1.

Dalton’s atomic theory was put forward in 1808, according to that theory matter contain small indistinguishable
particles called atoms which cannot be further be subdivided into smaller ones by any physical and chemical means.
Dalton’s atomic theory got failed when it was found that an atom could be further sub divided into three
fundamental particles and approximately 35 sub-atomic particles.
Electron (e-): J.J. Thomson (Cathode ray tube experiment)
ATOM Proton (P+): E. Goldstein (Anode or canal ray experiment)
Neutron (N): James Chadwick (Atomic Mass experiment)
Atomic models: (RECAP WHAT U HAD DONE IN IX CLASS).
J.J. Thomson Plum pudding model Failed Rutherford’s model Rutherford’s model (Discovery of
Nucleus) In 1913 Neil Bohr’s model explain the quantization of energy
He explains the angular momentum of an Bohr’s model was able to gave
Electron moving in a particular orbit is quantised the concept of stationary state
(Has a definite value) which is an integral ratio of h/2
So, Bohr’s model of the hydrogen atom was the first model based on the quantization of energy.
But Bohr’s model got failed because he got main challenges from two new discoveries:
1. Wave nature of electron (state of electrons behaves as wave) or Dual nature (particle & wave nature). Also, called as De-
broglie’s principle and
2. Heisenberg’s uncertainty principle (movement of electron in a define path or orbital has uncertainty in position or
momentum, which are not accurately calculated simultaneously).
2. Iso electronics: The species (atoms of ions) containing same number of electrons.
N3 -, O2- , F-, Ne, Na+, Mg2+, Al3+: 10 electrons, P3 -, S2- , Cl-, Ar, K+, Ca2+ are Iso electronic species.
3. Dual nature of matter and radiations: Newton proposed light as a beam of particles or corpuscles (corpuscular
theory of light). It explained the laws of reflection and refraction of light but failed to explain the interference and
diffraction effects of light. These two-effect interference and diffraction can be explained only on the basis of Wave
theory. So, we can say light has dual nature i.e., particle and wave nature.
Einstein in 1905, explain dual nature of light i.e., particles as well as wave characters. As above facts can only be
regarded on the basis of wave theory, Huygens explains the wave nature of light (Electromagnetic wave theory).
4. Electromagnetic nature of radiations: In 1856, James Clark Maxwell proposed that light and other forms of
radiant energy propagate themselves in the form of waves, through space. Some important characteristics are:
(a) Electromagnetic wave consists of electric and
magnetic fields that oscillate perpendicular to each
other and also to the direction the waves travel.
(b) All electromagnetic waves travel with a velocity equal
to that of light i.e. (3.0 x 108 m s-1 or 3.0 x 105 Km s-1)
(c) Electromagnetic radiations do not require any medium
for propagation for e.g., light from the sun travels
through empty space to reach us, unlike sound waves that require medium for propagation.
5. Definitions:
(a) Wave length (λ): The distance between two adjacent crests
or two adjacent troughs is called wavelength. It is denoted by
the Greek letter λ (lambda) and is generally expressed in
terms of Angstrom units denoted as Å.
(b) Frequency (υ): The number of waves, which pass through a
given point in one second, is known as frequency. It is
denoted by the Greek letter n (nu). The unit of frequency is cycle per second or simply reciprocal second (s-1).
A cycle is said to be completed when a wave consisting of one crest and one trough, passes through a point.
Frequency is also denoted by the term Hz (hertz) and 1Hz = 1cycle per second.

1 CHAPTER 2: CLASS XI: ATOMIC STRUCTURE

 (c) Amplitude: The maximum height or depth of a wave is amplitude. Amplitude determines the intensity or
brightness of a wave. It is denoted by the letter 'A'
(d) Velocity (v): The distance traveled by a wave in one second. It is generally denoted by the letter 'c'.
(e) Wave number: It is the number of wavelengths per centimeter. It is equal to the inverse of a wavelength

expressed in centimeter. .
(f) Period (τ): It is the time taken for one wave to pass through a given point. It is reciprocal of frequency (υ)
and expressed in s-1.
The relationship that follows between wavelength, frequency and velocity is, velocity = wavelength x frequency.
c = υ X λ.
6. Electromagnetic spectrum: While all electromagnetic waves travel at the same speed (i.e., velocity 'c' is
constant), the type of their radiation differs in the duration of wavelength and consequently their frequencies.
7. WAVE NATURE OF RADIATIONS. Huygens explained the property of light such as reflection, interference,
diffraction, and refraction on the basis of wave character of light. In 1956, James Maxwell proposed that light and
other radiation are transmitted and propagated through space continuously in the form of electromagnetic waves.
These waves are associated with electrical and magnetic fields acting perpendicular to the direction of their
propagation. Therefore, these radiations are known as electromagnetic radiations or electromagnetic waves.
8. LIMITATIONS OF WAVE CHARACTERS OF RADIATIONS. Wave theory of light explained the phenomenon of
interference and diffraction but it failed to explain phenomena such as photoelectric effect and black body radiation.
It can be explained by considering light radiation possesses dual nature i.e. wave nature as well as particle nature
9. BLACK BODY RADIATIONS. An ideal black body is perfect absorber and a perfect emitter of radiations. This
means that a black body absorbs all the radiation's falling on it, when such body is heated, it emits radiations and it
has been shown that no other body can emit radiant energy more than a black body. When such a body is heated it
emits radiations and becomes red. As the temperature is further increased, the colours of the radiation emitted
changes from red to yellow and then finally it becomes white and finally blue at a very high temperature. These
observations could not be explained by Classical Wave theory of light. According to classical wave theory radiation
emitted by the body should have the same colours (or frequency), though the intensity of colour might change with
variation in temperature. So, the energy emission and absorption are not continuous but a discontinuous process. At a
given temperature, intensity of radiation emitted increases with decreases of wavelength, reaches a maximum value
at a particular wavelength and then start decreasing with further decrease of wavelength. (Graph in NCERT).
10. PHOTOELECTRIC EFFECT: In 1887, H. Hertz performed an experiment in which electrons (or electric
current) were ejected when certain metals (for example potassium, rubidium, Caesium etc.) were exposed to a beam
of light as shown in figure. Once these ejected electrons hit the target, they produce electricity. This phenomenon is
called as photoelectric effect.
The phenomena of ejection of electron from the surface of a metal
whenever an appropriate frequency of radiation is allowed to fall
on the surface of a metal like Caesium occurs. This is called
photoelectric effect. The electrons coming out are called
photoelectrons.
The results observed in this experiment were:
(i) The electrons are ejected from the metal surface as soon as the
beam of light strikes the surface, i.e., there is no time gap between the striking of light beam and the ejection of
electrons from the metal surface.
(ii) The number of electrons ejected is proportional to the intensity or brightness of light and is independent of
frequency i.e. on increasing intensity of radiations number of photoelectrons increases but not the kinetic energy

2 CHAPTER 2: CLASS XI: ATOMIC STRUCTURE

(iii) For each metal, there is a characteristic minimum frequency, (also known as threshold frequency) below
which electron can’t be ejected out.
(iv) The maximum kinetic energy of the emitted photoelectrons is directly proportional to the frequency of the
incident radiation, but independent of its intensity, (Fig. given below).

11. Photoelectric effect is not observed if υ < .

At a frequency , the ejected electrons come
out with certain kinetic energy.
The kinetic energies of these electrons increase
with the increase of frequency of the light used. A
part of this energy is used up in overcoming the
attractive forces, and the residual energy is
possessed by the ejected electron as kinetic energy.
Definitions:
(a) Threshold Frequency ( ): The minimum frequency that must be supplied to eject the valence electron
from the surface of Caesium metal or any metal.
(b) Work Function (hυo): The minimum amount of work that must be done in order to pull out the electron or to
overcome the electrostatic force of attraction between the outermost electron and the nucleus.
(c) Falling Frequency (υ): The amount of frequency that must be allowed to fall on the surface of a metal.
12. If an electron has to be ejected out there are three conditions to be followed:
(a) Falling Frequency > Threshold Frequency = electron will be ejected out + they posses K.E to hit the target.
(b) Falling Frequency = Threshold Frequency = electron will be ejected out but no K.E to hit the target.
(c) Falling Frequency < Threshold Frequency = electron will not be ejected out.

PINK BOX 2.3. The Vividh Bharati station of All India Radio, Delhi, broadcasts on a frequency of 1,368 kHz (kilo
hertz). Calculate the wavelength of the electromagnetic radiation emitted by transmitter. Which part of the
electromagnetic spectrum does it belong to?
PINK BOX 2.4 The wavelength range of the visible spectrum extends from violet (400 nm) to red (750 nm). Express
these wavelengths in frequencies (Hz). (1nm = 10–9 m).
PINK BOX 2.5: Calculate (a) wave number and (b) frequency of yellow radiation having wavelength 5800 Å.
EXAMPLE. What is the minimum energy that a photon should possess in order to produce photoelectric effect with
a metal whose threshold frequency is 1.3 × 1025 s–1?

Example: The wavelength of a beam of light is 2.80 × 10–5 m. Calculate its; (i) wavelength in cm, (ii) frequency, and
(iii) Energy of one of its photons.
13. Particle like character of radiations: Failure of classical EM theory of radiation to explain the photoelectric
effect led to the Plank's quantum theory of radiation. This theory gave the particle like characters of radiation.
14. Planck’s quantum theory. The main points of this theory are
(a) Radiant energy is not emitted or absorbed continuously but discontinuously in the form of small packets of

3 CHAPTER 2: CLASS XI: ATOMIC STRUCTURE

energy called quanta. Each wave packet or quantum is associated with definite amount of energy. In the case of
light, the quantum of energy is called photon.
(b) The amount of energy associated with quantum of radiation is proportional to the frequency of radiation.
E
E = h . [Where ‘h’ is called Planck's constant and is equal to 6.625 x 10 -34 Joule sec or 6.625 x 10 -27 erg sec].
The energy of light (Photon) in terms of wave length and velocity of light c is given as E = h
=hc/ (as c = . So, = c / ).
(c) A body can emit or absorb energy only in terms of whole number multiples of quantum i.e. quantization of energy
E = n h , where n = 1, 2, 3, 4- - - - - -
This means that a body can emit or absorb energy equal to h ,2 h , 3 h , 4 h - - - - but it cannot emit or absorb
energy in fractional values of h such as 1.5 h or 2.5 h . It is also called quantization of energy i.e. energy is
always in simple whole number.

15. Failure of Rutherford’s model: Rutherford's model got failed, as could not explain the stability of the atom in-
spite of the revolving electrons around the nucleus. According to James Clark Maxwell if any charge body is moving
under the influence of any other charge body it continuously emit radiations in the form of electromagnetic
radiations. So, if an electron is moving towards the nucleus it should emit radiations and lose energy. They should
slow down, gradually move towards the nucleus, follow a spiral path and then fall into the nucleus. This would make
the atom collapse and hence unstable, which is not true.
PINK BOX 2.6: Calculate energy of one mole of photons of radiation whose frequency is 5 X 1014 Hz.
PINK BOX 2.7: A 100-watt bulb emits monochromatic light of wavelength 400 nm. Calculate the number of
photons emitted per second by the bulb.
****PINK BOX 2.8: When electromagnetic radiation of wavelength 300 nm falls on the surface of sodium,
electrons are emitted with a kinetic energy of 1.68 X 105 J mol–1. What is the minimum energy needed to remove an
electron from sodium? What is the maximum wavelength that will cause a photoelectron to be emitted?
PINK BOX 2.9: The threshold frequency v0 for a metal is 7.0 X1014 s–1. Calculate the kinetic energy of an electron
emitted when radiation of frequency n =1.0 X 1015 s–1 hits the metal. [CHECK NCERT BOOK FOR SOLUTION]
16. Bohr’s Model of an Atom: In 1913, Neils Bohr proposed a model of an atom based on the Planck's quantum
theory of radiation. The basic postulates of Bohr's theory are:
(a) An atom consists of a small, heavily positively charged dense nucleus at the centre of an atom where most of
the mass is concentrated and around which electrons revolve in definite circular paths called orbits. These
orbits are associated with definite energies called energy shells/energy levels. They are designated as K, L, M,
N. etc. shells or numbered as 1, 2, 3, 4, …. etc. from the nucleus. Electrons move and remain in particular
shell as centripetal force (towards centre) and centrifugal forces (outward) are equal.
(b) As long as the electron remains in a particular orbit /shell it neither lose energy neither it gains energy i.e. its
energy remains constant. He introduces the word ‘stationary state’ for the energy of an electron. It accounts
for the stability of an atom. Stationary does not mean that an electron is stationary it means that its energy is
stationary but it revolves.
(c) Only those orbits are permitted in which angular momentum of the electron is a whole number multiple of

where ‘h’ is Planck’s constant. Any moving body taking a circular orbit has an angular momentum

4 CHAPTER 2: CLASS XI: ATOMIC STRUCTURE

 equal to the product of its mass (m), velocity of movement (v) and radius of orbit (r). In other words, the
angular momentum of an electron.

