Prepared by: Dawood Ilyas Minhas (M. Phil.

Chemistry, GCU, Lahore)

REVISED EDITION

Chapter No. 5 Atomic structure

DISCOVERY OF ELECTRON
I. Why the current is not passed through the gas at ordinary pressure in the discharge tube
even in the presence of a high voltage?
The current is not passed through the gas at ordinary pressure due to greater no. of gas molecules
in the tube. These gaseous molecules do not allow electrons to reach the anode.

II. Why is a glow produced when the cathode rays pass in the discharge tube? Why it is
disappeared? (IMP)
The glow in the discharge tube is produced because of the excitations (due to cathode rays) and
de-excitations of the electrons in the atoms/molecules of the gas present in the discharge tube.
This glow disappears due to the ionization of the atoms at low pressure.

III. What do you mean by the fluorescence?

The emission of the light when electrons or some other particles strike with a surface like that of
ZnS is called fluorescence. . This emission is due to excitation and de-excitation of the electrons.

IV. How we come to know that cathode rays are material particles with negative charge?
(IMP)
Cathode rays rotate a pin wheel. The vans of pin wheel get the momentum from the particles of
the cathode. Hence, these are material particles.
In 1897, J. J. Thomson established their electric charge by the application of electric field. The
cathode ray deflected towards positive plate showing their negative charged.

V. What is the reason for the production of canal rays? (IMP)

When high speed electrons (cathode rays) strike the atoms/molecules of residual gas on
discharge tube, they knock out electrons from the outer most shell of atoms/molecules of residual
gas and positive ions are produced which start moving towards cathode as positive rays.
M + e- → M+ + 2e-

DISCOVERY OF PROTON

I. The e/m value for positive rays is always less than that of electrons?
As the mass of the positive rays is always greater than that of the electrons and so the value of
charge to mass ratio will be smaller for the positive rays. Heavier the gas, smaller the e/m value
and vice versa.

II. The e/m value for the positive rays is the maximum for hydrogen gas. Why? (IMP)
The value of e/m will be higher if the value of mass of the atom is the smaller, because the value
of „m‟ (mass) is the lowest for the positive particle obtained from the hydrogen gas. Hence,
positive particle obtained from hydrogen gas is the lightest among all the positive particles.

III. Why the anode rays depend upon the nature of gas? (IMP)
Anode rays are cations of residual gas. The mass of every anode ray particles depends upon the
nature of gas, so the anode rays for all gaseous substances are different. Positive rays are
produced due to ionization of gases present in the discharged tube. Each gas produces different
nature of (cations) positive ion. e.g., consider the ionization of He gas and Ne gas.
He + e- → He+ (Positive ray) + 2e-
Ne + e- → Ne+ (Positive ray) + 2e-

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REVISED EDITION
Therefor e/m of positive rays depends upon the nature of gas. Lighter the gas greater the e/m
value and vice versa.

DISCOVERY OF NEUTRON
I. Which particles are produced by self-decomposition of a neutron?
Free neutron decomposes into a proton, an electron and a neutrino.
→ + +
Where, „ ‟ is neutron, „ is proton, is electron and „ is neutrino (energy).

II. What prediction of Rutherford was about neutron? (IMP)

Rutherford predicted that atoms must have some neutral particles having masses equal to that of
proton. He noticed that atomic masses cannot be explained by only electrons and protons.

III. Describe the experiment for the discovery of neutron? (IMP)

Chadwick discovered the neutron by throwing α- particles on the nucleus of beryllium. Be was
changed into carbon and a neutral particle with mass almost equal to that of proton was emitted.
This particle was named as neutron.
+ → +
V. What do you mean by the fast and slow neutrons? Which are effective for nuclear
fission? (IMP)
The neutrons travelling with energy of 1.2 MeV are called fast neutrons but those with energy
below 1 eV are called slow neutrons. Slow neutrons are effective in nuclear fission. Slow
neutrons hit the copper metal and gamma radiations are emitted, giving us a new isotope of
copper i. e., , which is again radioactive.
+ → + hv (Gamma-radiation)
→ + (Beta-radiation)

VI. Differentiate between fast and slow moving neutron. (IMP)

Fast neutron Slow neutron

i. They travel with energy of 1.2 MeV. i. They travel with energy less than of 1 eV.
ii. They are less effective in fission reaction. ii. They are more effective in fission reaction
iii. They mostly produced alpha –particles. iii. They mostly produced beta-rays and
e.g. + → + (alpha- gamma –rays. e.g.
particles) + → + hv (Gamma-radiation)
→ + (Beta-radiation)

VII. What are the differences between the electron, proton and neutron?

Particle Charge (C ) Relative charge Mass (kg)

Electron - 1.6022 × 10-19 -1 9.1095 × 10-31
Proton + 1.6022 × 10-19 +1 1.6726 × 10-27
Neutron 0 0 1.6750 × 10-27

VIII. Write balanced equation for any two nuclear reactions. (IMP)
i. + → + (alpha- particles)
ii. + → + hv (Gamma-radiation)

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REVISED EDITION
RUTHERFORD E XPERIMENT

I. Why did most of α-particles pass through gold foil and some were deflected? (IMP)
The most of the space in the atom is empty and therefore the most of α- particles pass through it
un-deflected. But very few were deflected at large angles due to head to head collision with
nucleus.

II. What do you mean by the planetary model of atom proposed by Rutherford?
According to this model, a tiny nucleus in an atom is surrounded by an appropriate number of
electrons. Atom being a neutral particle must have same number of electrons and protons.

