STRUCTURE OF ATOM

Dual nature of electromagnetic radiation:

o Radiations possess both wave like and particle like properties.
o Wave nature of radiation was proposed by Huygen and explained by Maxwell.
o Experimental evidences for wave nature of radiation are diffraction and interference.
o Particle nature of radiation was proposed by Newton and explained by Max Planck.
o Experimental evidences for particle nature of radiation are black body radiation,
photoelectric effect, variation of heat capacity of solid with temperature and line
spectra of atoms.
Maxwell’s electromagnetic theory (or) Wave theory of radiation:
o Light is transmitted in the form of electromagnetic waves.
o When electrically charged particles are accelerated, electric and magnetic fields are
produced. These fields are transmitted in the form of waves hence are called
electromagnetic waves.
o These electric and magnetic fields are perpendicular to each other and perpendicular
to the direction of propagation.
o These do not require any medium and can move in vacuum.
Characteristics of electromagnetic radiation:
(i) Wave length (λ):
It is defined as the distance between two neighbouring crests or troughs of the wave. It
is measured in pico metres (pm), Angstrom units (Ǻ) or nanometers (nm).
1 pm = 10—12 m, 1 A0 = 10—10 m and 1 nm = 10—9 m
(ii) Frequency (ν):
It is defined as the number of waves that pass through a point in one second. Its units
are: Cycles per second (cps) or Hertz (Hz)
1 cps (or) 1 s-1 = 1Hz,
1 KHz = 103 Hz and
1 MHz = 106 Hz.
(iii) Velocity:
The distance traveled by a wave in one second is called velocity of the wave.
Frequency (ν) and wavelength (λ) are related to velocity (c) by the following relation:
ν = c
λ
Velocity of all electromagnetic radiations in space or in vacuum is same and is equal
to 3 × 108 m/sec or 3 × 1010 cm /sec.
(iv) Wave number:
It is defined as the number of wavelengths per centimeter. It is equal to the inverse
of wavelength expressed in centimetre. It is denoted by ν.
It units are cm-1.
 2

νˉ = 1 = ν
λ c
(v) Amplitude:
It is the height of the crest or depth of the trough of a wave. The amplitude of a wave
determines the intensity of radiation.
Planck’s quantum theory of radiation (or) particle nature of radiation:
o Radiation energy is emitted or absorbed discontinuously in the form of small packets
called quanta. Each packet or quantum is associated with a definite amount of
energy. In case of light the quantum is called photon.
o The amount of energy associated with a quantum of radiation is proportional to the
frequency of radiation.
Eαν
E=hν
Where h is Planck’s constant and is equal to 6.626 × 10—34 J s.
E=hν=hc
Λ
o A body can emit or absorb energy only in integral multiples of quantum.
E = nhν where n = 1, 2, 3, 4
n is number of photons or quanta.
Photoelectric effect:
(i) The phenomenon of ejection of electrons from the surface of a metal when a light of
suitable frequency strikes it is known as photoelectric effect. The electrons ejected are
called photoelectrons.
(ii) The electrons are ejected as soon as the light strikes the surface.
(iii) The number of electrons emitted is proportional to the intensity or brightness of the
light.
(iv) Threshold frequency νo or critical frequency is the minimum frequency required to
emit the electrons from a metal surface.
(v) Threshold energy hνo or Work function of the metal (Wo) is the minimum energy
required to emit the electrons from a metal surface.
(vi) If hν > hνo, the difference in energy is transferred to the photoelectron as its kinetic
energy which is given by Einstein’s photoelectric equation.
K.E. = hν - hνo = h(ν-νo)
K.E. = ½ mv2 = hν - hνo = h(ν-νo)
(vii) Threshold frequency is characteristic of a metal and it is related to the ionization
enthalpy of the metal.
(viii) Metals like potassium, rubidium and caesium show photoelectric effect with visible
rays due to their low ionization enthalpy. Hence they are used in photoelectric cells.
 3

Black body radiation:

An ideal body which emits and absorbs all frequencies uniformly is called a black body
and the radiation emitted by black body is called black body radiation.
Black body is an imaginary object. But some objects behave close to a black body. For
example, carbon black behaves approximately as a blackbody. A cavity with a tiny hole is
another example of a black body.
When a black body is heated it becomes red hot which on further heating becomes
yellow then white and finally purple at very high temperature. That is wavelength of
radiation emitted by a black body decreases with increase in temperature. (or) The
frequency of radiation emitted by black body increases with increase in temperature.
Spectrum:
Spectrum is the arrangement of different colours in order of their increasing
wavelengths. It is produced by passing white light through a prism.
When light is passed through prism, the wave with shorter wavelength bends more than
the one with a longer wavelength and it is spread out into a series of coloured bands which
is known as spectrum.
Emission spectrum:
When radiation emitted by a substance is directly passed through prism and then
received on photographic plate, the spectrum obtained is called an emission spectrum.
There are two types of emission spectra:
(i) Band spectrum or continuous spectrum:
When white light is passed through a prism and analysed by spectrograph, it is
observed that it splits up into seven different bands of colours (VIBGYOR). These bands
are continuous and merge with each other. Hence the spectrum is called continuous
spectrum. Since it is produced by molecules, it is also called molecular spectrum.
(ii) Line spectrum:
When energy emitted by atoms or ions is analysed by spectrograph, the spectrum
consists of isolated lines separated from each other by dark spaces hence the spectrum is
called line spectrum. Since it is produced by atoms, it is also called atomic spectrum.
Significance (or) use of line spectrum (or) atomic spectrum:
The lines in the atomic spectra are used to identify unknown atoms because each
element has a unique line emission spectrum (similar to finger prints in humans).
The elements He, Rb, Cs, etc were discovered by spectroscopic method.
Distinguish line spectrum and band spectrum:
Line spectrum Band spectrum
It is produced by atoms hence also called as It is produced by molecules hence also
atomic spectrum. called as molecular spectrum.
The spectrum consists of bright lines The spectrum consists of bright overlapping
separated from each other by dark spaces bands.
E.g., Hydrogen spectrum E.g., Visible light spectrum (Rainbow)
 4

Emission Spectrum
The emission spectrum is the spectrum of electromagnetic radiation emitted by an atom
or molecule that undergoes transition from a high energy state to a lower energy state.
Absorption spectrum:
The absorption spectrum consist of dark lines in an otherwise continuous spectrum
which corresponds to the radiations absorbed by an atom or molecule. It is produced by
passing white light through a sample and the transmitted light is analyzed with a
spectrograph.
Electromagnetic spectrum:
It is the arrangement of different types of electromagnetic radiations in order of their
increasing wavelengths or decreasing frequencies.
Electromagnetic spectrum consists of
Gamma () rays < X-rays < Ultraviolet rays < Visible rays < Infrared < Microwaves
< Radio waves. ( Giant X is Usually Visible In Music Room)
Gamma rays have wavelength ranging from 10—16 to 10—11 m, X – rays from 10—10 to
10—8 m, UV rays from 10—8 to 10—7 m, visible rays from 3.8 x 10—7 to 7.5 x 10—7 m,
Infrared rays from 10—7 to 10—3 m, Microwaves from 10—3 to 10—1 m and Radio waves
from10—1 to 107 m
Line spectrum of hydrogen:
When an electric discharge is passed through gaseous hydrogen, the H2 molecules
dissociate to form hydrogen atoms. These hydrogen atoms absorb energy and excited.
These excited hydrogen atoms emit electromagnetic radiation of discrete frequencies. The
hydrogen spectrum consists of several series of lines: (i) Lyman series, (ii) Balmer series,
(iii) Paschen series, (iv) Brackett series and (v) Pfund series.
Lyman series are the series of lines produced in hydrogen spectrum when the excited
electrons in hydrogen atoms come down to the ground or first energy level. These lines
appear in ultraviolet region of the spectrum.
The first line in Lyman series corresponds to the transition from n=2 to n=1 and it is
the transition that corresponds to lowest frequency or highest wavelength.
Balmer series are the series of lines produced in hydrogen spectrum when the excited
electrons in hydrogen atoms come down to the second energy level. These lines appear in
visible region of the spectrum.
The first line in Balmer series corresponds to the transition from n=3 to n=2 and
produces red line. The second line in Balmer series corresponds to the transition from n=4
to n=2 and produces green line. The third line in Balmer series corresponds to the
transition from n=5 to n=2 and produces blue line. The fourth line in Balmer series
corresponds to the transition from n=6 to n=2 and produces violet line.
Paschen series are the series of lines produced in hydrogen spectrum when the
excited electrons in hydrogen atoms come down to the third energy level. These lines
appear in infrared region of the spectrum.
 5

