitted, more is the saturation current.

BOARDS MAIN
Bohr’s Model

Rutherford’s nuclear model simply stated that atoms had a nucleus and the negative charged
electrons were present outside the nucleus. It did not say anything as to how and where those
electrons were arranged. It also could not explain why electrons did not fall into the nucleus due
to electrostatic attraction. Niels Bohr proposed a new model of atom that explained some of these
things and also the emission spectrum of hydrogen. Bohr’s theory was based on Planck’s quantum
theory and was built on the following postulates:

Note

The model is valid only for single electron species like H, He+, Li2+, etc.

Postulates of Bohr’s Model

1.  The electrons revolve around the nucleus in a fixed circular orbit of definite energy. As long as
the electron stays in this energy level, it does not radiate energy. These orbits are known as
stationary orbits.
  Each stationary orbit is associated with a definite amount of energy and it is also known as
energy levels. The greater the distance of the energy level from the nucleus, the more is the
energy associated. The different energy levels are numbered as 1, 2, 3, 4… (or K, L, M, N).

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 04

4
N-shell
3
M-shell
2 L-shell
1 K-shell
+
Positively charged nucleus
K
L
M

N
Fig. 4: The energy level of the stationary orbits
2.  Of the infinite number of circular orbits around the nucleus, an electron can revolve only in
those orbits where its angular momentum (mvr) is an integral multiple of h (where h is
2𝜋
Planck’s constant and the value is 6.626 × 10-34 Js ).
nh
mvr = (Where n is an orbit number in which electron is present)
2π
Or an electron revolves only in those orbits where angular momentum is quantised.
Where, m = Mass of electron
v = Velocity of the electron
r = Radius of the orbit
n = 1, 2, 3, etc.
By putting the values 1, 2, 3, etc. for n, we can have the angular momentum, respectively.
h 2h 3h
, , - - - - etc.
2π 2π 2π
There can be no fractional value of n
3.  Energy is emitted or absorbed only when an electron jumps from one energy level to another.
When an electron absorbs energy, it jumps to a higher energy orbit. This is known as an
excited state. An electron in an excited state can emit energy and fall to a lower energy state,
as the excited state is unstable.
  An atom in a ground state, in which transferring one or more electrons to different orbits,
cannot lower the total energy of the electrons. Thus, in a ground-state atom, all the electrons
are in the lowest possible energy levels.
n=2 n=2

n=1 n=1

Fig. 5: Electronic transition from lower energy Fig. 6: Electronic transition from higher energy
state to higher energy state state to lower energy state

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 05

4. In an atom, the electrons and nucleus are held together by the electrostatic forces of attraction.
Like in a solar system, planets and sun are held together by gravitational force.
The centripetal force required for the circular motion of electrons around the nucleus is being
provided by the electrostatic force of attraction between the nucleus and the electrons.
Therefore,

FFelectrostatic
electrostatic == FFcentripetal
centripetal

kq1qq2 kZe22
F = kq 1 2 = − kZe .... ( 1 )
Felectrostatic = r2 = − r22 .... (1)
electrostatic 2
r r
2
mv
....((22))
2
FFcentripetal
centripetal = = mv ....
rr Fcentripetal
Equating the
Equating equation ((11))and
the equation equation ((22)),,
and equation
kZe22 mv
kZe mv22
2
=
= r Fig. 7: Centripetal force acting on
rr2 r an electron in an atom
where,
k = Electrostatic constant (9 × 109 N m2 C-2 , when the medium is vacuum)
e = Charge of an electron
z = Atomic number
m = Mass of an electron

