Chapter:2 Atomic structure theory notes

Introduction to Bohr’s Atomic Model

Ernest Rutherford successfully demonstrated that atoms consist of a tiny,

positively charged nucleus surrounded by negatively charged electrons. He
compared the movement of electrons around the nucleus to the planets
orbiting the sun. However, this comparison was flawed because planets are
neutral bodies, whereas electrons carry charge.

If electrons moved like planets, they would continuously lose energy, causing
them to spiral into the nucleus. Additionally, if electrons emitted energy
continuously, a continuous spectrum would be observed. However, in reality,
neither of these phenomena occur. Instead, atoms produce a line spectrum.

These issues were resolved by the Danish physicist Niels Bohr in 1913. His
atomic model was based on Planck’s quantum theory and provided a better
explanation of atomic structure.

Bohr’s Postulates of Atomic Theory

1. Electrons in Fixed Orbits

Electrons revolve around the nucleus in specific circular orbits (energy levels)
with fixed energy.

2. No Energy Change in Stable Orbit

While in a particular orbit, electrons neither lose nor gain energy.

3. Excitation of Electrons

When an electron absorbs energy, it moves to a higher energy level (excited

state).

4. De-excitation of Electrons

After a very short time, the electron returns to its original (ground) state,
emitting energy in the form of light.

5. Centripetal Force
The electrostatic attraction between the nucleus and the electron provides
the necessary centripetal force for the electron’s motion.

6. Quantization of Angular Momentum

An electron can only revolve in those orbits where its angular momentum is
an integer multiple of h/2π (Planck’s constant).

7. Stability of Energy Levels

The ground state (lowest energy level) is the most stable, while excited
states are less stable.

Defects of Bohr’s Atomic Model

While Bohr’s atomic model successfully addressed the confusions in

Rutherford’s model, it also had several limitations:

1. Limited Applicability

Bohr’s model applies only to hydrogen and similar species with a single
electron (e.g., He⁺, Li²⁺, Be³⁺). It fails to explain the spectra of multi-electron
atoms like helium, lithium, and boron.

2. Circular Orbit Assumption

Bohr suggested that electrons revolve around the nucleus in circular orbits.
However, later research showed that electrons move in three-dimensional
space rather than a single plane.

3. Violation of Heisenberg’s Uncertainty Principle

Bohr’s model assumes that electrons have a fixed position and velocity,
which contradicts Heisenberg’s Uncertainty Principle stating that both cannot
be precisely known simultaneously.

4. Neglect of Wave Nature of Electrons

Bohr’s model only considers the particle nature of electrons and does not
explain their wave-like behavior, which was later proposed by de Broglie’s
hypothesis.

Due to these limitations, Bohr’s model was eventually refined and expanded
by quantum mechanical models of the atom.
 Spectrum and Its Types

Definition of Spectrum

A spectrum refers to the range of colors or wavelengths of electromagnetic

radiation that a substance can emit or absorb. It is an essential concept in
understanding the behavior of light and atomic structure.

Types of Spectrum
The spectrum can be broadly classified into two main types:

1. Continuous Spectrum
A continuous spectrum contains all possible wavelengths of light without any
gaps.

It appears as a smooth gradient of colors blending into one another.

Example: The sunlight spectrum, which consists of all visible colors

(VIBGYOR) ranging from violet (4000Å) to red (7000Å).

When white light passes through a prism, it splits into seven colors forming a
continuous spectrum.

2. Line Spectrum (Discontinuous Spectrum)

A line spectrum consists of distinct lines of color separated by a dark
background, indicating the specific wavelengths absorbed or emitted by
atoms. There are two types:

a) Absorption Line Spectrum

This spectrum is formed when light passes through a gas, and the gas atoms
absorb specific wavelengths of radiation.

It appears as dark lines against a bright continuous background.

Example: The dark lines in the solar spectrum, caused by gases in the sun’s
atmosphere absorbing certain wavelengths.

b) Emission Line Spectrum

This spectrum is produced when excited gas atoms release energy in the
form of light.

It appears as bright colored lines on a dark background.

Example: Neon lights, fluorescent dyes, and fireworks display emission

spectra.

Hydrogen Spectrum

Formation of Hydrogen Spectrum

When high-voltage electricity or heat is applied to hydrogen gas, molecular

hydrogen (H₂) breaks into atomic hydrogen (H). These hydrogen atoms
absorb energy and move to an excited state. As the electrons return to their
lower energy levels, they emit light of specific wavelengths, forming the
hydrogen spectrum.