Spectral lines for hydrogen atom: ( Little Big Planet is Beautiful Planet)
Series Ground level (n1) Excited level (n2) Spectral region
Lyman 1 2, 3, 4 … Ultraviolet
Balmer 2 3, 4, 5 … Visible
Paschen 3 4, 5, 6 … Infrared
Brackett 4 5, 6, 7 … Infrared
Pfund 5 6, 7, 8 … Infrared
Humphry 6 7, 8, 9 … Far Infrared
Rydberg equation:
The wave number of radiation emitted or absorbed when electron undergoes
transition is given by Rydberg equation.
ν─ = 1 = 1.097 x 105 1 1 cm1 where n1 < n2
λ n12 n22
The constant 109,677 cm1 (or) 1.097 x 105 cm1 is called Rydberg’s constant.
Bohr’s theory of atom:
o An atom consists of small, heavy positively charged nucleus in the centre and the
electrons revolve around it in circular orbits.
o The electrons revolve around the nucleus only in selected circular paths of fixed
radius and energy. These paths are called orbit, stationary states or allowed energy
states, These orbits are associated with definite energies and are called energy shells
or energy levels. These orbits are arranged concentrically around the nucleus. These
are numbered as 1, 2, 3….etc. or designated as K, L, M … etc.
o Only those orbits are permitted in which the angular momentum of the electron is in
integral multiples of h/2π.
mvr = n h where n = 1,2,3 ..etc.
2π
where, m is mass, v is velocity of electron and r is the radius of the orbit.
o The energy of an electron in a an orbit (En) is given as
En = ─ 2.18 x 10-18 J/atom
n2
o The energy of electron is quantized. As long as the electron remains in a particular
orbit, it does not lose or gain energy. Hence these orbits are also called stationary
states.
o Radius of nth orbit (rn) is given as
rn = 52.9 x n2 pm
o When energy is supplied to the electron, it jumps to some higher energy level by
absorbing a definite amount of energy (equal to the difference in energy between the
energy levels). When the electron comes back to the lower energy level it radiates
same amount of energy in the form of a photon of radiation (hν)
 6

∆ E = E2 – E1 = hν = 2.18 x 10-18 1 1 J/atom

n12 n22

Where ν is the frequency of the radiation emitted when electron jumps from energy
level E2 to E1.
o Bohr’s theory is applicable for hydrogen like ions e.g. He+, Li2+ etc.
En = -2.18 x 10-18 x Z2 J/atom Z is atomic number.
n2
rn = 52.9 x n2 pm Z is atomic number.
Z
Q. Bohr’s orbits are called stationary states. Why?
Because the orbits are associated with fixed energy.
Q. What do you mean by quantization of energy?
The energy of electron in an atom is restricted to definite or discrete values and not any
continuous value. This is called quantization of energy.
Q. Angular momentum of electrons in an atom is quantized. Explain
Angular momentum of electrons can have values only in integral multiples of h/2π.
Q. What does the negative electronic energy (En) for hydrogen atom mean?
The negative sign means that the energy of the electron in the atom is lower than the
energy of a free electron at rest. A free electron at rest is an electron that is far away from
the nucleus and has zero energy. As the electron gets closer to the nucleus its energy
decreases and hence En becomes more and more negative.
Q. Although hydrogen atom has one electron hydrogen spectrum produces large number
of lines. Why?
A sample of hydrogen contains large number of atoms hence large numbers of
different type of downward transitions take place. Therefore large numbers of lines are
obtained in emission spectrum of hydrogen.
What are the successes of Bohr’s model of atom?
(i) Bohr’s theory could explain the stability of atom.
(ii) Bohr’s theory helped in calculating the energy of electron in hydrogen and hydrogen
like ions.
(iii) Bohr’s model could explain the atomic spectrum of hydrogen.
Limitations of Bohr’s theory:
(i) It could not explain hyperfine splitting (or) splitting of spectral lines when hydrogen
spectrum was observed in a sophisticated spectrograph.
(ii) It could not explain Zeeman effect i.e. the splitting of spectral lines in the presence of
magnetic field is called Zeeman effect.
(iii) It could not explain Stark effect i.e. the splitting of spectral lines in the presence of
electric field is called Stark effect.
 7

(iv) It was unable to explain the spectrum of multielectron atoms.