BOARDS MAIN
Radius of the Bohr’s Orbit

There are two forces acting on the electrons in the Bohr’s orbit. The centripetal force is the
electrostatic force of attraction between the electron and the nucleus and the centrifugal force is
the force that acts on the electron that pulls the electron out of the orbit.
In order for the electron to be in orbit,
Fcentripetal = Felectrostatic Substituting the value of v in equation (1), we get,
2
mv 2 kZe2  nh  1
Fcentripetal = =  × 2
r rm  2π  r × m2
kZe2
Felectrostatic = − 2 Substituting
= , h 6.626 × 10−34 Js
r
kZe 2
mv 2 e 1.6 × 10−19 C
=
then, 2 =
r r = 9.1 × 10−31 kg
m
2
kZe k= 9 × 109 N m2 C −2
On rearranging, v 2 = ......... (1 )
mr
nh n2 o
mvr = rn = 0.529 × A
2π Z
nh
Hence, v =
2 πmr

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 06

Calculating the ratio of the radii of the orbits of ions

Calculate the ratio of radii for the second orbit of He+ ion and third orbit of Be3+ ion.

Solution

Step 1:
Calculate the radii of He+ and Be3+
Radius of the nth orbit of an atom can be
given as follows:
n2 
rn = 0.529 × A
Z
Where n is the orbit number and Z is the atomic number
For second orbit of He+ ion For third orbit of Be3+ ion
n = 2, Z = 2 n = 3, Z = 4
So, the radius 32 
=
rBe3+ 0.529 × A .... ( 2)
22  4
=
rHe+ 0.529 × A .... (1)
2
Step 2:
Calculate the ratio of radii
Taking the ratio of equation (1) and equation (2),
So, the ratio will be
22
rHe+ 0.529 ×
= 2
rBe3+ 32
0.529 ×
4
2
2 4
= 2×
3 2
8
=
9
rHe+ 8
=
rBe3+ 9

Therefore,
8
The ratio of radii for the second orbit of He+ ion to the third orbit of Be3+ ion = .
9

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 07

Calculating the radius of the orbit of an ion

If the radius of the second orbit of Li2+ ion is x, then find the radius of the first orbit of He+ in terms
of x.

Solution

Radius of second orbit of Li2+ ion ( rA ) is as follows

22  
rA =0.529 × A =x A
3
Now, radius of first orbit of He+ ion ( rB ) is as follows
12 
=rB 0.529 × A
2
Dividing rA by rB , we get
x 22 2 8
= × 2 =
rB 3 1 3
3
rB = x
8
The radius of the first orbit of He+ in terms of x = 3 x.
8

BOARDS MAIN
Calculation of the Velocity of an Electron in Bohr’s Orbit

Angular momentum,
nh
mvr =
2π
nh
v= ....(i)
2πrm
2
 nh  1 (Derived in case of radius of Bohr’s orbit)
r=  ×
 2π  mkZe
2

Substituting the value of r in equation (i), we get,

2
nh  2π 
v= ×  × mkZe2
2πm  nh 
On putting the values of π, e, h and k
Z
=v 2.18 × 106 × m. sec −1
n

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 08

BOARDS MAIN
Time Period of the Revolution (T) of an Electron in an Orbit

It is the time taken by an electron to complete one revolution around the nucleus.
circumference
T=
velocity
2πrn
T= ....(1)
vn
Radius of a stationary state in H-like species is,
a0 n2 n2
rn = = 0.529 × ….. (2), where a0 = 0.529 Å, Z = Atomic number
Z Z
Velocity of an electron revolving in an orbit in H-like species is,
Z ms-1 ….. (3)
v n = 2.189 × 106 n
Substituting the values in equation (1), we get,
 n2 
2π  0.529 × 10-10 × 
2πrn Z 
T= = 
vn Z
2.189 × 106 ×
n

-16 n3
T 1.52 × 10 × 2 sec
Z

BOARDS MAIN ADVANCED

Energy of an Electron

Felectrostatic

Fig. 8: Electrostatic force of attraction between nucleus and electrons

Energy of an electron in the nth orbit is derived as follows:
Fcentripetal = F electrostatic Since
mv 2 mv 2
Fcentripetal = Kinetic energy =
r 2
kZe2 Therefore,
FElectrostatic = − 2
r kZe2 mv 2
kZe mv2 2 =
= 2r 2
r2 r

