Atomic Spectra Band Spectrum

When an electron transitions from one energy level to another, it emits light or A band emission spectrum is generally obtained from various line
photon with a specific wavelength. In any given set of conditions, the collection of spectra. Gases such as carbon dioxide in a discharge tube produce a band
all these specific wavelengths is what constitutes the atomic spectrum. spectrum. Each band consists of a series of lines very close together at
the sharp edge or head of the band and farther apart at the other end or
Heated solids emit light with continuous spectrum of wavelength / frequency. This tail
radiations is assumed to be due to oscillations of atoms and molecules.
There are two types of spectra
❑ Emission spectra
❑ Absorption spectra
Emission spectra are classified into line, band or continuous spectra. ➢ Continuous Spectra
➢ Line spectra: Line spectra are obtained from atoms in gases such as hydrogen or The spectrum formed from white light and contains all colours is known
neon at low pressure in a discharge tube. Hydrogen, for example can be excited as continuous spectrum. They are produced by all incandescent solids
to emit light by applying a high voltage to a discharge tube containing the gas at and liquids and by gases under high pressure.
low pressure.
➢ The emitted spectrum is found to be discrete but not continuous. Since excited
gases emit light of only certain wavelengths, when this spectrum is analyzed
through the slit of a spectrometer, a line spectrum is seen rather than a continuous
spectrum. The line spectrum is composed of individual lines at specific
frequencies characteristic of the gas, rather than a continuous band of all Absorption Spectrum
frequencies
When a continuous spectrum goes through a thin (rarefied) gas, we
see dark lines in the spectrum that match the wavelengths of light
usually emitted by the gas.
VB G R
 Conclusively, emission spectra are produced when light is emitted by a substance Balmer Series
after excitation, while absorption spectra are observed when light is absorbed by a 1 1 1
substance, resulting in dark lines or bands in the transmitted light. Both types of =R𝑍 2 ( 2 - ), where n =3,4,5,6 for the four visible lines
𝜆 2 𝑛2
spectra provide valuable information about the energy levels and transitions within Lyman Series
atoms, molecules, or substances. 1 1 1
THE SPECTRUM OF HYDROGEN ATOM =R𝑍 2 ( 2 - ), where n = 2, 3 …, wavelengths from 91nm to
𝜆 1 𝑛2
The spectrum of atomic hydrogen is a crucial aspect of quantum mechanics, 122nm
illustrating the quantized nature of energy levels in atoms. Considering the
hydrogen spectrum with respect to the work of J.J. balmer (1825 – 1898). Hydrogen Paschen Series
has the simplest spectrum because it has only one electron. Balmer showed the four
1 1 1
lines in the visible portion of the hydrogen spectrum have wavelength that fit in the =R𝑍 2 ( 2 - ), where n = 4, 5…,
𝜆 3 𝑛2
formula:
1 1 1
=R𝑍 2 ( 2 - ) Brackett Series
𝜆 𝑛1 𝑛ℎ 2
• Where, 1 1 1
• 𝜆 is the wavelength =R𝑍 2 ( 2 - ), where n = 5, 6…,
𝜆 4 𝑛2
• R is the Rydberg constant has the value 1.09737✕107 m-1
• Z is the atomic number
• nl is the lower energy level
• nh is the higher energy level
Pfund Series
1 1 1
The spectrum of atomic hydrogen illustrates the quantized nature of energy levels in =R𝑍 2 ( 2 - ), where n = 6, 7…,
𝜆 5 𝑛2
atoms, as described by the Rydberg formula and the Bohr model, providing
fundamental insights into atomic structure and behaviour.
Bohr Model
Bohr incorporated the quantum theory into
Rutherford’s planetary model of the atom. Bohr
proposed that electron move about the nucleus in
certain circular orbits. This implies that only certain
orbits are allowed for the movement of electrons in an
atom. An electron in this orbits would have definite
energy and would move in the orbit without radiating
energy. Hence, this orbits are called stationary states.
When an electron jumps from a higher (upper) stationary state to
another state of lower energy, a single photon of light is emitted
whose energy is given by:
ℎ𝑓 = 𝐸𝑈 − 𝐸𝐿 , where
𝐸𝑈 refers to the energy of the upper state and 𝐸𝐿 the energy of
the lower state
Recall, angular momentum L of an electron orbiting the nucleus is
𝑛ℎ
quantized and given as 𝐿 = , where n = 1,2,3….
2𝜋
𝑣
𝐿 = 𝐼𝜔 = (𝑚𝑟 2
𝑟
= 𝑚𝑣𝑟, 𝑤ℎ𝑒𝑟𝑒 𝐼 𝑖𝑠 𝑡ℎ𝑒 𝑚𝑜𝑚𝑒𝑛𝑡 𝑜𝑓 𝑖𝑛𝑒𝑟𝑡𝑖𝑎 𝑎𝑛𝑑
𝜔 𝑖𝑠 𝑡ℎ𝑒 𝑎𝑛𝑔𝑢𝑙𝑎𝑟 𝑣𝑒𝑙𝑜𝑐𝑖𝑡𝑦
𝑛ℎ 𝑛ℎ
𝐿= = m𝑣𝑟𝑛 , v=
2𝜋 2𝜋𝑚𝑟𝑛
The electric force of attraction between the nucleus and the
electron is given by coulomb’s law
1 (𝑍𝑒)(𝑒)
𝐹= 2
, 𝑤ℎ𝑒𝑟𝑒 𝑍𝑒 𝑖𝑠 𝑡ℎ𝑒 𝑐ℎ𝑎𝑟𝑔𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑛𝑢𝑐𝑙𝑒𝑢𝑠,
4𝜋𝜀0 𝑟𝑛
𝑍 𝑖𝑠 𝑡ℎ𝑒 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑝𝑜𝑠𝑖𝑡𝑖𝑣𝑒 𝑐ℎ𝑎𝑟𝑔𝑒𝑠 𝑖. 𝑒 𝑝𝑟𝑜𝑡𝑜𝑛𝑠 ,
𝑒 𝑖𝑠 𝑡ℎ𝑒 𝑐ℎ𝑎𝑟𝑔𝑒 of an electron and a proton, and
𝑟𝑛 𝑖𝑠 𝑡ℎ𝑒 𝑟𝑎𝑑𝑖𝑢𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑐𝑖𝑟𝑐𝑢𝑙𝑎𝑟 𝑜𝑟𝑏𝑖𝑡 𝑜𝑓 𝑡ℎ𝑒 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛.
Calculating Bohr Radius
1 (𝑍𝑒)(𝑒) 𝑚𝑣 2
= ……… (1)
4𝜋𝜀0 𝑟𝑛 2 𝑟𝑛
𝑛ℎ
Substituting for v= in eqn 1
2𝜋𝑚𝑟𝑛
1 (𝑍𝑒)(𝑒) 𝑚 𝑛ℎ 2
= 𝑥( )
4𝜋𝜀0 𝑟𝑛 2 𝑟𝑛 2𝜋𝑚𝑟𝑛
 1 (𝑍𝑒)(𝑒) 𝑚 𝑛ℎ
= 𝑥( )2
4𝜋𝜀0 𝑟𝑛 2 𝑟𝑛 2𝜋𝑚𝑟𝑛