This postulate introduces the concept of quantization of angular momentum, which can be calculated if you know
the shell in which electron is present.
(d) Electrons can either lose or absorb energy abruptly, when they jump from one energy level to another. For
instance when an electron moves from the 'normal or ground state - E1' of an atom i.e., the state of lowest
energy as required by its 'n' and 'l' values, to a higher level, it causes the atom to be in its 'excited state - E2'
i.e., where electrons in an atom occupy energy levels higher than those permitted by its 'n' and 'l' values. The
reverse is also true and the change in energy is ΔE. ΔE = E2 - E1 = hυ
The stability of an atom. Bohr postulated that as long an electron remains in a particular orbit it does not emit
radiation i.e. lose energy. Hence it does not become unstable.

The atomic spectrum of hydrogen was explained due to the concept of definite energy levels. The one electron of
hydrogen being closest to the nucleus is in its lowest energy shell (n =1) or normal ground state. It can absorb a
definite amount of energy and jump to a higher energy state. This excited state being unstable, the electron comes
back to a lower energy level.
When the energy emitted during transition, strikes a photographic plate, it gives its impression in the form of a line.
This difference is also the energy of photon expressed as E2 - E1 = hυ

The frequency of the emitted radiation is: , .

Since E2 and E1 have only definite values and are characteristic of energy levels of atoms, the values will also be
definite and characteristic of the atoms. Thus, each transition will produce a light of definite wavelength, which is
observed as a line in the spectrum. For example, if the electron jumps down from the third to the first energy level

having energies E3 and E1 respectively, then the wavelength of the spectral line would be
Similarly, when the electron jumps down from the fourth to the first energy level having energies E4 and E1
respectively or from the fifth to the second i.e., E5 and E2, then we have

These will give different lines in the spectrum of the atom corresponding to different transitions having definite
wavelengths.
The sample of hydrogen gas contains a large number of atoms and when energy is supplied, the electrons in different
hydrogen atoms absorb different amounts of energies. These are raised to different energy states. For example, the
electrons in some atoms may jump to second energy level (L), while in others it may be to the third (M), fourth (N)

5 CHAPTER 2: CLASS XI: ATOMIC STRUCTURE

or fifth (O) and so on. These electrons come back from the higher energy levels to ground state in one or more jumps
emitting different amount of energies.

Different lines depending upon the difference in energies of the levels concerned can be summarized in the form of
series named after the scientists who have discovered them. The energy of the electron in a particular orbit of
hydrogen atom could be calculated by Bohr's theory. The energy of the electron in the 'nth' orbit has been found to be:

,
Where 'm' is the mass and 'e' is the charge of the electron. The energy expression for hydrogen like ions or species
such as He+, Li2+ , Be3+ can be written as:

,
Where 'Z' is the nuclear charge, which is equal to atomic number.
SIGNIFICANCE OF ELECTRONIC ENERGY: The energy of the electron in a hydrogen atom has a negative sign for all
possible orbits in the above expression. This negative sign is called as electronic energy. This negative sign means
that when free electron at rest is infinitely far away from the nucleus and is assigned the energy value approximately
equal to zero. [It is obtained if you put ‘n’ equal to infinity in the energy equation]. As the electron gets closer to the
nucleus (as n decreases), it loses energy and it becomes larger in absolute value and becomes more and more
negative. The most negative energy value is given by n=1 which corresponds to the most stable orbit. We call this the
ground state. If the electron is present in the infinite (∞) shell then it is said to be in ionized state.
(e) The radii of the stationary states are expressed as:
Where a0 = 52.9 pm. Thus, the radius of the first stationary state of hydrogen atom is, called the Bohr radius, is 52.9
pm. normally the electron in the hydrogen atom is found in this orbit (that is n=1). As ‘n’ increases the value of ‘r’
will increase. In other words, the electron will be present away from the nucleus.
The radii expression for hydrogen like ions or species such as He+, Li2+, Be3+ can be written as:

, where Z= 2, 3, 4 for He+, Li2+, Be3+ respectively.

(f) Velocities of an electron was also calculated.
17. Spectra. It is observed that when a ray of white light is passed through a prism, the wave with shorter wavelength
bends more than the one with a longer wavelength. Since ordinary white light consists of waves with all the
wavelengths in the visible range, a ray of white light is spread out into a series of coloured bands called spectrum.
The light of red colour which has longest wavelength is deviated the least while the violet light, which has shortest
wavelength, is deviated the most. The spectrum of white light, that we can see, is continuous spectrum. As violet
merges into blue, blue into green and so on. A similar spectrum is produced when a rainbow forms in the sky. But
remember that visible light is just a small portion of the electromagnetic radiation. When electromagnetic radiation
interacts with matter, atoms and molecules may absorb energy and reach to a higher energy state. With higher
energy, these are in an unstable state. For returning to their normal (more stable, lower energy states) energy state,
the atoms and molecules emit radiations in various regions of the electromagnetic spectrum.
Atomic Spectra. A spectrum is an assembly of energy levels in the form of radiations emitted by an atom in its
excited state. Every atom gives discontinuous line spectra. Each line in the spectra corresponds to a specific
wavelength and it is unique to a given element. No two elements give same pattern of lines in their spectra.
ATOMIC EMISSION SPECTRA: When a substance is heated to a high temperature, the atoms in the vapours get
energized. These energized atoms then return to the ground state by emitting electromagnetic radiations of certain

6 CHAPTER 2: CLASS XI: ATOMIC STRUCTURE

definite wavelength. A series of bright lines separated from each other by dark spaces is obtained and this is called
atomic emission spectra. For example, when sodium chloride is heated in Bunsen burner flame then we will try to
see yellow flame. Similarly, barium gives apple green or grassy green colour, calcium gives brick red colour etc.

ATOMIC ABSORPTION SPECTRA: When the atomic vapours from a sample are placed in the path of white
light from an arc lamp, it absorbs the light of certain characteristic wavelengths and the light of other wavelengths get
transmitted. In such conditions a series of dark lines on a white background are formed. This is called an absorption
spectrum. The dark lines in the absorption spectrum and the bright lines in the emission spectrum of a given element
appear at the same wavelength. Since each element gives a definite pattern of lines at certain definite frequencies or
wavelengths, the atomic spectra are used in chemical analysis to identify and estimate the elements present in any
sample. The study of emission or absorption spectra is referred to as spectroscopy. The spectrum of the visible light,
as discussed above, was continuous as all wavelengths (red to violet) of the visible light are represented in the
spectra. The emission spectra of atoms in the gas phase, on the other hand, do not show a continuous spread of
wavelength from red to violet, rather they emit light only at specific wavelengths with dark spaces between them.
Such spectra are called line spectra or atomic spectra because the emitted radiation is identified by the appearance
of bright lines in the spectra Line emission spectra are of great interest in the study of electronic structure. Each
element has a unique line emission spectrum. The characteristic lines in atomic spectra can be used in chemical
analysis to identify unknown atoms in the same way as finger prints are used to identify people. The exact matching
of lines of the emission spectrum of the atoms of a known element with the lines from an unknown sample quickly
establishes the identity of the latter, German chemist, Robert Bunsen (1811-1899) was one of the first investigators to
use line spectra to identify elements.
Line /Emission spectra of Hydrogen. Hydrogen with one electron has played a significant role in the development
of atomic structure. In the emission spectrum of hydrogen, when an electric discharge is passed through hydrogen
gas, the molecules of hydrogen break into atoms.

7 CHAPTER 2: CLASS XI: ATOMIC STRUCTURE

The hydrogen atoms get energized and go into an excited state. The excited atoms then return to the ground state by
emitting light. Hydrogen atoms emit bluish light. On passing this light through a prism, a discontinuous line
spectrum consisting of several sharp lines is obtained. This is the line spectrum of hydrogen. Four sharp coloured
lines were observed in the visible region of this spectrum by Balmer, in the ultra violet region by Lyman, in the
infrared region by Paschen, Brackett and Pfund. These series of lines are named after these scientists who discovered
them. Balmer expressed these lines in terms of inverse of their wavelength ( ) by a mathematical relation, which was

later modified by Rydberg. .

Where 'RH' is the Rydberg's constant and 'n1', 'n2' are integers with values equal to or greater than 3 and 'λ' is the
wavelength.

S.No. Emission Spectra Absorption Spectra

1. It is obtained when radiations emitted by the It is obtained when the white light is first passed
excited substance are analyzed directly in a through the substance (in gaseous or liquid or solution
spectroscope. form) and the transmitted light is then analyzed in a
spectroscope.
2. It consists of bright colored lines separated by It consists of dark lines in an otherwise continuous
dark spaces. spectrum.
PINK BOX 2.10: What are the frequency and wavelength of a photon emitted during a transition from n = 5 state to
the n = 2 state in the hydrogen atom?
Extra Question: Calculate the wavelength of the spectral line when the electron in the hydrogen atom undergoes a
transition from 4th energy level to 2nd energy level. What is the colour of the radiation? [NCERT Question 13]
Solution: According to Rydberg's equation:

Here, n1 = 2, n2 = 4 and R = 109678 cm-1

= 486 x 10-9 m = 486 nm

Extra question: If the energy difference between the electronic states of hydrogen atom is 214.68 kJ mol-1, what will
be the frequency of light emitted when the electron jumps from the higher to the lower energy state? (Planck's
constant = 39.79 x 10-14 kJ mol-1)

8 CHAPTER 2: CLASS XI: ATOMIC STRUCTURE

The frequency (υ) of emitted light is related to the energy difference of two levels (ΔE) as:

E = 214.68 kJ mol-1, h = 39.79 x 10-14 kJ mol-1

= 5.39 x 1014 s-1

Extra Question: The wavelength of first spectral line in the Balmer series is 6561 Å units. Calculate the wavelength
of the second spectral line in Balmer series

According to Rydberg equation: For the first line in Balmer series, n1 = 2, n2 =

3 for the second line in Balmer series, n1 = 2, n2 = 4.

