CHEMISTRY STUDY MATERIAL

CLASS – XI (2022-23)
CHAPTER: STRUCTURE OF ATOM

Characteristics of cathode rays:

The nature of these rays was extensively investigated by William Crookes (1876), J. Perrin
(1895), and J. J. Thomson (1897).
The characteristics of cathode rays are as follows:
1. The properties of cathode rays are independent of the nature of the gas present in the
discharge tube or the nature of cathode.
2. They travel in a straight line perpendicular to the surface of the cathode.
3. They possess momentum and kinetic energy by the virtue of which they can cause
mechanical motion.
4. These are deflected by electric and magnetic field. The mode of deflection indicates that
they consist of minute particles carrying negative charges named as electrons.

Characteristics of anode rays.

The nature of these rays was investigated by Goldstein (1886). The particles present in the rays
were found to bear positive charges. The characteristics of anode rays are as follows:

1. The anode rays particles are positively charged and the masses are dependent on the nature
of the residual gas in the discharged tube.
2. They travel in the straight line.
3. These are deflected by electric and magnetic field. The mode of deflection indicates that
they consist of minute particles carrying positive charges called as protons.
4. The charge to mass ratio of this rays is very low compared to the cathode rays and the
values are dependent on the nature of gases in the tube.
5. They can attack the photographic plate.
Charge and mass of different sub-atomic particles:
Particle Discoverer Symbol Mass Charge
Electron J. J. Thomson (1897) e, −10𝑒 9.108x 10-31 kg -1.602x10-19 C
1
Proton E. Rutherford (1911) 𝑝, 1𝐻 1.6725x 10-27 kg 1.602x10-19 C
1
Neutron J. Chadwick (1932) 𝑛, 0𝑛 1.675x 10-27 kg -----
Rutherford’s atomic model:
From the observations of α-particle scattering experiment, Rutherford had explained the facts
in the year 1911.
1. All the positive charges of the atom along with most of the atomic mass are concentrated
within a very small central region of the atom designated as nucleus.
2. Nucleus has a diameter of 10-13cm whereas atomic diameter is of the range of 10-8cm. thus
within an atom, most of the region is vacant.
3. The atom is not a charged one. Thus the total positive charge possessed by the nucleus is
balanced by the negative charge of electrons.
4. Electrons are revolving around the nucleus in different circular orbits.

Q: Why was the gold plate taken too thin in α-particle scattering experiment by
Rutherford?
It is worth mentioning that the foil must be sufficiently thin so that,
1. Cross-sections of the adjacent nuclei never overlap.
2. An α-particle suffers deflection from an encounter with a single nucleus.
3. It does not reduce the velocity of α-particle.

Drawbacks of Rutherford’s model?

The drawbacks of Rutherford’s model are as follows:
1. Instability of Rutherford’s atom:
Though it was attempted to explain the stability of atoms by considering centrifugal force
and electrostatic attraction force, it could not be supported by electromagnetic theory, a
revolving electron under an acceleration will radiate its energy in the form of
electromagnetic radiation. Thus, by losing its energy, it will gradually spiral down into the
nucleus and the atom will get destroyed.
2. No explanation of atomic line spectra:
According to electromagnetic theory, the energy radiated in the form of electromagnetic
radiation from the revolving electron should lead to a continuous spectrum covering all the
 frequency range. But, experimentally well-defined spectral lines of definite frequencies
were noted (i.e. line spectrum).
Line spectrum
Spectra consisting of narrow, discrete regions (so called lines) are called line spectra. They are
emitted by the atoms of the elements in the gaseous state.
Assumptions of Bohr’s theory:
1) Bohr’s theory is applicable for hydrogenic system i.e. an atomic system which contains
only one electron revolving around nucleus (H, He+, Li2+ etc.).
2) Nucleus is the positively charged massive area at the center holding almost entire mass of
the atom.
Postulates of Bohr’s theory.
A. Idea of stationary state:
An electron is revolving around the nucleus in a hydrogenic system in certain discrete
circular orbits. During rotation, it neither accept nor radiate any energy. This situation is
called stationary state.
B. Location of stationary state and angular momentum of an electron:
In a stationary state, the angular momentum of an electron is conserved and it is expressed
as an integral multiple of h/2п.
mvr = nh/2п
Where, r = radius of the orbit, m = rest mass of electron, v = linear velocity of electron, n=
extent of quantization, h = Planck’s constant.
C. Attraction force:
This model obeys the laws of classical physics, such as, for a revolving electron in a circular
orbit in a stationary state, the electrostatic
Coulombic force of attraction between the
nucleus and the electron is balanced by the
centrifugal force (mv2/r) due to angular
motion of electron as obtained from Newton’s
law of motion.
mv2 Z𝑒 2
=
r 4п𝜖0 𝑟 2
Ze = charge of nucleus, e = charge of electron, ϵo= permittivity in zero medium, r = distance
of electron from nucleus.
D. Explanation of atomic spectrum:
When an electron jumps from an orbit of energy Ei to another orbit of energy Ef, a definite
amount of energy in the form of radiation is emitted or absorbed depending upon whether
the final state is at lower or higher energy compared to initial one respectively.

