UNIT-3: Structure of the Atom

Historical Development of Atomic Theories

 Scientific Theory: A well-tested explanation based on experiments, explaining

many observations in nature.
 Ancient Ideas:
o Empedocles (5th century BC): Proposed that all materials are made of four
elements—earth, air, water, and fire.
o Democritus (460–370 BC): Suggested that matter is made up of tiny,
indivisible particles called atoms (from the Greek word atomos, meaning
uncuttable).
o Key ideas by Democritus:
1. Atoms are too small to see and cannot be divided further.
2. There is empty space (void) between atoms.
3. Atoms are solid and have no internal structure.
4. Atoms differ in size, shape, and weight.
 Drawbacks: Early philosophers used reasoning without experiments, so their
ideas were often rejected, including Democritus's atomic theory.

Laws of Chemical Reactions

 Scientific Laws: General statements verified through experiments, describing

natural phenomena.
 Key Laws in Chemistry:
1. Law of Conservation of Mass (Lavoisier, 1789): Mass is neither created
nor destroyed in chemical reactions.
 Example: Mass of reactants = Mass of products.
2. Law of Definite Proportions (Proust, 1794): A compound always contains
the same elements in the same proportion by mass.
 Example: Water (H₂O) always has hydrogen and oxygen in a mass
ratio of 1:8.
3. Law of Multiple Proportions (Dalton, 1803): When two compounds are
made from the same elements, the ratio of the masses of one element
with a fixed mass of the other is a small whole number.
 Example: In CO, 1.33 g oxygen combines with 1 g carbon; in CO₂,
2.66 g oxygen combines with 1 g carbon. The ratio of oxygen
masses is 1:2.
Calculations in Chemistry

 Molecular Weight: Sum of atomic masses in a molecule.

o Example: Ammonium ion (NH₄⁺):
 Nitrogen = 14
 Hydrogen (4 atoms) = 4
 Total = 14 + 4 = 18
 Moles: Number of particles in a substance.
o Formula: Number of moles=Given mass / Molecular mass
o Example: 2 g of NH₄⁺ = 2/18≈0.11 moles
o These laws and calculations form the foundation for modern chemistry
and help explain the behavior of matter.

Atomic Theory

 A scientific theory explains natural phenomena and can be repeatedly tested

using observations, measurements, and experiments.
 Atomic Theory: An interpretation of facts about atoms.

Dalton’s Atomic Theory (1803)

 John Dalton proposed the first scientific atomic theory based on observations and
experiments, including Proust’s Law of Definite Proportions.
 Key Tenets:
1. Elements are made of small particles called atoms.
2. Atoms cannot be created or destroyed.
3. Atoms of the same element are identical in mass and size.
4. Atoms of different elements differ in mass and size.
5. Atoms combine in simple whole-number ratios to form compounds.

Modern Atomic Theory

 Builds upon Dalton’s theory with new discoveries about subatomic particles.
 Postulates:
1. Elements are made of atoms.
2. Atoms cannot be created or destroyed in chemical reactions.
 3. Atoms of the same element have the same atomic number but may differ
in mass (isotopes).
4. Atoms of different elements are distinct.
5. Atoms combine in small whole numbers to form compounds.

Development of Modern Atomic Theory

 Chronological discoveries about atoms:

o 1886: Eugene Goldstein discovered positively charged particles (protons)
using anode ray experiments.
o 1897: J.J. Thomson discovered electrons and their charge-to-mass ratio.
o 1904: Thomson proposed the "Plum Pudding" model.
o 1909: Robert Millikan measured the charge and mass of the electron.
o 1911: Rutherford proposed the planetary model of the atom.
o 1913: Niels Bohr introduced orbits for electrons.
o 1920: Rutherford confirmed the existence of protons in the nucleus.
o 1932: James Chadwick discovered neutrons.