Dividing equations (i) by (ii)

Extra Question: The wavelength of first spectral line in the Balmer series is 656 nm. Calculate the wavelength of
the second spectral line and limiting line in Balmer series. [Do it ourselves].
[For second line λ = 485.9 nm and for limiting line λ = 364.4 nm].
Extra question: Calculate the wavelength of the spectral line obtained in the spectrum of Li2+ ion when the
transition takes place between two levels whose sum is 4 and the difference is 2.
[n1 + n2 = 4 and n2 - n1 = 2. On solving λ = 1.14 X 10-6 cm].
18. Failure of Bohr’s model: (a) It fails to account for the finer details (doublet, that is two closely spaced lines) of
the hydrogen atom spectrum observed by using sophisticated spectroscopic techniques. This model is also unable to
explain the spectrum of multielectron system. Further, Bohr’s theory was also unable to explain the splitting of
spectral lines in the presence of magnetic field (Zeeman Effect) or an electric field (Stark effect).
But the main cause of the failure of Bohr’s model was because of two things:
1. Dual behaviour of matter or De-broglie’s principle. 2. Werner Heisenberg uncertainty principle.
19. Dual nature of radiations: De Broglie suggested that light exhibits wave and particle properties. All
microscopic material particles in motion such as electrons, protons, atoms, ions, molecules etc. also have dual nature.
In other words, the microscopic particles in motion possess both the particle and wave character.
According to De Broglie ‘All material particles in motion possess wave characteristics.’
Dual nature of matter –The de-Broglie equation:
In 1924, de-Broglie proposed that matter also has dual nature (i.e. particle and wave character) just like radiations (as
suggested by Einstein). He put forward this theory based on certain hypothesis:
(a) The whole universe is composed of matter waves and electromagnetic radiations.
(a) Nature love symmetry as the radiations has dual nature; matter should also follow dual nature. As per de Broglie
hypothesis, a moving material particle (electron, proton, and neutron) has dual property associated with it. The
wave properties associated with moving particles are called as Matter waves or Pilot waves or de-Broglie waves.
According to as the photon has momentum as well as wavelength, electrons should also have momentum as well as
wavelength.
Derivation of de-Broglie relationship:
Combining the mass - energy relationship proposed by Max Planck and Einstein, had derived the relationship.
The energy of photon of frequency is given by
E = h - (i) And also according to Einstein equation
E = mc2 - (ii) Where m is the mass of the photon.
2
From equation (i) and (ii) mc = h

9 CHAPTER 2: CLASS XI: ATOMIC STRUCTURE

 mc2 = h c / (c = n and n = c / )
OR
= hc / mc2
= h / mc. The equation is valid for a photon.
De Broglie suggested that on substituting the mass of the particle ‘m’ and its velocity in place of velocity of
light c, the equation could also be applied to material particle.
Thus, = h / mv = h/p
this equation is called De Broglie's equation.
= h/P = Planck's constant / Momentum
Or 1/P. Therefore, wavelength of particle in motion is inversely proportion to its momentum.
The wave associated with the material a particle is in motion is called as matter waves. Or De Broglie equation.
So, we say that de Broglie’s principle is for macroscopic particles having mass of the order of few grams, and
travelling with normal speeds, the de Broglie wavelengths are so small that their measurement is not possible.
These waves are different from the electromagnetic waves.
S. No. Electromagnetic waves Matter waves.
1 These are associated with the magnetic & These do have magnetic & electric field, which are
electric fields that are perpendicular to each perpendicular to each other. However, matter
other and also to the direction of propagation of waves obtained by charge particles are associated
radiations. with electric & magnetic field.
2 The velocities of all electromagnetic radiations The velocities of all matter waves are always less
are equal to the velocity of light i.e. 3 X 108 m/s. than the velocity of light i.e. 3 X 108 m/s. They
They do not require medium for propagation. require medium for propagation.
3 The energies are quantized. The energies are not quantized.
4 Wave length is much larger & given by Wavelength is much smaller & given by de-
relationship given below. Broglie’s relationship.
5. It follows the formula where wavelength is It follows the formula where formula is
λ=c λ=h
υ mv
20. Significance of de Broglie waves: Dual nature of matter is applicable to all material objects but it is significant
for microscopic bodies only. For example, if we take a large body, the wavelength associated with the body will be
very small and cannot be measured by any available method thus we can say that heavy body have no wavelength.
Verification of Dual nature of electron can be verified on the basis of the following observations:
1. Particle nature: If an electron strikes a screen coated with Zinc Sulphide (ZnS), it produces a spot of light known
as Scintillation. One electron is producing only one Scintillation point. It means that striking electron is localized
and not spread out like a wave. In other words, we can say that electrons behave like a particle.
2. Wave nature: in 1927 Davison and Germer experimentally verified wave nature of electron by their experiment.
When a stream of fast-moving electrons was made to strike on a nickel crystal which is used as grating, concentric
dark and bright rings were formed on the screen. This diffraction pattern of electrons by crystal was similar to that
which was observed by X-rays. Since X-rays have wave characters so electrons must also have wave character. It
was also found those wavelengths determined by diffraction experiment were found to be in agreement with the
values calculated from De Broglie equation.
Difference between particle and wave.
S. No Particle Wave
1 They are always localized in space. They are always delocalized (spread) in space.

10 CHAPTER 2: CLASS XI: ATOMIC STRUCTURE

 2 Not more than one particle is present at a More than one wave is present at a given position
given position in space. in space.
3. Their mathematical sum is always equal Their sum is always less than or greater than their
to their total numbers. total values.

Derivation of Bohr’s postulates of quantization of angular momentum from de-Broglie’s relationship

According to the Debroglie’s principle whenever an electron is revolving around the nucleus it always tries to move
in the form of a wave and particle and hence according to it.
Circumference of the circle = n (wave length of the electron)
2πr=nλ
As per de Broglie’s principle wavelength (λ) = h
mv
2πr=nλ
2 π r = n h.
mv
On rearranging we get mvr = n h
2π
This is the Bohr’s postulate of the angular momentum is an integral model of an atom.
PINK BOX 2.12: What will be the wavelength of a ball of mass 0.1 kg moving with a velocity of 10 m s–1?
PINK BOX 2.13: The mass of an electron is 9.1 X 10–31 kg. If its K.E. is 3.0X 10–25 J, calculate its Wavelength.
PINK BOX 2.13: Calculate the mass of a photon with wavelength 3.6 Å.
PROBLEM: Calculate momentum of a particle which has a de Broglie wavelength of 0.1nm. (h = 6.6 × 10–34 kg
m2 s–1).

PROBLEM: Calculate the de-Broglie wavelength of an electron moving with 1% of the speed of light.
[Ans. 2.43 x 10-10 m]
PROBLEM: Two particles A and B are in motion. If λ of A is 5 × 10–8 m, then calculate the λ of B, if its momentum
is half that of A.
PROBLEM: The kinetic energy of a sub-atomic particle is 5.65 × 10–25 J. Calculate the frequency of the particle
wave. (Planck’s constant, h = 6.626 × 10–34 kg m2 s–1). [Answer: 1.7 × 109 s–1]
PROBLEM: When would wavelength associated with an electron become equal to the wavelength associated with a
proton? (me = 9.1 x 10-28, mp = 1.67 x 10-24 g). [Answer ve = 1836 vp]
EXTRA QUESTION: Calculate the de Broglie wavelength of an electron traveling at 1% of the speed of light?
EXTRA QUESTION: A microscope using suitable photon is employed to locate an electron in an atom with in a
distance of 0.1A. What is the uncertainty involved in the measurement of its velocity?
21. WERNER HEISENBER’S UNCERTAINITY PRINCIPLE: W. Heisenberg (1927) put this fact in the form of
well-known principle, called Heisenberg's uncertainty principle. It states that
We can never measure simultaneously both the position & the velocity (and momentum) of a microscopic particle
such as an electron with absolute accuracy or certainty. So, it is not possible to talk trajectory of an electron.
OR
It is not possible or impossible to measure simultaneously both the position and velocity (or momentum) of a
microscopic particle with absolute accuracy or certainty.
This is the direct consequence of the dual nature of matter & radiations.

11 CHAPTER 2: CLASS XI: ATOMIC STRUCTURE

Mathematically, uncertainty principle may be put as - the product of uncertainty, in position and momentum, is
always constant.
x. p h
4 [where x = Uncertainty in position and p = uncertainty in momentum].
The above relation can also be written as: x. m v h / 4
The sign means that the product of x and p can be greater than or equal to h / 4 . It can never be less than h /
4 . For minimum uncertainty x . p = h/4

Since product of x. p is constant.

We can say x = 1 X h .
px4
or x 1 / P (Where, h/4 is constant)
It follows that if uncertainty in position ( x) is less, then uncertainty in momentum ( p) would be large. Similarly,
if uncertainty in momentum ( p) is less, then uncertainty in position ( x) would be large.
PHYSICAL CONCEPT OF UNCERTANITY PRINCIPLE: To determine the position of an object, we must be able to see
the object. To observe the position of an object light of suitable wavelength is made to fall on the surface of the
object, which scatters light, enters into our eyes. We can only see the object. If the object is of small size
(microscopic particle) like electron, proton the impact of the striking photon causes a large displacement from its
normal path. As a result of which both the velocity (and momentum) and the position (or path) of the electron
changes and this sends the electron to a new unpredictable path. So, we find that it is impossible to measure
simultaneously & accurately both the position and momentum of an electron or any other microscopic particle.
SIGNIFICANCE OF HEISENBERG’S UNCERTAINTY PRINCIPLE: Consider the following two cases:
Case1: If uncertainty is applied to an object (suppose dust particle) of mass 10-6 Kg or milligram (10-3 g)
Then, x. v = h = 6.626 X 10-34 J s = 5.29 X 10-28 m2 s-1
4 m 4 X 3.14 X 10 kg
-6 where [1J = kg m2s-2].
The value of x. v obtained is extremely small therefore one may say about a milligram size or heavier
objects, uncertainty of such small dimensions are hardly of any real consequence.
Case 2: In the case of a microscopic object like an electron on the other hand x. v obtained is much larger &
such uncertainty are of some real consequence. For example: for an electron whose mass 9.1X 10-31 kg,
according to Heisenberg’s uncertainty principle
x. v = h = 6.626 X 10-34 J s = 10-4 m2 s-1 [1J = kg m2s-2].
4 .m 4 X 3.14 X 9.11 X 10-31 kg
It therefore means that if one tries to find the exact location of the electron whose uncertainty in its position is 10-8 m
then the uncertainty in v in velocity would be 10-4 m2 s-1 = 104 m s-1
So, form the above data it is clear that the classical picture of electron moving in the Bohr’s orbit does not hold
good. It therefore means that the position & momentum of electron have to be replaced by statement of
probability picture of an electron around the nucleus.
NUMERICAL: Calculate the uncertainty in the velocity ( v) of an electron if the uncertainty in its position ( x) is
100 pm? Mass of the electron is 9.1 x 10 -31 Kg. Planck's constant h = 6.6 x 10 -34 Joule second
Solution: We know x x p = h/4 or hence, x = 100 pm = 100 x 10-12 m = 10 -10 m
Putting all the known value 10 -10 x m x v = 6.6 x 10 -34 / 4
v = 6.6 x 10 -34 / 4 x 22/7 x 10 -10 x 9.1 x 10 -31m/s = 5.7 x 10 5m/s.
We see in the above question that uncertainty in the velocity of electron is very huge and so there is no point in
talking about its actual velocity. Consequently, talking about the trajectory of an electron makes no sense.
NUMERICAL: On the basis of Heisenberg’s uncertainty principle prove that an electron cannot exits in the
nucleus?

12 CHAPTER 2: CLASS XI: ATOMIC STRUCTURE

Pink box 2.15: A microscope using suitable photons is employed to locate an electron in an atom within a distance of
0.1 Å. What is the uncertainty involved in the measurement of its velocity?
Pink box 2.16: A golf ball has a mass of 40g, and a speed of 45 m/s. If the speed can be measured within accuracy
of 2%, calculate the uncertainty in the position.
PROBLEM: Calculate the uncertainty in the velocity (Δv) of an electron if the uncertainty in its position is 2 × 10–10
m. [Answer: 2.9 × 105 m s–1].
PROBLEM: Using the mathematical expression for the uncertainty principle, show that the simultaneous
measurement of position and momentum of a particle with absolute accuracy is not possible.
22. WAVE MECHANICAL MODEL OF ATOM---------------CONCEPT OF ATOMIC MODEL
(a) In 1927, E Schrodinger described the behaviour of electron around the nucleus by mathematical second
differential equation to calculate the solution of wave function  called as wave function.

