EPH 112: PRINCIPLE OF CHEMISRTY

1. Evidence of Atomic Structure

A. Effect of Electricity on Gases:
● When high-voltage electricity is passed through gases at low pressure, it causes
the gas to emit light (called cathode rays).
● These experiments helped reveal the properties of atoms and the existence of
subatomic particles, particularly electrons.
B. Cathode Rays:
● Cathode rays are streams of electrons that flow from the cathode (negative
electrode) to the anode (positive electrode) in a vacuum tube.
● They were first observed by J.J. Thomson, leading to the discovery of the
electron as a subatomic particle with a negative charge.
C. Discovery of Electrons:
● In 1897, J.J. Thomson discovered the electron, a negatively charged particle
with negligible mass compared to the atom.
● The discovery was made through experiments with cathode rays.
D. Discovery of Nucleus:
● Ernest Rutherford’s gold foil experiment (1909) showed that atoms have a tiny,
dense nucleus at their center, and the rest of the atom is mostly empty space.
● Alpha (α)-particles were used in the experiment to bombard a thin gold foil.
● Most particles passed through, but some were deflected, indicating a small,
positively charged nucleus.
E. Isotopes:
● Isotopes are atoms of the same element that have the same number of protons
but a different number of neutrons, thus differing in atomic mass.
● Example: Carbon has isotopes like Carbon-12 and Carbon-14.
F. Mass Numbers and Relative Atomic Masses:
● The mass number is the total number of protons and neutrons in an atom.
● The relative atomic mass is the weighted average mass of the isotopes of an
element compared to 1/12th the mass of carbon-12.

2. Development of Atomic Models

A. Thomson’s Model (Plum Pudding Model):
● Proposed that the atom is a positively charged "pudding" with negatively
charged electrons embedded like "plums" within it.

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 ● This model was eventually disproved by Rutherford’s experiment.
B. Rutherford’s Model:
● Proposed that the atom consists of a dense, positively charged nucleus at the
center, with electrons orbiting around it in a large empty space.
● Introduced the concept of the nuclear atom.
C. Bohr’s Model:
● Bohr introduced fixed energy levels (orbits) where electrons could move without
radiating energy.
● Electrons could jump between orbits by absorbing or emitting a fixed amount of
energy (quanta), explaining the discrete spectral lines in atomic spectra.
D. Quantum Mechanical Model:
● The quantum mechanical model of the atom, developed by Schrödinger and
others, replaced Bohr’s fixed orbits with the concept of orbitals—regions in space
where the probability of finding an electron is highest.
● Electrons exhibit both particle and wave-like behavior.

3. Electronic Structure and Configuration

A. Energy Levels and Quantum Numbers:
● Energy levels correspond to the main electron shells (n = 1, 2, 3…).
● Each energy level can hold a specific number of electrons (2n²).
● Quantum numbers describe the position and behavior of an electron in an atom:
1. Principal quantum number (n): Defines the energy level.
2. Azimuthal quantum number (l): Defines the shape of the orbital.
3. Magnetic quantum number (mₗ): Defines the orientation of the orbital.
4. Spin quantum number (mₛ): Describes the electron’s spin (± 1/2).
B. Orbitals and Orbits:
● Orbits: Specific paths around the nucleus where electrons are likely to be found
(Bohr’s model).
● Orbitals: Probability distributions describing where electrons are likely to be
found (Quantum model). Types of orbitals include s, p, d, and f.
C. Spin, Hund’s Rule, and Pauli Exclusion Principle:
● Spin: Electrons have a property called spin, which can be either +1/2 or -1/2.
● Hund’s Rule: Electrons fill degenerate orbitals (orbitals of the same energy level)
singly first, with parallel spins, to minimize repulsion.
● Pauli Exclusion Principle: No two electrons in an atom can have the same set of
quantum numbers.

