Pre-University Remedial

Chemistry Course

March 2023
 1. Atomic Structure and Periodicity

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1.1 The concept of the atom
 The Greek philosopher ,Democritus expressed the belief that all

matter consists of very small, indivisible particles, which he named

atomos (meaning uncuttable or indivisible)

 His idea was not accepted by many of his contemporaries (notably

Plato and Aristotle).

 John Dalton, formulated a precise definition of the indivisible

building blocks of matter that we call atoms

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Dalton’s Atomic Theory
 Elements are composed of extremely small particles, called atoms.

 All atoms of a given element are identical, having the same size, mass, and chemical

properties.

 Compounds are composed of atoms of more than one element. In any compound, the

ratio of the numbers of atoms of any two of the elements present is either an integer

or a simple fraction.

 A chemical reaction involves only the separation, combination, or rearrangement of

atoms

How the Modern Theory Explains the Mass Laws

Activity

Write modern atomic theory

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Which of Dalton's postulates inconsistent with later observations?
 Dalton’s concept of an atom was far more detailed and specific than Democritus

 The third hypothesis suggests that, to form a certain compound, we need not only

atoms of the right kinds of elements, but the specific numbers of these atoms as
well
 Proust’s law of definite proportions states that different samples of the same

compound always contain its constituent elements in the same proportion by mass.
 law of multiple proportions this law states, if two elements can combine to form

more than one compound, the masses of one element that combine with a fixed
mass of the other element are in ratios of small whole numbers
 Modern measurement techniques indicate that one atom of carbon combines with

one atom of oxygen in carbon monoxide and that one atom of carbon combines
with two oxygen atoms in carbon dioxide.
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 Dalton’s fourth hypothesis is another way of stating the law of conservation of

mass, which is that matter can be neither created nor destroyed.

The Structure of the Atom

 On the basis of Dalton’s atomic theory, we can define an atom as the basic unit of

an element that can enter into chemical combination.

 Investigations that began in the 1850s and extended into the twentieth century

clearly demonstrated that atoms actually possess internal structure;

 This research led to the discovery of three subatomic particles

 electrons

 protons, and

 neutrons

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1.2. Discoveries of subatomic Particles
Discovery of the Electron
 Some investigators tried passing current from a high-voltage source through nearly
evacuated glass tubes fitted with metal electrodes that were sealed

 The rays were called cathode rays because they originated at the negative
electrode (cathode) and moved to the positive electrode (anode).

 in place and connected to an external source of electricity.

 J. J. Thomson, used a cathode ray tube and his knowledge of electromagnetic

theory to determine the ratio of electric charge to the mass of an individual electron
(e-/m) -1.76 x 10-8 C/g.

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fig.1 Formation of cathode rays
 The rays were called cathode rays because
they originated at the negative electrode
(cathode) and moved to the positive electrode
(anode).
travel in a straight line,
in a magnetic field the path is bent, indicating
Fig.2 Thomson’s cathode ray tube, which was
that the particles are charged, and in an electric used to measure the charge-to-mass ratio for
the electron.
field the path bends toward the positive plate

It was concluded that cathode rays consist of negatively charged particles found in all
matter
The rays appear when these particles collide with the few remaining gas molecules in the
evacuated tube. Cathode ray particles were later named electrons.
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 After studying many droplets, Millikan calculated that the various charges of the

droplets were always some whole-number multiple of a minimum charge.

 R. A. Millikan, an American physicist, found the charge of an electron to be

1.6022 x 10-19 C. From these data he calculated the mass of an electron

 This mass is 1/1837 the mass of a hydrogen atom

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Radioactivity and Discovery of Nucleus

Radioactivity
 Radioactivity is the spontaneous emission of radiation from the unstable nuclei of

certain isotopes.
 Isotopes that are radioactive are called radioactive isotopes or radioisotopes

e.g.
 Radioactive decay is defined as a nuclear breakdown in which particles or

(electromagnetic) radiation is emitted

 three types of rays were identified in the emanations from radioactive substances.

alpha (α) particles which consist of particles that have a mass that is about four times that of
a hydrogen atom

 They also have a charge twice the magnitude of an electron but positive rather

than negative.
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 known to be a doubly-ionized helium atom, that is, He 2+
Beta (β) particles- consist of negatively-charged particles, identical to cathode rays
 are electrons and are deflected by the negatively charged plate.