Where, y = (psi) is a wave function of space coordinates 'x', 'y', 'z' and represents the amplitude of the electron wave.
, m = mass of the electron, E = the total permissible energy level, which the electron can have.
V = potential energy of the electron given by ze2/r. h = Planck's constant having the value 6.626 x 10-34 J s.
D = (delta) stands for infinitesimal change.
(b) Significance of  (Amplitude of wave function): The wave function  itself has no significance. But the square of
the wave function significance. As a moving electron is associated with a wave and the wave is completely defined
by its amplitude, therefore  refers to amplitude of electron wave. The square of  i.e. 2 has a physical significance,
just like light radiations where square of amplitude gives the intensity of light. Similarly here 2 give the intensity of
electron at any point or the probability density of an electron around the nucleus. By knowing the value of 2 we can
predict whether electron is there or not. Thus 2 is called probability density. If 2 are zero it means there is no
electron and that place where probability of finding the electron is zero is called as nodal plane.
(c) Failure of Bohr’s model on the basis of quantum mechanics: In the light of Heisenberg’s uncertainty principle and
dual nature. Bohr’s model postulating that the electron moves along define circular path and hence their position
and angular momentum can be determining with absolute accuracy at any instant of time became acceptable around
the nucleus. (mvr =nh/2 as per Bohr’s rule). So, the quantum mechanics said all atomic models which were
postulated before the quantum mechanics follows classical mechanics or Newtonian mechanics. Newtonian
mechanics is only related to the macroscopic objects and not to the microscopic objects. So, all the concepts of
structure of atom that was put before the concept of Quantum mechanics were found to be wrong. Also, the concept
put forward by the Bohr’s model regarding the orbits and the actual trajectory of electron can be calculated seems to
be wrong because of the Heisenberg’s uncertainty principle. So, we cannot give the exact position and the velocity of
an electron around the nucleus at any instant of time. Now, Quantum mechanics said the picture of electron should
be given in terms of probability density rather than the using the word exact i.e. we can speak only in terms of
probability picture. Also, concept of atomic orbitals or Orbitals rather than the concept of orbit (Given by Bohr’s
model) that talked in terms of exact position and momentum.
So, Orbital is defined as the place around the nucleus where probability or chance of finding the electron is
maximum. The concept of electron probability put forward by Quantum mechanics was helpful in explaining the
hypothetical experiments in which we take a set of pictures that are represented by small dots. The density of the dots
will give the probability density of an electron around the nucleus. It is examined that the density of the electron
around the nucleus is greater and decreases as the distance from the nucleus is increased. Hence, if the probability
density or electron density gives you the concept of definite radius. However, for our convenience a boundary
surface is usually drawn with in which the probability density is maximum. That is usually called as atomic orbital.

13 CHAPTER 2: CLASS XI: ATOMIC STRUCTURE

From the above paragraph we conclude that the precise statement of the position and momentum of electron have to
be replaced by the statement of the probability picture of an electron in terms of its position and angular momentum
by giving the concept of atomic orbitals.
23. Probability picture of electrons: It is impossible to determine simultaneously the exact position and exact
velocity of an electron in an atom; it is not possible to determine paths or trajectory of an electrons in an atom.
Therefore, the concept of Bohr's model and its well-defined orbits is incorrect. Best way of describing an electron in
an atom is to estimate the probability of finding an electron in any region or space around the nucleus.
Orbital concept: Atomic orbital is the space around the nucleus where probability of finding the electron is
maximum.
DIFFERENCE BETWEEN ORBIT AND ORBITAL
S.No. Orbit Orbital
1. These are the circular path around the It is the place around the nucleus where the
Nucleus where the electrons revolve around probability or chance of finding the electron is
the nucleus. It is represented by K, L, M etc. maximum i.e. 90 to 95%.
2. Orbit is generally a planar or 2-Dimensional An orbital is a three-dimensional concept.
concept.
3. Orbits are circular in shape. Orbitals are not circular except s-orbital that is
spherically symmetrical.
4. Orbits are usually non directional in nature. Orbitals are usually directional in nature except s-
orbital that is spherically symmetrical.
5. The number of electrons that are An orbital can accommodate two electrons and
accommodated in an orbit are ‘2n2’ they must have opposite spin.
6. Orbits are not as per the concept o Orbits are as per the concept o Heisenberg’s
Heisenberg’s uncertainty principle and dual uncertainty principle and dual behaviour.
behaviours.
24. Quantum numbers: A set of magical number which gives the address of a particular electron. In order to specify
energy, size, shape and orientation of the electronic orbital, three quantum numbers are required. These are principal
quantum number (n), azimuthal quantum number (l) and magnetic quantum number (mL). These follow
directly from solutions of Schrodinger wave equation. In order to designate the electron, an additional quantum
number called spin quantum number (ms) is needed to specify spin of the electron. Thus, each orbital in an atom is
designated by a set of three quantum numbers and each electron is designated by a set of four quantum numbers.
(a) Principal or Primary quantum number (n): 1. This quantum number determines the main energy level or shell
in which the electron is present. It is usually denoted by n and values as whole number as n =1, 2, 3, 4, - - - - -etc.
When n = 1, it is called K shell, n =2, it is called L shell, n =3, it is called M shell, n = 4, it is called N shell.
2. It tells us the average distance of an electron from the nucleus. Or in other words it tells us the size of an atom.
3. It helps us to calculate the energy values of various energy levels in a hydrogen atom.
As the values of n increases, the electron gets farther away from the nucleus and its energy increases. The higher the
value of n, the higher is the electronic energy. En = (-1312 / n2) kJ/mol
(b) The angular momentum quantum number or azimuthal quantum number (l): This quantum number denotes
the sublevel or sub-shell in a main shell to which an electron belongs. This is also called secondary quantum
number. It is designated by l and corresponding to each value of n, there are n possible values of l ranging from 0 to
one less than n for that state. This quantum number gives the energy of the electron due to the angular momentum of
the electron, angular momentum of electron is given by a relation : Angular Momentum = , when value of
l increase, angular momentum is also increases. Designation of the sub Shell Table 1.04 Designation of the sub Shell
Value of l Designation of sub shell Spectroscopic term
l=0 s Sharp
l=1 p Principal

14 CHAPTER 2: CLASS XI: ATOMIC STRUCTURE

 l=2 d Diffuse
l=3 f Fundamental
The shape of the orbital depends upon the value of l that’s why this quantum number is also called orbital
quantum number.
(c) Magnetic Quantum Number (m): This quantum number is denoted by m and refers to the different orientation
of electron cloud in a particular sub shell. It can have all integral values from -l to + l through 0. Thus for a given l
value there are = l + 1 values of m as under - l, (-l+1), (-l+2) --------- 0, 1, 2, 3, ----------, ( l - 1 ) , l.
Suppose l = 0 (i.e. s sub shell), m can have one value m = 0. It means that s sub shell has only one orbital.
If l = 1 (p sub shell) m can have -1, 0, 1. This implies that p sub shell has three orbitals.
If l =2 (d sub shell) m can have -2, -1, 0, 1, 2 values. This means d sub shell have five orbitals.
If l = 3 (f sub shell) m can have -3, -2, -1, 0, 1, 2, 3 values.
This means f sub shell have seven orbitals.
On the basis of magnetic behavior substances are divided as diamagnetic and paramagnetic substances.
(i) Diamagnetic substance: Those substances that feebly repelled by the magnetic field as they do not contain any
unpaired electrons are called diamagnetic substances.
(ii) Paramagnetic substances: Those substances that feebly attracted by the magnetic field as they contain few
unpaired electrons are called paramagnetic substances.
(d) The spin quantum number (s): It is denoted by s and can have only two values for an electron i.e. + ½ and - ½.
These two values may be considered to correspond to clockwise and anticlockwise spins. (The electron is capable of
spinning about its own axis). The clockwise spin is represented by an arrow ( or ) pointing upward, while the
anticlockwise spin is represented by an arrow ( or ) pointing downward. An orbital can accommodate two electrons
having opposite spins. The permitted values of various quantum numbers and their relationship are as under.
1. K shell n = 1, l = 0, m = 0, S = ½ , Total number of electrons in the shell = 2
2. L shell n = 2, l = 0, 1, m = 0, -1, 0, +1. S = ½ ; ½ , ½ , ½ .Total no. Of electron in L shell=8
3. M shell n = 3, l = 0, 1,2.M = 0; -1, -0, 1; -2, -1, 0, 1, 2; S = ½ ½ , ½ , ½ , ½ , ½ , ½ , ½ , ½
Total number of electron in M shell = 18
4. N shell n = 4, l =0, 1, 2, 3.M =0 -1, -0, 1; -2, -1, 0, 1, 2 ,S = ½, ½, ½, ½; ½, ½ , ½ , ½ , ½ ; ½ , ½ , ½
, ½, ½ , ½ , ½ . Total number of electron in N shell = 32.
RELATION AMONG THE VALUES OF n, l, m.

15 CHAPTER 2: CLASS XI: ATOMIC STRUCTURE

 Principal
Possible Designs.
Energy quantum Possible value Number of
values of sub
level number of m orbital
of l shell
n
Sub Energy
shell level
K 1 0 1s 0 1 1
L 0 2s 0 1
2 4
1 2p -1,0,+1 3
M 0 3s 0 1
3 1 3p -1,0,+1 3 9
2 3d -2,-1,0,+1,+2 5
N 0 4s 0 1
1 4p -1,0,+1 3
4 2 4d -2,-1,0,+1,+2 5 16
-3,-2,-
3 4f
1,0,+1,+2,+3 7

25. Calculation of number of nodes: It is a place where the chance or probability of finding the electron is zero, i.e.
a place where 2 is zero. There are two kinds of nodes
(a) Radial or spherical nodes: The formula to calculate the radial nodes is (n-ℓ-1).
(b) Planar nodes: They are always equal to ‘ℓ’ & Total numbers of nodes are (n-1).
Orbital Value of n Value of ℓ Planar node (ℓ) Radial nodes (n-ℓ-1) Total nodes (n-l)
1s 1 0 0 0 0
2s 2 0 0 1 1
2p 2 1 1 0 1
3s 3 0 0 2 2
3p 3 1 1 1 2
2
Shape of orbitals: The probability diagram can be described in terms of the distribution of electron cloud in the
space surrounding the nucleus. The density of electron cloud at any point is proportional to the value of 2 at that
point. Since, 2 is not uniform hence, the density of the electron cloud is also not uniform. The cloud being denser in
some regions and less dense in other region. Now we will discuss shapes of s, p, d and f orbitals.

16 CHAPTER 2: CLASS XI: ATOMIC STRUCTURE

1. Shape of s-orbital: For s orbital l = 0. s- orbitals are non-directional and spherically symmetrical. It means the
probability of finding the electron is same in all direction at a particular distance from the nucleus.
Nodal surface or node. Surface where probability of finding the electron is zero is called nodal surface or node. 2s
orbital differs from 1s orbital as being larger in size and having a nodal surface. The higher s orbitals have also
spherical shapes and number of nodal surfaces for any given energy level is (n – 1), where n is the energy level.

2. Shape of p orbital: For p-orbital l = 1 and m = -1, 0, +1 and we can say there are three possible orientation of
electron cloud. It is denoted by Px, Py and Pz or P+1, P-1, Po where Px orbital is oriented along x axis, Py orbital is
oriented along y axis and Pz orbital is oriented along z axis (chosen as internuclear axis). Figure of p-orbitals are as
under each orbital have two lobes, which are separated by a nodal plane. Nodal plane is the plane where
probability of finding the electron is zero. Each p orbital is shaped like dumb - bell shaped.
3. Shape of d orbital: For d orbital l = 2, and magnetic quantum number is +2, +1, 0, -1, -2. It has five possible
orientation of electron cloud. These are designated by dxy , dyz , dxz , dx2-y2 and dz2.Figures of d orbitals are as under .
Here orbital dxy is in xy plane; dyz is yz place dxz is in xz plane, they are identical in shape, only difference is their
orientation. They have four lobes. dx2-y2 orbital has four lobes which lie along x and y axis. dz2 orbital have two lobes
along z axis and a ring of high electron density in xy plane.