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 09

Total energy = Potential energy + Kinetic energy

kZe2 kZe2 We get,

T.E . = - +
r 2r
kZe 2 2π2Z2e4 mk 2
T.E . = - T.E. = En = -
2r n 2 h2
Substituting the value of r,
2 Z2
 nh  1 E n = - 13.6 × eV / atom
r=   × n2
 2π  mkZe
2
Z2
On putting the values of π, e, h and k, we get, En = - 2.18 × 10-18 × 2 J. atom-1
n
Z2 Z2
E n = - 13.6 × eV / atom E n = - 2.18 × 10-11 × 2 erg. atom-1
n2 n
2
Z2 Z
En = - 2.18 × 10-18 × 2 J. atom-1 E n = -313.6 × 2 kcal. mol -1
n n
Z2 1
E n = - 2.18 × 10-11 × 2 erg. atom-1 T.E. = -K.E. = P.E.
n 2
2
Z
E n = -313.6 × 2 kcal. mol -1
n
Note= 1 P.E.
T.E. = -K.E.
2
The potential energy of the electron at infinite distance from the nucleus is zero
The kinetic energy of the electron at the infinite distance from the nucleus is zero

Calculating the energy and the radius of the orbit of an ion

Calculate the energy associated(in eV) with the first orbit of He+. What is the radius of this orbit?

Solution
Step 1: Step 2:
+
Finding the energy of first orbit of He Finding the radius of first orbit
Z2  n2  o
E n = - 13.6 × eV rn = 0.529  A
n2  Z 
For first orbit of He+ ion, 1 o
= 0.529 × A
n=1,Z=2 2
So, energy of the first orbit of He+ ion, = 0.2645 × 10-10 m
22 = 2.645 × 10-11 m
EHe+ = - 13.6 eV
12  n2 
rn = 0.529  
= -54.4 eV  Z 
1
= 0.529 ×
2
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 10

Z2
E2 = - 2.18 × 10-18 × 2 J.atom-1
n ratio of the energies of the orbits of ions
Calculating the
42
E2 = - 2.18 × 10-18 × 2 J.atom-1
Calculate energy ratio2 for the third orbit of Li ion and second orbit of Be ion.
2+ 3+

 32 
- 2.18 × 10-18 ×  2 
E1
Solution
Hence, = 3 
E2 -18  42 
- 2.18 × 10
Energy associated with the n  orbit × 
22  of an atom can be given as follows
th

E1 × 10
1 -18 ×
Z2
E n = - 2.18
∴ = 2
J.atom-1
E2 4 n
For Li2+ ion, n = 3 , Z =23
3 -1
× 10-18 ×(E )2 for
E1 = -2.18 Energy
Therefore J.atom
third orbit of Li2+ ion:
31
32
E1 = -2.18 × 10-18 × 2 J.atom-1
3
For Be3+ ion, n = 2, Z = 4
Energy (E2) for second orbit of Be3+ ion
ZZ22
EE22 == --2.18 10-18
2.18 ×× 10 -18
×× 22
J.atom-1-1
J.atom
nn
4422
EE22 == --2.18
2.18 ×× 1010-18
-18
J.atom-1-1
×× 22 J.atom
22
-18
-18 3322 
--2.18
2.18 ×× 10 10 ××  22 
Hence,
Hence,
EE11
== 33 
EE22  4422 
--2.18
2.18 ×× 10 10-18
-18
××  22 
 22 
EE 11
∴ 11 ==
∴
EE22 44
3322
EE11 == -2.18 10-18
-2.18 ×× 10 -18
×× 22
J.atom-1-1
J.atom
33
BOARDS MAIN 22 ADVANCED
33 Energy difference between two energy levels
EE11 == -2.18 10-18
-2.18 ×× 10 -18
J.atom-1-1
×× 22 J.atom
33
n=2 n=∞ E=0
n=6
n=5
n=1 n=4 Higher energy
states
n=3
n=2

Ground state
Fig. 9: Electronic transition n=1
from lower energy state to Fig. 10: Energy level diagram
higher energy state

It is the energy difference between any two states. It decreases with an increase in the value of nL
(n lower) and nH (n higher).