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D. Aufbau’s Principle:
Definition: The Aufbau Principle (from the German "aufbauen," meaning "to build up") is
a fundamental concept in atomic theory that explains how electrons are arranged in
atoms. According to this principle, electrons fill atomic orbitals starting from the lowest
energy level before moving to higher energy levels. This principle helps to determine the
electron configuration of elements.
Key Points:
1. Electrons in an Atom:
o Electrons are arranged in shells (energy levels) and subshells (orbitals
within each shell).
o The lower the energy of an orbital, the more stable it is, and therefore
electrons will occupy these orbitals first.
2. Order of Filling Orbitals:
o Orbitals are filled in a specific order based on increasing energy. The order is
not simply based on the principal quantum number n alone but also
includes the azimuthal quantum number l.
o The order of orbital filling is determined by the sum of the principal
quantum number n and the azimuthal quantum number l. Orbitals with
lower n+l values are filled first. If two orbitals have the same n+l value, the
orbital with the lower n is filled first.
Order of Orbital Filling:
1. 1s
2. 2s
3. 2p
4. 3s
5. 3p
6. 4s
7. 3d
8. 4p
9. 5s
10. 4d
11. 5p
12. 6s
13. 4f
14. 5d
15. 6p

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16. 7s
17. 5f
18. 6d
19. 7p
Example:
o Carbon (C): Its atomic number is 6, meaning it has 6 electrons. According to
the Aufbau principle:
● 2
The 1s orbital fills first: 1s
● 2
Then the 2s orbital: 2s
● 2
Finally, the 2p orbital: 2p
2 2 2
● Therefore, the electron configuration of carbon is: 1s 2s 2p .
1. Hund’s Rule of Maximum Multiplicity:
o When electrons are placed in degenerate orbitals (orbitals with the same
energy, such as the three p-orbitals), electrons will first occupy each orbital
singly before pairing up. Electrons in singly occupied orbitals have parallel
spins (both +1/2 or both −1/2) to minimize electron-electron repulsion.
2. Energy Considerations:
o The Aufbau principle also follows the general rule that lower-energy orbitals
fill first, which is related to the stability of the atom. This means that the
lower energy orbitals (such as s, then p, then d, and f) will be filled before
higher-energy orbitals.
Example of Electron Configuration Using Aufbau’s Principle:
● Oxygen (O): Atomic number 8. Oxygen has 8 electrons, and according to the
Aufbau principle, the electron configuration is:
2 2 4
o 1s 2s 2p This means:
o 2 electrons in the 1s orbital,
o 2 electrons in the 2s orbital,
o 4 electrons in the 2p orbitals.
Exceptions to the Aufbau Principle: While the Aufbau principle is generally followed,
there are a few known exceptions, particularly with transition metals and elements in the
d-block and f-block. These exceptions occur due to electron-electron repulsion and
stability effects like half-filled or fully filled d or f subshells being more stable. For
example:
● Chromium (Cr): Atomic number 24. Instead of the expected electron
2 4 1 5
configuration [Ar]4s 3d , chromium actually has the configuration [Ar]4s 3d . This
configuration is more stable because a half-filled d-subshell is particularly stable.
2 9
● Copper (Cu): Atomic number 29. The expected configuration would be[Ar]4s 3d ,

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 1 10
but copper actually follows[Ar]4s 3d for greater stability.
o

4. Periodic Table
A The Periodic Table is one of the most fundamental tools in chemistry. It organizes all
known chemical elements based on their atomic number, electron configurations, and
recurring chemical properties. The structure of the periodic table allows chemists to
predict the behavior of elements, their reactions, and their trends across periods and
groups. Let's break down the key aspects of the periodic table:

1. Structure of the Periodic Table:

The periodic table is arranged into rows (called periods) and columns (called groups or
families).
A. Periods (Rows):
● Definition: Periods are the horizontal rows of the periodic table. There are 7
periods in total, each representing a new electron shell being added.
● Trend Across Periods:
o As you move from left to right across a period, atomic number increases
(i.e., the number of protons and electrons increases).
o Electrons are added to the same energy level, but the effective nuclear
charge increases, pulling electrons closer to the nucleus.
o Properties change across a period: Elements move from metals (on the left)
to nonmetals (on the right), and properties like ionization energy,
electronegativity, and electron affinity generally increase from left to right.
B. Groups (Columns):
● Definition: Groups are the vertical columns in the periodic table. There are 18
groups in total.
● Trend Within Groups:
o Elements in the same group have the same number of valence electrons
and exhibit similar chemical properties.
o As you move down a group, the size of the atoms increases due to the
addition of electron shells, and elements tend to become more metallic.
o Properties within a group: The elements generally show trends in atomic
radius, ionization energy, and reactivity. For example, alkali metals in
Group 1 are highly reactive and have low ionization energies.