III. Why the outer electrons in an atom are not stationary in Rutherford’s model?
If the electrons were stationary then they would gradually attracted by the nucleus till they
ultimately fall into it. Therefore, to have a stable atomic structure, the electrons were supposed to
be moving around the nucleus in closed orbits.

IV. How did Rutherford’s model of an atom first of all proved the existence of nucleus of
an atom? (IMP)
Rutherford observed in an experiment that most of the alpha –particles passes straight through
the gold foil without any deflection from the path and very few of them were deflected to an
angle greater than 900. He concluded that atom contains heavy and positively charged particle at
the center called nucleus.

V. What are the defects of Rutherford atomic model? (IMP)

There are three defects in Rutherford atomic model.
i. The revolving electron should emit the energy continuously and it should ultimately fall into
the nucleus. But actually the don‟t do it.
ii. The atom should give continuous spectra, but they give the line spectra.
iii. It is based on the laws of the motion and the gravitation. These laws are not applicable for the
charged bodies like electron.

PLANK’S QUANTUM THEORY

I. Write the postulates of Planck’s Quantum Theory (in 1900)? (IMP)

The postulates of Planck‟s Quantum Theory are given below:
i. Energy is not emitted or absorbed continuously. Rather, it is emitted or absorbed in a
discontinuous manner.
ii. The energy of quanta is proportional to the frequency of the radiation.
Eα𝜈 ⇒ E = h𝜈 where h = Planck‟s constant and its value is 6.626 x 10 -34 js.
𝜈 = frequency
iii. Each wave packet or quantum is associated with a definite amount of energy. In case of light,
the quantum of energy is often called photon.

II. How does Bohr introduce the Plank’s quantum theory in his model? (IMP)
Bohr proposed that electrons move around the nucleus in the fixed orbits with definite energies.
Whenever, they change the orbits they emit or absorb the energy in terms of photons which was
suggested by Plank in 1900.

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REVISED EDITION
III. Define frequency, wave number and wavelength?
Frequency is the number of waves passing through a point in one second. It is represented by
„υ‟. Wave number is the number of waves present per unit length. It is represented by „ῡ‟.
Wavelength is the distance between two adjacent crests or troughs. It is represented by λ.

BHOR’S ATOMIC MODEL

I. Write the postulates of Bohr’s Theory of atomic model? (IMP)

The postulates of Bohr‟s Theory of atomic model are:
i. Electrons revolve in one of the circular orbits having fixed energy outside the nucleus.
ii. When electron is present in an orbit, there is no emission or absorption of radiations.
iii. Energy is absorbed when an electron jumps from lower orbit to the higher orbit and is
evolved when an electron jumps from higher orbit to the lower orbit. The difference is given as,
ΔE = E2 – E1
iv. Electrons revolve only in the orbits having fixed angular momentum given as,
mvr = ℎ/2𝜋 where n = 1,2,3,………

II. Find the values of radii of first three orbits of hydrogen atom? (IMP)
The general formula for the radii of the hydrogen atoms is:
r = 0.529 A0 (n)2 where n = no. of shell or orbit:
0 2
r1 = 0.529 A (n) ⇒ 0.529 A0 (1)2 ⇒ 0.529 A0
r2 = 0.529 A0 (n)2 ⇒ 0.529 A0 (2)2 ⇒ 2.11 A0
r3 = 0.529 A0 (n)2 ⇒ 0.529 A0 (3)2 ⇒ 4.75 A0
r2 – r1 = 2.11 – 0.529 A0 ⇒ 1.581 A0
r3 – r2 = 4.75 – 2.11 A0 ⇒2.64 A0
r4 – r3 = 8.464 – 4.75 A0 ⇒ 3.714 A0
r2 – r1 < r3 – r2 < r3 – r2 < r4 – r3 …………….

III. Which postulate of Bohr’s model correct the defects of Rutherford’s atomic model?
According to Rutherford‟s atomic model, revolving electron is continuously radiate energy. But
according to second postulate of Bohr‟s atomic model “electron present in a particular orbit
does not radiate energy. The energy is only emitted or absorbed when an electron jumps from
one orbit to another”. So second postulate of Bohr‟s atomic model is used to correct the defect
of Rutherford‟s atomic model.

IV. How Bohr quantized the angular momentum of moving electron? (IMP)
According to 4th postulate of Bohr‟s atomic model:
“Electron can revolve only in those orbits having a fixed angular momentum”.
Angular momentum of an orbit depends upon its quantum number and integral multiple of the
factor h/2π i. e., mvr = nh/2π where n = 1, 2, 3, …
By putting the different values of „n‟ in above equation, angular momentum is:
For n = 1 mvr = h/2π
For n = 2 mvr = 2h/2π
For n = 3 mvr = 3h/2π
An electron is bound to remain in one of these orbits and not between them. So angular
momentum (mvr) is quantized.