ΔE = Ef - Ei
Where, f and i are the final and initial states respectively.

Different spectral series of H atom:

Name of Position in
series Equation spectrum

1 1
Lyman ῡ = 𝑅𝐻 (12 - 𝑛2 ) n=2, 3, 4… ultraviolet
1 1
Balmer ῡ = 𝑅𝐻 (22 - 𝑛2 ) n= 3, 4, 5… visible
1 1
Paschen ῡ = 𝑅𝐻 ( - ) n=4, 5, 6… IR
32 𝑛2
1 1
Brackett ῡ = 𝑅𝐻 (42 - 𝑛2 ) n=5, 6, 7… far- IR
1 1
Pfund ῡ = 𝑅𝐻 (52 - 𝑛2 ) n=6, 7, 8… far- IR
1 1
Humphreys ῡ = 𝑅𝐻 ( - ) n=7, 8, 9… far- IR
62 𝑛2

Merits of Bohr’s theory:

1. It explains the stability of the atoms by introducing the concept of stationary state.
2. This model explains the atomic spectra of hydrogenic system along with the mathematical
formulation.
3. It first introduces the concept of principle quantum number.
4. It accounts for the radius of hydrogen atom which is satisfactory close to the experimental
value.
5. It gives the mathematical formulation that can calculate the energy of electron in different
energy states.
6. It gives a theoretical basis of Moseley’s law.
7. Bohr’s theory gives the value of Rydberg constant.
Limitations of Bohr’s theory:
1. It can’t account for the atomic spectrum of poly-electronic system.
2. The fine structure of atomic spectra observed under high resolutions cannot be explained
by Bohr’s theory.
3. It cannot account for the three dimensional structure of an atom.
4. It cannot explain Zeeman effect and Stark effect.
5. According to this theory, the position and momentum of an electron can be estimated
simultaneously. Hence, it is contradictory to Heisenberg’s uncertainty principle.
Quantum number:
A set of discrete numbers are required to locate a revolving electron around the nucleus.
The set of numbers are unique and significant for every electrons. These are called quantum
numbers.
Significance of principle quantum number (n).
The principle quantum number gets originated in classical mechanics from Bohr’s postulate
to quantize the angular momentum of an electron which is given by mvr = n(h/2п). In wave
mechanical model, n is come from the solution of Schrӧdinger wave equation.
Physical significance:
1. In Bohr’s model, the energy of an electron in a specified orbit is solely governed by n. The
expression of energy of the electron at nth orbit is (E) = (-) mZ2e4 / 8n2h2ϵo2.
2. In Bohr’s model, the distance of an electron in nth orbit is governed by rn=a0 (n2/z).
3. In wave mechanics, the radial nodes of an orbital is given by n-l-1.
4. For a particular quantum number, the number of total electrons in a particular shell is given
by 2n2.

Limitations of 2n2 rule:

For a particular principle quantum number, the number of total electrons in a particular shell is
given by 2n2. But is has few limitations:
1. ‘n’ can be greater than 4 but the total electrons in a particular shell never exceeds 32.
2. Outermost shell can contain only 8 electrons.
3. The penultimate shell can have only 18 electrons.
4. If the electrons are filled in the outermost shell before the penultimate shells, then outermost
shell contains only 2 electrons.
Significance of azimuthal quantum number (l).
Azimuthal quantum number gets originated from Sommerfeld’s atomic model in the concept
of elliptical orbit. In wave mechanical model, ‘l’ is originated from schrӧdinger wave equation
of polar co-ordinate.
Physical significance:
1. In Sommerfeld’s atomic model, l denotes the ellipticity of the different orbitals.
2. Different l value gives corresponding s, p, d, f orbitals.

Orbitals s p d f
l value 0 1 2 3

3. In radial wave function, number of radial nodes is given by n-l-1 and number of angular
nodes is given by l.

4. The orbital angular momentum is given by 𝑝𝑙 = √𝑙(𝑙 + 1)(h/2п) in quantum mechanics.

Significance of magnetic quantum number (m).

