Jigjiga university

College of natural and computational science

Department of chemistry

Pre-University Remedial program for the 2014 E.C.

Chapter one

Atomic Structure and Periodicity

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The Concept of the Atom
Atoms are the building blocks of matter and they are the basis of all the structures and
organisms in the universe.

The planets, the sun, grass and trees, the air we breathe, and people are all made up of
different combinations of atoms.

The idea of atoms was invented by two Greek philosophers, Democritus and Leucippus in
the fifth century BC.

The Greek word atom means indivisible because they believed that atoms could not be
broken down into smaller pieces.

This theory was not based on the experimental evidences.

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Aristotle was part of the generation that succeeded Democritus but He did not believe in
atomos.

Aristotle thought that all matter was continuous i.e. if one proceeded on breaking down a
substance, it would be impossible to reach to the last indivisible particle.

In 1803, however, John Dalton proposed a completely different theory of matter.

His theory was based on scientific experimental observations and logical laws.

These scientific assumptions were very closely related to what is presently known about
the atom

John Dalton is often referred to as the father of modern atomic theory.

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Dalton also worked on the relative masses of atoms and gave symbols to some elements
as illustrated in Figure below.

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Models of the Atom
Nowadays, we know that atoms are made up of a positively charged nucleus in the
Centre surrounded by orbiting negatively charged electrons.

However, in the past, before the structure of the atom had been discovered, scientists
came up with lots of different models or pictures to describe what atoms look like.
Dalton’s Atomic Model
 The Plum Pudding Model
 Rutherford’s Model
 The Bohr Model
The Wave Model / Quantum Mechanical Model

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Dalton’s Atomic Model
This model of atoms was accepted for 100 years without serious challenge.

He thought of atoms as solid indestructible spheres. He called it the billiard ball model.

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Thomson Model (The Plum Pudding Model)
After the electron was discovered (by J.J. Thomson in 1897), people realized that atoms
were made up of even smaller particles and the plum pudding model was proposed.

In this picture, atoms are thought of as the negative electrons floating in a soup of
positive charge like plums in a pudding or raisins in a fruit cake!

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Rutherford’s Model of the Atom
Radioactive elements emit different types of particles.

Some of these are positively charged alpha (α) particles.

Rutherford carried out a series of experiments where he bombarded sheets of gold foil with
these particles, to get a better understanding of where the positive charge in the atom was.

A simplified diagram of his experiment is shown in figure a & b below

Figure (a) shows the path of the α particles after they hit the gold sheet.

Figure (b) shows the arrangement of atoms in the gold sheets, and the path of the α particles in
relation to this
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Rutherford set up his experiment so that a beam of alpha particles was directed at the
gold sheets.

most of the alpha particles passed through the foil undisturbed, and could be detected on
the screen directly behind the foil (A).

Some of the particles ended up being slightly deflected onto other parts of the screen
(B).

But what was even more interesting was that some of the particles were deflected
straight back in the direction from where they had come (C)

These were the particles that had been repelled by the positive protons in the gold atoms.
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If the Plum Pudding model of the atom were true, then Rutherford would have expected much
more repulsion since the positive charges distributed throughout the atom.

His model described the atom as a tiny, dense, positively charged core called a nucleus,
surrounded by lighter, negatively charged electrons.

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The Bohr Model
Rutherford's model proved that the plum pudding model was wrong and pictured the atom
like a mini solar system

There were some problems with this model.

He could not explain that atoms only emit light at certain wavelengths or frequencies.

Niels Bohr solved this problem by proposing that the electrons could only orbit the
nucleus in certain special orbits with particular energies i.e. energy levels.

The exact energies of the orbitals depends on the type of atom, for example Helium has
different energy levels to Carbon.
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Bohr calculated the size of the Hydrogen atom (nucleus plus one electron) by calculating
the distance between the nucleus and the electron in its lowest energy level.

This distance is known as the Bohr radius. a0 = 5.29177210810-11 m

Based on the Rutherford's atomic model, Bohr made the following modifications.