1 (𝑍𝑒)(𝑒) 𝑚 𝑛2 ℎ 2
2 = x 2 2 2
4𝜋𝜀0 𝑟𝑛 𝑟𝑛 4𝜋 𝑚 𝑟𝑛
1 (𝑍𝑒)(𝑒) 1 𝑛2 ℎ2
= x
𝜀0 1 𝑟𝑛 𝜋𝑚
Cross multiplying,
𝑛2 ℎ2 𝜀0
𝑟𝑛 = , where n = 1, h =6.626𝑥10−34 , 𝜀0 = 8.85𝑥10−12 ,
𝑍𝑒 2 𝑚𝜋
𝑚 = 6.626𝑥10−34 , Z = 1, e = 1.6𝑥10−19
𝑟1 = 0.529𝑥10−19 m
Note that n = 1 for the smallest orbit and Z = 1 for hydrogen atom. The
radius of the smallest orbit in hydrogen, 𝑟1 is usually referred to as the
Bohr Radius
Energy
The total energy of an electron in a particular orbit is equal
to the sum of the kinetic and potential energies
1 2 1 2
E = U + K = qV + 𝑚𝑣= −𝑒𝑉 + 𝑚𝑣 , where V is the
2 2
potential due to a point charge +Ze
1 𝑍𝑒 2 1
𝐸𝑛 = − + 𝑚𝑣𝑛 2
4𝜋𝜀0 𝑟𝑛 2
 𝑛ℎ 𝑛2 ℎ2 𝜀0
Substitute 𝑣𝑛 = , and 𝑟𝑛 = 2
2𝜋𝑚𝑟𝑛 𝑍𝑒 𝑚𝜋
𝑍2𝑒 4𝑚 1
𝐸𝑛 = −( 2 2 )( 2), n =1, 2, 3,….
8𝜀0 ℎ 𝑛
𝑍 2 2.1703𝑥10 −18 𝑍 2
𝐸𝑛 = -(2.1703𝑥10−18 𝐽) 2 =-( −19 )( 2 )
𝑛 1.6𝑥10 𝑛
𝑍2
𝐸𝑛 =-(13.6eV) ( 2 )
𝑛
The energies of the various orbits in hydrogen atom are
13.6𝑒𝑉
given by 𝐸𝑛 =- 2 , 𝑤ℎ𝑒𝑟𝑒 𝑛 = 1,2,3 … ,
𝑛
The lowest energy level ( n= 1) for hydrogen is 𝐸1 =
− 13.6𝑒𝑉. It is called the ground state.
The higher states are given by:
13.6𝑒𝑉 13.6𝑒𝑉
𝐸2 =- 2 =-3.40eV, 𝐸3 =- 2 = -1.51eV
2 3
They are called excited states. The energy required to raise
an atom from its ground state to an excited state is called
the excitation energy of the atom. The excitation energy
needed to raise a hydrogen atom from the ground state
𝐸1 𝑜𝑟 − 13.6𝑒𝑉 to energy level 𝐸3 𝑜𝑟 1.51 𝑒𝑉 𝑖𝑠
𝐸3 − 𝐸1 = (-1.51eV) - (-13.6eV) = 12.09eV
The excitation potential for this jump is 12.09V
Ionization Energy or Binding Energy
This is the minimum energy required to remove
an electron from an atom initially in the ground
state. The ionization level has a value of 0, hence
the ionization energy for hydrogen is 13.6eV and
the ionization potential is 13.6V
If an atom is excited from the ground state to a higher
energy state, say 𝐸4, it becomes
unstable and falls back to one of the lower energy state say
𝐸2. The atom emits energy in the
form of electromagnetic radiation. Bohr proposed that from
quantum theory, the radiation
emitted is given by
ℎ𝑐
𝐸4 - 𝐸2 = ℎ𝑓 = , where c is the speed of electromagnetic
𝜆
waves in a vacuum and 𝜆 is the
Wavelength of the radiation.
 Failures of Bohr Model
o Bohr model was a major step toward understanding the
quantum theory of the atom - not in fact a correct
description of the nature of electron orbits.