Series of Hydrogen Spectrum

The emitted light appears in different spectral series based on the energy
level transitions:

1. Lyman Series – Ultraviolet region (transitions to n=1)

2. Balmer Series – Visible region (transitions to n=2)
3. Paschen Series – Infrared region (transitions to n=3)
4. Brackett Series – Infrared region (transitions to n=4)
5. Pfund Series – Infrared region (transitions to n=5)
 Max Planck’s Quantum Theory
Max Planck’s Quantum Theory explains the emission and absorption of
radiation in discrete energy packets rather than a continuous manner.

Postulates of Quantum Theory

1. Discontinuous Energy Absorption and Emission

Atoms cannot absorb or emit energy continuously.

2. Photon (Quanta) Concept

The absorption or emission of energy occurs in specified amounts called

quanta (packets of energy).

A quantum of light energy is often called a photon.

3. Energy-Frequency Relationship

The amount of energy in a quantum is directly proportional to the frequency

of the radiations emitted or absorbed by a body.

Mathematically, it is given by Planck’s equation:

E=hv

Where:

E = Energy of the photon

h= Planck’s constant (6.626 × 10⁻³⁴ Js)

v = Frequency of radiation

X-Rays

Discovery of X-Rays

In 1895, W. Roentgen observed that when fast-moving electrons (cathode

rays) collide with a metal anode in a discharge tube, highly penetrating,
short-wavelength radiations are produced.

These rays were initially called Roentgen rays, but later they were named X-
rays.
X-rays can penetrate materials such as paper, glass, rubber, metal, and
human flesh.

Types of X-Rays
Moseley conducted experiments using different anode elements and
categorized X-rays into two series based on their wavelengths:

1. K-Series

Produced by elements with large atomic numbers.

Have short wavelengths and high energy due to a large energy difference
between levels.

2. L-Series

Produced by elements with small atomic numbers.

Have long wavelengths and low energy due to a small energy difference
between levels.

Production of X-Rays
X-rays are produced in a special discharge tube under specific conditions. A
high voltage of around 5000V is applied while maintaining a very low
pressure of 0.001mmHg. Cathode rays (electrons) emitted from the cathode
travel at high speed toward the anode. When these high-energy electrons
collide with the anode, their kinetic energy is converted into X-ray photons
due to electronic transitions within the anode atoms..

Properties of X-Rays
1. Short-wavelength, high-energy electromagnetic radiation.

2. Wavelength range: 0.1 Å to 10 Å

3. Travel at the speed of light.

4. Move in a straight line like cathode rays.

5. Unaffected by electric or magnetic fields.

Uses of X-Rays

1. Medical Diagnosis – Used in imaging bones and detecting fractures.

2. Dental Examination – Dentists use them to detect cavities or damaged

teeth.

3. Cancer Treatment – Used to destroy cancer cells.

4. Security Scanning – Airports use X-rays to detect hidden metallic objects

like knives and weapons.

5. Crystallography – Helps in determining the structure of crystals.

6. Industrial Inspection – Used for analyzing metal structures and detecting

defects in machinery.

Radioactivity

Discovery of Radioactivity

Radioactivity was discovered in 1896 by Henri Becquerel, a French scientist,

while working on a uranium mineral called pitchblende. He observed that this
mineral continuously emitted invisible rays that had the following effects:

 Produced bright spots on photographic plates.

 Ionized gases and penetrated thin metal sheets.
 Created fluorescence on a zinc sulfide screen.
 Were not affected by heating, cooling, expansion, or compression.
 Could be blocked by wrapping pitchblende in a lead sheet.
 Initially, these rays were called Becquerel rays, but later Marie Curie
named them radioactive rays.

Definition of Radioactivity
Radioactivity is a spontaneous and uncontrollable process in which certain
unstable elements emit invisible rays. These elements, known as radioactive
elements, undergo continuous decay, releasing energy in the form of
radiation. This emission process, called radioactivity, occurs naturally and is
unaffected by external factors such as temperature, pressure, or chemical
changes.

Contribution of Marie and Pierre Curie

Marie Curie and her husband Pierre Curie isolated the radioactive
components of pitchblende and discovered two new radioactive elements:

Polonium (Po)

Radium (Ra)

Characteristics of Radioactive Rays

 Discovered by Henri Becquerel.

 Unit of measurement: Becquerel (Bq).
 These rays cause spots on photographic plates.
 They produce glow (fluorescence) on screens.
 Heating, cooling, expansion, and compression do not affect
radioactivity.
 They can be blocked by a lead sheet.

Example of a Radioactive Element

Uranium (U-238) is a radioactive element.