The magnetic quantum number gets originated in quantum mechanics due to special
quantization of orbital angular momentum vector in presence of eternal magnetic field. . In
wave mechanical model, ‘m’ is originated from Schrödinger wave equation of polar co-
ordinate.
Physical significance:
1. In presence of external magnetic field, each energy level (corresponding to a principle
number) is divided into some region having very close energy difference. The probability
of finding electron is maximum in these regions. These regions are called orbitals.
2. For a definite l value, m has (2l+1) number of values, each designates an orbital.
3. Positive value of m implies the orbitals are inclined towards to external magnetic field.
l value Sublevel m value No. of m value No. of orbitals No. of electrons
0 s 0 1 s (1) 2
1 p -1,0,1 3 p (3) 6
2 d -2,-1,0,1,2 5 d (5) 10
3 f -3,-2,-1,0,1,2,3 7 f (7) 14

Significance of spin quantum number (s).

The spin quantum number gets originated in quantum mechanics to distinguish two electrons
in the same orbital. Uhlenbeck and Goudsmidt had introduced this quantum number to explain
the very fine structure of spectral lines in a magnetic field.
Physical significance:
1. Spin quantum number suggests the direction of electron spin around the nucleus.
2. Due to this opposite spin, there is a very small difference in energy of two electrons in the
same orbital. The two s values are = +1/2 and -1/2.

Pauli’s exclusion principle.

The assignment of quantum numbers to the electrons in an atom is restricted by Pauli’s
exclusion principle (1925). It states that no two electrons in the same atom can have the same
values for the four quantum numbers.

Hund’s rule.
All the electrons initially singly occupy the orbitals having same energy being of parallel spins.
The additional electrons (if present) will then go to each orbital to form paired (or, coupled)
electrons of opposed spins.
Aufbau principle.
Aufbau principle states that,
The electrons are always going to the available lowest energy containing orbitals and
subsequently go to the higher energy containing orbitals. Thus the sequence of orbitals to be
filled up as follows:
1s<2s<2p<3s<3p<4s<3d<4p<5s<4d<5p<6s<4f<5d<6p<7s<5f<6d<7p………
Boundary surface diagram for s-orbital.
For s-orbital, l=0; m=0.

Boundary surface diagram for s-orbital.

For p-orbital, l=1; m= -1, 0, 1.
 𝒑𝒚 𝒑𝒛 𝒑𝒙

Q37: Draw different d-orbitals.

For d-orbital, l = 2; m = -2,-1, 0, 1, 2.

Differences between orbit and orbital.

Orbit Orbital
Orbital is the three dimensional region
Orbits are the circular or elliptical path, on
where probability of finding an electron is
which electrons are revolving around nucleus.
maximum.
It is a 3-D region. Orbitals have directional
This is a 2-D area having no definite direction.
properties (except s-orbital).
s-orbital is circular, p-orbital is dumbbell
Orbits are circular or elliptical
shaped etc.
It is possible to determine the position and It is not possible to find out exact position of
momentum simultaneously. electron during revolution.

Orbit can contain 2n2 no. of electrons. Only two electron can reside in an orbital.
de Broglie wave-particle duality.
In 1924, de Broglie advanced the hypothesis that all matter possesses wave properties along
with the particle properties. He postulated that, for every moving particle, there is an associated
wave given by the equation, λ= h/mv.

Prove the equation λ= h/p.

In quantum theory, the energy (E) of a photon of frequency ν is given by E=hν.

According to Einstein’s mass-energy equivalence, the photon must have a finite mass m is
related with its energy E as follows: E=mc2

Comparing the two equations, mc2 = hν or, mc = h (ν/c)

or, mc = h/λ or, λ = h/(mc) i.e. λ = h/p
Heisenberg’s uncertainty principle.
Heisenberg’s uncertainty principle states that it is impossible to determine the exact position
and velocity (or, momentum) of a subatomic particle simultaneously. The mathematical
formulation is,
Δx.Δpx ≥ (h/4п)
Isotope:
The isotopes are having same number of proton in the nucleus but due to different number of
neutrons, they have different mass number. Isotopes have similar chemical and physical
properties.
238
E.g. 𝑈(𝑝𝑟𝑜𝑡𝑜𝑛 = 92; 𝑛𝑒𝑢𝑡𝑟𝑜𝑛 = 146; 𝑎𝑡𝑜𝑚𝑖𝑐 𝑤𝑒𝑖𝑔ℎ𝑡 = 238) and
92
234
𝑈(𝑝𝑟𝑜𝑡𝑜𝑛 = 92; 𝑛𝑒𝑢𝑡𝑟𝑜𝑛 = 142; 𝑎𝑡𝑜𝑚𝑖𝑐 𝑤𝑒𝑖𝑔ℎ𝑡 = 234) are isotopes.
92
Uses of Isotopes.
The followings are the uses of isotopes:
14
1. 𝐶 is used to determine the age of fossils, old trees, and archaeological bodies.
6
32 60 131
2. 𝑃, 𝐶𝑜, 𝐼 are used to determine cancer, thyroid etc.
15 27 53
13 2 18
3. 𝐶, 𝐻, 𝑂 are used to evaluate the mechanism of a chemical reaction.
6 1 8
4. Radioactive isotopes are used in growth process of plants.