Drawbacks of Dalton’s Theory

1. Indivisibility of atoms: Proven false; atoms consist of protons, neutrons, and

electrons.
2. Identical atoms: Atoms of the same element may differ in mass (isotopes).
3. Mass differences: Some elements with the same atomic mass are different
(isobars).
4. Whole-number ratios: Not always valid for complex compounds (e.g., C12H22O11).
Discovery of Subatomic Particles

Protons

 Discovered by Goldstein in 1886 using anode ray (canal ray) experiments.

 Properties of Anode Rays:
1. Travel in straight lines.
2. Consist of material particles.
3. Deflected by electric and magnetic fields.
4. The nature of the rays depends on the gas used.
5. Consist of positively charged ions.

Electrons

 Discovered by J.J. Thomson in 1897 using cathode ray experiments.

 Key Experiments:
o Straight-line travel: Cathode rays create shadows, proving they travel in
straight lines.
o Particle nature: A paddle wheel placed in the path rotates, showing
cathode rays consist of particles.
o Negative charge: Cathode rays are attracted to positive plates, indicating
they are negatively charged (electrons).

Significance of Discoveries:

 Electrons and protons proved that atoms are divisible, leading to the
development of modern atomic models.

J.J. Thomson’s Atomic Model (Plum Pudding Model)

 Proposed in 1904, this model compared the atom to a plum pudding or

watermelon.
 The positively charged matter is like the soft part of the watermelon, and the
electrons are like seeds embedded in it.
 While it explained the electrical neutrality of atoms, it failed to describe how
positive and negative charges coexist without neutralizing each other.
Millikan’s Oil Drop Experiment

 In 1909, Robert Millikan performed an experiment using oil droplets to measure

the charge of an electron.
 Process:
1. Ionized air caused electrons to stick to oil drops.
2. A balanced electric field kept the droplets suspended.
 Findings:
o The smallest charge on any drop was 1.59 × 10⁻¹⁹ C, the charge of an
electron.
o Using this and Thomson’s charge-to-mass ratio, the mass of an electron
was calculated to be 9 × 10⁻²⁸ g.

Discovery of the Nucleus (Rutherford’s Experiment)

 In 1920, Ernest Rutherford conducted his famous gold foil experiment:

o A stream of α-particles was directed at thin gold foil.
o Most particles passed through, but a few deflected or bounced back,
proving the existence of a dense, positively charged nucleus.

Rutherford’s Findings:

1. Nucleus: A tiny, positively charged core that contains most of the atom's mass.
2. Electrons: Occupy the large empty space outside the nucleus.
3. Atomic Stability: Explained by a balance between:
o Electrostatic force pulling electrons inward.
o Centrifugal force pushing electrons outward.

Limitations:

 Classical physics suggested that electrons in circular motion should lose energy
and spiral into the nucleus, causing the atom to collapse.
 It couldn’t explain atomic spectra (patterns of light emitted by atoms).
Bohr’s Atomic Model

 In 1913, Niels Bohr refined Rutherford’s model using Quantum Theory:

1. Electrons revolve in specific stable orbits (energy levels) around the
nucleus.
2. Each orbit has a fixed energy, increasing with distance from the nucleus.
3. Energy levels are labeled as K, L, M, N, etc.
4. Electrons do not lose energy as long as they stay in a specific orbit.

Key Improvement:

 Bohr’s model explained the stability of atoms and atomic spectra.

Summary of Models:

1. Thomson: Atom is a uniform sphere of positive charge with embedded electrons

(like watermelon seeds).
2. Rutherford: Atom has a dense nucleus with electrons in vast empty space.
3. Bohr: Electrons move in stable energy levels around the nucleus, explaining
atomic stability and spectra.