(v) It could not explain the ability of atoms to form molecules by chemical bonds.
(vi) It did not consider the wave nature of electron.
(vii) It is not in accordance with Heisenberg’s uncertainty principle.
De Broglie’s concept (Dual nature of matter):
De Broglie suggested that like light, matter behaves not only as particle but also as
wave. Any matter has dual character. The wavelength associated with a particle of mass m
and velocity v can be derived using the two relations, mass in Kg and velocity in m/s
E = mc2 and E= h
E = mc2
E= h = hc where c - is velocity of light,
λ
For ordinary particles, v – is velocity, hence the relations become
E = mv2
E= h = hv
λ
Equating both,
mv2 = hv
λ
λ = h = h
mv p where p is momentum of particle.
The waves associated with a particle are known as matter waves or De Broglie waves.
Unlike electromagnetic waves, matter waves cannot be radiated in space, do not have
electric or magnetic fields. They are waves associated with the particles.
Characteristics of De Broglie waves (or) matter waves:
o Speed of matter waves is very much less than the speed of electromagnetic waves.
o Matter waves cannot be radiated in empty space unlike electromagnetic waves.
o Matter waves are just associated with the particle, not emitted by it.
o Matter waves have smaller wave lengths than electromagnetic waves.
Distinction between EM waves and matter waves:
Electromagnetic waves Matter waves
EM waves are associated with electric and Matter waves are not associated with
magnetic fields. electric and magnetic fields.
EM waves can be emitted or radiated in Matter waves are neither emitted nor
space. radiated into space but are associated with
particles.
All EM waves travel with the same velocity Matter waves travel with different
velocities.
Have larger wavelength Have smaller wavelength
 8

Difference between wave and particle

Wave Particle
A wave is delocalized in space A particle is localized in space.
Two or more waves can simultaneously Particles cannot exist together in the same
exist at a given region in space. space
Shows interference Doesn’t show interference
Heisenberg’s Uncertainty principle:
It is impossible to determine the exact position and exact velocity of an electron
simultaneously and accurately.
∆x . ∆p ≥ h
4π
∆x . ∆v ≥ h
4πm
Where, ∆x is the uncertainty in position and ∆p is the uncertainty in momentum (or ∆v
is the uncertainty in velocity) of the particle.
Significance of uncertainty principle:
o Heisenberg Uncertainty Principle rules out existence of definite paths of electrons
around the nucleus. Hence orbit is replaced by orbital.
o This principle is significant only for motion of microscopic objects and is negligible
for that of macroscopic objects.
Quantum numbers:
The numbers that describe the orbitals and electrons in an atom are known as
quantum numbers.
In an atom each orbital is designated by a set of three quantum numbers (i) Principal
quantum number, (ii) Azimuthal quantum number and (iii) Magnetic quantum number.
Each electron in an atom is designated by a set of four quantum numbers
(i) Principal quantum number, (ii) Azimuthal quantum number, (iii) Magnetic quantum
number and (iv) Spin quantum number.
Give the significance of quantum numbers:
(1) Principal quantum number (n):
(i) The principal quantum number determines the size and energy of the electron (or)
orbit.
(ii) The principal quantum number ‘n’ is a positive integer with value of n = 1,2,3.... α
n 1 2 3 4
Shell K L M N
(iii) The principal quantum number also identifies the shell and sub-shell.
(iv) The number of sub-shells in an orbit is given by ‘n’
(v) The number of orbitals in a main shell is given by ‘n2’
(vi) The number of electrons in an orbit is given by the formula ‘2n2’
(v) Both energy and size of the orbit increases with increase in ‘n’ value.
 9