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 ∆ E =  -13.6    -  -13.6  2   eV atom
2
11   nH
   nL  
  Z2   Z2   -1
∆ E = 13.6   2  -  2   eV atom
  nL   nH  
∆ E = Ehigher - Elower
2 1 1  -1
∆ E = 13.6 × Z  2 - 2  eV atom
  Z2     Z2   -1  nL nH 
∆ E =  -13.6  2   -  -13.6  2   eV atom
  nH     nL   -18 2  1 1  -1
∆ E = 2.18 × 10 × Z  2 - 2  J atom
  Z2   Z2   -1  nL nH 
∆ E = 13.6   2  -  2   eV atom
  nL   nH  
2 1 1  -1
∆ E = 13.6 × Z  2 - 2  eV atom
n nH 
Finding theL frequency and wavelength of emitted photon
-18 2  1 1  -1
∆ Ephoton
A 10 ×during
= 2.18is×emitted Z  an 2
- 2 
electronicJ atom
transition from n = 5 state to the n = 2 state in a hydrogen
atom. What is the frequency n
 L andn H 
the wavelength of the photon?

Solution
Step 1: Step 2:
Calculate the ΔE Calculate the wavelength
Energy difference associated when the hc
transition occurs can be given as follows: Now, ∆ E =
λ
-18 1 1  Where λ is the wavelength of photon emitted,
∆ E = 2.18 × 10  n2 - n2  J ν is the frquency of photon emitted and h is
 L H
planck's constant .
Where n L = lower energy orbit
n H = higher energy orbit hc
λ=
∆E
According to the question,
-34 8 -1
n L = 2, n H = 5 6.626 × 10 ( Js ) × 3 × 10 ms
λ= -19
4.578 × 10 J
-18  1 1 
∆ E = 2.18 × 10
 22 - 52  -7
λ = 4.342 × 10 m
-18 21
= 2.18 × 10 × Step 3:
100
-19 Calculate the frequency.
= 4.578 × 10 J
cc
ν
ν==
λ
λ
8 -1
10 ms
3 8 -1
3×× 10 ms
ν
ν== -7
10 m
4.342 -7
4.342 ×
× 10 m
14 -1
10 ss
ν 14 -1
ν== 6.909
6.909 ×
× 10

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 12

BOARDS MAIN ADVANCED

Ionisation Energy

It is the minimum energy required to move an electron from the ground state to infinity. Ionisation
energies for H, He+ and Li2+ are 13.6, 54.4 and 122.4 eV, respectively.
 Z2 
I.E. = E∞ - E1 = 0 -  -13.6 2  Where Z = Atomic number
 1  For H-like species, ground state is 1
Z 2
ΔE = Ionisation energy
∆ E = 13.6 2 eV atom-1
1

BOARDS MAIN
Ionisation potential

The potential difference through which a free electron must be accelerated from rest, such that
its kinetic energy becomes equal to the ionisation energy of the atom is known as the ionisation
potential of the atom. I.E. of H and He+ are 13.6 and 54.4 eV, respectively.
I.P. = (I.E.) eV/e = (K.E.) eV/e
I.P. = (13.6 Z2) V

BOARDS MAIN
Excitation Energy

The minimum energy required to excite an electron from the ground state of an atom to any of the
excited states is known as excitation energy.
 1 1 
∆ E = 13.6 × Z 2  2
- 2  eV atom
-1

 nL nH 
First excitation energy = E2 - E1
Fifth excitation energy = E6 - E1
Excitation energy when the electron is excited to first excited state from ground state for H-atom
is as follows:
 1   1
=  -13.6 × 2  -  -13.6 × 2  eV atom-1
 2   1 
= 10.6 eV

BOARDS MAIN
Excitation Potential

The difference in potential between an excited atomic state and ground state.
In other words we can say, the excitation potential is the potential, which is required for an electron
to jump from the ground state to any one of its excited states.

