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UNIT 12 » ATOMIC SPECTRA

Spectroscopy:
The study of wavelength and intensity of electromagnetic radiations emitted or absorbed by
atoms is called spectroscopy.

Spectrum:
Set of all the wavelength of electromagnetic radiations emitted or absorbed by a substance is
called spectrum.

TYPES OF SPECTRUM

1. Line spectrum:
 “Spectrum which consists of sharp lines with each line representing a specific
wavelength emitted or absorbed by atoms is called line spectrum.”
 Line spectrum is characteristics of emitting elements.
 Line spectrum is due to transition of electrons between energy levels within an atom.
 Each element has a unique set of energy levels, hence each element has a unique line
spectrum.
 It is used to identify the gas or element.
 It is also known as atomic spectrum.
Line emission spectrum Line absorption spectrum
Line spectrum of electromagnetic radiations Line spectrum obtained by passing
emitted by a substance is called emission line electromagnetic radiations though a
spectrum` substance is called absorption line spectrum.
Each line represents the energy or wavelength Each line represents the energy or wavelength
emitted by the substance. absorbed by the substance.
Shows colored lines with a dark background. Shows dark lines with a bright background.

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Band- spectrum:
“Spectrum which consists of group of lines so closely spaced that each group appears to be a
band is called band spectrum or molecular spectrum.”
For example; Nitrogen spectrum
 Band spectrum is produced when molecules radiate their rotational and vibrational
energies.

2. Continuous- spectrum:
“Spectrum in which there is no gap or space between spectral lines is called continuous
spectrum.”
 All the solids, liquids and very dense gases when heated produced continuous spectrum.

HYDROGEN EMISSION SPECTRUM

When hydrogen gas is placed in a discharge tube and high voltage is applied across the tube the
gas starts glowing and give off bluish red light.
There were five types of series observed in emission spectrum of hydrogen atom

1. Lyman Series:

 Lyman series lies in ultraviolet region of spectrum.

 Lyman series is produced when an electron jumps from higher energy level to I st energy
level.
 The Rydberg formula for Lyman series is Rydberg constant

RH  1.0974 107 m1

1 1 1
 RH (  ) Where n = 2, 3 ………
 22 n 2
Minimum wavelength of Lyman series is Maximum wavelength of Lyman series is
produced when electron jumps from infinite produced when electro jumps from 2nd to 1st
to 1st shell of hydrogen atom. shell of hydrogen atom.

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min 
1
 91nm max   122nm
RH 3RH

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2. Balmer Series:
 Balmer series lies in visible region of spectrum.
 Balmer series is produced when an electron jumps from higher energy level to 2nd
energy level.
 The Rydberg formula for Balmer series is

1 1 1 Where n = 3, 4 …….
 RH (  )
 22 n 2

Minimum wavelength of Balmer series is Maximum wavelength of Balmer series is

produced when electron jumps from infinite produced when electron jumps from 3rd to 2nd
to 2nd shell of hydrogen atom. shell of hydrogen atom.

4 36
min   365nm max   656nm
RH 5RH

3. Paschan Series:
 Paschan series lies in infrared region of spectrum.
 Paschan series is produced when an electron jumps from higher energy level to 3 rd
energy level.
 The Rydberg formula for Balmer series is

1 1 1
 RH (  ) Where n = 4, 5, 6 ………..
 32 n2

Minimum wavelength of Paschan series is Maximum wavelength of Balmer series is

produced when electron jumps from infinite produced when electron jumps from 4th to 3rd
to 3rd shell of hydrogen atom. shell of hydrogen atom.
9 144
min   820nm max   1874nm
RH 7 RH

4. Bracket Series:
 Bracket series lies in infrared region of spectrum.

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 Bracket series is produced when an electron jumps from higher energy level to 4 th
energy level.
 The Rydberg formula for bracket series is

1 1 1
 RH (  )
 42 n 2 Where n = 5,6,7 ………

Minimum wavelength of Bracket series is Maximum wavelength of Bracket series is

produced when electron jumps from infinite produced when electron jumps from 5th to 4th
to 4th shell of hydrogen atom. shell of hydrogen atom.
16 400
min   1458nm min  4050nm 
RH 9 RH

5. Pfund Series:
 Pfund series lies in infrared region of spectrum.
 Pfund series is produced when an electron jumps from higher energy level to 5 th energy
level.
 The Rydberg formula for Pfund series is

1 1 1
 RH (  )
 52 n2 Where n = 6,7,8 ………

Minimum wavelength of Pfund series is Maximum wavelength of Pfund series is

produced when electron jumps from infinite produced when electron jumps from 6th to 5th
to 5th shell of hydrogen atom. shell of hydrogen atom.
25 900
min   2278nm max   7455nm
RH 11RH

BOHR’S MODEL
 In order to explain emperical results obtained
According to classical physics
by Rydberg formulated a model of hydrogen
an accelerating charge such as
atom. orbiting electron must
 Bohr’s model is semi classical model based on continuously radiate
following postulates. electromagnetic energy.