 The electrons in an atom can exist only in a restricted number of stable orbits with energy
levels in which they neither absorb nor emit energy.

These orbits designated by a number called the principal quantum number, n.

The principal quantum number has the values of 1, 2, 3, . . .

The energy levels are also called shells which represented by K, L, M, . . . etc.
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K-shell is the first shell, the L-shell is the second shell, the M-shell is the third shell, etc.

When an electron moves between orbits it absorbs or emits energy.

 According to Bohr, for each element, the number of energy levels or shells is fixed.

 The maximum number of electrons that the main energy level can have is given by the
general formula 2n2, where n is equal to the main energy level.

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 When electrons fill the various energy levels in an atom, they first occupy the shell with
the lowest energy level.
 When the lowest energy level is filled, according to the 2n2 rule, then the electrons enter
the next higher energy level.
 The outermost shell of an atom cannot accommodate more than eight electrons, even if it
has the capacity to hold more electrons.
 This is because having more than eight electrons in the outermost shell makes the atom
unstable. 15
The Wave Model / Quantum Mechanical Model
Quantum mechanics or wave mechanics to describe the behavior of very small particles
at very small distances.

In this model, particles can be described as waves instead of little billiard balls.

the properties of the particle (its position or velocity) are described by probabilities.

In the quantum mechanical model of the atom, you can imagine the electron as a wave.

Then the electron does not move along a specific path in its orbit, but rather along all
imaginable paths with different probabilities.

the electron can be found anywhere around the nucleus, very close to or far from it.
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  the probabilities of finding the electron at
different distances from the nucleus would be
different.
 If you picture the electron as a cloud around
the nucleus then in some places this cloud
will be denser (thicker) while in other places
it will be less dense (thinner).

 The density of the cloud corresponds to the probability of finding the electron in a
particular place
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The results of such a calculation for the hydrogen atom are shown in Fig. below.

On the y-axis is the probability of finding the electron and on the x-axis is the distance
away from the center of the nucleus.

the highest point on the curve is the same as the Bohr radius.

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The larger the energy value of n, the farther the electrons are found from the nucleus.

This model introduces the concept of sublevel for each main energy level.

there are four types of sublevels designated by the letters s, p, d, and f.

The number of sublevels within each energy level is equal to the numerical value of n

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 Quantum Numbers
The four quantum numbers are:

1. The principal quantum number (n) is a positive integer provide us the following info:

(i) Relative size of the orbital or the relative distance of the electron from the nucleus.

(ii) Energy of the orbital. Higher the n value, greater is the energy.

when the electron occupies an orbital with n = 1, the hydrogen atom is in its ground state

It has lower energy than when the electron occupies an orbital with n = 2 (first excited
state).

iii) Maximum number of electrons present in any shell (given by the formula 2n2).
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2. The azimuthal quantum number (l) is also known as angular momentum

It is an integer having values from 0 to (n – 1).

For an orbital with n = 1, l can have a value only of 0.

orbitals with n = 2, l have a value of 0 or 1; for those with n = 3, l can be 0, 1 or 2; etc.

So, the number of possible l values equals the value of n.

For a given value of n, the maximum possible value of l is (n – 1).

The azimuthal quantum number gives the following information:

(i) Number of subshell present within any shell and shape of the orbital
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3. The magnetic quantum number (ml) is the orbital-orientation quantum number.

It is an integer having values from –l through 0 to +l.

 The possible values of an orbital's magnetic quantum number are set by its angular momentum
quantum number (that is, l determines ml).

An orbital with l = 0 can have only ml = 0.

an orbital with l = 1, can have ml value of –1, 0, or + 1; thus there are three possible orbitals
with l = 1 each with its own spatial orientation.

The number of possible ml values or orbitals for a given l value is (2l + 1).

It prescribes the orientation of the orbital in the three-dimensional space about the nucleus
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4. The electron spin quantum number (ms) has two possible values, +½ (↑) and – ½ (↓).

The name electron spin quantum suggests that electrons have a spinning motion.