2. The Organization of Elements:

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The periodic table can be divided into various blocks and categories:
A. Blocks:
● s-block: Groups 1 and 2, plus helium (He) from Group 18. These elements have
their outermost electrons in s orbitals.
o Examples: Alkali metals (Group 1) and alkaline earth metals (Group 2).
● p-block: Groups 13 to 18 (excluding Helium). These elements have their
outermost electrons in p orbitals.
o Examples: Halogens (Group 17) and noble gases (Group 18).
● d-block: Transition metals, located in Groups 3 to 12. These elements have their
outermost electrons in d orbitals.
o Examples: Iron (Fe), Copper (Cu), and Silver (Ag).
● f-block: Lanthanides and actinides, often placed below the main body of the
table. These elements have their outermost electrons in f orbitals.
o Examples: Lanthanides like Lanthanum (La) and Actinides like Uranium (U).
B. Categories of Elements:
● Metals:
o Found on the left side and middle of the table (except for Hydrogen).
o Generally shiny, conductive, malleable, and ductile.
o Examples: Iron (Fe), Copper (Cu), Gold (Au).
● Nonmetals:
o Found on the right side of the table.
o Poor conductors of heat and electricity, often brittle, and can exist as gases,
liquids, or solids.
o Examples: Oxygen (O), Nitrogen (N), and Chlorine (Cl).
● Metalloids:
o Elements found between metals and nonmetals, exhibiting properties of
both.
o Examples: Silicon (Si), Arsenic (As), and Boron (B).
C. Special Groups:
● Alkali Metals (Group 1):
o Highly reactive metals that react vigorously with water.
o Examples: Lithium (Li), Sodium (Na), Potassium (K).
● Alkaline Earth Metals (Group 2):
o Less reactive than alkali metals but still reactive, especially with water.
o Examples: Magnesium (Mg), Calcium (Ca).

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 ● Halogens (Group 17):
o Nonmetals known for their high reactivity, particularly with alkali metals.
o Examples: Fluorine (F), Chlorine (Cl), Iodine (I).
● Noble Gases (Group 18):
o Extremely stable and inert gases due to their full valence electron shell.
o Examples: Helium (He), Neon (Ne), Argon (Ar).

3. Key Trends in the Periodic Table:

The periodic table reveals several trends across periods and groups that are critical for
understanding the behavior of elements:
A. Atomic Radius:
● Trend Across Periods: Atomic radius decreases as you move from left to right
across a period. This is because the increasing nuclear charge pulls electrons
closer to the nucleus, reducing the size of the atom.
● Trend Within Groups: Atomic radius increases as you move down a group
because additional electron shells are added, which increases the distance
between the outermost electrons and the nucleus.
B. Ionization Energy:
● Trend Across Periods: Ionization energy increases as you move from left to right
across a period. This is because the increasing nuclear charge makes it harder to
remove electrons.
● Trend Within Groups: Ionization energy decreases as you move down a group
because the outermost electrons are farther from the nucleus and experience
more shielding from the inner electrons, making them easier to remove.
C. Electronegativity:
● Trend Across Periods: Electronegativity increases as you move from left to right
across a period. Elements on the right side of the table (like the halogens) have
higher electronegativity because they have a stronger pull on electrons in a bond.
● Trend Within Groups: Electronegativity decreases as you move down a group
because the increasing number of electron shells reduces the nucleus’s ability to
attract bonding electrons.
D. Metallic Character:
● Trend Across Periods: Metallic character decreases across a period. As you
move from left to right, elements become less metallic and more non-metallic.
● Trend Within Groups: Metallic character increases down a group. The elements
at the bottom of the groups are more metallic in nature (e.g., alkali metals).
E. Electron Affinity:

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 ● Trend Across Periods: Electron affinity generally becomes more negative (i.e.,
more exothermic) across a period as elements tend to gain electrons more easily
to achieve a stable electron configuration.
● Trend Within Groups: Electron affinity decreases down a group as the added
electron is farther from the nucleus and is less strongly attracted.

5. Chemical Bonding and Structure

A. Chemical bonding is the force that holds atoms together in compounds. It is
responsible for the formation of molecules and solids, and it dictates the properties of
substances. There are three primary types of chemical bonds: ionic bonds, covalent
bonds, and metallic bonds. These bonds differ in how they involve the electrons of the
atoms involved and lead to distinct structural arrangements. Let's discuss these bonds,
bonding theories, and the forces that hold molecules together in more detail.