Q. Principal quantum number, n cannot be zero. Why?

If n is zero, which means there is no orbit and hence the electrons exist inside the nucleus.
That’s not possible.
(2) Azimuthal quantum number (l):
(i) It defines the three dimensional shape of the orbital.
(ii) Azimuthal quantum number. ‘l’ is also known as orbital angular momentum or
subsidiary quantum number.
(iii) For a given value of n, l can have n values ranging from 0 to n – 1, that is, for a given
value of n, the possible value of l are: l = 0, 1, 2, ......(n–1)
For example, when n = 1, l = 0 ( only s-sub shell)
When n = 2, l = 0 and 1 ( s and p sub shells)
When n = 3, l = 0,1 and 2 ( s, p and d sub shells)
When n = 6, l = 0,1, 2 and 3 ( s, p, d and f sub shells)
(iv) Each shell consists of one or more subshells or sub-levels. The number of subshells
in an orbit is equal to the value of n. Each sub-shell is assigned an azimuthal quantum
number (l).
(v) The number of orbitals in a sub-shell is given by (2l+1)
(vi) The number of electrons in a sub-shell is given by 2(2l+1)
(vii) s orbital has spherical shape, p orbital has dumbbell shape, four d orbitals have
double dumbbell (o) cloverleaf shape and one d orbital has a dumbbell with a doughnut
around its middle.
Value for l 0 1 2 3 4 5
Sub-shells s p d f g h

Sub-shells s p d f g
No. of electrons 2 6 10 14 18

(3) Magnetic quantum number (ml):

(i) It gives information about the spatial orientation of the orbitals.
(ii) It can have values ranging from –l through 0 to +l. For a given value of l, (2l+1) values
of ml are possible.
For example,
when l = 0, ml = 0
one orientation for s orbital hence it is represented with a single box;
when l = 1, ml = -1, 0, +1
three orientations for p orbitals hence three boxes;
when l = 2, ml = -2, -1, 0, +1, +2
five orientations for d orbitals hence five boxes;
when l = 3, ml = -3, -2, -1, 0, +1, +2, +3
seven orientations for f orbitals hence 7 boxes;
 10

(4) Spin quantum number (ms):

Spin angular momentum of the electron can have two orientations relative to the axis
of rotation. These two orientations are distinguished by the spin quantum numbers ms
which can take the values of +½ or –½.
Orbital.
It is defined as the three-dimensional region around the nucleus in an atom in which
the probability of finding the electron is maximum (90 to 95%)

Distinguish orbit from orbital.

Orbit Orbital
1. It is circular path followed by electron It is the three dimensional region around the
around the nucleus. nucleus in which the probability of finding
the electron is maximum.
2. It is 2-D motion of electron. It is 3-D motion of electron.
3. Orbits are circular in shape. Orbitals have different shape. Eg. s-orbital
is spherical, p-orbital is dumb-bell etc
4. The maximum number of electrons in an Orbital cannot have more than two
orbit is 2n2. electrons.
5. It is against Heisenberg’s uncertainty It is in accordance with Heisenberg’s
Principle. uncertainty Principle.
Significance of Ψ and Ψ in Schrodinger wave equation:
2

o Ψ is known as orbital wave function. It refers to the amplitude of the electron wave.
o Ψ2 is known as probability density. It gives the maximum probability of finding the
electron around the nucleus in an atom. Ψ2 for orbital is 90 to 95%
Q. What are nodal surfaces? (or) Nodes?
The region in an atom at which the probability of finding the electron is zero are called
nodal surfaces or nodes. Ψ2 is zero for node.
The number of radial nodes is given by the formula (n-l-1)
The number of angular nodes is given by l
Total number of nodes can be calculated by the formula (n-1)
Q. What are degenerate orbitals?
Orbitals of a given sub shell having the same energy are called degenerate orbitals. For
example the orbitals px, py and pz are all degenerate orbitals of p-subshell.
Q. What is effective nuclear charge?
It is the net positive charge experienced by outer electrons. 2s electrons experience
greater effective nuclear charge than 3s electrons.
Q. What are isoelectronic ions? Give example.
Ions containing same number of electrons but different atomic number are called
isoelectronic ions. E.g. N3-, O2-, F-, Na+, Mg2+ and Al3+ are isoelectronic ions.
 11