The letters s, p, d, and f are derived from the names of spectroscopic lines: s, sharp; p,
principal; d, diffuse; and f, fundamental.

the sublevel with n = 2, l = 0 is 2s sublevel; the only orbital in this sublevel has n = 2, l =
0 and ml 0.

 A sublevel with n = 3, l = 1, is a 3p sublevel.

 It has three possible orbitals: one with n = 3, l = 1 and ml = –1 ; another with n = 3, l = 1

and ml = 0 and the third n = 3, l = 1, and ml = +1

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 Number of orbitals = n2 in a shell.
 Number of orbitals in a subshell = 2l+1.

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Discoveries of Subatomic Particles

In the late 1880’s, John Dalton thought atoms were indivisible.

However, a series of investigations and discoveries clearly demonstrated that atoms are
made up of smaller particles, called subatomic particles.

The three fundamental subatomic particles of an atom are

Electrons

protons, and

neutrons.

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Discovery of the Electron
The electron was the first subatomic particle to be identified.

In 1879, William Crooke studied electrical discharges in partially evacuated tubes called
discharge tubes.

Two electrodes from a high-voltage source are sealed into a glass tube from which air
has been evacuated.

The negative electrode is the cathode and the positive one is the anode.

When the high-voltage current is turned on, the glass tube emits a greenish light and a
beam of light is seen at the anode.
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These rays flow from the cathode towards the anode in a straight line.

They are called cathode rays.

Later on, in 1897, J.J. Thomson found that the beam was deflected by both electrical and
magnetic fields.

In an electric field, they bend toward the positive plate.

From this he concluded that the cathode rays are made up of very small negatively
charged particles, which he named electrons.

He concluded that electrons are constituents of all matter, because he obtained the same
results when he changed the gas and the electrode in the tube.
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 Properties of Cathode Rays
Cathode rays possess the following properties:

1. An object placed between the cathode and the opposite end of the tube, casts a shadow
on the glass.
This shows that the cathode rays travel in a straight line.

2. A paddle wheel placed in the path of cathode rays rotates.

This indicates that cathode rays are of particle nature-the particles strike the paddle
and therefore move the wheel.

3. When an electric or magnetic field is applied in the path of cathode rays, they
are deflected towards the positive plate. 29
Charge and Mass of an Electron
J.J. Thomson studied the deflection of cathode rays under the simultaneous application
of electric and magnetic fields, that are applied perpendicular to each other.

His experiment led to the precise determination of the charge-to-mass ratio (e–/m) of an
electron, and this ‘e–/m’ value was found to be 1.76 × 108 coulomb/g.

In 1909, Robert Millikan determined the charge of an electron (e–), using the oil drop
experiment.

He found the charge of an electron to be 1.60 × 10–19 coulombs.

Combination of e–/m and e– values are used to determine the mass of an electron, which
is found to be 9.11 × 10–31 kg.
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From Thomson’s experiment, e–/m = 1.76 × 108 C/g

From Millikan’s experiment, e– = 1.60 × 10–19 C

From the above discussion, it follows that:

 An electron is a fundamental particle of an atom carrying a negative charge and having
a very small mass.
 The mass of an electron is approximately 1 1837 times the mass of a hydrogen atom.
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The Bohr Theory of the Hydrogen Atom
Bohr proposed the following three postulates for his model.

1. The hydrogen atom has only certain allowable energy levels, called stationary states.
2. The atom does not radiate energy while in one of its stationary states.

3. The electron moves to another stationary state only by absorbing or emitting a photon
whose energy equals the difference in the energy between the two states.

 A spectral line results from the emission of a photon of specific energy, when the
electron moves from a higher energy state to a lower one
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An atomic spectrum appears as lines rather than as a continuum because the atom’s
energy has only certain discrete energy levels or states.

the quantum number n (n = 1, 2, 3, ...) is associated with the radius of the electron’s
orbit, which is directly related to the atom’s energy.

The lower the quantum number, the smaller is the radius of the orbit and the lower is the
energy level of the atom.

When the electron is in the orbit closest to the nucleus (n = 1), the atom is in its lowest
(first) energy level, which is called the ground state.