1. Types of Chemical Bonds:

A. Ionic Bonding:
Definition:
● An ionic bond is a type of chemical bond that forms when electrons are
transferred from one atom to another, resulting in the formation of oppositely
charged ions.
● Ionic compounds are generally formed between metals and nonmetals.
Mechanism:
● Electron Transfer: In an ionic bond, one atom (usually a metal) loses electrons
to become a positively charged ion (cation), while the other atom (usually a
nonmetal) gains these electrons to become a negatively charged ion (anion).
● Electrostatic Attraction: The oppositely charged ions are held together by
electrostatic forces of attraction, forming a stable ionic compound.
Example:
● Sodium Chloride (NaCl):
o Sodium (Na), a metal, loses one electron to become Na⁺.
o Chlorine (Cl), a nonmetal, gains that electron to become Cl⁻.
o The Na⁺ and Cl⁻ ions are held together by the electrostatic force of
attraction, forming the ionic compound NaCl.
Properties of Ionic Compounds:
● High melting and boiling points due to the strong electrostatic forces between
ions.
● Conduct electricity when dissolved in water (because the ions are free to move).

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 ● Typically soluble in water but insoluble in nonpolar solvents.
● Generally form crystalline structures.

B. Covalent Bonding:
Definition:
● A covalent bond forms when two atoms, usually nonmetals, share one or more
pairs of electrons to achieve a stable electron configuration.
Mechanism:
● Electron Sharing: In covalent bonding, atoms share electrons in order to fill their
valence electron shells. Each shared pair of electrons constitutes a covalent bond.
● The bond can involve one pair (single bond), two pairs (double bond), or three
pairs (triple bond) of electrons.
Example:
● Hydrogen (H₂):
o Each hydrogen atom has one electron, and by sharing this electron with
another hydrogen atom, each achieves a stable electron configuration
(similar to helium).
o The shared pair of electrons forms a single covalent bond.
● Water (H₂O):
o Oxygen shares two pairs of electrons with two hydrogen atoms to form two
single covalent bonds, resulting in a stable molecule with a bent shape.
o

Properties of Covalent Compounds:

● Lower melting and boiling points compared to ionic compounds.
● Poor conductors of electricity, as they do not contain free ions or electrons.
● Solubility depends on polarity: polar covalent compounds dissolve in polar
solvents (e.g., water), while nonpolar covalent compounds dissolve in nonpolar

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 solvents (e.g., oil).

C. Metallic Bonding:
Definition:
● A metallic bond is the bond that occurs between metal atoms, where electrons
are not shared or transferred but instead form a "sea of electrons" that move
freely around a lattice of positive metal ions.
Mechanism:
● In metallic bonding, metal atoms release some of their electrons, which are free
to move throughout the metal structure. This creates a "sea of delocalized
electrons" that surrounds a lattice of metal cations.
● The metal cations are held together by the electrostatic attraction to the
delocalized electrons.
Example:
● Copper (Cu):
o In metallic copper, the outermost electrons of copper atoms are delocalized
and free to move. These electrons hold the copper ions together and allow
them to conduct electricity.
Properties of Metallic Compounds:
● High electrical and thermal conductivity due to the free-moving electrons.
● Malleability and ductility (can be hammered into sheets or drawn into wires).
● Typically high melting and boiling points.
● Often have a shiny, metallic appearance.

2. Bonding Theories:
To understand how chemical bonds form and the resulting structures of molecules,
several bonding theories have been developed:
A. Valence Bond Theory (VB Theory):
Definition:
● Valence Bond Theory explains how atoms form bonds by considering the
overlap of atomic orbitals. According to VB theory, a bond forms when atomic
orbitals of two atoms overlap and their electrons pair up.
Key Concepts:
● Orbital Overlap: The greater the overlap of atomic orbitals, the stronger the bond.
● Hybridization: Atomic orbitals mix to form hybrid orbitals that are more suitable
for bonding. For example, in methane (CH₄), carbon undergoes sp³ hybridization
to form four equivalent bonds with hydrogen.

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The chemical bonding of two hydrogen atoms as per the valence bond theory is
illustrated below.