Shapes of orbitals:
Boundary surface diagram:
Shape of 1s-orbital y
z
x

Shapes of 2px, 2py and 2pz orbitals

y y y

z z z

x x x

2px 2py 2pz

Shapes of 3d orbitals
y y x

x z z

3dxy 3dyz 3dxz

y z

x x

3dx2-y2 3dz2
 12

Electronic configuration:
The distribution of electrons into orbitals of an atom is called its electronic
configuration.
There are two ways to represent the electronic configuration.
(i) Using s, p, d, f notation
(ii) Orbital diagram (or) box diagram
Arrangement of electrons in various orbitals is determined by three rules (i) Aufbau
principle, (ii) Pauli’s exclusion principle and (iii) Hund’s rule.
(i) Aufbau principle:
In the ground state of an atom, electrons enter the various orbitals in their increasing
order of energies starting with the orbital of lowest energy.
Relative energies of orbitals can be predicted by another rule (n+l) rule or Bohr-Bury’s
rule.
(n+l) rule or Bohr-Bury’s rule:
(i) A sub-shell with lower value of (n+l) has lower energy.
For example 4s orbital has lower energy than 3d orbital. Because (n+l) value for 4s
orbital is 4 where as for 3d orbital (n+l) value is 5.
(ii) If two sub-shells have the same (n+l) value then the sub-shell with lower n has lower
energy.
For example 3p orbital has lower energy than 4s orbital although both have the same
(n+l) value.
(c) Energy of the orbitals in the same subshell decrease with increase in the atomic
number.
For example, energy of 2s orbital of hydrogen atom is greater than that of 2s orbital
of lithium.
Increasing order of energies of orbitals:
1s

2s 2p

3s 3p 3d

4s 4p 4d 4f

5s 5p 5d 5f

6s 6p 6d 6f

7s 7p 7d 7f

8s 8p 8d 8d
 13

(ii) Pauli exclusion principle:

No two electrons in an atom can have the same set of all the four quantum numbers.
(OR)
An orbital can have only two electrons and these electrons must have opposite spins.
(iii) Hund’s rule:
The pairing of electrons in the orbitals of a given sub-shell is not possible until all the
available orbitals are occupied with an electron each with same spins.
For example, the electronic configuration of nitrogen atom is
1s2, 2s2, 2px1, 2py1, 2pz1
Three electrons in p-orbitals occupy singly and have same spin.
Exceptional electronic configuration:
Chromium (24) has the electronic configuration [Ar]18 4s1 3d5. Because of the greater
stability of half filled d-sub-shell.
Copper (29) has the electronic configuration [Ar]18 4s1 3d10. Because of the greater
stability of completely filled d-sub-shell. Half filled and completely filled sub-shells are
more stable than partially filled sub-shells due to symmetry and exchange energy.
Q. Half filled and completely filled sub-shells are more stable than partially filled sub-
shells. Why?
(i) They have symmetrical distribution of electrons around the nucleus.
(ii) Have high exchange energy.
Shielding effect or screening effect:
Due to the presence of electrons in the inner shells, the electron in the outer shell will
not experience the full positive charge on the nucleus. This is called screening effect. Due
to the screening effect, the net positive charge experienced by the electron from the
nucleus is lowered and is known as effective nuclear charge. Effective nuclear charge
experienced by the orbital decreases with increase of azimuthal quantum number (l).

Questions:

1. Calculate the frequency of a radiation having wavelength 600 nm.

2. The wave number of a beam of light is 400 cm-1. Calculate its wavelength and
frequency.
3. Calculate the energy of light having wavelength 300 nm.
4. Calculate and compare the energies of two radiations with wavelengths 4000 Ao and
8000 Ao.
5. A 100 watt bulb is emitting monochromatic radiation of wavelength 450 nm. How
many photons are emitted by the bulb in one second?
 14

6. Nitrogen laser produces a radiation at a wavelength of 337.1 nm. If the number of

photons emitted is 5.6 x 1024, calculate the power of this laser.
7. 3 x 1018 photons of certain light radiation are found to produce 1.5 J of energy.
Calculate the wavelength of light radiation.
8. Calculate the energy in kJ possessed by one mole of photons with frequency
5 x 1010 /s
9. The threshold frequency νo for a metal is 7.0 x 1014 s–1. Calculate the kinetic energy
of an electron emitted when radiation of frequency ν =1.0 x 1015 s–1 hits the metal.
10. 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?
11. A photon of wavelength 4 x 10–7 m strikes on metal surface, the work function of the
metal being 2.13 eV. Calculate (i) the energy of the photon, (ii) the kinetic energy of
the photoelectron, and (iii) the velocity of the photoelectron. (1 eV= 1.602 × 10–19 J).
12. Electromagnetic radiation of wavelength 242 nm is just sufficient to ionize the
sodium atom. Calculate the ionization energy of sodium in kJ mol–1.
13. Electrons are emitted with zero velocity from a metal surface when it is exposed to
radiation of wavelength 6800 Å. Calculate threshold frequency (νo) and work
function (W0) of the metal.
14. When electromagnetic radiation of wavelength 400 nm falls on the surface of a
metal, electrons are emitted with a K.E. of 1.72 x 10─19 J. Calculate the threshold
frequency, work function of the metal and the maximum wavelength that will cause
a photoelectron to be emitted.
15. 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?
16. Calculate the frequency of radiation absorbed by an electron when it is excited from
second energy level to fourth energy level.
17. An electron in hydrogen atom is in 5th energy level. It undergoes transition by
emitting wavelength 4.342 x 10─7 m. Calculate to which level the electron comes
down and to which series the emitted radiation belongs.
18. Calculate the energies of first and third orbit in hydrogen atom. Also calculate the
energy released when electron jumps from third orbit to first orbit.
19. Calculate the energy associated with the first orbit of He+. What is the radius of this
orbit?
20. Using Bohr’s equation calculate the energy required for an electron to move from
first orbit to seventh orbit in He+
21. Using Bohr’s equation, calculate the ionisation energy of hydrogen atom if the
electron is in ground state.
22. Calculate the energy absorbed, frequency and wavelength when an electron with
 15