o Some of the shortcomings of the model are:

1. Fails describe why certain spectral lines are brighter than others
=> no mechanism for calculating transition probabilities.

1. Violates the uncertainty principle which dictates that position

and momentum cannot be simultaneously determined.

o Bohr model gives a basic conceptual model of electrons

orbits and energies. The precise details can only be
solved using the Schrödinger equation.
PY3P05
SOLVED QUESTIONS AND ANSWERS
Q-1: Atomic spectra is also known as a) continuous spectra
b) line spectra c) Spectra of absorption d) The emission
spectrum
Answer: b) line spectra
Explanation: Line spectra are obtained as a result of
absorption and subsequent emission of energy by the
electrons in the individual atoms of the element. Hence, the
line spectrum is also called atomic spectrum.
SOLVED QUESTIONS AND ANSWERS
2+
Q-2: The atomic spectrum of 𝐿𝑖 should be similar to that
of a) He + b) Na c) He d) H
Answer: a) and d)
Explanation: The atomic spectrums of mono electronic
species are identical. A mono electronic species is a specie
that contains only one electron. He + and H contain only
one electron. Hence their atomic spectrum is similar to
mono electronic specie 𝐿𝑖 2+ .
Q-3: Calculate the radius ratio for 2nd orbit of 𝐻𝑒 + ion and 3rd orbit of
𝐵𝑒 3+ ion.
𝑛2
Answer: The formula for radius is given by:𝑟𝑛 = 𝑎
𝑧 0
For 𝐻𝑒 + ion, z=2, n=2( 2nd orbit)
22
𝑟2 = 𝑎0
2
=2 𝑎0
For 𝐵𝑒 3+ ion, z=4, n= 3 (3rd orbit)
32
𝑟3 = 𝑎0
4
9
= 𝑎0
4
The radius ratio for 2nd orbit of 𝐻𝑒 + ion and 3rd orbit of 𝐵𝑒 3+ ion comes out
9
to be 2 𝑎0 / 𝑎0 = 8/9.
4
Q-4: The energy of an electron in a hydrogenic atom with
nuclear charge Z varies as a) Z b) 𝑧 2 c) 1/Z d) 1/ 𝑧 2
2
Answer: b) ) 𝑧
Explanation: The expression for the energy calculation of
an electron in a hydrogenic atom with nuclear charge Z and
−13.6𝑧 2
orbit number, n is given by: E =
𝑛2
As a result, we can clearly see that it is proportional to 𝑧 2 .
Q-5:The potassium salts are placed in a Bunsen flame to
obtain the line spectrum, the colour of the light emitted is a)
yellow b) violet c) green d) white
Answer: b) violet
Explanation: The colour of the light emitted depends upon
the nature of the substance. For example, sodium and its
salts emit yellow light while potassium or its salts give out
violet light.
Q-6: Name the gas that is used in the discharge tube to
obtain the hydrogen absorption spectrum?
Answer: 𝐻2 gas
Explanation: When 𝐻2 gas is introduced into the discharge
tube, a series of lines such as lyman, balmer, paschen,
bracket, and pfund that are located in different regions are
obtained.
Q-7: A 𝛼- line of Balmer series corresponds to a) shortest
wavelength with 𝑛2 =2 b) longest wavelength with 𝑛2 =2 c)
longest wavelength with 𝑛2 =3 d) shortest wavelength with
𝑛2 =3
Answer: c) longest wavelength with 𝑛2 =3 Explanation: 𝛼-
line of Balmer series is the first line of Balmer series. For the
Balmer series, 𝑛1 = 2 and for the first line, 𝑛2 = n1+1 = 2+1
=3
Q-8: The wavelength of lyman series lies in the a) Visible
region b) Radio Waves region c) Ultraviolet region d)
Infrared region Answer: c) Ultraviolet region
Q-9: What is the name of the equipment used to analyse
sunlight by splitting it into its various colours? a)
monochromator b) spitter c) spectrometer d) spectrograph
Answer: c) and d)
Explanation: A spectrograph, also known as a spectroscope
or spectrometer, divides light from a single material into its
component colours in the same way that a prism divides
white light into a rainbow. It captures this spectrum,
allowing scientists to analyse the light and learn about the
properties of the material interacting with it.
.
Q-10: Distinguish between the emission and absorption spectra.