Gamma (γ) rays- is a form of electromagnetic radiation much like the X-rays but of even
higher energy
 Like X rays, rays have no charge and are not affected by an external electric or
magnetic field.

Discovery of Nucleus
 In 1910, Rutherford carried out a series of experiments using very thin foils of

gold and other metals as targets for particles from a radioactive source
 They observed that the majority of particles penetrated the foil either un

deflected or with only a slight deflection.

 They also noticed that every now and then an α- particle was scattered (or

deflected) at a large angle.

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 In some instances, an α- particle actually bounced back
 From results of the α -scattering experiment, Rutherford devised a new model of

atomic structure
 The atom’s positive charges, are all concentrated in the nucleus, a dense central

core within the atom

Figure 3 Rutherford’s α -scattering experiment

 What you conclude from the deflection of each rays?

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 The diameter of an atom is on the order of 10 −10 m,
 whereas the diameter of the nucleus is roughly 10 −15 m about 100,000 times
smaller.

 Rutherford suggested that the smallest positive-ray particle was the fundamental
unit of positive charge in all nuclei
 A proton is a nuclear particle having a positive charge equal to that of the
electron and a mass more than 1840 times that of the electron.
 A proton has a mass of mp = 1.67262 × 10–27 kg

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The Discovery of Neutron
 In 1932, James Chadwick, in 1932. When Chadwick bombarded a thin sheet of

beryllium with particles, a very high energy radiation similar to rays was
emitted by the metal.
 The exp’t revealed that electrically neutral particles having a mass slightly

greater than that of protons obtained. Chadwick named these particles neutrons.
 It has an actual mass 1.674 x10-24 g which is only very slightly greater than that of
a proton

Mass and Charge of Subatomic Particles

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1.3. The Bohr Theory of the hydrogen atom
 According to Rutherford’s nuclear model, the atom consists of a nucleus with
most of the mass of the atom and a positive charge, around which move
enough electrons to make the atom electrically neutral.

 Niels Bohr introduced the atomic Hydrogen model in 1913. He described it

as a positively charged nucleus, comprised of protons and neutrons,
surrounded by a negatively charged electron cloud.

Emission Spectra
 Is expressed as either continuous or line spectra of radiation emitted by
substances.

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  Bohr set down the following postulates to account for;
Bohr’s Postulates

 The stability of the hydrogen atom (that the atom exists and its
electron does not continuously radiate energy
and spiral into the nucleus) and the line spectrum of the atom.
1. Energy-level Postulate - An electron can have only specific
energy values in an atom, which are called its energy levels.
 He derived the following formula for the energy levels of the
electron in the hydrogen atom.
Rydberg constant,
RH = 2.179*10-18 J
n= principal quantum
number

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 Cont’d
2. Transitions Between Energy Levels- An electron in an atom can
change energy only by going from one energy level to another
energy level.
 According to Bohr, the emission of light from an atom occurs as
follows. An electron in a higher energy level (initial energy level,
Ei) undergoes a transition to a lower energy level (final energy
level, Ef), explained by Balmer’s formula.

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 Cont’d
Examples
1. What is the wavelength of light emitted when the electron
in a hydrogen atom transitions from an energy level with n
= 4 to an energy level with n = 2?

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 Cont’d

 What are the limitations of Bohr's theory of a hydrogen atom?

 It violates the Heisenberg Uncertainty Principle.
 The Bohr atomic model theory made correct predictions for
smaller sized atoms like hydrogen, but poor spectral predictions
are obtained when larger atoms are considered.
 Failed to explain Stark effect when the spectral line gets split up
into fine lines in the presence of electric field.