energy 217.9 x 10-21 J jumps to an energy level with energy 544.8 x 10-20J.
23. How much energy is required to ionize a H atom if the electron occupies n = 5
orbit?
24. What is the maximum number of emission lines when the excited electron of a H
atom in n = 6 drops to the ground state?

25. (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.
26. If the energy difference between two electronic states is 348.2 KJ/mole, find the
frequency of radiation emitted when an electron jumps from the higher to the lower
level.
27. Calculate the wave number for the longest wavelength transition in the Balmer
series of atomic hydrogen.
28. What transition in the hydrogen spectrum would have the same wavelength as the
Balmer transition n = 4 to n = 2 of He+ spectrum?
29. The electron energy in hydrogen atom is given by En = (–2.18 x10–18) /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?
30. Calculate the wavelength of a body of mass 0.1mg moving with a velocity of 10 m/s.
31. Calculate the de Broglie wavelength of a bullet of mass 2.2 x 10-3 Kg fired with a
velocity of 300 m/s.
32. The mass of an electron is 9.1 x 10–31 kg. If its K.E. is 5.0 x 10–25 J, calculate its de
Broglie wavelength.
33. Calculate the mass of a photon with wavelength 3.6 A0.
34. Calculate the wavelength of an electron moving with a velocity of 10% that of light.
35. Calculate the De Broglie wavelength of a bullet of mass 20 g and velocity 200 m/s.
36. Two particles A and B are in motion. If the momentum of A is half of that of B and
if the wavelength of A is 4.5 x 102 nm, what is the wavelength of B?
37. Calculate the speed of an electron if its de Broglie wavelength is twice its
displacement in one second.
38. When would the wavelength associated with an electron be equal to the wavelength
associated with a proton?
39. 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.
40. An electron is located in an atom within a distance of 0.1 Å. What is the uncertainty
involved in the measurement of its velocity?
41. The uncertainty in the position of a moving bullet of mass 10 g is 10-5m. Calculate
the uncertainty in its velocity.
 16