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REVISED EDITION
V. How did Bohr calculate the ionization energy of H-atom? (IMP)
The formula of energy difference between any two orbits for H-atom is:
ΔE =
This is the equation for one atom of hydrogen. If we multiply this by NA and divided by 1000,
we get the following equation:
ΔE =
ΔE =
If we put the value n1 = 1 and n2 = ∞, then we can get the ΔE value for the ionization of H-atom.
ΔE = ⇒1313.31

SPECTRUM

I. What are the spectral series? Write their names and the regions?
Hydrogen in a discharge tube glows with bluish color at low pressure and emits some radiations
which give some lines in different series in the spectrum. These are called spectral series.
i. Lyman series (U.V. region) ii. Balmer series (Visible region)
iii. Paschen series (I.R. region) iv. Brackett series (I.R. region)
v. Pfund series (I.R. region)

II. How are the different spectral series of hydrogen produced? (IMP)
When hydrogen is heated, the electrons jump to some higher shell and emit radiations on coming
back. Thus, different spectral series are produced on coming the electron back in different shells.

i. Lyman series (n1 = 1) (U.V. region) ii. Balmer series (n1 = 2) (Visible region)
iii. Paschen series (n1 = 3) (I.R. region) iv. Brackett series (n1 = 4) (I.R. region)
v. Pfund series (n1 = 5) (I.R. region)

III. What is meant by limiting line? Write values and regions of limiting lines of Lyman
and Balmer series? (IMP)
When an electron jumps from infinity to any shell of the spectral series, the line produced is
called the limiting line of that spectral series.
For Lyman series:
n1 = 1 n2 = ∞
ῡ = 1.09678 ×107 [( )–( )] ⇒ 1.09678 ×107 [( )–( )]
ῡ = 109.68678 × 105 m-1 (U.V. region)
For Balmer series:
n1 = 2 n2 = ∞
ῡ = 1.09678 ×107 [( )–( )] ⇒ 1.09678 ×107 [( ) – ( )]
ῡ = 27.421 × 105 m-1 (U.V. region)

IV. The lines appear bright on dark background in emission spectrum and dark on bright
background in absorption spectrum. Explain it?
In emission spectrum, the lines appear bright because the corresponding wavelengths are being
emitted by the element. In absorption spectrum, the lines appear dark because the corresponding
wavelengths are being absorbed by the element.

V. Radio waves have less energy than gamma rays. Why? (IMP)
Frequency of radio waves is less than that of gamma rays. According to Plank‟s equation (E = h
𝑣), energy is directly proportional to the frequency and inversely proportional to wavelength. So

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REVISED EDITION
radio waves will have less energy than gamma rays due to low frequency and greater
wavelength.

VI. What are the colors present in visible spectrum and write also its range?
The colors present in visible spectrum in the order of decreasing wavelength are as, Red, Orange,
Yellow, Green, Blue, Indigo, Violet. The range of the spectrum is from 400 nm to 750 nm.

VII. The energy associated with violet color is greater than that with red color in the visible
spectra. Why? (IMP)
Frequency of violet rays is more than that of red rays. According to Plank‟s equation (E = h 𝑣),
energy is directly proportional to the frequency and inversely proportional to wavelength. So
violet rays will have more energy than red rays due to high frequency and lower wavelength
(400-420 nm) than red rays.

VIII. Why the photographic plate is white and few dark lines are there in the line
absorption spectra of a substance? (IMP)
Some of photons are absorbed by sample to excite the electrons of substance from lower energy
levels to higher energy levels. These photons of light do not reach the photographic plate. Rest of
the light reaches the photographic plate, so the plate is white. Only those places are dark in the
form of sharp lines where the photons don‟t reach.

IX. Why the photographic plate is dark and few white lines are there in the line emission
spectra of a substance? (IMP)
The sample of hydrogen is taken in a glass tube. Electric current is passed through the gas.
Electrons of atoms or molecules are excited to higher energy levels. These electrons fall back to
the lower levels and emit the photons of light. These emitted photons produce bright lines and
rest of the plate is dark.

X-RAYS & ATOMIC NUMBER

I. What are X-rays and how they are produced? (IMP)

X-rays are produced when rapidly moving electrons collide with heavy metal anode in the
discharge tube. When electron strikes the metal target, it throws away an electron form an inner
shell. The space of that shell is filled by higher shell electrons, and radiations are emitted called
X-rays.

II. How X-rays are analyzed?

The X-rays are passed through a slit of platinum plate and then emerged through aluminum
window. This is thrown on a crystal of K4[Fe(CN)6] which diffracted the X-ray beam and a line
spectrum of it is obtained. This spectrum is characteristic of target material (metal) used.

III. State and write the postulates of Moseley’s law? (IMP)

It is stated as; “The frequency of a spectral line in X- ray spectrum is directly proportional to
square of the atomic no. of the element emitting the rays”. The postulates of Moseley‟s Law are:
i. The spectral lines can be of shorter wavelength like K-series or longer wavelength like L-
series.
ii. X-rays of shorter wavelength are produced from a target of higher atomic number.
iii. The frequency of X-ray is related to the atomic number as:
= a (Z-b)
Where a = proportionality constant and b = screening constant

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IV. How was the idea of atomic number derived from the discovery of X-rays?
The frequency of X-ray is related to the atomic number as:
= a (Z-b)
Where a = proportionality constant and b = screening constant Z = atomic no. of the target
element (metal) and 𝑣 = frequency of X – rays produced.

VI. Write the applications of the Moseley’s law? (IMP)

The applications of the Moseley‟s law are
i. Some elements like Ar, Co, Ni and K were arranged in Mendeleev‟s periodic table.
ii. Many new elements like Tc, Pr, and Rh were discovered.
iii. The atomic number of rare earth metals is found by this law.

VI. Why do we say that the graph obtain from the Mosley’s law are straight lines? (IMP)
According to Mosley‟s law; “The frequency of a spectral line in X- ray spectrum is directly
proportional to square of the atomic no. of the element emitting the rays”. Mathematically:
= a (Z-b)
Where a = proportionality constant and b = screening constant Z = atomic no. of the target
element (metal) and 𝑣 = frequency or X – rays produced.