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Postulate1:
“Electron in an atom can move around nucleus in
Certain circular orbit without radiating. These orbits
are called discrete stationary states of the atom.”
Bohr’s 1st postulated is contradiction of classical
Physics.

Postulate II:

“Only those circular orbits or stationary states are

allowed for which orbital angular momentum is an
h
integral multiple of
2

h
h mvr  n( )
L  n( ) OR 2
2
Where n is principle Quantum number and
n = 1, 2, 3 ….
Example:
What is the ratio between angular momentum
of electron in 1st and 3rd shell of hydrogen atom
(a) 1:3 ✓ (b) 3:1
(c) 1:9 (d) 9:1
Example:
In which of the following shell the electron in hydrogen atom will highest angular momentum
(a) K-shell (n=1) (b) L- shell (n=2) (c) M- shell (n=3) (d) N- shell (n=4) ✓
Example:
Angular momentum of electron in 3rd shell of hydrogen atom is
(a) 1.05 1034 J .s (b) 2.10 1034 J .s (c) 3.15 1034 J .s ✓ (d 4.20 1034 J .s

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First shell 2nd shell 3rd shell 4th shell 5th shell
h
L( )h
2 L  2(
h
)  2h L  3(
h
)  3h L  4(
h
)  4h h
2 2 2 L  5( )  5h
2

1.05 1034 J .s 2.11034 J .s 3.15 1034 J .s 4.2 1034 J .s 5.25 1034 J .s

Postulate III:
“When an electron jumps from high energy
State En to a low energy state E p a photon
Of energy hf is emitted so that,”

hf  En  E p

De-Broglie’s Interpretation
“According to De-Broglie electron in an orbit behave like a wave and produce stationary wave
in the orbit. So length will be n . ”
l  n
h
2 r  n( )
mv

h
mvr  n( )
2

Quantized Radii:
 Electron can move in certain circular orbits.
 Radius of nth shell is given as

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n2h2
rn  2
4 kme 2
rn  n 2

 Short cut relation to find radius

rn  n2 r1 Where r1 = 0.053 nm

First shell 2nd shell 3rd shell 4th shell 5th shell
r1 r2  4r1 r3  9r1 r4  16r1 r5  25r1

0.053nm 0.212nm 0.477nm 0.848nm 1.325nm

 As ‘n’ increases radius of orbit increases and distance between two consecutive orbits
are also increases.

Quantized Velocity:
Electron moving around the nucleus has discrete velocities.
 Velocity of electron in nth-shell is given as

1
2 ke 2 vn 
vn  n
nh

 In moving from lower to higher shell velocity

decreases
 Short-cut relation to find velocity

1 Where v1  2.19 106 m / s

vn 
n

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Example:
Find the velocity of electron in 3rd shell

v1 2.19 106
v3   m / s  7 105 m / s  7 105 m / s
3 3

First shell 2nd shell 3rd shell 4th shell 5th shell
v1  2.19 106 v1 v1 v1 v1
v2  v3  v4  v5 
2 3 4 5

v1  2.19 106 v2  1.09 106 v3  7.3 105 v4  5.5 105 v5  4.4 105

Quantized Energies: Note:

Orbital electrons have specific
i. Potential Energy:
amount of energies as free
 Electron possess P.E due to attraction between electron can have any amount of
electron and nucleus. energy.
 Electron moving around the nucleus
kq1q2 k (e)(e) ke2
has discrete values of P.E given as: P.En   
rn rn rn
 Short relation to find P.E is
Note:
2 E0 1 By increasing n, P.E increases
P.En  ( P.E  )
n2 n2

Where E0  13.6ev
ii. Kinetic Energy:
 Electron possess kinetic energy due to its motion.
 Electron moving around nucleus has discrete values of K.E

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1 ke2
K .En  mvn 2 
2 2rn

 Short cut relation to find K.E is

E0 1
K .En  K .En 
n2 n2

iii. Total Energy:

ke2 ke2 ke2 2 k 2 me4
 T.E of electron is given as En  P.En  K .En    
rn 2rn 2rn n2 h2
 Short relation to find energy of electron

 Ev 1
En  ( En  )
n2 n2

 Ratio between K.E and total energy of electron is always 1:-1

 Ratio between P.E and total energy of electron is always 2:1
 Ratio between K.E and P.E of electron is always 1:-2

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Example 2:
In any shell P.E of electron will be
P.E of electron in ground state will be:
double of its total energy but negative
(a) 13.6 eV (b) -13.6 eV
(c) -27.2 eV (d) zero eV

Answer:
For ground state n = 1 and E = -13.6 eV so
P.E = 2(-13.6 eV) = -27.2 eV
Example 1:
in any shell K.E of an electron will be
What is K.E of electron in 1st excited state. equal to its total Energy and will be
(a) 13.6 eV (b) 3.4 eV positive
(c) 10.2 eV (d) 12.1 eV
Answer:
For 1st excited state n = 2 and
E = -3.4 eV so K.E = +3.4 eV