Pauli’s Exclusion Principle: This principle states that

‘No two electrons in an atom can have same value of all the set of four quantum Numbers’. ↑↓
Suppose we want to write all the quantum numbers of 1s orbital.
For 1 s orbital n = 1, l = 0, m = 0 and s = ½ here we see that this orbital having two electrons one rotating in
clockwise direction where spin quantum number s = + ½ and second electron is rotating in anticlockwise direction
where spin quantum number s = - ½.
Now we can say that only two electrons can be accommodated in one orbital and they must have opposite spin either
it will not follow the above principle.
So, an orbital can orbital can accommodate two electrons and that must be of opposite spin. If we want to put
two electrons in an orbital then the entire four quanta will not be same, they have to be different. If even the first
three quantum numbers are same then the spin quantum must be different (mean the electrons will have different
spin). That’s why it is called as EXCLUSION PRINCIPLE i.e. you must have to exclude at least one quantum
number to define the address of an electron in a particular shell.
A direct implication of this principle is that it is not possible to accommodate more than two electrons in an orbital.
Each sub shell holds a maximum of two electrons in an orbital. It can be thus concluded that

17 CHAPTER 2: CLASS XI: ATOMIC STRUCTURE

So, the maximum number of orbitals in each shell is n2 and the maximum number of electrons is 2n2.
Electronic configuration of atoms: The distribution of electron in various orbital is known as electronic
configuration of atom.
Rules for filling of orbitals in an atom (Bohr - Bury's rule (n+l) rule )
According to this rule: (a) The orbitals having the lowest value of n + l, is occupied first by the electron.
(b) When two orbitals have the same value of (n+l) then the one with lower value of ‘n’ fills up first. Suppose we are
taking 2s and 2p orbital. For 2s orbital n + l = 2+0 = 2 and for 2p orbital (n+l) = 2+1 = 3, so electron will go in 2s
orbital and then in 2p orbital. We may take another example. If we want to see in which orbital of 3d or 4s electron
go first. Here for 3d, n+1 = 3 + 2 = 5 and for 4 s, n + l = 4+0 = 4 so, as above electron will go in 4 s orbital first.
Question: In the orbital 3d and 4p where will the electron go first?
Answer: Here for 3d, (n + 1) = 3+2 = 5 and for 4p, (n+1) = 4 + 1 = 5
so, according to Bohr-Bury's second rule, electron will go to that orbital which have value of lowest n. So, electron
will go in 3d orbital.
Aufbau rule or principle (Building Block rule): According to this rule electron are added progressively to various
orbitals in the order of increasing energy starting with the orbital of the lowest energy level. The relative energies of
various orbitals are as under 1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s.
The filling of the orbitals is done as per the Bohr’s-Bury rule (n+l) rule.
Orbital Value of n Value of l (n+ l) value
1s 1 0 1
2s 2 0 2
2p 2 1 3
3s 3 0 3 (Orbital with lower value ‘n’ is filled)
3p 3 1 4
4s…….etc.
Hund's rule of maximum multiplicity: According to this rule, electron pairing will not take place in orbitals of
same energy until each orbital is singly filled’.
Electron pairing will not take place in degenerated orbitals (i.e. orbitals with equivalent energy) until each
orbital is singly filled’
So, first simply or singly filled with paralleled spin then doubly filled. For example, three p orbitals i.e. px, py, pz
have equal energy. How should these orbitals be filled? Let us take an example in
which 3 electrons are to be filled in p orbitals. There can be two possibilities.
According to Hund's rule II is the correct configuration. The basis of this rule is if
two electrons are in same orbital just like in fig.1 above, they feel more electrostatic repulsion. So, we should avoid
the pairing of electron. If electrons are singly occupied in the orbital of same energy with parallel spin, energy of the
system will be lower and this configuration will be more stable. (You can also write it on the basis of spin
multiplicity term (2S + 1).

18 CHAPTER 2: CLASS XI: ATOMIC STRUCTURE

Electronic configuration of atoms

19 CHAPTER 2: CLASS XI: ATOMIC STRUCTURE

In some cases, the actual configuration differs slightly from the expected ones e.g., Cu (atomic number 29) and Cr
(atomic number 24) because of the extra stability of half-filled and completely filled sub shell configuration.
The extra stability of half-filled and completely filled sub shell configuration is due to the following two reasons.
1. Symmetry of orbitals: The configurations with half-filled or completely filled involve symmetrical distribution of
electrons. Symmetry of electronic distribution leads to extra stability. Example

2. Stability Due to Exchange Energy: The half-filled or fully filled degenerate orbitals (means having equal
energy, i.e. 2px, 2py, 2pz have equal energy) have large energy of exchange stabilization. Exchange means shifting of
electron in degenerated orbitals. Electron of 3dxy orbital can go to 3dyz, 3dxz, and 3dx2-y2, 3dz2 orbitals because all are
having equal energy. Total number of exchanges =4 +3+2+1=10. We see in 3d 4 4s 2 configuration 6 exchanges are
possible but in 3d54s1, 10 exchanges are possible. So, 3d5 4s1 electronic configuration is more stable as energy of the
system have become lower due to greater number of exchanges.
Similarly, for 3d 10 and 3d 9, 3d 10 electronic configurations are more stable, as number of exchanges is more as
compared to 3d9 configuration. The distribution of electrons in different orbitals for the remaining elements may be
worked out in the same manner, as no new principles are required.
For cations the electronic configuration is written by determining the number of electrons. The number of electrons is
found by subtracting the number of positive charges on the cation from the atomic number).
Na+, atomic number = 11, number of positive charges = 1.
Number of electrons in Na+ = (11 - 1) = 10. Electronic configuration is. 1s2 2s2 2px2 2py2 2pz2
For anions the electronic configuration is written by determining the number of electrons. The number of electrons is
found by adding the number of negative charges on the anion to the atomic number.
Cl-, atomic number = 17, number of negative charges = 1.
Number of electrons in Cl- = (17 + 1) = 18. Electronic configuration is 1s2 2s2 2px2 2py2 2pz2 3s23px2 3py2 3pz2 .

20 CHAPTER 2: CLASS XI: ATOMIC STRUCTURE

The ions and atoms having the same number of electrons are termed as isoelectronic e.g., O2-, Na+, Al3+, Mg2+ and
Ne (each containing ten electrons.
The total number of sublevels or sub-shells possible in each energy level is equal to the numerical value of 'n'. Thus
'n' = 1 energy level can have only one sublevel which is 'l' = 0 or the’s’ orbital, 'n' = 2 energy level can have two
sublevels corresponding to 'l' = 0 (s) and 'l' = 1(p). Similarly, 'n' = 3 energy level can have 3 sublevel’s’, 'p' and’d’
Electronic configuration of Ions: Electronic configuration of anions or cations may be written in the same way to
those of the atoms. For example, suppose we want to write for Na atom here atomic number of Na is 11
+ 2 2 6 1 +
11Na = 1s 2s 2p 3s . So for Na we have to remove one electron. The outer most orbit 3s is having one electron,
we will remove that one so for 11 Na+ = 1s 2 2s 2 2p 6
similarly for 12Mg = 1s 2 2s 2 2p 6 3s2 and for ++ 2 2 6
12Mg = 1s 2s 2p some more example.
2 2 6 2 6 6 2 ++
26 Fe = 1s 2s 2p 3s 3p 3d 4s & 26 Fe = 1s 2 2s 2 2p 6 3s 2 3p 6 3d 6
+++
26 Fe = 1s 2 2s 2 2p 6 3s 2 3p 6 3d 5 & 2 2 6
28 Ni = 1s 2s 2p 3s 3p 3d 4s
2 6 8 2
++
28 Ni = 1s 2 2s 2 2p 6 3s 2 3p 6 3d 8 & 2 2 6
27 Co = 1s 2s 2p 3s 3p 3d 4s
2 6 7 2
3+
27 Co = 1s 2 2s 2 2p 6 3s 2 3p 6 3d 6 & 2 2
29 Cu = 1s 2s 2p 3s 3p 3d
6 2 6 10
4s 1
+ 2 2 6 2 6 10 ++ 2 2 6 2 6 9
29 Cu = 1s 2s 2p 3s 3p 3d & 29 Cu = 1s 2s 2p 3s 3p 3d
We should remember that in cases of Fe , Fe , Co , Cu Cu , Ni++ electrons have been removed from 4s orbital
3+ ++ 3+ + ++

first and then from 3d orbital.

PINK BOX 2.17. What is the total number of orbitals associated with the principal quantum number n = 3 ?
PINK BOX 2.18: Using s, p, d, f notations, describe the orbital with the following quantum numbers
(a) n = 2, l = 1, (b) n = 4, l = 0, (c) n = 5, l = 3, (d) n = 3, l = 2
SOME IMPORTANT QUESTIONS
1. State Heisenberg’s principle. An electron has a velocity of 50 m/s accurate up to 99.99%. Calculate the uncertainty
in locating its position? (Mass of electron = 9.1 X 10-31 kg, h= h=6.626 x 10-34 Js).
2. Write down the electronic configuration of chromium. (Atomic number of Cr=24) & Copper (Atomic number of
Cu=29). {[Ar]18 3d5 4s1 & [Ar]18 3d10 4s1}.
3. Show that the Heisenberg’s uncertainty principle is of negligible significance for an object for an object of10-6 Kg
mass. (h = 0.528 X 10-34 kg m2 s-1).
4П
Solution. x. v = h / 4 m. = 0.528 X 10-34 kg m2 s-1 = 5.28 X 10-29 m2 s-1.
10-6 Kg
Statement: Since the product of uncertainty in position & velocity is extremely small, therefore Heisenberg’s
uncertainty principal is of negligible significance for an object of 10-6 Kg mass.
4. Show that the Heisenberg’s uncertainty principle is of negligible significance for an object for an object of 10-3 g
mass. (h = 0.528 X 10-34 kg m2 s-1).
4П
SOLVED NCERT QUESTIONS
1. (i) Calculate the number of electrons which will together weigh one gram.
(ii) Calculate the mass and charge of one mole of electrons.
Solution: (i) Mass of one electron = 9.10939 × 10–31 kg, Number of electrons that weigh 9.10939 × 10–31 kg = 1
Number of electrons that will weigh 1 g = (1 × 10–3 kg)

= 0.1098 × 10–3 + 31 = 0.1098 × 1028 = 1.098 × 1027 (standard form).

(ii) Mass of one electron = 9.10939 × 10–31 kg,
Mass of one mole of electron = (6.022 × 1023) × (9.10939 ×10–31 kg) = 5.48 × 10–7 kg
Charge on one electron = 1.6022 × 10–19 coulomb
Charge on one mole of electron = (1.6022 × 10–19 C) (6.022 × 1023) = 9.65 × 104 C
21 CHAPTER 2: CLASS XI: ATOMIC STRUCTURE
2. (i) Calculate the total number of electrons present in one mole of methane. (ii) Find (a) the total number and (b) the
total mass of neutrons in 7 mg of 14C. (Assume that mass of a neutron = 1.675 X10–27 kg).
(iii) Find (a) the total number and (b) the total mass of protons in 34 mg of NH3 at STP. Will the answer change if the
temperature and pressure are changed?
(i) Number of electrons present in 1 molecule of methane (CH4) = {1(6) + 4(1)} = 10.
Number of electrons present in 1 mole i.e. 6.023 × 1023 molecules of methane = 6.022 × 1023 × 10 = 6.022 × 1024
(ii) (a) Number of atoms of 14C in 1 mole= 6.023 × 1023.
Since 1 atom of 14C contains (14 – 6) i.e., 8 neutrons, the number of neutrons in 14 g of 14C is (6.023 × 1023) ×8. Or,
14 g of 14C contains (6.022 × 1023 × 8) neutrons.