42. An electron has a velocity of 300 m/s which is accurate to 0.01%. What is the
uncertainty in measuring its position?
43. Calculate the uncertainty in the velocity of a cricket ball if the mass is 150g.
Uncertainty in the position is 1 angstrom.
44. If the position of the electron is measured within an accuracy of + 0.002 nm,
calculate the uncertainty in the momentum of the electron.
45. Show that Heisenberg Uncertainty Principle is significant only for motion of
microscopic objects and is negligible for that of macroscopic objects.
46. Using Heisenberg Uncertainty Principle show that an electron cannot exist inside the
nucleus. Radius of nucleus is 10-15 m.
47. Write the electronic configuration of the following elements:
(i) N (7), (ii) S (16), (iii) Ar (18), (iv) Ca (20), (v) Zn(30), (vi) Br (35), (vii) Kr (36)
(viii) Xe (54), (ix) Ba (56), (x) Pb (82) (xi) Rn (86) and (xii) U (92)
48. Write the electronic configuration of the following ions:
(i) F- (9), (ii) S2- (16), (iii) Ca2+ (20), (iv) Cr3+ (24), (v) Fe2+ (26) and (vi) Zn2+ (30)
49. Indicate the number of unpaired electrons in:
(i) P (15), (ii) Si (14), (iii) Cr (24), (iv) Fe (26) and (v) Kr (36).
50. Using s, p, d notations, describe the orbital with the following quantum numbers.
(i) n=1, l=0; (ii) n = 3; l=1 (iii) n = 4; l =2; (iv) n=4; l=3 (v) n=2, l=0 (vi) n=6, l = 4
(vii) n= 2, l=3
51. What is the lowest value of n that allows (i) f- orbital to exist (ii) g- orbital to exist?
52. List the quantum number values for the valence electrons in
(i) Mg (ii) Al
53. Write the quantum number values for the unpaired electrons in nitrogen atom.
54. Write all possible quantum number values for the unpaired electrons in nitrogen
atom.
55. Write the quantum number values for the unpaired electrons of nickel
Ni-28
56. List quantum numbers for the unpaired electrons in
(i) C (6), (ii) Mn2+ (Z = 25) (iii) Fe2+ (26)
57. Write the quantum number values for the 19th electron in potassium
58. An electron is in one of the 3d orbitals. Give the possible values of n, l and ml for
this electron.
59. How many electrons are possible in
(i) 4p (ii) 6s (iii) 5pz (iv) 3d (v) 3dxy (vi) M shell (vii) Subshell with l = 3
60. How many electrons in an atom may have the following quantum numbers?
(i) n = 4 (ii) n=4, l=3 (iii) n=4, l=3, s= -½ (iv) n=3, l=1, ml=0 (v) n=5
(vi) n=3, l=2 (vii) n=5, s=+ ½ (viii) n=2, l=0, ml=0, s= ½ (ix) n=4, ml= 0
61. How many electrons are there in an atom of zinc with magnetic quantum number
zero? ( Zn 30)
 17

62. Which one of the following ions is more stable and why?
(i) Fe2+ or Fe3+ (ii) Mn2+ or Mn3+ (iii) Cu+ or Cu2+ (iv) Zn2+ or Zn3+
63. Which one of the following ions contains more number of unpaired electrons?
(i) Fe2+ or Fe3+ (ii) Cr2+ or Cr3+
64. What is the total number of (i) sub shells and (ii) orbitals associated with the
principal quantum number n=3?
65. (i) How many sub-shells are associated with n = 4? (ii) How many electrons will be
present in the sub-shells having ms value of -1/2 for n = 4?
66. What are the atomic numbers of elements whose outermost electrons are represented
by (i) 3s1 (ii) 2p3 (iii) 3p5
67. Which atoms are indicated by the following configurations?
(i) [He] 2s1 (ii) [Ne]3s2 3p3 (iii) [Ar] 4s2 3d1
68. 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.
69. Calculate the number of angular nodes, radial nodes and total number of nodes in the
following orbitals.
(i) 2s (ii) 3p (iii) 5p (iv) 7s (v) 3d (vi) 5f (vii) 7d
70. A certain particle carries 2.5 x 10-16 C of static electric charge. Calculate the number
of electrons present in it.
71. An atom has 6 electrons in 2p orbital, 6 electrons in 3p orbital and 5 electrons in 4p
orbital. Which of these electrons experience the lowest effective nuclear charge?
72. The quantum numbers of six electrons are given below. Arrange them in order of
increasing energies. If any of these combinations have the same energy list them:
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
73. Explain, giving reasons, which of the following sets of quantum numbers are not
possible.
(a) n = 0, l = 0, ml = 0, ms = + ½
(b) n = 1, l = 0, ml = 0, ms = – ½
(c) n = 1, l = 1, ml = 0, ms = + ½
(d) n = 2, l = 1, ml = 0, ms = – ½
(e) n = 3, l = 3, ml = –3, ms = + ½
(f) n = 3, l = 1, ml = 0, ms = + ½
74. If the diameter of carbon atom is 0.15 nm, calculate the number of carbon atoms
which can be placed side by side in a straight line across the scale of length 20 cm.
 18

75. Calculate the energy required for the process

He+ (g) → He 2+ (g) + e—
76. Show that the circumference of Bohr orbit for the hydrogen atom is an integral
multiple of the de Broglie wavelength associated with the electron revolving around
the orbit.
77. Which rule is violated in the following electronic configuration? State the rule.
[Ne]3s2 3px2, 3py1
78. What are the possible ml values of f-subshell?
79. How many electron waves are possible in the third orbit of hydrogen atom?