WAVE PARTICLE NATURE

I. What is Louis de- Broglie’s hypothesis (1924) and how was it confirmed? (IMP)

The moving particles have also dual nature like light. So a particle can have wave like properties.
The mathematical form of this hypothesis is:
λ = ℎ/𝑚𝑣
Where, λ = wavelength of particle, h = Planck‟s constant, m = mass of the particle, v = velocity
of the particle This hypothesis was confirmed by Davisson and Germer in 1927. They proved
that accelerated electrons undergo diffraction like waves on falling on a nickel crystal.

II. Do large moving bodies not have wavelength? Or Is wavelength not associated with
large moving bodies?
Heavy material particles have waves associated with them but they have small values that cannot
be measured. So we say that the macroscopic bodies do not have the waves.

III. Who verified the dual nature of matter and how?

In 1927, Davisson and Germer proved the wave nature of electrons by an experiment. Electrons
were produced from heated tungsten filament and accelerated by applying potential difference
through charged plates. They proved that accelerated electrons undergo diffraction like waves on
falling on a nickel crystal.

HESENBERG’S UNCERTAINTY PRINCIPLE

I. What is uncertainty principle? What is its limitation? (IMP)
The position and momentum of an electron cannot be found accurately at the same time. This
means that if we measure position accurately then there will be much uncertainty about the
momentum of the particle and vice versa. This principle was confirmed by Compton‟s effect.
Mathematically expression:
Δx . Δp ≥ ℎ/4𝜋

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Where Δx = uncertainty in the position, Δp = uncertainty in the momentum, h = Planck‟s
constant.
Limitation: It is applicable only for microscopic bodies.

II. Why X-rays are used rather than visible light in Compton’s effect?
This is because the wavelength of visible light is million times greater than the diameter of
electron. So it will not give the better picture of electron. We used x-rays because x-rays have
smaller wavelength and greater energy than visible light.

III. How does Compton’s effect help us to understand the uncertainty principle?
When a photon of X-rays strikes an electron, the momentum of electron will change. It means
that when we try to find the position of electron with the help of X-rays, the uncertainty of
momentum will appear due to change in velocity of electron.

IV. What is wave mechanical model of atom?

According to Schrodinger, although the position of an electron cannot be found exactly, the
probability of finding an electron at a certain position at any time can be found. He gave a wave
equation for hydrogen atom whose solution gives probability of finding an electron present in a
given small region of space.
QUANTUM NUMBERS
I. What are the shapes of the s, p and d sub-shell and what information do they convey?
The s – orbital is spherical & symmetrical with one orientation, p – orbital is dumb-bell like with
three orientations and d – orbital is complicated one with five orientations. These orbitals show
the probability of finding the electron around the nucleus.

II. Why a line seems to be further divided into several very fine lines, when seen through a
high resolving spectrometer?
Each shell is divided into subshells and so more lines are seen due to these subshells. If magnetic
field is applied then these subshells are oriented differently in the space and the lines are further
divided into different orbitals.

III. What do you mean by degenerate orbitals? (IMP)

The orbitals having same energy in the absence of magnetic field are called degenerate orbitals.
All the three p – orbitals have the same energy in the absence of magnetic field. Similarly all the
five d – orbitals have same energy in the absence of magnetic field

ELECTRONIC DISTRIBUTION

I. What is doublet line structure? Or why each line in a line spectrum consists of a pair of
lines?
When the spectrum is observed by means of high resolving power spectrometer, each line in the
spectrum is found to consist of a pair of lines. This is called doublet line.
The clockwise and anticlockwise motion of electrons is responsible for this doublet line
structure.

II. What do you mean by self-rotation of electrons? (IMP)

The electrons rotate around their own axis, clockwise or anticlockwise. This is called self-
rotation of electron and is represented by spin quantum number, s = + 1/2 for clockwise motion
and s = - 1/2 for anticlockwise motion.

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III. How many motions are shown by an electron in an orbital? (IMP)
An electron can revolve clockwise or anticlockwise. An orbital contains two electrons. One
electron rotates anticlockwise and the other rotates clockwise. This motion is represented by spin
quantum no. s = + 1/2 for clockwise motion and s = - 1/2 for anticlockwise motion.

EXERCISE
Q4 (a). Why is it necessary to decrease the pressure in the discharge tube to get the cathode
rays?
At high pressure large amount of gas is present in the discharged tube. It will cause hindrance for
the movement of electrons (cathode rays). Thus, conduction of electricity is difficult. When the
pressure is decreased, the no. of gas molecules in the discharge tube also decreases. Thus due to
less no. of molecules, there are less chances of collision between the rays and these molecules
and cathode rays can easily pass through the tube between the electrodes.

(b) Whichever gas is used in the discharge tube, the nature of cathode rays remains the
same. Why? Or why e/m value of the cathode rays for all gases is same?
The cathode rays are actually electrons. Electrons are fundamental particles of atoms of every
element. Therefore the production of cathode rays results always in production of electrons with
same e/m value. Hence, nature of cathode rays remains the same, whichever gas is used.

(c) Why e/m value of the cathode rays is just equal to that of electron?
Sir J. J. Thomson in 1897, by a series of experiments determined e/m of particles of cathode
rays. It was found to be 1.7588 x 1011 C kg-1. This value was exactly same as that e/m of
electron. So it was concluded that cathode rays are streams of negatively charged particles called
electrons.