Number of neutrons in 7 mg = 2.4092 × 1021

(b) Mass of one neutron = 1.67493 × 10–27 kg, Mass of total neutrons in 7 g of 14C = (2.4092 × 1021) (1.67493 × 10–27
kg)
= 4.0352 × 10–6 kg
(iii) (a) 1 mole of NH3 = {1(14) + 3(1)} g of NH3 = 17 g of NH3 = 6.022× 1023 molecules of NH3.
Total number of protons present in 1 molecule of NH3 = {1(7) + 3(1)} = 10.
Number of protons in 6.023 × 1023 molecules of NH3 = (6.023 × 1023) (10) = 6.023 × 1024
⇒ 17 g of NH3 contains (6.023 × 1024) protons.

Number of protons in 34 mg of NH3 = 1.2046 × 1022..

(b) Mass of one proton = 1.67493 × 10–27 kg
Total mass of protons in 34 mg of NH3 = (1.67493 × 10–27 kg) (1.2046 × 1022) = 2.0176 × 10–5 kg.
The number of protons, electrons, and neutrons in an atom is independent of temperature and pressure conditions.
Hence, the obtained values will remain unchanged if the temperature and pressure is changed.
5. Yellow light emitted from a sodium lamp has a wavelength (λ) of 580 nm. Calculate the frequency (ν) and wave
number ( ) of the yellow light.

Solution: From the expression, , We get, …….. (i)

Where, ν = frequency of yellow light, c = velocity of light in vacuum = 3 × 108 m/s
λ = wavelength of yellow light = 580 nm = 580 × 10–9 m

Substituting the values in expression (i):

Thus, frequency of yellow light emitted from the sodium lamp = 5.17 × 1014 s–1

Wave number of yellow light,

6. Find energy of each of the photons which (i) correspond to light of frequency 3× 1015 Hz. (ii) have wavelength of
0.50 Å.
Solution: (i) Energy (E) of a photon is given by the expression, E = , E = (6.626 × 10–34) (3 × 1015)
–18
E = 1.988 × 10 J

(ii) Energy (E) of a photon having wavelength (λ) is given by the expression,
h = Planck’s constant = 6.626 × 10–34 Js, c = velocity of light in vacuum = 3 × 108 m/s

Substituting the values in the given expression of E:

7. Calculate the wavelength, frequency and wave number of a light wave whose period is 2.0 × 10–10 s.

22 CHAPTER 2: CLASS XI: ATOMIC STRUCTURE

Solution: Frequency (ν) of light

Wavelength (λ) of light , Substituting the value in the given expression of λ:

Wave number of light

8. What is the number of photons of light with a wavelength of 4000 pm that provide 1 J of energy?
Solution: Energy (E) of a photon = hν, Energy (En) of ‘n’ photons = nhν

, Substituting the values in the given expression of n:

Hence, the number of photons with a wavelength of 4000 pm and energy of 1 J are 2.012 × 1016
9. A photon of wavelength 4 × 10–7 m strikes on metal surface, the work function of the metal being 2.13 eV.
Calculate (i) the energy of the photon (eV), (ii) the kinetic energy of the emission, and (iii) the velocity of the
photoelectron (1 eV= 1.6020 × 10–19 J). [IMPORTANT QUESTION]

(i) Energy (E) of a photon = hν or

(ii) The kinetic energy of emission Ek

(iii) The velocity of a photoelectron (ν) can be calculated by the expression,

or or v = 5.84 × 105 ms–1

10. Electromagnetic radiation of wavelength 242 nm is just sufficient to ionise the sodium atom. Calculate the
ionisation energy of sodium in kJ mol–1.

Solution: Energy of sodium (E)

= 4.947 × 105 J mol–1 = 494.7 × 103 J mol–1 = 494 kJ mol–1 .
11. A 25 watt bulb emits monochromatic yellow light of wavelength of 0.57μm. Calculate the rate of emission of
quanta per second.

Solution: Power of bulb, P = 25 Watt = 25 Js–1 , Energy of one photon, E = hν

Rate of emission of quanta per second

12. Electrons are emitted with zero velocity from a metal surface when it is exposed to radiation of wavelength 6800
Å. Calculate threshold frequency ( ) and work function (W0) of the metal.

Solution: Threshold wavelength of radian = 6800 × 10–10 m

Threshold frequency of the metal = 4.41 × 1014 s–1

23 CHAPTER 2: CLASS XI: ATOMIC STRUCTURE

Thus, the threshold frequency of the metal is 4.41 × 1014 s–1.
Hence, work function (W0) of the metal = hν0 = (6.626 × 10–34 Js) (4.41 × 1014 s–1) = 2.922 × 10–19 J.
13. What is the wavelength of light emitted when the electron in a hydrogen atom undergoes transition from an
energy level with n = 4 to an energy level with n = 2 ?
Solution: The ni = 4 to nf = 2 transition will give rise to a spectral line of the Balmer series. The energy involved in

the transition is given by the relation, , Substituting the values in the given expression of
E:

= – (4.0875 × 10–19 J)
The negative sign indicates the energy of emission.

Wavelength of light emitted

14. How much energy is required to ionize an ‘H’ atom if the electron occupies n = 5 orbit? Compare your answer
with the ionization enthalpy of H atom (energy required to remove the electron from n =1 orbit).

Solution: The expression of energy is given by,

For ionization from n1 = 5 to , [Ionization means electron is present in infinite level].

Energy required for n1 = 1 to n = ,

Hence, less energy is required to ionize an electron in the 5th orbital of hydrogen atom as compared to that in the
ground state.
15. What is the maximum number of emission lines when the excited electron of an H atom in n = 6 drops to the
ground state?
Solution: When excited electron of an H atom in n = 6 drops to the ground state, the following transitions are
possible: Hence, a total number of (5 + 4 + 3 + 2 + 1) 15 lines will be obtained in the emission spectrum.

Formula to calculate number of spectral line is to the ground state is given by .

n = 6, Number of spectral lines = 15

16. (i) The energy associated with the first orbit in the hydrogen atom is –
2.18 × 10–18 J atom–1. What is the energy associated with the fifth orbit?
(ii) Calculate the radius of Bohr’s fifth orbit for hydrogen atom
Solution: (i) Energy associated with the fifth orbit of hydrogen atom is calculated as:

24 CHAPTER 2: CLASS XI: ATOMIC STRUCTURE

 , E5 = –8.72 × 10–20 J
(ii) Radius of Bohr’s nth orbit for hydrogen atom is given by, rn = (0.0529 nm) n2
n = 5, r5 = (0.0529 nm) (5)2 = 1.3225 nm
17. Calculate the wave number for the longest wavelength transition in the Balmer series of atomic hydrogen.

Solution: For the Balmer series, ni = 2. Thus, wave number is given by,

Wave number is inversely proportional to wavelength of transition. Hence, for the longest wavelength transition,
has to be the smallest.
For to be minimum, nf should be minimum. For the Balmer series, a transition from ni = 2 to nf = 3 is allowed.
Hence, taking nf = 3, we get:

= 1.5236 × 106 m–1

18. What is the energy in joules, required to shift the electron of the hydrogen atom from the first Bohr orbit to the
fifth Bohr orbit and what is the wavelength of the light emitted when the electron returns to the ground state? The
ground state electron energy is –2.18 × 10–11 ergs.

Solution: Energy (E) of the nth Bohr orbit of an atom is given by,
Ground state energy = – 2.18 × 10–11 ergs = –2.18 × 10–11 × 10–7 J = – 2.18 × 10–18 J.
Energy required shifting the electron from n = 1 to n = 5 is given as: ΔE = E5 – E1

19. The electron energy in hydrogen atom is given by En = (–2.18 × 10–18)/n2 J. Calculate the energy required to
remove an electron completely from the n = 2 orbit. What is the longest wavelength of light in cm that can be used to
cause this transition?

Solution: Given,
Energy required for ionization from n = 2 is given

by,
= 0.545 × 10–18 J , ΔE = 5.45 × 10–19 J

Here, longest ‘λ’ causing the transition. = 3647 × 10–10 m = 3647 Å

20. Calculate the wavelength of an electron moving with a velocity of 2.05 × 10 ms–1.
7

25 CHAPTER 2: CLASS XI: ATOMIC STRUCTURE

Solution: According to de Broglie’s equation, OR

21. The mass of an electron is 9.1 × 10–31 kg. If its K.E. is 3.0 × 10–25 J, calculate its wavelength.

Solution: From de Broglie’s equation,

Given, Kinetic energy (K.E) of the electron = 3.0 × 10–25 J.

Substituting the value in the expression of λ:

22. Which of the following are isoelectronic species i.e., those having the same number of electrons?
Na+, K+, Mg2+, Ca2+, S2–, Ar
Solution: Isoelectronic species have the same number of electrons.
Number of electrons in sodium (Na) = 11, Number of electrons in (Na+) = 10
Number of electrons in K+ = 18, Number of electrons in Mg2+ = 10, Number of electrons in Ca2+ = 18
Number of electrons in Sulphur (S) = 16, Number of electrons in S2- = 18
Number of electrons in argon (Ar) = 18. Hence, the following are isoelectronic species:
1) Na+ and Mg2+ (10 electrons each) 2) K+, Ca2+, S2– and Ar (18 electrons each).
23. (i) Write the electronic configurations of the following ions: (a) H– (b) Na+ (c) O2–(d) F– (ii) What are the atomic
numbers of elements whose outermost electrons are represented by (a) 3s1 (b) 2p3 and (c) 3p5? (iii) Which atoms are
indicated by the following configurations? (a) [He] 2s1 (b) [Ne] 3s2 3p3 (c) [Ar] 4s2 3d1.
(i) (a) H– ion: The electronic configuration of H atom is 1s1. Electronic configuration of H– = 1s2
(b) Na+ ion: 10elelctrons) = 1s2 2s2 2p6 3s0 or 1s2 2s2 2p6, (c) O2– ion (10electrons):1s2 2s2 p6
(d) F– ion: (10electrons) = 1s2 2s2 2p6
(ii) (a) 3s1: Electron configuration of the element as:1s2 2s2 2p6 3s1. Atomic number of the element = 11
(b) 2p3: 1s2 2s2 2p3. Atomic number of the element = 7 , (c) 3p5: 1s2 2s2 2p5 3s2 3p5. Atomic number of the element
=9
(iii) (a) [He] 2s1 : Electronic configuration : [He] 2s1 = 1s2 2s1. Atomic number of the element = 3. Element is
Lithium.
(b) [Ne] 3s2 3p3: Electronic configuration: [Ne] 3s2 3p3 = 1s2 2s2 2p6 3s2 3p3. Atomic number of the element =
15.Hence, the element with the electronic configuration [Ne] 3s2 3p3 is phosphorus (P).
(c) [Ar] 4s2 3d1: Electronic configuration [Ar] 4s2 3d1= 1s2 2s2 2p6 3s2 3p6 4s2 3d1. Atomic number of the element =
21.
Hence, the element with the electronic configuration [Ar] 4s2 3d1 is scandium (Sc).
24. What is the lowest value of n that allows ‘g’ orbitals to exist?
Solution: For g-orbitals, l = 4.
As for any value ‘n’ of principal quantum number, the Azimuthal quantum number (l) can have a value from zero to
(n – 1).
For l = 4, minimum value of n = 5
25. An electron is in one of the 3d orbitals. Give the possible values of n, l and ml for this electron.
26 CHAPTER 2: CLASS XI: ATOMIC STRUCTURE
Answer: For the 3d orbital: Principal quantum number (n) = 3, Azimuthal quantum number (l) = 2,
Magnetic quantum number (ml) = – 2, – 1, 0, 1, 2.
26. An atom of an element contains 29 electrons and 35 neutrons. Deduce (i) the number of protons and (ii) the
electronic configuration of the element.
Answer: (i) For an atom to be neutral, the number of protons is equal to the number of electrons =29.
(ii) The electronic configuration of the atom is 1s2 2s2 2p6 3s2 3p6 4s2 3d10.
27. Give the number of electrons in the species , H2 and
Solution: (i) :Number of electrons present in hydrogen molecule (H2) = 1 + 1 = 2, Number of electrons in =2
–1=1
(ii) H2: Number of electrons in H2 = 1 + 1 = 2.
: Number of electrons present in oxygen molecule (O2) = 8 + 8 = 16. Number of electrons in = 16 – 1 = 15
28. (i) An atomic orbital has n = 3. What are the possible values of l and ml ? (ii) List the quantum numbers (ml and l)
of electrons for 3d orbital. (iii) Which of the following orbitals are possible? 1p, 2s, 2p and 3f
Answer: (i) n = 3 (Given) For a given value of n, l can have values from 0 to (n – 1).
For n = 3, l = 0, 1, 2, For a given value of l, ml can have (2l + 1) values.
For l = 0, m = 0, l = 1, m = – 1, 0, 1. l = 2, m = – 2, – 1, 0, 1, 2.
For n = 3, l = 0, 1, 2, m0 = 0, m1 = – 1, 0, 1, m2 = – 2, – 1, 0, 1, 2
(ii) For 3d orbital, l = 2. For a given value of l, ‘ml’ can have (2l + 1) values i.e., 5 values. For l = 2, m2 = – 2, – 1, 0,
1, 2
(iii) Among the given orbitals only 2s and 2p are possible. 1p and 3f cannot exist. For p-orbital, l = 1. For a given
value of n, l can have values from zero to (n – 1). For l is equal to 1, the minimum value of n is 2.
Similarly, For f-orbital, l = 4. For l = 4, the minimum value of n is 5. Hence, 1p and 3f do not exist.
29. Using s, p, d notations, describes the orbital with the following quantum numbers.
(a) n = 1, l = 0; (b) n = 3; l =1 (c) n = 4; l = 2; (d) n = 4; l =3.
(a) n = 1, l = 0 (Given). The orbital is 1s. (b) For n = 3 and l = 1. The orbital is 3p.
(c) For n = 4 and l = 2. The orbital is 4d. (d) For n = 4 and l = 3. The orbital is 4f.
30. Explain, giving reasons, which of the following sets of quantum numbers are not possible.