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 Cont’d

Beginning with Rutherford

Problems with Rutherford’s Model

 It didn’t explain WHY metals and metal compounds give off

characteristic colors when they are flame tested
 It didn’t explain why metals glow when heated – first red, orange
yellow and then white
 It didn’t explain the CHEMICAL properties of elements

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 Bohr’s Theory

• Electrons are located at specific energy levels surrounding the

nucleus
• The higher the energy level – the farther it is from the nucleus

Bohr Model

• First model of the electron structure

• Gives levels where an electron is most likely to be found
• Incorrect today, but a key in understanding the atom

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 Cont’d
Bohr’s model gave hydrogen atom energy levels consistent with
the hydrogen emission spectrum.
• Ground state – lowest possible energy state (n = 1)
• Bohr’s model is incorrect. This model only works for hydrogen.
• Electrons do not move around the nucleus in circular orbits.
Electronic
Electronic Transitions in the
Transitions in the Bohr Model for
Bohr Model for the the Hydrogen
Hydrogen Atom Atom

a) An Energy-Level b) An Orbit-
Diagram for Transition
Electronic Transitions Diagram, Which
Accounts for the
Experimental
Spectrum

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 1.4 . The quantum mechanical model of the atom
 The Dual Nature of the Electron
 De Broglie reasoned that if light waves can behave like a stream of particles
(photons), then perhaps particles such as electrons can possess wave properties.

 According to de Broglie, an electron bound to the nucleus behaves like a standing

wave.
 De Broglie deduced that the particle and wave properties are related by the
expression

λ=h/mu
where λ, m, and u are the wavelengths associated with a moving particle, its mass, and
its velocity, respectively.

Example
1. What is the wavelength (in picometers) associated with an electron, whose mass is
9.11 * 10-31 kg, traveling at a speed of 4.19*106 m/s?

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 Werner Heisenberg (Heisenberg uncertainty principle): It is impossible to know
simultaneously both the momentum (mass times velocity) and the position of a particle
with certainty.
The probability of finding the electron in a certain region in space is proportional to the
square of the wave function, ψ2.

The square of the wave function, ψ2, defines the distribution of electron density in three-
dimensional space around the nucleus (schrodinger ).

• He agreed that electrons have a specific amount of energy

• Quantum – the amount of energy needed to move from one energy level to
another
• The electrons move in regions of probability around the nucleus called
Orbitals

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 Cont’d…

 Quantum theory, also called wave mechanics, describes the

arrangement and space occupied by electrons.
 Orbitals refers to the three-dimensional regions in space where
there is a high probability of finding an electron around an atom.

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 Characteristics of Electrons Energy of Electrons
When atoms are heated, bright lines
Extremely small mass
appear called line spectra
Located outside the nucleus Electrons in atoms arranged in
Moving at extremely high speeds in a discrete levels.
An electron absorbs energy to
sphere
“jump” to a higher energy level.
Have specific energy levels When an electron falls to a lower
energy level, energy is emitted.

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 Cont’d
Quantum numbers

 Quantum Numbers are used to define:

 The energy of the electron
 The electron’s relative distance from the nucleus
 The size and shape of the ORBITAL
 The pairings of the electrons

 According to quantum mechanics, each electron in an atom is

described by four different quantum numbers.

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 Cont’d
1. Principal Quantum Number (n)
• Average distance from the nucleus increases with increasing

principal quantum number, therefore n designates the size of the

electron cloud.

 Maximum of electrons in each energy level is calculated by 2n2

where n = the energy level (1-7).

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 2. The angular momentum quantum number (l)

 The number of sublevels equals the value of the principal

quantum number (n) for that level.

 Sublevels are named in the following order - s, p, d, f.

 The l number designates the shape of the electron cloud

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 3. The magnetic quantum number (ml)

 The space occupied by a pair of electrons in a certain sublevel.

Sublevel; s - 1 orbital

p - 3 orbitals

d - 5 orbitals

f - 7 orbitals

• Each orbital can hold two electrons.

• m represents the orientation in space of the orbitals (x axis, y

axis, z axis)

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 4. The spin quantum number (ms)

• Distinguishes between the electrons in the same orbital.