(d) How the bending of the cathode rays in the electric and magnetic fields shows that they
are negatively charged?
In the absence of electric or magnetic field, cathode rays move in straight line perpendicular to
the cathode surface. In 1895, J. Perrin showed that when cathode rays are passed between poles
of magnet, the path of cathode rays is changed which showed that they have charge.
In 1897, J. J. Thomson established their electric charge by the application of electric field. The
cathode ray deflected towards positive plate showing their negative charge.

(e) Why positive rays are called canal rays?

In 1886, E. Goldstein discovered the positive rays by using a perforated cathode in discharge
tube. He observed that not only cathode rays are formed in discharge tube but some other rays
after passing through the perforated cathode produce a glow on the wall opposite to anode. The
positively charged rays produced in the discharge tube are called canal rays because they pass
through the holes or canals of perforated cathode.

(f) The e/m value of positive rays obtained for the different gases are different but that of
cathode rays are same for different gases. Why?
Positive rays are produced due to ionization of gases present in the discharge tube. Every gas has
a different nature of positive ion produced. e.g., consider the ionization of He and Ne.
He + e- → He+ (Positive ray) + 2e-
Ne + e- → Ne+ (Positive ray) + 2e-
Therefor e/m of positive rays depends upon the nature of gas. Lighter the gas greater the e/m
value and vice versa. Cathode rays are only electrons whose nature remains same in all atoms.
Thus e/m ratio is same for different gases of electrons.

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(g) The e/m values of positive rays obtained from the hydrogen gas (or proton) is 1836
times less than that of the cathode rays (electrons). Justify it?
An atom of hydrogen consists of one proton and one electron. When hydrogen gas is taken in the
discharge tube, the positive ray particles are just proton. The mass of a proton is 1836 times more
than that of an electron (cathode rays) but charge is equal to the electron. Thus, the e/m value of
a proton will be 1836 times less than that of electron or cathode rays.

Q5. (c) Calculate the mass of an electron having charge of 1.6022 ×10-19 C and charge to
mass ratio of 1.7588×1011 Ckg-1?
Given:
Charge on electron (e-) = C
Charge/mass ratio ( /𝑚) = C kg-1
Required:
Mass of electron (m) =?
Solution:
C

= C

m=
m= 9.1095 × 10-31 kg

Q7. (a) Which postulate tells us that orbits are stationary and energy is quantized?
The first postulate of Bohr‟s model is, “Electron revolves in one of the circular orbits having
fixed energy outside the nucleus”. So, 1st postulate tells us that an orbit is stationary and its
energy is quantized.

Q7. (c) How does Bohr’s equation tell you that radius?
i. radius is directly proportional to the square of the number of the orbits.
ii. The radius is inversely proportional to the atomic number (Z).
According to Bohr‟s equation:
rn=
Where π, h2, m, e2 and are constant. By putting the values of these constant values and solving
Bohr‟s equation we obtain:
rn = 0. 529 Ao ( )
Hence, equation shows that:
i. The radius is directly proportional to the square of the number of the orbits.
ii. The radius is inversely proportional to the atomic number (Z) which corresponds to the
number of protons in the nucleus.

Q7. (d) How do you come to know that the velocities of electrons in higher orbits are less
than those in lower orbits of hydrogen atom? OR The speed of electrons near the nucleus is
greater than that in the higher orbits? Justify. (IMP)
According to Bohr‟s theory, the equation for velocity of an electron in any orbit is:
v2 = OR v2 α
The above equation shows that square of velocity of electron is inversely proportional to the
radius of orbit (r). Its means electron revolve faster in an orbit of smaller radius nearer to the
nucleus. As the electron moves to higher orbits of larger radius, its velocity is decreased.

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Q7. (e) Justify that the distance gaps between different orbits go on increasing from the
lower to the higher orbits?
The general formula for the radii of the hydrogen atoms is: r = 0.529 A0 (n)2 where n = no. of
shell or orbit. The radius is directly proportional to the square of the number of the shell. By
putting the values of n as 1,2,3,4 …., the radii of orbits of hydrogen atom are:
n=1 r1 = 0.529 A0 (n)2 ⇒ 0.529 A0 (1)2 ⇒ 0.529 A0
n=2 r2 = 0.529 A0 (n)2 ⇒ 0.529 A0 (2)2 ⇒ 2.11 A0
n=3 r3 = 0.529 A0 (n)2 ⇒ 0.529 A0 (3)2 ⇒ 4.75 A0
n=4 r4 = 0.529 A0 (n)2 ⇒ 0.529 A0 (4)2 ⇒8.464 A0
The comparison of radii shows that the distance between orbits of H-atom goes on increasing as
we move from 1st orbit to higher orbits. The orbits are not equally spaced.

Q8. (a) Total energy of the bounded electron is negative. Justify?

According to Bohr‟s theory:
Potential energy (P. E.) =
The minus sign indicated that the energy decrease when the electron is brought from infinity to a
distance “r”. At infinity, electron is not attracted by anything and potential energy of system is
zero. Whereas, at a point nearer to the nucleus, it will be attracted by the nucleus and potential
energy of electron is less than zero (Attraction force decreases the P. E.). The quantity less than
zero is negative. Therefore P. E. of electron is negative from infinity to at a point a distance “r”
from nucleus.

Q8. (b) Total energy of bonded electron is negative?