Answer: (a) Set of quantum numbers is not possible because the value of n cannot be zero.
(b) The given set of quantum numbers is possible. (c) The given set of quantum numbers is not possible.
For a given value of n, ‘l’ can have values from zero to (n – 1). For n = 1, l = 0 and not 1.
(d) The given set of quantum numbers is possible.
(e) The given set of quantum numbers is not possible. For n = 3, l = 0 to (3 – 1) l = 0 to 2 i.e., 0, 1, 2
(f) The given set of quantum numbers is possible.

31. How many electrons in an atom may have the following quantum numbers?(a) n = 4, (b) n = 3, l = 0
2
(a) Total number of electrons in an atom for a value of n = 2n . For n = 4,
Total number of electrons = 2 (4)2= 32. The given element has a fully filled orbital as1s2 2s2 2p6 3s2 3p6 4s2 3d10.
Hence, all the electrons are paired. (Diamagnetic)

27 CHAPTER 2: CLASS XI: ATOMIC STRUCTURE

Number of electrons (having n = 4 and ) = 16.
(b) n = 3, l = 0 means, electrons are present in 3s orbital. So, the number of electrons having n = 3 and l = 0 is 2.
32. Show that the circumference of the Bohr orbit for the hydrogen atom is an integral multiple of the de Broglie’s
wavelength associated with the electron revolving around the orbit.
Since a hydrogen atom has only one electron, according to Bohr’s postulate, the angular momentum of that electron
is given by:

where, n = 1, 2, 3, …

According to de Broglie’s equation: or

Substituting the value of ‘mv’ from expression (2) in expression (1):

Since ‘2πr’ represents the circumference of the Bohr orbit (r), it is proved by equation (3) that the circumference of
the Bohr orbit of the hydrogen atom is an integral multiple of de Broglie’s wavelength associated with the electron
revolving around the orbit.
33. What transition in the hydrogen spectrum would have the same wavelength as the Balmer transition n = 4 to n = 2
of He+ spectrum? [IMPORTANT QUESTION].
Solution: For He+ ion, the wave number associated with the Balmer transition, n = 4 to n = 2 is given by:

Where, n1 = 2, n2 = 4 , Z = 2 [Atomic number of helium].

According to the question, the desired transition for hydrogen will have the same wavelength as that of He+.

By hit and trail method, the equality given by equation (1) is true only when n1 = 1and n2 = 2.
The transition for n2 = 2 to n1 = 1 in hydrogen spectrum would have the same wavelength as Balmer transition n = 4
to n = 2 of He+ spectrum.

34. Calculate the energy required for the process: . The ionization energy for the H atom in the
ground state is 2.18 ×10–18 J atom–1

Solution: Energy associated with hydrogen-like species is given by,

For ground state of hydrogen atom,

. An electron is removed from n = 1 to n = ∞.

28 CHAPTER 2: CLASS XI: ATOMIC STRUCTURE

35. If the diameter of a carbon atom is 0.15 nm, calculate the number of carbon atoms which can be placed side by
side in a straight line across length of scale of length 20 cm long.
Solution: 1 m = 100 cm, 1 cm = 10–2 m. Length of the scale = 20 cm = 20 × 10–2 m
Diameter of a carbon atom = 0.15 nm = 0.15 × 10–9 m

Number of carbon atoms that can be placed in a straight line:

36. 2 × 108 atoms of carbon are arranged side by side. Calculate the radius of carbon atom if the length of this
arrangement is 2.4 cm
Solution: Length of the given arrangement = 2.4 cm, Number of carbon atoms present = 2 × 108

37. The diameter of zinc atom is .Calculate (a) radius of zinc atom in pm and (b) number of atoms present in a
length of 1.6 cm if the zinc atoms are arranged side by side lengthwise.

Solution: (a) Radius of zinc atom ,

(b) Length of the arrangement = 1.6 cm = 1.6 × 10–2 m, Diameter of zinc atom = 2.6 × 10–10 m

Number of zinc atoms present in the arrangement

38. A certain particle carries 2.5 × 10–16C of static electric charge. Calculate the number of electrons present in it.
Charge on one electron = 1.6022 × 10–19 C, 1.6022 × 10–19C charge is carried by 1 electron.

Number of electrons carrying a charge of 2.5 × 10–16 C.

39. In Milikan’s experiment, static electric charge on the oil drops has been obtained by shining X-rays. If the static
electric charge on the oil drop is –1.282 × 10–18C, calculate the number of electrons present on it.
Solution: Charge on the oil drop = 1.282 ×10–18C, Charge on one electron = 1.6022 × 10–19C, Number of electrons

present on the oil drop.

40. In Rutherford’s experiment, generally the thin foil of heavy atoms, like gold, platinum etc. have been used to be
bombarded by the α-particles. If the thin foil of light atoms like aluminium etc. is used, what difference would be
observed from the above results?
Solution: A thin foil of lighter atoms will not give the same results as given with the foil of heavier atoms. Lighter
atoms would be able to carry very little positive charge. Hence, they will not cause enough deflection of α-particles
(positively charged). On the other hand, the heavier particle would deflect more.
41. Symbols can be written, whereas symbols are not acceptable. Answer briefly.
Solution: The general convention of representing an element along with its atomic mass (A) and atomic number (Z) is
Hence, is acceptable but is not acceptable. can be written but cannot be written because the
atomic number of an element is constant, but the atomic mass of an element depends upon the relative abundance of
its isotopes. Hence, it is necessary to mention the atomic mass of an element
42. An element with mass number 81 contains 31.7% more neutrons as compared to protons. Assign the atomic
symbol.
Solution: Let the number of protons in the element be x.
Number of neutrons in the element: = x + 31.7% of x = x + 0.317 x = 1.317 x
Mass number of the element = 81, (Number of protons + number of neutrons) = 81.

29 CHAPTER 2: CLASS XI: ATOMIC STRUCTURE

Since the atomic number of an atom is defined as the number of protons present in its nucleus, the atomic number of
the given element is 35.The atomic symbol of the element is .
43. An ion with mass number 37 possesses one unit of negative charge. If the ion contains 11.1% more neutrons than
the electrons, find the symbol of the ion.
Solution: Let the number of electrons in the ion carrying a negative charge be x.
Number of neutrons present: x + 11.1% of x, = x + 0.111 x = 1.111 x
Number of electrons in the neutral atom = (x – 1). (When an ion carries a negative charge, it carries an extra electron)
Number of protons in the neutral atom = x – 1.
Mass number of the ion = 37, (x – 1) + 1.111x = 37, 2.111x = 38, x = 18. The symbol of the ion is
44. An ion with mass number 56 contains 3 units of positive charge and 30.4% more neutrons than electrons. Assign
the symbol to this ion.
Solution: Let the number of electrons present in ion Number of neutrons in it = x + 30.4% of x = 1.304 x
Since the ion is tripositive, Number of electrons in neutral atom = x + 3, Number of protons in neutral atom = x + 3

Mass number of the ion = 56 or

Number of protons = x + 3 = 23 + 3 = 26, the symbol of the ion
45. Arrange the following type of radiations in increasing order of frequency: (a) radiation from microwave oven (b)
amber light from traffic signal (c) radiation from FM radio (d) cosmic rays from outer space and (e) X-rays.
Solution: The increasing order of frequency is as follows:
Radiation from FM radio < amber light < radiation from microwave oven < X- rays < cosmic rays
Increasing order of wavelength: Cosmic rays < X-rays < radiation from microwave ovens < amber light < radiation
of FM radio
46. Nitrogen laser produces a radiation at a wavelength of 337.1 nm. If the number of photons emitted is 5.6 × 1024,
calculate the power of this laser.
Solution: Power of laser = Energy with which it emits photons

Power or = 0.3302 × 107 J = 3.33 × 106 J.

47. Neon gas is generally used in the sign boards. If it emits strongly at 616 nm, calculate (a) the frequency of
emission, (b) distance traveled by this radiation in 30 s (c) energy of quantum and (d) number of quanta present if it
produces 2 J of energy. Wavelength of radiation emitted = 616 nm = 616 × 10–9 m (Given)

(a) Frequency of emission , Substituting values : = 4.87 ×108×109×10–3 s–1 = 4.87 × 1014 s–1.
(b) Velocity of radiation, (c) = 3.0 × 108 ms–1
Distance travelled by this radiation in 30 s = (3.0 × 108 ms–1) (30 s) = 9.0 × 109 m
(c) Energy of quantum (E) = hv = (6.626 × 10–34 Js) (4.87 × 1014 s–1) = 32.27 × 10–20 J
(d) Energy of one photon (quantum) = 32.27 × 10–20 J. Therefore, 32.27 × 10–20 J of energy is present in 1 quantum.

Number of quanta in 2 J of energy = 6.19 ×1018 = 6.2 ×1018

48. In astronomical observations, signals observed from the distant stars are generally weak. If the photon detector
receives a total of 3.15 × 10–18 J from the radiations of 600 nm, calculate the number of photons received by the
detector.

30 CHAPTER 2: CLASS XI: ATOMIC STRUCTURE

Solution: We know energy of one photon (E), = 3.313 × 10–19 J

Number of photons received with 3.15 × 10–18 J energy = 9.5.

49. Lifetimes of the molecules in the excited states are often measured by using pulsed radiation source of duration
nearly in the nano second range. If the radiation source has the duration of 2 ns and the number of photons emitted
during the pulse source is 2.5 × 1015, calculate the energy of the source.

Solution: Frequency of radiation (v), = 5.0 × 108 s–1

Energy (E) of source = N hv, E = (2.5 × 1015) (6.626 × 10–34 Js) (5.0 × 108 s–1) = 8.282 × 10–10 J
50. The longest wavelength doublet absorption transition is observed at 589 and 589.6 nm. Calculate the frequency of
each transition and energy difference between two excited states.