• Describes the electrons spin as either clockwise or counter-

clockwise

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 Quantum Numbers for the First Four Levels of Orbitals in
the Hydrogen Atom

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 Exercise

1. For principal quantum level n = 3, determine the number of

allowed subshells (different values of l), and give the
designation of each.
2. For l = 2, determine the magnetic quantum numbers (ml) and the
number of orbitals.

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 1.4.1 The electromagnetic radiation and atomic spectra
• Planck discovered that atoms and molecules emit energy only
in certain discrete quantities, or quanta.
• Energy is continuous, which meant that any amount of energy
could be released in a radiation process.
• Electromagnetic radiation is the emission and transmission of
energy in the form of electromagnetic waves.

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 • Light consists of electromagnetic waves.
• Electromagnetic radiation includes the following spectrum.

Fig. The electromagnetic spectrum showing the boundaries between different

regions.

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 Waves
 Parts of a wave:
Amplitude, crest, trough
Frequency“𝜈 ”: the number of oscillations of the field that occurs
per second.
Wavelength, “λ”: the linear distance between successive maxima
or minima of a wave. Mostly measured in nm = 10-9m.
 Speed of light can be expressed as where “λ” is the
wavelength;“𝜈 ”is the frequency, and “c”the speed of light in a
medium.
 wavenumber, “ṽ” another unit used to describe the wave
properties of electromagnetic radiation which is the reciprocal of
wavelength (i.e. )

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37
 Wave Equations

Frequency is inversely related to the wavelength by the speed of

light.
c = 

where  = wavelength,  = frequency, and c = speed of light = 3

x 108 m/s

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Dual Nature of Light
 EMR, or light, is described by the properties of both waves and
particles nature.
 Wave nature of light: In dealing with phenomena such as
reflection, refraction, interference, and diffraction, but
electromagnetic radiation is conveniently modeled as waves.
 An electromagnetic wave is characterized by several
fundamental properties, including its frequency, velocity,
amplitude, phase angle, polarization, and direction of
propagation.

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 Cont’d
Particle Nature of light: When matter absorbs
electromagnetic radiation it undergoes a change in energy.
 The interaction between matter and EMR is easiest to
understand if we assume that radiation consists of a beam of
energetic particles called photons.
 When a photon is absorbed by a sample it is “destroyed,” and
its energy acquired by the sample.
 The energy of a photon, in joules, is related to its frequency,
wavelength, and wavenumber.
 ,where“h” is Planck's constant = 6.63 x 10–34J
s
 NB:

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 E.g.1. The energy difference between the 3p and the 3s orbitals in
a sodium atom is 2.107 eV. Calculate the (in nm) that would be
absorbed in exciting the 3s electron to the 3p state (l eV = 1.60 X
10–19 J).
Solution :

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 1.4.2 Electronic Configuration and Periodic Table
Electron Configurations

 Aufbau Principle – electrons enter orbitals of lowest energy

first.
 Pauli Exclusion Principle – only 2 electrons can occupy an
orbital and they must have opposite spins.
 Hund’s Rule – When electrons occupy orbitals of equal energy
(degenerate orbitals), one electron enters each orbital until all
the orbitals contain one with parallel spins, then they will pair
up.

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43
 Periodic Table
• The periodic table is structured so that elements with the same type of valence electron
configuration are arranged in columns.

• The left-most columns include the alkali metals and the alkaline earth metals. In these
elements the valence s orbitals are being filled
• On the right hand side, the right-most block of six elements are those in which the valence
p orbitals are being filled
• In the middle is a block of ten columns that contain transition metals. These are elements
in which d orbitals are being filled
• Below this group are two rows with 14 columns. These are commonly referred to the f-
block metals. In these columns the f orbitals are being filled
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 Important facts to remember:
• 2, 6, 10 and 14 are the number of electrons that can fill the s,
p, d and f subshells (the l=0,1,2,3 azimuthal quantum number)
• The 1s subshell is the first s subshell, the 2p is the first p
subshell
• 3d is the first d subshell, and the 4f is the first f subshell

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