Isobar:
The isobars are having same atomic mass but different atomic numbers due to different number
40
of protons present in the nucleus. E.g. 𝐴𝑟(𝑝𝑟𝑜𝑡𝑜𝑛 = 18; 𝑛𝑒𝑢𝑡𝑟𝑜𝑛 = 22; 𝑎𝑡𝑜𝑚𝑖𝑐 𝑤𝑒𝑖𝑔ℎ𝑡 =
18
40
40) and 𝐶𝑎(𝑝𝑟𝑜𝑡𝑜𝑛 = 20; 𝑛𝑒𝑢𝑡𝑟𝑜𝑛 = 20; 𝑎𝑡𝑜𝑚𝑖𝑐 𝑤𝑒𝑖𝑔ℎ𝑡 = 40) are isobars.
20
Multiple choice questions:

1. Which of the following statements is not correct about the characteristics of

cathode rays?
(a) They start from the cathode and move towards the anode.
(b) They travel in straight line in the absence of an external electrical or magnetic
field.
(c) Characteristics of cathode rays do not depend upon the material of electrodes
in cathode ray tube.
(d) Characteristics of cathode rays depend upon the nature of gas present in the
cathode ray tube.

2. Two atoms are said to be isobars if

(a) They have same atomic number but different mass number.
(b) They have same number of electrons but different number of neutrons.
(c) They are same number of neutrons but different number of electrons.
(d) Sum of the number of protons and neutrons is same but the number of
protons is different.

3. The number of radial nodes for 3p orbital is:

(a) 3 (b) 4 (c) 2 (d) 1

4. Number of angular nodes for 4d orbital is __________ .

(a) 4 (b) 3 (c) 2 (d) 1

5. Which of the following is responsible to rule out the existence of definite paths or
trajectories of electrons?
(a) Pauli’s exclusion principle
(b) Heisenberg’s uncertainty principle
(c) Hund’s rule of maximum multiplicity
(d) Aufbau principle

6. Total number of orbitals associated with third shell will be _______.

(a) 2
(b) 4
(c) 9
(d) 3

Numericals:
1. The Balmer series in the hydrogen spectrum corresponds to the transition from n1 = 2 to
n2 = 3, 4,……… This series lies in the visible region. Calculate the wave number of line
associated with the transition in Balmer series when the electron moves to n = 4 orbit. (R H =
109677 cm-1).

2. The ejection of the photoelectron from the silver metal in the photoelectric effect
experiment can be stopped by applying the voltge of 0.35 V when the radiation of 256.7nm
is used. Calculate the work function of the silver metal.

3. Calculate the shortest and longest wavelength in H spectrum of Lyman series.(R H =

109678cm-1)

4. The ionization energy of He+ is 19.6 x 10-18 J/atom. Calculate the energy of first stationary
state of Li2+

ASSERTION – REASONING:

Read the assertion and reason carefully to mark the correct option out of the options given
below - :
(a) If both assertion and reason are true and the reason is the correct explanation of the
assertion.
(b) If both assertion and reason are true but reason is not the correct explanation of the
assertion.
(c) If assertion is true but reason is false.
(d) If assertion is false but reason is true.

1. Assertion: The position of an electron can be determined exactly with the help of an
electron microscope.
Reason: The product of uncertainty in the measurement of its momentum and the uncertainty
in the measurement of the position cannot be less than a finite limit.

2. Assertion: Threshold frequency is a characteristic for a metal.

Reason: Threshold frequency is a maximum frequency required for the ejection of electron
from the metal surface.

3. Assertion: Energy of the orbitals increases as

1s  2s = 2p  3s = 3p  3d  4s = 4p = 4d = 4 f  ......
Reason: Energy of the electron depends completely on principal quantum number.
4. Assertion: Two electrons in an atom can have the same values of four quantum numbers.
Reason: Two electrons in an atom can be present in the same shell, sub-shell and orbital
and the same spin.

5. Assertion: Absorption spectrum consists of some bright lines separated by dark spaces.
Reason: Emission spectrum consists of dark lines.