Solution: For λ1 = 589 nm, Frequency of transition = 5.093 × 1014 s–1

For λ2 = 589.6 nm, Frequency of transition = 5.088 × 1014 s–1

Energy difference (ΔE) between excited states = E1 – E2 , ΔE = hv1 – hv2 = h(v1 – v2)
= (6.626 × 10–34 Js) (5.093 × 1014 – 5.088 × 1014) s–1 = (6.626 × 10–34 J) (5.0 × 10–3 × 1014), ΔE = 3.31 × 10–22 J.
51. The work function for caesium atom is 1.9 eV. Calculate (a) the threshold wavelength and (b) the threshold
frequency of the radiation. If the caesium element is irradiated with a wavelength 500 nm, calculate the kinetic
energy and the velocity of the ejected photoelectron.
Solution: It is given that the work function (W0) for caesium atom is 1.9 eV.

(a) From the expression, , we get: or = 6.53 × 10–7 m.

(b) , we get: , = 4.593 × 1014 s–1 (1 eV = 1.602 × 10–19 J)

(c) According to the question: Wavelength used in irradiation (λ) = 500 nm

Kinetic energy = h (v –v0) = 9.32 × 10–20 J

Since K.E , , v = 4.52 × 105 ms–1

52. Following results are observed when sodium metal is irradiated with different wavelengths. Calculate (a)
threshold wavelength and, (b) Planck’s constant.
λ (nm) 500 450 400

v × 10–5 (cm s–1) 2.55 4.35 5.35

(a) If threshold wavelength to be , the kinetic energy:

Three different equalities can be formed by the given value as:

,
31 CHAPTER 2: CLASS XI: ATOMIC STRUCTURE
Similarly, and
Dividing equation (3) by equation (1):

or

Threshold wavelength = 540 nm.

53. The ejection of the photoelectron from the silver metal in the photoelectric effect experiment can be stopped by
applying the voltage of 0.35 V when the radiation 256.7 nm is used. Calculate the work function for silver metal.
Solution: From the principle of conservation of energy, the energy of an incident photon (E) is equal to the sum of
the work function (W0) of radiation and its kinetic energy (K.E) i.e.,
E = W0 + K.E, or W0 = E – K.E

Energy of incident photon (E) = 4.83 eV

The potential applied to silver metal changes to kinetic energy (K.E) of the photoelectron. Hence,
K.E = 0.35 V or K.E = 0.35 eV or Work function, W0 = E – K.E = 4.83 eV – 0.35 eV = 4.48 eV

54. If the photon of the wavelength 150 pm strikes an atom and one of its inner bound electrons is ejected out with a
velocity of 1.5 × 107 ms–1, calculate the energy with which it is bound to the nucleus. Emission transitions in the
Paschen series end at orbit n = 3 and start from orbit n and can be represented as v = 3.29 × 1015 (Hz) [1/32 – 1/n2]
Solution: Calculate the value of n if the transition is observed at 1285 nm. Find the region of the spectrum.
Wavelength of transition = 1285 nm = 1285 × 10–9 m (Given)

(Given) or = 2.33 × 1014 s–1

n = 4.98 ≈ 5
The spectrum lies in the infra-red region.
55. Emission transitions in the Paschen series end at orbit n = 3 and start from orbit n and can be represented as
v = 3.29 × 1015 (Hz) [1/32 – 1/n2]. Calculate the value of n if the transition is observed at 1285 nm. Find the region of
the spectrum.
Solution: Wavelength of transition = 1285 nm = 1285 × 10–9 m (Given)

(Given) or = 2.33 × 1014 s–1

32 CHAPTER 2: CLASS XI: ATOMIC STRUCTURE

Substituting the value of ν in the given expression,

n = 4.98 or n ≈ 5.
The spectrum lies in the infra-red region.
56. Calculate the wavelength for the emission transition if it starts from the orbit having radius 1.3225 nm and ends
at 211.6 pm. Name the series to which this transition belongs and the region of the spectrum.

The radius of the nth orbit of hydrogen-like particles is given by,

For radius (r1) = 1.3225 nm = 1.32225 × 10–9 m = 1322.25 × 10–12 m = 1322.25 pm

. Similarly,

or n1 = 5 and n2 = 2.
Thus, the transition is from the 5th orbit to the 2nd orbit. It belongs to the Balmer series.

Wave number for the transition is given by, 1.097 × 107 m–1 = 2.303 × 106 m–1

Wavelength (λ) with the emission transition is given by, = 0.434 ×10–6 m , λ = 434 nm
57. Dual behaviour of matter proposed by de Broglie led to the discovery of electron microscope often used for the
highly magnified images of biological molecules and other type of material. If the velocity of the electron in this
microscope is 1.6 × 106 ms–1, calculate de Broglie wavelength associated with this electron.

Solution: From de Broglie’s equation, = 4.55 × 10–10 m = 455 pm.

58. Similar to electron diffraction, neutron diffraction microscope is also used for the determination of the structure
of molecules. If the wavelength used here is 800 pm, calculate the characteristic velocity associated with the neutron.

From de Broglie’s equation, or = 4.94 × 102 ms–1, v = 494

ms–1
59. If the velocity of the electron in Bohr’s first orbit is 2.19 × 106 ms–1, calculate the de Broglie wavelength
associated with it.
Solution: According to de Broglie’s equation,

OR = 332 pm
5 –1
60. The velocity associated with a proton moving in a potential difference of 1000 V is 4.37 × 10 ms . If the hockey
ball of mass 0.1 kg is moving with this velocity, calculate the wavelength associated with this velocity.

Solution: ,

From Heisenberg’s uncertainty principle, or = 2.637 × 10–23

Jsm–1
Δp = 2.637 × 10–23 kgms–1 (1 J = 1 kg ms2 s–1), Uncertainty in the momentum of the electron =2.637 × 10–23 kgms–1.

33 CHAPTER 2: CLASS XI: ATOMIC STRUCTURE

Actual momentum = 1.055 × 10–24 kgms–1 .
Since the magnitude of the actual momentum is smaller than the uncertainty, the value cannot be defined.
61. If the position of the electron is measured within an accuracy of + 0.002 nm, calculate the uncertainty in the
momentum of the electron. Suppose the momentum of the electron is h/4πm × 0.05 nm, is there any problem in
defining this value.

Solution: or = 2.637 × 10–23 Jsm–1

–23 –1 2 –1
Δp = 2.637 × 10 kgms (1 J = 1 kgms s ) Uncertainty in the momentum of the electron = 2.637 × 10–23 kgms–1.

Actual momentum = 1.055 × 10–24 kgms–1. Since the magnitude of the

actual momentum is smaller than the uncertainty, the value cannot be defined.
62. The quantum numbers of six electrons are given below. Arrange them in order of increasing energies. If any of
these combination(s) has/have the same energy lists:
1. n = 4, l = 2, ml = –2 , ms = –1/2 2. n = 3, l = 2, ml= 1 , ms = +1/2, 3. n = 4, l = 1, ml = 0 , ms = +1/2.
4. n = 3, l = 2, ml = –2 , ms = –1/2, 5. n = 3, l = 1, ml = –1 , ms= +1/2 ,6. n = 4, l = 1, ml = 0 , ms = +1/2.
Answer: For n = 4 and l = 2, the orbital occupied is 4d. For n = 3 and l = 2, the orbital occupied is 3d. For n = 4 and l
= 1, the orbital occupied is 4p. So, the six electrons i.e., 1, 2, 3, 4, 5, and 6 are present in the 4d, 3d, 4p, 3d, 3p, and
4p orbitals respectively. Therefore, the increasing order of energies is 5(3p) < 2(3d) = 4(3d) < 3(4p) = 6(4p) < 1 (4d).
63. The bromine atom possesses 35 electrons. It contains 6 electrons in 2p orbital, 6 electrons in 3p orbital and 5
electrons in 4p orbital. Which of these electron experiences the lowest effective nuclear charge?
Answer: Nuclear charge experienced by an electron (present in a multi-electron atom) depends upon the distance
between the nucleus and the orbital. As the distance increases, the effective nuclear charge also decreases.
Among p-orbitals, 4p orbitals are farthest from the nucleus of bromine atom with (+35) charge. Hence, the electrons
in the 4p orbital will experience the lowest effective nuclear charge. These electrons are shielded by electrons present
in the 2p and 3p orbitals along with the s-orbitals. Therefore, they will experience the lowest nuclear charge
64. Among the following pairs of orbitals which orbital will experience the larger effective nuclear charge? (i) 2s and
3s, (ii) 4d and 4f, (iii) 3d and 3p.
Answer: Nuclear charge is defined as the net positive charge experienced by an electron in the orbital of a multi-
electron atom. The closer the orbital, the greater is the nuclear charge experienced by the electron (s) in it.
(i) The electron(s) present in the 2s orbital will experience greater nuclear charge (being closer to the nucleus) than
the electron(s) in the 3s orbital.
(ii) 4d will experience greater nuclear charge than 4f since 4d is closer to the nucleus.
(iii) 3p will experience greater nuclear charge since it is closer to the nucleus than 3f.
65. The unpaired electrons in Al and Si are present in 3p orbital. Which electrons will experience more effective
nuclear charge from the nucleus?
Answer: Nuclear charge is defined as the net positive charge experienced by an electron in a multi-electron atom.
The higher the atomic number, the higher is the nuclear charge. Silicon has 14 protons while aluminium has 13
protons. Hence, silicon has a larger nuclear charge of (+14) than aluminium, which has a nuclear charge of (+13).
Thus, the electrons in the 3p orbital of silicon will experience a more effective nuclear charge than aluminium.
66. Indicate the number of unpaired electrons in: (a) P, (b) Si, (c) Cr, (d) Fe and (e) Kr.
Also, mention the magnetic behavior (Paramagnetic or diamagnetic).
Answer. (a) Phosphorus (P): Atomic number = 15, The electronic configuration of P is: 1s2 2s2 2p6 3s2 3p3

The orbital picture of P can be represented as: (Paramagnetic substance)

34 CHAPTER 2: CLASS XI: ATOMIC STRUCTURE
From the orbital picture, phosphorus has three unpaired electrons. (Half-filled p-orbital configuration).
(b) Silicon (Si): Atomic number = 14, The electronic configuration of Si is: 1s2 2s2 2p6 3s2 3p2

The orbital picture of Si can be represented as: (Paramagnetic substance)

From the orbital picture, silicon has two unpaired electrons.
(c) Chromium (Cr): Atomic number = 24, The electronic configuration of Cr is: 1s2 2s2 2p6 3s2 3p6 4s1 3d5

The orbital picture of chromium is: (Paramagnetic substance)

From the orbital picture, chromium has six unpaired electrons.
(d) Iron (Fe): Atomic number = 26, The electronic configuration is: 1s2 2s2 2p6 3s2 3p6 4s2 3d6

The orbital picture of chromium is: (Paramagnetic substance)

From the orbital picture, iron has four unpaired electrons.
(e) Krypton (Kr): Atomic number = 36 , The electronic configuration is: 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6

The orbital picture of krypton is: (Diamagnetic substance)

Since all orbitals are fully occupied, there are no unpaired electrons in krypton.
67. (a) How many sub-shells are associated with n = 4?
(b) How many electrons will be present in the sub-shells having ms value of –1/2 for n = 4?
Answer. (a) n = 4 (Given), For a given value of ‘n’, ‘l’ can have values from zero to (n – 1). ∴ l = 0, 1, 2, 3
Thus, four sub-shells are associated with n = 4, which are s, p, d and f.
(b) Number of orbitals in the nth shell = n2.For n = 4, Number of orbitals = 16, If each orbital is taken fully, then it

will have 1 electron with ms value of . Number of electrons with ms value of is 16.

35 CHAPTER 2: CLASS XI: ATOMIC STRUCTURE