We know that total energy of a system is sum of kinetic energy and potential energy.
E = P. E. + K. E.
By solving the P. E. + K. E. for electron the values, we get:
Total energy (En) = ( )
The minus sign indicated that the energy decrease when the electron is brought from infinity to a
distance “r”. At infinity, electron is not attracted by anything and potential energy of system is
zero. Whereas. At a point nearer to the nucleus, it will be attracted by the nucleus and potential
energy of electron is less than zero (Attraction forces decreases the P. E.).

Q8. (c)Energy of an electron is inversely proportional to “n2”, but energy of higher orbits is
always greater than those of the lower orbits. Justify?
According to Bohr‟s theory, the energy of electron in nth orbit of hydrogen atom is given as:
En = ( ) OR En α 1/ n2
i. Thus, equation shows that: the energy of electron is inversely proportional to n2.
ii. The negative sign indicates the attraction between electron and nucleus. As the electron moves
to higher orbits, its attraction with nucleus decreases and hence its potential energy increases.
From the above relationship, it is concluded that smaller the value of n, greater will be the value
of E with negative sign and vice versa. Less negative values are actually larger while more
negative values are smaller.
Example:
For n = 1 E1 = ( ) ⇒-1313.13
For n = 2 E2 = ( ) ⇒-328.32
Thus, the energy “E2” is greater than “E1”

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Q8. (d) The energy difference between adjacent levels goes on decreasing sharply. Justify?
According to Bohr‟s theory, the energy of electron in nth orbit of hydrogen atom is given as:
En = ( )
This equation shows that the energy of electron is inversely proportional to n2.
For n = 1 E1 = ( ) ⇒-1313.13
For n = 2 E2 = ( ) ⇒-328.32
For n = 3 E3 = ( ) ⇒-145.92
For n = 4 E4 = ( ) ⇒-82.08
E2 - E1 = (-328.32) – (-1313.13) ⇒ 984.99
E3 – E2 = (-145.92) – (-328.32) ⇒ 182.40
E4 – E3 = (-82.08) – (-145.92) ⇒ 63.84
E2 - E1 > E3 – E2 > E4 – E3 > ……..
Hence, energy difference between adjacent levels goes on decreasing sharply.

Q9. a (i) Give an expression for energy difference between two levels n 1 and n2, for
hydrogen atom.
According to Bohr‟s equation:
En = ( )
We can calculate the values of E1 and E2 for n1 and n2 as follows:
For hydrogen Z = 1
For n1: E1 = ( )

For n2: E2 = ( )
We can say that:
ΔE = E2 - E1
ΔE = ( ) ( )

ΔE = ( ) ] OR

ΔE = ( ) [ ]

Q9. a (ii) How expression for ΔE from Bohr’s equation can be used to calculate the
frequency of emitted or absorbed photon?
According to Bohr’s equation:
ΔE = hυ ……. (i)
ΔE = ( ) [ ] ………… (ii)
But Z = 1 for hydrogen atom. Hence, equation (ii) becomes:
ΔE = ( ) [ ] (iii)
We can substitute the value of ΔE from equation (i) in equation (iii):
hυ = ( ) [ ]

υ=( ) [ ] (iv)
So frequency (υ) of emitted or absorbed proton can be calculated by using equation (iv).

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Q9. a (iii) How wave number is calculated from Bohr’s equation?
According to Bohr‟s equation for frequency of photon:
υ=( ) [ ] [∴υ = c ῡ]

cῡ=( ) [ ]

ῡ=( )[ ]
After calculating the constants of equation we obtain:
ῡ = 1.096 x 107 [ ] m-1 (i)
So wave number of photon can be calculated by using equation (i)

Q10. (a) What is spectrum? Differentiate between continuous and line spectrum.
Spectrum: Visual display or dispersion of components of white light, when it is passed through
a prism is called spectrum. OR The band of different colors is called spectrum.

Comparison of continuous and line spectrum:

Continuous spectrum Line spectrum
1. There is no boundary line between the 1. There is a dark space between different
different colors in this spectrum. colors in this spectrum.
2. One color merges into other without any 2. Distinct coloured lines are separated by dark
dark space. spaces.
3. It is the property of matter in bulk. 3. It is the property of an atom.
4. For example, rainbow, white light of sun and 4. For example, hydrogen spectrum and
light from incandescent source. sodium spectrum.

Q10. (b) Compare line emission and line absorption spectra.

Atomic emission line spectra Atomic absorption line spectra
1. It is a spectrum formed by elements or their 1. The spectrum produced by a light from
compounds when they are heated in flame or which certain wavelengths have been absorbed
subjected to electric discharge. by a substance is called atomic absorption
spectrum.
2. Sample is in gaseous state and excited state. 2. Sample is in gaseous, liquid or solid states.
3. Spectrum of this radiation consists of bright 3. Here spectrum appears in the form of dark
lines against a dark background. lines bright background.

Q10. (c) What is the origin of line spectrum?

When hydrogen is filled in a discharge tube at a very low pressure, a bluish light is emitted from
the discharge tube due to excitation and de-excitation of electron in hydrogen. This light when
viewed through a spectrometer shows several isolated sharp lines.