This second energy level and all higher levels are called excited states.
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The hydrogen atom in the second energy level (first excited state) can return to the
ground state by emitting a photon of a particular frequency

where Eg and Ee represent the ground and the excited energy states, respectively.

 When a sample of atomic hydrogen absorbs energy, different hydrogen atoms absorb
different amounts
 When an electron drops from orbits with n > 3 (second excited state), the infrared
series of spectral lines is produced i.e, Paschen Series.
 The visible series arises from the photons emitted when an electron drops to the n = 2
orbit i.e., Balmer Series (first excited state)
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the ultraviolet series arises when these higher energy electrons drop to the n = 1 orbit
(ground state).

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Since a larger orbit radius means a higher atomic energy level, the farther the electron
drops, the greater is the energy (higher v, shorter λ) of the emitted photon.

The spectral lines of hydrogen become closer together in the short wavelength (high
energy) region of each series

Each specified energy value (E1, E2, E3,...) is called an energy level of the atom.

A very useful result from Bohr’s work is an equation for calculating the energy levels of
an atom,

where RH is the Rydberg constant, has a value of, RH = 2.18 × 10–18 J.

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n is an integer principal quantum number (n = 1, 2, 3, ...). Z is the charge of the nucleus.

The negative sign in the equation appears because it is defined as zero energy when the
electron is completely moved form the nucleus

En = 0 when n =∞, so, En < 0 for any smaller n. For the H atom, Z = 1, so we have

Therefore, the energy of the ground state n = 1 is –2.18 × 10–18 J. This equation is easily
adapted to find the energy difference between any two levels:

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The Electromagnetic Radiation and Atomic Spectra
Electromagnetic radiation is the emission and transmission of energy in the form of
electromagnetic waves.

The wave properties of electromagnetic radiation are described by two interdependent

variables, frequency and wavelength.

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Speed of light is the product of its frequency (cycles per second) and its wavelength
(metres per cycle)

 In vacuum, light travels at a speed of 2.99792458 × 108m s–1 (3.00 × 108 m s–1 to three
significant figures).
 The speed of an electromagnetic wave depends on the nature of the medium through
which the wave is travelling.
 Another characteristic of a wave is its amplitude, the height of the crest (or depth of the
trough) of the wave.
 It is related to the intensity of the radiation (brightness in the case of visible light).

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Visible light occupies a small portion of the continuum of radiant energy which is
known as the electromagnetic spectrum.

The electromagnetic waves in the different spectral region travel at the same speed but
differ in frequency and wavelength

different wave lengths (or frequencies) of visible light as different colors, from red (λ =
750 nm) to violet (λ = 400 nm).

Light of a single wavelength is called monochromatic (Greek “one color”), whereas

light of many wavelengths is polychromatic (Greek “many colors”).

White light is polychromatic.

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Atomic Spectra
Atomic or line spectra are produced from the emission of photons of electromagnetic
radiation (light).

When an element is vaporized, and thermally or electrically excited, it emits light with
discrete frequencies.

If dispersed by a prism, the light does not create a continuous spectrum, or rainbow, as
sunlight does.

Rather, it produces a line spectrum, a series of fine lines of individual colors separated
by colorless (black) spaces.
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The wavelengths at which the colored lines occur are characteristic of the element.

A line spectrum that consists of only relatively few wavelengths that is produced from
light emitted by excited atoms is the unique feature of an element and used for
identification purposes

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Electronic Configuration and Periodic Table
The arrangement of electrons in an atom is known as the electron configuration of the
atom.

Because atoms of different elements have different numbers of electrons, a distinct

electronic configuration exists for the atoms of each element.

electrons in atoms tend to assume arrangements that have the lowest possible energies.

The lowest energy arrangement of the electrons in an atom is called the ground state
electron configuration.

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The quantum mechanical model is designated by the following notation:

a coefficient which shows the main energy level, a letter that denotes the sublevel that an
electron occupies, and a superscript that shows the number of electrons in that sublevel.

2 electrons in the first s-sublevel and 1 electron in the 2nd s-

sublevel.