Emission Spectra Absorption Spectra

Emission spectrum is It is obtained when the white
obtained when the radiation light is first passed through
from the source is directly the substance and the
analysed in the spectroscope. transmitted light is analysed
in the spectroscope
It consists of bright coloured It consists of dark lines.
lines separated by dark spaces
It can be continuous or It is always discontinuous
discontinuous
Q-11 If an electron makes transition from the 7 th excited
state to 2 nd state in a H-atom sample, find the maximum
number of spectral lines observed.
Answer: The maximum number of spectral lines(N) can be
(𝑛2 −𝑛1 )(𝑛2 −𝑛1 +1)
calculated using the below formula: 𝑁 =
2
Here, 𝑛2 = 8(for 7th excited state) and 𝑛1 = 2. Substituting in
the formula,
(8−2)(8−2+1)
N=
2
we get N= 21
Q-12: Which of the following is an example of line
absorption spectrum? a) Mercury vapour lamp b) Sunlight
Spectrum c) Spectrum of oil flame d) Solar spectrum
Answer: b) Sunlight Spectrum is an example of line
absorption spectrum
Q-13: The correct order of Bohr radius is a) 𝑟1 > 𝑟2 > 𝑟3 > 𝑟4
b) 𝑟1 < 𝑟2 < 𝑟3 < 𝑟4 (c) ) 𝑟1 = 𝑟2 = 𝑟3 = 𝑟4 (d) ) 𝑟1 < 𝑟2 >
𝑟3 < 𝑟4
Answer :b
Explanation: Bohr radius is represented by 𝑟𝑛 where n is the
orbit number. It is given by the formula:
𝑛2
𝑟𝑛 = 𝑎0
𝑧
As a result, as the value of n increases, so does the bohr
radius. Therefore the correct order is
𝑟1 < 𝑟2 < 𝑟3 < 𝑟4
Q-14: A line at 3802 𝑐𝑚−1 is obtained in the infrared region
of the atomic spectrum of hydrogen. Determine the energy
of this photon. Answer: Given, 𝝀 = (1/3802) cm We know
that, Energy, E= h𝝂= hc/𝝀 Where h is the planck’s constant
and c is the speed of light, h= 6.63× 10−34 Js , c= 3× 108 m/s
= 3× 1010 cm/s
ℎ𝑐 6.63× 10−34 𝑥 3× 1010 cm/s −20
𝐸= = 1 = 7.56 x 10 𝐽
𝜆
3802
Q-15: Which theory was able to explain the line spectra of
hydrogen? a) Dalton’s Atomic theory b) Bohr’s theory c)
Rutherford’s model d) Thomson’s Atomic model Answer: b)
Bohr’s theory Explanation: The most remarkable
achievement of Bohr's theory is that it provides a
satisfactory explanation for the hydrogen line spectrum.
Q-16: Calculate the frequency of light emitted when an
electron drops from the higher to the lower state if the
energy difference between the two electronic states is
214.68 kJ/mol. (Planck’s constant,
h= 39.79×10−14 kJs/mol)
Answer: ΔE= h𝝂
−14
214.68 kJ/mol = 39.79× 10 kJs/mol × 𝝂
𝝂 = 5.395 × 1014 /s
Q-17: The principal quantum number of an atom is related
to the a) size of the orbital b) orientation of the orbital in
space c) spin angular momentum d) orbital angular
momentum Answer: a) size of the orbital