Q11. (a) Hydrogen and He+ are mono-electronic systems but the size of He+ is much smaller
than that of H+. Why?
The charge on the He+ nuclei is double than that of H+ due to more no. of protons. So due to
more attraction of nucleus the size of He+ is much smaller than that of H+.
No of protons in He+= 2 No of protons in H= 1
+
Force of attraction between two protons of He for one electron is greater than force of attraction
between one proton and one electron in H-atom. Therefore, Size of He+ is much smaller than H-
atom. We can prove this by Bohr‟s equation as well.
rn = 0.529 ( ) A0

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0 0
For H-atom: rH = 0.529 ( ) A ⇒ 0.529 A

For He+: r He+ = 0.529 ( ) A0 ⇒ 0.2645 A0

The comparison of radius of first orbit of two species shows that the size of He+ is nearly half the
size of hydrogen.

Q11. (b) Do you think that the size of Li+2 is even smaller than He+? Justify with
calculation?
Both He+ and Li+ ions have one electron in their outermost shell. However, the nucleus of Li+2
has greater positive charge (due to three protons) than that of He+ ion (due to two protons).
Therefore, nucleus of Li+2 attracts its electron more powerfully as compared to He+. Hence, size
Li2+ smaller than He+.
No of protons in He+= 2 No of protons in Li+2= 3
We can prove this by Bohr‟s equation as well.
According to Bohr‟s equation the radius of first/outermost shell of Li+2 and He+ are given as,
rn = 0.529 ( ) A0

For He+: r He+ = 0.529 ( ) A0 ⇒ 0.2645 A0

For Li+2: r Li+2 = 0.529 ( ) A0 ⇒ 0.176 A0

Due to greater atomic number, the size and radius of Li+2 is smaller than that of He+.

Q12. (b) How does Bohr’s model justify Moseley’s equation? (IMP)
According to Bohr‟s model, the frequency of a photon is:
υ=( ) [ ] OR
υ α Z2 ⇒ αZ
Thus, when the electrons jump from higher orbit (n2) to lower orbit (n1), the square root of
frequency of emitted photon is directly proportional to the atomic number of element. Which is
the Mosley‟s law i. e, according to Moseley‟s equation also, the frequency of X-rays is directly
proportional to the square of atomic number of the target metal. .
= a (Z-b)
„a‟, „Z‟ and „b‟ is a proportionality constant, atomic number and screening constant. Frequency is
reduced by screening constant.

Q13. (b) How Bohr’s model defects are partially covered by dual nature of electron and
Heisenberg’s uncertainty principle?
i. Bohr consider electrons as a material particle of small mass moving around the nucleus in
fixed circular orbits. But De-Broglei suggested that an electron has a dual nature i.e., wave as
well as particle (material). It means orbits of electrons are the waves of electrons around the
nucleus.
ii. Bohr in his fourth postulate determined the angular momentum (𝑚𝑣 ) of electron and
calculated radius of orbit (position of electron) at the same time accurately. It is not possible
according to Heisenberg. He proved that at a time you can determine either the position of
electron or its momentum accurately.

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Q14. (a) Briefly discuss the wave mechanical model of atom. How has it given the idea of
orbital? Compare orbit and orbitals.
Wave mechanical model: This model was represented by Schrodinger. According to this model,
an atom has a positively charged nucleus surrounded by a standing or stationary wave. This
model describes electron as three dimensional wave in the electric field of positively charged
nucleus.
Idea of orbital: According to Schrodinger, the position of electron cannot found exactly. The
probability of finding the electron at a certain position at any time can be found. The solution of
Schrodinger‟s wave equations gives the probability of finding the electron present in a small
region of space. It is defined as:
“The volume of space around the nucleus in which there is 95% chance of finding the electron is
called atomic orbital.
Comparison of orbit and orbitals:
Orbit Orbital
i. It is a circular path in which electron revolve i. The volume of space around the nucleus in
around the nucleus. which there is 95% chance of finding the
electron is called atomic orbital.
ii. It is represented by K, L, M, N ….. ii. It is represented by s,p d and f.
iii. It is two dimensional or flat. iii. It is three dimensional.
iv. Number of electron in orbit is given by the iv. Each orbital contain maximum two
formula „2n2‟. Where „n‟ is the number of electrons.
orbit.
v. In orbit exact position of electron is v. In orbital exact position and momentum of
indicated. an electron cannot be measured with certainty.
vi. Orbits are spherical in shape. vi. Orbitals have different shapes.
vii. This term is used in Bohr‟s atomic model vii. This term is used in quantum mechanical
theory. model.

Q14. (b) What are quantum numbers? Discuss their significance?

Quantum numbers: Quantum numbers are the sets of numerical values which give the
acceptable solutions to Schrodinger wave equation for hydrogen atom. The significance of four
quantum numbers is as follows:
i. Principal Quantum Number (n): Principle quantum number tells us size and energy of a
shell. Greater the value of „n‟ greater will be the energy and size of shell. It also tells us no. of
electrons in a shell by „2n2‟ formula. Where „n‟ is the number of orbit.
ii. Azimuthal Quantum Number (𝓵): Azimuthal Quantum Number tells us the shapes of
subshells and energy of subshell. It also tells us maximum no. of electrons in subshell by
(2n + 1) formula. It explains the splitting of spectral lines in spectrometer.
iii. Magnetic Quantum Number (m): Magnetic Quantum Number tells us the no. of
orientations (orbitals) in the space along x-, y- and z- axes in subshell. An orbital can have
maximum of two electrons. It explains the splitting of spectral lines in magnetic field (Zeeman
Effect).
iv. Spin Quantum Number (s): Spin Quantum Number tells us the spin of electron about its
own axis and direction of magnetic field produce due to spin.