It eventually decays into Lead (Pb), a stable element.

Types of Radiations
Radioactive elements emit three main types of radiations: alpha (α) particles,
beta (β) particles, and gamma (γ) rays.
Alpha particles (α) consist of two protons and two neutrons, making them
helium nuclei. They are positively charged (+2), heavy, and slow-moving.
Their penetration power is low, as they can be stopped by paper or human
skin, but they are highly ionizing.

Beta particles (β) are high-speed electrons or positrons emitted from the
nucleus. Electrons carry a negative charge (-1), while positrons have a
positive charge (+1). They are lighter and faster than alpha particles, with
moderate penetration power, as they can be stopped by aluminum foil. They
are less ionizing than alpha particles.

Gamma rays (γ) are high-energy electromagnetic waves rather than

particles. They have no charge and no mass. Their penetration power is very
high, requiring thick lead or concrete to stop them. Although weakly ionizing,
they are highly dangerous due to their deep penetration ability.

Properties of radiations

Uses of Nuclear Radiations

Nuclear radiations have several important applications in various fields:

1. Medical Field: They are used for diagnosing, monitoring, and treating
diseases, such as cancer treatment.
2. Agriculture: Radioisotopes help in treating seeds to develop new crop
varieties.
3. Energy Production: Nuclear power plants, like the Karachi Nuclear
Power Plant, generate electricity using nuclear energy.
4. Industries: They are used to monitor product quality, such as
measuring the density of metals and the thickness of plastics.
5. Geology: Scientists use nuclear radiations to study rocks and geological
formations.
6. Archaeology: The Carbon-14 isotope is used to determine the age of
fossils and ancient artifacts.

Quantum Numbers and Orbitals

According to Bohr’s theory, electrons move in circular paths around the

nucleus. However, de Broglie considered electrons to exhibit wave-like
motion, and Schrödinger described their movement as waves in a three-
dimensional space around the nucleus. An orbital is a three-dimensional
region around the nucleus where the probability of finding an electron is
highest.

Schrödinger developed a wave equation that led to the calculation of

quantum numbers, which describe the energy levels, sub-levels, and
orbitals available for an electron.

There are four types of quantum numbers:

1. Principal Quantum Number (n)

Describes the size and energy of an orbital.

Denoted by n (always a positive integer: 1, 2, 3, 4…).

Energy levels are represented as K, L, M, N… for n = 1, 2, 3, 4…

Maximum number of orbitals in an orbit = n²

Maximum number of electrons in an orbit = 2n²

2. Azimuthal Quantum Number (l)

Describes the shape of an orbital.

Denoted by l (value ranges from 0 to (n – 1)).

Determines sub-shells:

L = 0 → s orbital

L = 1 → p orbital

L = 2 → d orbital

L = 3 → f orbital

Maximum number of orbitals in a sub-shell = (2l + 1)

Maximum number of electrons in a sub-shell = 2(2l + 1)

3. Magnetic Quantum Number (m)

Describes the orientation of orbitals in an atom.

Denoted by m (values range from -l to +l).

4. Spin Quantum Number (s)

Describes the spin of an electron in an orbital.

Denoted by s, with two possible values:

 +1/2 (Clockwise spin)

 -1/2 (Counterclockwise spin)
In the same orbital, electrons must have opposite spins due to the Pauli
Exclusion Principle.
 Orbitals and Their Types
Orbitals are regions of space around the nucleus where the probability of
finding an electron is highest. Each orbital has a specific size, shape, and
orientation in space.

s-Orbital
The s-orbital has a spherical shape, meaning the probability of finding an
electron is evenly distributed around the nucleus. It has only one
orientation in space and spreads uniformly along all three axes. Since it
has no directional preference, it has no nodal plane. The size of the s-
orbital increases as the principal quantum number (n) increases.

p-Orbital
The p-orbital has a dumbbell shape and is oriented along three mutually
perpendicular axes: px, py, and pz. These three orbitals are degenerate,
meaning they have equal energy. Each p-orbital consists of two lobes, one
marked (+) and the other (-). The region between the two lobes where the
probability of finding an electron is zero is called the nodal plane.
d-Orbital
The d sub-shell contains five orbitals: dxy, dyz, dxz, dx²-y², and dz². These
orbitals have complex shapes and are oriented in different directions
when placed in a magnetic field. The d-orbitals have higher energy than s
and p orbitals.

f-Orbital
The f sub-shell consists of seven orbitals, which exist in seven different
orientations under the influence of a magnetic field. These orbitals have
even more complex shapes and higher energy levels than d-orbitals.