Discovery of the Neutron and Atomic Structure

Discovery of the Neutron

 Why Neutrons Were Predicted: Scientists noticed that the atomic mass of
elements was higher than expected if only protons were present. This hinted at
the existence of another particle.
 Early Experiments: Frederic and Irene Joliot-Curie bombarded beryllium with
alpha particles, which released unknown radiation that could eject protons from
substances. They thought it was gamma rays.
 James Chadwick's Contribution:
o He repeated the experiment and found:
1. A paddle wheel moved when hit by the radiation, proving the
presence of particles with mass.
2. The radiation was unaffected by an electric field, indicating the
particles were neutral.
o He named these particles neutrons.
Alpha Particles

 Alpha particles consist of 2 protons and 2 neutrons (like a helium nucleus).

 They are emitted during radioactive decay.

Atomic Composition

Atoms consist of three main subatomic particles:

1. Protons:
o Positive charge (+1).
o Found in the nucleus.
o Mass: ~1 atomic mass unit (amu).
2. Neutrons:
o No charge (neutral).
o Found in the nucleus.
o Mass: Slightly more than 1 amu.
3. Electrons:
o Negative charge (-1).
o Orbits around the nucleus.
o Mass: ~1/2000 of a proton (almost negligible).

Atomic Number and Mass Number

1. Atomic Number (Z):

o The number of protons in an atom.
o It identifies the element. For example, hydrogen has 1 proton, so its
atomic number is 1.
2. Mass Number (A):
o The total number of protons and neutrons in the nucleus.
o Formula: Mass Number = Protons + Neutrons

Isotopes

 Definition: Atoms of the same element with the same number of protons but
different numbers of neutrons.
 Example:
o Hydrogen has 3 isotopes:
1. Protium: 1 proton, no neutron.
2. Deuterium: 1 proton, 1 neutron.
3. Tritium: 1 proton, 2 neutrons.
  Stability:
o Stable isotopes have a balanced ratio of protons to neutrons.
o Unstable isotopes are radioactive and undergo decay.

Atomic Mass

 Definition: The weighted average mass of all isotopes of an element.

 Calculated using the formula:

Summary of Key Differences

Particle Charge Mass Location

Proton +1 ~1 amu Nucleus
Neutron 0 (neutral) ~1 amu Nucleus
Electron -1 ~0.0005 amu Orbits around nucleus

These notes simplify the details for easier understanding without losing the core
concepts.

Main Energy Levels

In 1913, Niels Bohr introduced the idea of electrons orbiting the nucleus in specific
paths, called main energy levels or shells. These levels are identified by numbers (1, 2,
3, 4, etc.) or letters (K, L, M, N, etc.). The farther the shell is from the nucleus, the higher
its energy, following this order: K < L < M < N or 1 < 2 < 3 < 4.

Electronic Configuration of Main Shells

Atoms have electrons arranged in shells around the nucleus. Each shell can hold a
maximum number of electrons calculated by the formula 2n², where n is the shell
number:

 K shell (n=1): 2 electrons

 L shell (n=2): 8 electrons
 M shell (n=3): 18 electrons
 N shell (n=4): 32 electrons

The distribution of electrons in these shells is called the electronic configuration.

Electrons fill shells starting from the one closest to the nucleus (K shell) and proceed
outward. The outermost shell is called the valence shell, the one before it is the
penultimate shell, and the next is the anti-penultimate shell.

The maximum electrons allowed in these shells are:

 Valence shell: 8 electrons

 Penultimate shell: 18 electrons
 Anti-penultimate shell: 32 electrons

Example:

1. Calcium (Atomic number = 20):

Electronic configuration: 2, 8, 8, 2
2. Argon (Atomic number = 18):
Electronic configuration: 2, 8, 8

Valence Electrons

The electrons in the outermost shell are called valence electrons. They determine an
atom's chemical properties and how it reacts with other atoms. Since these electrons
are farthest from the nucleus, they are easiest to lose or share during chemical
reactions.

Understanding the electronic configuration helps identify the number of valence

electrons and predict an element's behavior in reactions. For example:

 Calcium has 2 valence electrons in its outer shell.

 Argon has 8 valence electrons, making it stable and unreactive.