Q14. (a) When Azimuthal number has a value 3, then there are seven values of magnetic
quantum number. Give reasons.
Magnetic quantum number is used to find the no. of orientations of the subshells in the space
along x-, y- and z- axes. Its values are m = 0, ±1, ±2, ±3…
The value of magnetic quantum number „m‟ depends upon the values of Azimuthal quantum
number „𝓵‟. The total no. of orientations of a subshell can be found by the formula m = (2 𝓵 + 1).
When 𝓵 = 3, then „m‟ is,

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m = (2 𝓵 + 1) ⇒ (2 x 3 + 1) ⇒7
So f – subshell has different ways of orientation in space because it has 7 values of magnetic
quantum number (m = 0, ±1, ±2, ±3 total orientations = 7.

Q14. (b) Discuss rules for the distribution of electron in energy sub-levels and in orbits.
The rules for the distribution of electron in energy sub-shells and in orbits are as follows:
i. (n + 𝓵) rule ii. Aufbau principle
iii. Hund’s ru e iv. Pauli Exclusion Principle
For detail see book.
i. (n + 𝓵) rule: This rule says that the subshells are filled in the increasing order of n+ 𝓵 values.
Here n = Principal Quantum no. and 𝓵 = Azimuthal Quantum no. If two subshells have same n +
𝓵 values then that orbital is filled first which has low value of n. For example, 2s (2 + 0 = 2) is
filled first and 2p (2 + 1 = 3) is filled latter. Also 6d (6 + 2 = 8) is filled first than 7p (7 + 1 = 8).
ii. Aufbau Principle: Subshells are filled in increasing order of their energy values i.e.1s, 2s, 2p
and so on.
iii. Pauli’s Exclusion Principle: This principle can be stated as: “It is impossible for two
electrons residing in the same orbital of poly-electron atom to have the same values of four
quantum numbers. Two electrons in the same orbital will not have the same values of the four
quantum numbers and two electrons in the same orbitals should have opposite spin. For
example, for 1s2 both electrons have n = 1, 𝓵 = 0 and m = 1 but one has s = -1/2 (anticlockwise
rotation) and other has s = +1/2 (clockwise rotation).
iv. Hund’s Rule: If two or more degenerate orbitals are available for the electrons then they will
go to separate ones having same spin rather than pairing in one orbital
e.g. 6C = 1s2, 2s2, 2px1, 2py1, 2pz0.

Q15. (b) What is (n + 𝓵) rule? Arrange the orbitals according to this rule. Do you think that
this rule is applicable to degenerate orbitals.
For (n + 𝓵) rule and arrangement of orbitals see topic 5.9 from text book:
No, (n+ 𝓵) is not applicable to degenerate orbitals. E. g., 2px, 2py and 2pz. All have
degenerate having same ‘n’ va ue ( and as we as sa e (n va ue (3 No priority for
filling of electrons can be set on the basis of n+ 𝓵 rule. F r degenerate rbita s Hund’s ru e
is applicable.
Q15. (c) For distribution of electrons in various orbitals of La57, Cu29. Au79, I53 and Rn86 see
table 5.5 from text book:
Q20. (a) Calculate the energy of first five orbits of hydrogen atom and determine the
energy difference between them.
According to Bohr‟s theory, the energy of electron in nth orbit of hydrogen atom is given as:
E1 = J
This equation shows that the energy of electron is inversely proportional to n2.
For n = 1 E1 = ⇒ J

For n = 2 E1 = ⇒ J

For n = 3 E1 = ⇒ J

For n = 4 E1 = ⇒ 3 J

For n = 5 E1 = ⇒ J
Energy differences will be:
E2 - E1 = ( )–( ) ⇒ 3 J
E3 – E2 = ( )–( ) ⇒ 3 3 J

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E4 – E3 = ( 3 )–( ) ⇒ J
E5 – E4 = ( )–( 3 ) ⇒ J

Q20. (b) Justify that energy difference between second and third orbits is approximately
five times smaller than between first and second orbits.
Required: E2 - E1 (E3 – E2)5
Solution:
E2 - E1 = 3 J
E3 – E2 = 3 3 J
E2 - E1 (E3 – E2) 5
Substitute values of E2 - E1 and E3 – E2, thus:
3 ( 3 3 )5
3 J= 3 J
Hence, energy difference between E3 – E2 is approximately five times smaller than E2 - E1.

Q20. (c) Calculate the energy of first five orbits of He+ ion and justify that the energy
differences are different from those of hydrogen atom.
For He+ ions: Z=2
Therefore, energy for first five orbits is given as:
According to Bohr‟s theory, the energy of electron in nth orbit of hydrogen atom is given as:
E1 = J
This equation shows that the energy of electron is inversely proportional to n2.
For n = 1 E1 = ⇒ J

For n = 2 E1 = ⇒ J

For n = 3 E1 = ⇒ J

For n = 4 E1 = ⇒ J

For n = 5 E1 = ⇒ 3 J
Energy differences will be:
E2 - E1 = )– ( ) ⇒ J
E3 – E2 = ( )–( ) ⇒ J
E4 – E3 = ( )–( ) ⇒ 3 J
E5 – E4 = ( 3 )–( ) ⇒ J
Result: The energy differences of are greater than H-atom. So, photons of greater energies
are involved in the electron jumping. This is a due to greater nuclear charge of He ion than
that of hydrogen atom.

Q20. (d) Do you think that groups of spectral lines of He ions are at a different places than
those for hydrogen atom? Give reasons.
Since, energy differences between energy levels in He ion is different from hydrogen atom,
therefore spectral lines in He ions will be different from that of hydrogen spectrum.

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