This theory focuses on the concepts of electronic configuration, atomic orbitals (and
their overlapping), and the hybridization of these atomic orbitals. Chemical bonds are
formed from the overlapping of atomic orbitals wherein the electrons are localized in the
corresponding bond region.
The valence bond theory also goes on to explain the electronic structure of the
molecules formed by this overlapping of atomic orbitals. It also emphasizes that the
nucleus of one atom in a molecule is attracted to the electrons of the other atoms.

Postulates of Valence Bond Theory

The important postulates of the valence bond theory are listed below.
[Link] bonds are formed when two valence orbitals (half-filled) belonging to two
different atoms overlap on each other. The electron density in the area between the two
bonding atoms increases as a result of this overlapping, thereby increasing the stability
of the resulting molecule.
[Link] presence of many unpaired electrons in the valence shell of an atom enables it to
form multiple bonds with other atoms. The paired electrons present in the valence shell
do not take participate in the formation of chemical bonds as per the valence bond
theory.
[Link] chemical bonds are directional and are also parallel to the region
corresponding to the atomic orbitals that are overlapping.
[Link] bonds and pi bonds differ in the pattern that the atomic orbitals overlap in, i.e.
pi bonds are formed from sidewise overlapping whereas the overlapping along the axis
containing the nuclei of the two atoms leads to the formation of sigma bonds.
The formation of sigma and pi bonds is illustrated below.

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It can be noted that sigma bonds involve the head-to-head overlapping of atomic
orbitals whereas pi bonds involve parallel overlapping.

Number of Orbitals and Types of Hybridization

According to VBT theory the metal atom or ion under the influence of ligands can use its
(n-1)d, ns, np, or ns, np, nd orbitals for hybridization to yield a set of equivalent orbitals
of definite geometry such as octahedral, tetrahedral, square planar and so on. These
hybrid orbitals are allowed to overlap with ligand orbitals that can donate electron pairs
for bonding.
Example:
● Methane (CH₄):
o Carbon in methane has four unpaired electrons in its 2s and 2p orbitals.
These orbitals hybridize to form four sp³ hybrid orbitals, each overlapping
with a hydrogen 1s orbital to form a covalent bond.

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 3. Intermolecular Forces:
Intermolecular forces are forces that exist between molecules. These forces are
weaker than the intramolecular forces (bonds within molecules) but play a
crucial role in determining the physical properties of substances.
A. Van der Waals Forces (Dispersion Forces):
● These are weak intermolecular forces that arise due to temporary dipoles
formed when the electron distribution in an atom or molecule becomes
asymmetrical.
● London Dispersion Forces: Present in all molecules, especially in nonpolar
molecules, and increase with the size of the molecule.
B. Dipole-Dipole Interactions:
● These occur between polar molecules where the positive end of one molecule is
attracted to the negative end of another.

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C. Hydrogen Bonding:
● A type of strong dipole-dipole interaction where a hydrogen atom, bonded to a
highly electronegative atom like oxygen, nitrogen, or fluorine, interacts with
another electronegative atom in a different molecule.
Example:
● Water (H₂O):
o Water exhibits hydrogen bonding between the hydrogen atom of one
molecule and the oxygen atom of another. This accounts for water’s high
boiling point, surface tension, and other unusual properties.

4. Molecular Structure and Shapes:

The shape of molecules is crucial in determining their physical and chemical properties.
The Valence Shell Electron Pair Repulsion (VSEPR) Theory is used to predict the
geometry of molecules based on the repulsion between electron pairs around a central
atom.
VSEPR Theory:
● Electron pairs around a central atom arrange themselves to minimize repulsion,
leading to specific molecular shapes.
Common Molecular Shapes:
● Linear: 180° bond angle (e.g., CO₂).
● Bent or Angular: Less than 120° bond angle (e.g., H₂O).
● Trigonal Planar: 120° bond angle (e.g., BF₃).
● Tetrahedral: 109.5° bond angle (e.g., CH₄).
● Trigonal Bipyramidal: 90°, 120° bond angles (e.g., PCl₅).
● Octahedral: 90° bond angle (e.g., SF₆).
Coordination Distribution of Hybrid Orbitals
Type of Hybridisation
Number in Space
3
4 sp Tetrahedral
2
4 dsp Square planar
3
5 sp d Trigonal bipyramidal
3 2
6 sp d Octahedral
2 3
6 d sp Octahedral

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