First shell 2nd shell 3rd shell 4th shell 5th shell
 E  E  E  E  E
4 9 16 25

-13.6 ev -3.4 ev -1.51 ev -0.85 ev -0.54 ev

Ionization Energy:
“Energy required to remove the electron from an atom is called ionization energy.”
 It is the energy required to make the electron jump from present state to infinite state.
 Ionization energy of electron in nth shell is given as

 E 13.6ev
Eionization  Eionization  1
n2 Or n2 ( Eionization  )
n2

 When an electron jumps from lower to higher orbit ‘n’ increases and ionization energy
decreases.

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Example 3:
What is ionization energy of electron moving in
M-shell of hydrogen atom. In any shell ionization energy of
(a) 13.6 eV (b) 3.4 eV electron is equal to its total energy
(c) 1.5 eV (d) 12.1 eV but positive

Answer:
For M-shell n = 3 and
E = -1.5 eV so Eionization = 1.5 eV

Ionization Potential:

“Potential through which an external electron need to be accelerated so that on collision with
bound electron it may supply required ionization energy is called ionization potential.”

Vionization 
Eionization
Or Eionization  eVionization
e

Example 4:
Minimum potential required to accelerate
an external electron so that it may knock
out the electron for 1st excited state:
In any shell ionization energy is equal
(a) 13.6 V (b) 3.4 V to ionization potential, just remove 'e'

(c) 1.5 V (d) 1.5 V

Answer:
for 1st excited state n = 2 and E = -3.4 eV
so Eionization and Vionization =3.4 V

Excitation Energy:

 “Energy required to make the electron jump from lower state to higher energy state is
called excitation energy.”
 Minimum energy required to excite an atom is called excitation energy.
Eexcitation  E final  Einitial
Example 5:
Energy required to excite the hydrogen atom from ground state (n = 1) to 2nd excited state
(n = 3) is

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(a) 10.2 eV (b) 1.5 eV

(c) 12.1 eV (d) 3.4 eV
Answer:
Eexc = 13.6-1.5=12.1 eV

Excitation Potential:
“Minimum potential which an external electron need to accelerated so that on collision with
bound electron it may supply the required energy is called excitation potential.”

Eexcitation
Vexcitation 
e

Example 6:
Minimum potential required to excite the atom from ground state to first excited state is
(a) 10.2 V (b) 1.5 V
(c) 12.1 V (d) 3.4 V

Quantity Relation Electron jumps from Electron jumps from

Lower to higher state higher to lower state
Radius rn  n r1
2
Increases Decreases
Velocity v1 Decreases Increases
vn 
n
Momentum mv1 Decreases Increases
Pn 
n
Angular momentum h Increases Decreases
Ln  n( )
2
K.E  E Decreases Increases
K .En 
n2
P.E 2 E Increases Decreases
P.En 
n2
Total Energy  E Increases Decreases
En 
n2

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Ionization Energy  E Decreases Increases

l.En 
n2
Excitation Energy Eexc  En  E p Decreases Increases
Time Perion Tn  n3 Increases Decreases
No. of special lines or no. of possible transitions when an electron returns from ‘n’ shell to
ground state.
n(n  1)
No of spectral lines 
2
Example:
If hydrogen gas is excited from ground state to 3rd shell then no. of spectral lines emitted by
hydrogen will be:
(a) 1 (b) 2
(c) 3 (d) 6
Answer:
n(n  1) 3(3  1)
No of spectral lines =   6
2 2

SPECTRAL SERIES
When an electron jumps from high energy state En
to a low energy state E p a photon of energy hf is emitted
so that,

hf  En  E p
hcE E

 ( 2 )
 n 2
p
hc E E
  Short cut relation for min
 p 2 n2
1 E 1 1 P2
 ( 2  2) min 
 hc p n RH
1 1 1
 RH ( 2  2 ) Short cut relation for max
 p n
E
WhereRH    1.0974 107 m 1 P 2 ( P  1) 2
hc max 
RH (2 P  1)

Short cut relation for any wavelength

P 2 n2
min 
13 RH (n 2  p 2 )
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Series Name Transition from Maximum Minimum Region

Higher shell to Wavelength Wavelength
Lyman 1st shell 4 1 Ultraviolet
max  min 
3RH RH
P=1
 122nm  91nm

Balmer 2nd shell 36 4 Visible

max  min 
5RH RH
P=2
 656.1nm  365nm

Paschan 3rd shell 144 9 Infrared

max  min 
7 RH RH
P=3
 1874nm  820nm

Bracket 4th shell 400 16 Infrared

max  min 
9 RH RH
P=4
 4050nm  1458nm

Pfund 5th shell 900 25 Infrared

max  min 
11RH RH
P=5
 7455nm  2278nm

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