Excitation potential = (Excitation energy) eV/e

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 13

BOARDS MAIN
Binding Energy or Separation Energy

The energy required to move an electron from any state to an infinite shell is known as binding
energy of the state.
Binding energy of ground state = I.E. of atom or ion

Calculating the ionisation energy of an ion.

Calculate the ionisation energy for Li2+ ion.

Solution
Energy of nth orbit of hydrogen like atom
Z2
E n = - 13.6 × eV
n2
For Li2+ , outer most electron in n = 1, Z = 3
Ionisation energy = E∞ - E1
  32  
= 0 -  -13.6 ×  2  
  1 
= 13.6 × 9 eV
I.E. = 122.4 eV

Calculating the excitation energy of an ion.

Calculate the second excitation energy for He+ ion.

Solution
 Z2 
Energy of an electron in the nth orbit = - 13.6  2  eV
n 
First excitation energy = E2 - E1
Second excitation energy = E3 - E1
22
E1 = - 13.6 × = - 54.4 eV
12
22
E3 = - 13.6 × 2 = - 6.04 eV
3
So, second excitation energy = -6.04 - ( - 54.4 ) eV
             = 48.63 eV

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 14

Calculating the ionisation energy and the second excitation potential of a sample.

If the first excitation potential of a hydrogen-like sample is 15 V, find the I.E. and the second
excitation potential of the sample.

Solution
Step 1: Step 2:
Calculation of the I.E. Calculate second excitation potential
Energy of an electron in nth orbit Second excitation energy is the amount of
energy needed to bring the electron from the
 Z2 
E n = - 13.6  2  eV ground state, i.e, n = 1, to the second excited
n  state, i.e, n = 3
First excitation is from ⇒ ( n = 1 ) to ( n = 2 ) So, second excitation energy
First excitation potential = (E2 - E1 ) V  Z2   Z2 
=  -13.6 × 2  - - 13.6 × 2 
Z2  Z2   3   1 
E2 - E1 = - 13.6 × 2 - -13.6 × 2 
2  1  On putting, 13.6 × Z2 = E0
E2 - E1 = 15 eV Second excitation energy
Let, 13.6 × Z2 = E0 E0
= E0 -
E0 9
E0 - = 15 eV
4 20
= 20 -
Then, 9
E0 = 20 eV = 17. 77 eV
Ionisation energy ( I.E. ) = E∞ - E1 So, second excitation potential = 17. 77 V
  Z2  
I.E. = 0 -  -13.6 ×  2  
  1 
2
I.E. = 13.6 × Z = E0
So, I.E = 20 eV

n2
1. rn = 0.529 × Å
Z
Z
2. v = 2.18 × 106 × ms -1
n
n3
3. T = 1.52 × 10 × 2 sec
-16

Z
2
Z
4. E n = - 13.6 2 eV atom-1
n
Z2
5. E n = - 313.6 2 kcal mol -1
n
1 1
6. ∆ E = 13.6 × Z 2  2 - 2  eV atom-1
 nL nH 
1 1
7. ∆ E = 2.18 × Z 2 × 10-18  2 - 2  J atom-1
© 2020, BYJU'S. All rights reserved  nL nH 
2
 n
15 Z2
5. E n = - 313.6 2 kcal mol -1
n
1 1
6. ∆ E = 13.6 × Z 2  2 - 2  eV atom-1
 nL nH 
1 1
7. ∆ E = 2.18 × Z 2 × 10-18  2 - 2  J atom-1
 nL nH 
8. I.P. = 13.6 Z 2 V
Z2
9. I.E. = + 13.6 2 eV atom-1
n
10. Binding energy of ground state = I.E. of atom or ion

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