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Rules Governing Electron Configuration
Most of the electronic configuration of an atom can be explained in terms of the
building-up principle, or also known as the Aufbau principle.

According to this principle, an electron occupies the lowest energy orbital available
before entering a higher energy orbital.

The atomic orbitals are filled in order of increasing energy.

The orbital with the lowest energy is the 1s orbital.

The 2s orbital is the next higher in energy, then the 2p orbitals, and so on.

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The diagonal rule is a guide to the order of filling energy sublevels.

It is particularly helpful for atoms with atomic numbers higher than 18.

This is because for atoms with higher atomic numbers their sublevels are not regularly
filled.

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Periodic Classification of the Elements
Before the beginning of the 18th century, it was easy to study and remember the
properties of the elements because very few were known.

However, in the middle of the 19th century, many more elements were discovered.

Scientists then began to investigate possibilities for classifying the known elements in
a simple and useful manner.

After numerous attempts, the scientists were ultimately successful.

They grouped elements with similar properties together.

This arrangement is known as the classification of elements

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i) Dobereiner's Triads
He put together similar elements in group of three or triads.

when elements in a triad are arranged in the order of increasing atomic masses, the
middle element had the average atomic mass of the other two elements.

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ii) Newlands's Law of Octaves
In 1864, John Newlands, an English chemist, reported the law of octave, which is also
known as the law of eight.

He stated that when elements are arranged in increasing order of their atomic masses,
every eighth element had similar properties to the first element.

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The Modern Periodic Table
A. Mendeleev’s Periodic Law

Mendeleev's periodic law states that the properties of the elements are periodic functions of their
atomic masses.

Only 63 elements were known when Mendeleev constructed his table in 1871.

Mendeleev organized his table in columns, with each column containing elements that have
similar chemical properties.

Accordingly, elements in the same column gave family or groups of elements.

Mendeleev left blank spaces for the undiscovered elements and also predicted masses and other
properties of these unknown elements almost correctly
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e.g., neither gallium nor germanium were discovered when Mendeleev constructed his
periodic table

But he predicted the existence and properties of these unknown elements.

Mendeleev left two blank spaces for these two elements in the table, just under
aluminium and silicon.

He called these unknown elements 'eka-aluminium' and 'ekasilicon.' ('eka' means 'first').

What he meant by 'eka-aluminium' is "a currently known element (galium) following

aluminium“

In 1886, the element Germanium (eka-silicon) was discovered.

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in 1874, the element Gallium (eka-aluminium in Mendeleev's system) was discovered.

he properties of eka-silicon predicted by Mendeleev and compares them to the observed
properties of Germanium.

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Defects in Mendeleev's periodic table
1. Position of isotopes:

The isotopes were not given separate places in Mendeleev's periodic table.

Since elements are arranged in order of increasing atomic masses, the isotopes belong
to different groups (because isotopes have different masses).

2. Wrong order of atomic masses of some elements:

When certain elements are grouped on the basis of their chemical properties, some
elements with higher atomic masses precede those with lower atomic masses.

e.g., argon, with atomic mass of 39.95, precedes potassium with atomic mass of 39.1.
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B The Modern Periodic Law
Henry Mosley determined the atomic number of each of the elements by analyzing their
X-ray spectra.

He observed that when each element was used as a target in an X-ray tube, it gave out X-
rays with a characteristic wavelength.

The wavelength depends on the number of protons in the nucleus of the atom and was
constant for a given element.

By arranging the elements in order of decreasing wavelength, Mosley was able to assign
atomic number to each element.
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The atomic number of every element is fixed, and it clearly distinguishes one element

from another.

No two elements can have the same atomic number.

For example, atomic number 8 identifies the element oxygen. No other element can have

atomic number 8.

Therefore, the atomic number of an element is the fundamental property that determines

the chemical behavior of the element.

The discovery of atomic number led to the development of the modern periodic law.
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The modern periodic law states that: ‘‘the properties of the elements are periodic
function of their atomic numbers.’’

This means that when elements are arranged according to increasing atomic number,
elements with similar physical and chemical properties fall in the same group

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